U.S. patent application number 12/294683 was filed with the patent office on 2010-11-25 for polymerizable composition, and resin and optical part using the same.
This patent application is currently assigned to MITSUI CHEMICALS, INC.. Invention is credited to Hidetoshi Hayashi, Masao Imai, Seiichi Kobayashi, Osamu Kohgo, Mitsuo Nakamura, Hiroshi Naruse, Atsuo Otsuji, Shinichi Usugi, Hideki Yamamoto.
Application Number | 20100298519 12/294683 |
Document ID | / |
Family ID | 38655178 |
Filed Date | 2010-11-25 |
United States Patent
Application |
20100298519 |
Kind Code |
A1 |
Nakamura; Mitsuo ; et
al. |
November 25, 2010 |
POLYMERIZABLE COMPOSITION, AND RESIN AND OPTICAL PART USING THE
SAME
Abstract
A polymerizable composition including a compound represented by
following General Formula (1): ##STR00001## (in Formula (1), M
represents a metal atom; X.sub.1 and X.sub.2 each independently
represents a sulfur atom or an oxygen atom; R.sub.1 represents a
divalent organic group; m represents an integer of 0 or 1 or
greater; p represents an integer of 1 to n; n represents a valence
of a metal atom M; and Y's each independently represents an
inorganic or organic residue, where when n-p is 2 or greater, Y's
may be bonded to each other to form a ring containing a metal atom
M), and a thiol compound.
Inventors: |
Nakamura; Mitsuo; (Chiba,
JP) ; Naruse; Hiroshi; (Chiba, JP) ; Otsuji;
Atsuo; (Chiba, JP) ; Usugi; Shinichi; (Chiba,
JP) ; Imai; Masao; (Kanagawa, JP) ; Hayashi;
Hidetoshi; (Fukuoka, JP) ; Kohgo; Osamu;
(Fukuoka, JP) ; Yamamoto; Hideki; (Hiroshima,
JP) ; Kobayashi; Seiichi; (Fukuoka, JP) |
Correspondence
Address: |
BUCHANAN, INGERSOLL & ROONEY PC
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Assignee: |
MITSUI CHEMICALS, INC.
Minato-ku
JP
|
Family ID: |
38655178 |
Appl. No.: |
12/294683 |
Filed: |
March 29, 2007 |
PCT Filed: |
March 29, 2007 |
PCT NO: |
PCT/JP2007/000331 |
371 Date: |
September 26, 2008 |
Current U.S.
Class: |
528/9 |
Current CPC
Class: |
C08G 75/08 20130101;
C08G 75/06 20130101; G02B 1/04 20130101; G02B 1/04 20130101; C08L
81/00 20130101 |
Class at
Publication: |
528/9 |
International
Class: |
C08G 79/00 20060101
C08G079/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2006 |
JP |
2006-101138 |
Mar 31, 2006 |
JP |
2006-101143 |
Mar 31, 2006 |
JP |
2006-101147 |
Mar 31, 2006 |
JP |
2006-101156 |
Dec 27, 2006 |
JP |
2006-351001 |
Dec 27, 2006 |
JP |
2006-351002 |
Claims
1. A polymerizable composition comprising a compound represented by
General Formula (1): ##STR00141## (wherein, in General Formula 1, M
represents a metal atom; X.sub.1 and X.sub.2 each independently
represents a sulfur atom or an oxygen atom; R.sub.1 represents a
divalent organic group; m represents an integer of 0 or 1 or
greater; p represents an integer of 1 to n; n represents a valence
of a metal atom M; and Y's each independently represents an
inorganic or organic residue where when n-p is 2 or greater, Y's
may be bonded to each other to form a ring containing a metal atom
M), and a thiol compound.
2. The polymerizable composition as set forth in claim 1, wherein
in the compound represented by General Formula (1), m is 0.
3. The polymerizable composition as set forth in claim 1, wherein
in the compound represented by General Formula (1), m is 0 and
X.sub.1 is a sulfur atom.
4. The polymerizable composition as set forth in claim 3, wherein
said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane.
5. The polymerizable composition as set forth in claim 3, wherein
the compound represented by General Formula (1) is a compound
represented by following General Formula (13): ##STR00142##
(wherein, in General Formula (13), M is a Group 14 element in a
long form of the Periodic Table, n's are each the same as in
General Formula (1), and p is an integer of 2 to (n-1), where if
n-p is 1, R.sub.2 represents an optionally substituted, linear or
branched alkyl group having 1 to 3 carbon atom(s); and if n-p is 2
or greater, a plurality of R.sub.2's each independently represents
an optionally substituted, linear or branched alkyl group having 1
to 3 carbon atom(s); further, a plurality of R.sub.2's may be
bonded to each other to form a M-containing ring, in which the
alkyl chain forming the ring has 1 to 3 carbon atom(s), and the
moiety constituting the ring contains no sulfur atom).
6. The polymerizable composition as set forth in claim 5, wherein
said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane.
7. The polymerizable composition as set forth in claim 5, wherein
in the compound represented by General Formula (13), said metal
atom is a Sn atom.
8. The polymerizable composition as set forth in claim 3, further
comprising an episulfide compound.
9. The polymerizable composition as set forth in claim 8, wherein
said episulfide compound is any of bis(2,3-epithiopropyl)sulfide
and bis(2,3-epithiopropyl)disulfide.
10. The polymerizable composition as set forth in claim 3, further
comprising sulfur as a monomer.
11. The polymerizable composition as set forth in claim 3, further
comprising a thietane compound containing no metal atom in the
molecular structure.
12. The polymerizable composition as set forth in claim 11, wherein
said thietane compound containing no metal atom in the molecular
structure is bis(3-thietanyl)disulfide.
13. The polymerizable composition as set forth in claim 3, further
comprising an epoxy compound.
14. The polymerizable composition as set forth in claim 13, wherein
said epoxy compound is any of cyclohexanedimethanol diglycidyl
ether and bisphenol F/glycidyl ether.
15. The polymerizable composition as set forth in claim 3, further
comprising an iso(thio)cyanate compound.
16. The polymerizable composition as set forth in claim 15, wherein
said iso(thio)cyanate compound is
2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane,
2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, or a mixture
thereof.
17. The polymerizable composition as set forth in claim 3, further
comprising a compound having a carbon-carbon double bond.
18. The polymerizable composition as set forth in claim 17, wherein
said compound having a carbon-carbon double bond is triallyl
isocyanurate.
19. The polymerizable composition as set forth in claim 1, wherein
in said compound represented by General Formula (1), n=p, m=0, and
X.sub.1 is a sulfur atom.
20. The polymerizable composition as set forth in claim 19, wherein
in said compound represented by General Formula (1), said metal
atom is a Sn atom.
21. The polymerizable composition as set forth in claim 19, wherein
said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane.
22. The polymerizable composition as set forth in claim 1, wherein
in said compound represented by General Formula (1), said metal
atom is any one of Groups 4, 12, 13, 14 and 15 elements in a long
form of the Periodic Table.
23. The polymerizable composition as set forth in claim 22, wherein
in said compound represented by General Formula (1), said metal
atom is a Sn atom.
24. The polymerizable composition as set forth in claim 23, wherein
said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane.
25. The polymerizable composition as set forth in claim 1, wherein
said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane.
26. The polymerizable composition as set forth in claim 1, wherein
the content of said compound represented by General Formula (1) is
50% by weight or more.
27. The polymerizable composition as set forth in claim 1, wherein
the molar ratio of thiol groups in the polymerizable composition is
0.7 or more with respect to the total amount of the
iso(thio)cyanate groups, the epoxy groups, the episulfide groups,
the carbon-carbon double bonds, and the thietanyl groups in the
thietane compound containing no metal atom.
28. A method for preparing a resin, comprising a step of casting
polymerization of the polymerizable composition as set forth in
claim 1.
29. A resin obtained by polymerization of the polymerizable
composition as set forth in claim 1.
30. An optical part comprising the resin as set forth in claim 29.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polymerizable
composition, a resin obtained by polymerization of the
polymerizable composition, and an optical part composed of the
resin.
BACKGROUND ART
[0002] Since an inorganic glass has excellent general properties
such as excellent transparency and low optical anisotropy, the
inorganic glass has been widely used in many fields as a
transparent material. However, the inorganic glass has drawbacks
such that it is heavy and easily breaks, and has bad productivity
when producing a product by molding and processing. As a result, a
transparent organic polymer material (optical resin) has been used
as a material in place of the inorganic glass. As the optical part
obtained from such an optical resin, there are, for example, a
plastic lens such as a spectacle lens for vision correction or a
camera lens of a digital camera, and the like. The optical parts
have been put to practical use and have come into use. In
particular, for the purpose of use in a spectacle lens for vision
correction, the plastic lens is light-weight and hardly broken, and
can be tinted for granting great fashionability, as compared to the
lens made of an inorganic glass. Making good use of such merits,
the plastic lens has been widely used.
[0003] In the past, a crosslinking type resin obtained by casting
polymerization of diethylene glycol bis (allyl carbonate)
hereinafter, referred to as a DAC resin) as an optical resin used
for a spectacle lens under heating has been put to practical use.
It has merits such that transparency and heat resistance are
excellent, and the chromatic aberration is low. Due to such merits,
it has been used the most for a general-purpose plastic spectacle
lens for vision correction. However, there are problems like poor
wearing comfort and fashionability because the central or edge
thickness of the plastic lens becomes large due to the low
refractive index (nd=1.50). Therefore, a resin for a plastic lens
with a high refractive index capable of solving these problems has
been demanded and developed accordingly.
[0004] During such a trend, since polythiourethane containing a
sulfur atom obtained by casting polymerization of a diisocyanate
compound with a polythiol compound is excellent in its transparency
and impact resistance, while achieving highly superior
characteristics such as attaining a high refractive index (nd=1.6
to 1.7) and having relatively low chromatic aberration, and the
like, polythiourethane has been used for the purpose of a
high-quality plastic spectacle lens for vision correction in which
the thickness is thin and its weight is light.
[0005] On the other hand, in a trend to pursue an optical resin
having a much higher refractive index, there have been proposed
several resins such as a transparent resin obtained by
polymerization of a compound having an episulfide group (Patent
Documents 1 and 2) or a resin obtained by polymerization of a
compound having a thietane group (Patent Document 3), or a resin
obtained by polymerization of a Se-containing compound (Patent
Document 4). However, the transparent resin obtained by
polymerization of a compound having an episulfide group has a
problem in mechanical properties; the compound having a thietane
group has a problem in polymerizability; and the resin obtained by
polymerization of a Se-containing metal compound has a problem in
safety. Therefore, they have been demanded for further improvement.
In recent years, there has been demanded and developed an optical
resin with a high refractive index, having required general
properties (transparency, thermal properties, mechanical
properties, and the like) as a plastic lens, while attaining a much
higher refractive index (nd) exceeding 1.7, for example. Under
these circumstances, there has been newly developed a
metal-containing thietane compound, and there has been proposed an
optical resin having a high refractive index (nd) exceeding 1.7
(Patent Document 5).
[Patent Document 1] Japanese Patent Laid-Open No. 9-110979
[Patent Document 2] Japanese Patent Laid-Open No. 11-322930
[Patent Document 3] Japanese Patent Laid-Open No. 2003-327583
[Patent Document 4] Japanese Patent Laid-Open No. 11-140046
[Patent Document 5] Pamphlet of International Patent Publication WO
2005-095490
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0006] The present invention provides a polymerizable composition,
which has general properties (transparency, thermal properties,
mechanical properties, and the like) required for optical parts
such as plastic lenses, while attaining a very high refractive
index (nd) exceeding 1.7, a resin obtained by polymerization of the
composition, and an optical part and a lens, each composed of the
resin.
Means for Solving the Problems
[0007] In order to solve the above problems, the present inventors
have conducted an extensive study on a metal-containing thietane
compound, and as a result, they have found out that a resin
obtained by copolymerization of a metal-containing thietane
compound and a thiol compound is well-balanced in a refractive
index, mechanical properties, and color of the resin. Thus, the
present invention has been completed.
[0008] That is, the present invention includes:
[0009] [1] a polymerizable composition including a compound
represented by following General Formula (1):
##STR00002##
[0010] (in General Formula (1), M represents a metal atom; X.sub.1
and X.sub.2 each independently represents a sulfur atom or an
oxygen atom; R.sub.1 represents a divalent organic group; m
represents an integer of 0 or 1 or greater; p represents an integer
of 1 to n; n represents a valence of a metal atom M; Y's each
independently represents an inorganic or organic residue, where
when n-p is 2 or greater, Y's may be bonded to each other to form a
ring containing a metal atom M),
[0011] and a thiol compound;
[0012] [2] the polymerizable composition as set forth in [1],
wherein in the compound represented by said General Formula (1), m
is 0;
[0013] [3] the polymerizable composition as set forth in [1],
wherein in the compound represented by said General Formula (1), m
is 0; and X.sub.1 is a sulfur atom;
[0014] [4] the polymerizable composition as set forth in [3],
wherein said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0015] [5] the polymerizable composition as set forth in [3],
wherein the compound represented by said General Formula (1) is a
compound represented by following General Formula (13):
##STR00003##
[0016] (in General Formula (13), M is a Group 14 element in a long
form of the Periodic Table, n's are each the same as in General
Formula (1), and p is an integer of 2 to (n-1) where
[0017] if n-p is 1, R.sub.2 represents an optionally substituted,
linear or branched alkyl group having 1 to 3 carbon atom(s);
and
[0018] if n-p is 2 or greater, a plurality of R.sub.2's each
independently represents an optionally substituted, linear or
branched alkyl group having 1 to 3 carbon atom(s), further, a
plurality of R.sub.2's may be bonded to each other to form a
M-containing ring, in which the alkyl chain forming the ring has 1
to 3 carbon atom(s), and the moiety constituting the ring contains
no sulfur atom);
[0019] [6] the polymerizable composition as set forth in [5],
wherein said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0020] [7] the polymerizable composition as set forth in [5],
wherein in the compound represented by General Formula (13), said
metal atom is a Sn atom;
[0021] [8] the polymerizable composition as set forth in [3]
further including an episulfide compound;
[0022] [9] the polymerizable composition as set forth in [8],
wherein said episulfide compound is either
bis(2,3-epithiopropyl)sulfide or
bis(2,3-epithiopropyl)disulfide;
[0023] [10] the polymerizable composition as set forth in [3],
further including sulfur as a monomer;
[0024] [11] the polymerizable composition as set forth in [3],
further including a thietane compound containing no metal atom in
the molecular structure;
[0025] [12] the polymerizable composition as set forth in [11],
wherein the thietane compound containing no metal atom in said
molecular structure is bis(3-thietanyl)disulfide;
[0026] [13] the polymerizable composition as set forth in [3],
further including an epoxy compound;
[0027] [14] the polymerizable composition as set forth in [13],
wherein said epoxy compound is any of cyclohexanedimethanol
diglycidyl ether and bisphenol F/glycidyl ether;
[0028] [15] the polymerizable composition as set forth in [3],
further including an iso(thio)cyanate compound;
[0029] [16] the polymerizable composition as set forth in [15],
wherein said iso(thio)cyanate compound is
2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane,
2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, or a mixture
thereof;
[0030] [17] the polymerizable composition as set forth in [3],
further including a compound having a carbon-carbon double
bond;
[0031] [18] the polymerizable composition as set forth in [17],
wherein said compound having a carbon-carbon double bond is
triallyl isocyanurate;
[0032] [19] the polymerizable composition as set forth in [1],
wherein in the compound represented by General Formula (1), n=p,
m=0, and X.sub.1 is a sulfur atom;
[0033] [20] the polymerizable composition as set forth in [19],
wherein in the compound represented by General Formula (1), said
metal atom is a Sn atom;
[0034] [21] the polymerizable composition as set forth in [19],
wherein said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0035] [22] the polymerizable composition as set forth in [1],
wherein in the compound represented by General Formula (1), said
metal atom is any one of Groups 4, 12, 13, 14 and 15 elements in a
long form of the Periodic Table;
[0036] [23] the polymerizable composition as set forth in [22],
wherein in the compound represented by General Formula (1), said
metal atom is a Sn atom;
[0037] [24] the polymerizable composition as set forth in [23],
wherein said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0038] [25] the polymerizable composition as set forth in [1],
wherein said thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0039] [26] the polymerizable composition as set forth in [1],
wherein the content of the compound represented by General Formula
(1) is 50% by weight or more;
[0040] [27] the polymerizable composition as set forth in [1],
wherein the molar ratio of thiol groups in the polymerizable
composition is 0.7 or more with respect to the total amount of the
iso(thio)cyanate groups, the epoxy groups, the episulfide groups,
the carbon-carbon double bonds, and the thietanyl groups in the
thietane compound containing no metal atoms;
[0041] [28] a method for preparing a resin, the method including a
step of casting polymerization of the polymerizable composition as
set forth in [1];
[0042] [29] a resin obtained by polymerization of the polymerizable
composition as set forth in [1]; and
[0043] [30] an optical part composed of the resin as set forth in
[29].
EFFECTS OF THE INVENTION
[0044] The resin obtained by polymerization of the polymerizable
composition according to the present invention has high
transparency, and good heat resistance and mechanical strength,
while attaining a high refractive index (nd) exceeding 1.7.
Therefore, the resin of the present invention is useful as a resin
used in an optical part such as a plastic lenses.
BEST MODE FOR CARRYING OUT THE INVENTION
[0045] Hereinbelow, the present invention will be described in more
detail.
[0046] Furthermore, in the following description, the priority
order of the functional group when the component of the
polymerizable composition contains a plurality of functional groups
is as follows:
[0047] (i) a thiol group,
[0048] (ii) an isocyanate group,
[0049] (iii) an epoxy group,
[0050] (iv) an episulfide group,
[0051] (v) a carbon-carbon double bond, and
[0052] (vi) a thietanyl group.
[0053] For example, as used in the following description, the
compound having a thiol group and a thietanyl group is explained in
the section of a thiol compound. Further, for example, the compound
having an epoxy group and a carbon-carbon double bond is explained
in the section of an epoxy compound.
[0054] The polymerizable composition according to the present
invention includes a metal-containing thietane compound represented
by the following General Formula (1), and a thiol compound.
[0055] Hereinafter, the specific examples of each component are
described, but the present invention is not limited to the
exemplary compounds as below. Further, in the present invention,
for each component, the exemplary compounds may be used alone, or
in a combination of two or more kinds thereof.
[0056] First, the metal-containing thietane compound will be
described. This compound is represented by the following General
Formula (1).
##STR00004##
[0057] (in General Formula (1), M represents a metal atom, X.sub.1
and X.sub.2 each independently represents a sulfur atom or an
oxygen atom, R.sub.1 represents a divalent organic group, m
represents an integer of 0 or 1 or greater, p represents an integer
of 1 to n, n represents a valence of a metal atom M, Y's each
independently represents an inorganic or organic residue, and when
n-p is 2 or greater, Y's may be bonded to each other to form a ring
containing a metal atom M).
[0058] First, M in General Formula (1) will be described. In
General Formula (1), M represents a metal atom. Examples of M
include:
[0059] a Group 11 element in a long form of the Periodic Table,
such as a Cu atom, an Au atom, and an Ag atom (the same will be
applied in the below description);
[0060] a Group 12 element, such as a Zn atom;
[0061] a Group 13 element, such as an Al atom;
[0062] a Group 4 element, such as a Zr atom and a Ti atom;
[0063] a Group 14 element, such as a Sn atom, a Si atom, a Ge atom,
and a Pb atom;
[0064] a Group 15 element, such as a Si atom; and
[0065] a Group 8 or 10 element, such as a Fe atom and a Pt
atom.
[0066] M is preferably
[0067] a Group 14 element, such as a Sn atom, a Si atom, a Ge atom,
and a Pb atom;
[0068] a Group 4 element, such as a Zr atom and a Ti atom;
[0069] a Group 13 element, such as an Al atom; or
[0070] a Group 12 element, such as a Zn atom;
[0071] more preferably,
[0072] a Group 14 element, such as a Sn atom, a Si atom, and a Ge
atom; or
[0073] a Group 4 element, such as a Zr atom and a Ti atom;
[0074] and even more preferably,
[0075] a Sn atom.
[0076] Next, the group which bonds to M, including a thietanyl
group, in General Formula (1), will be described. In General
Formula (1), X.sub.1 and X.sub.2 each independently represents a
sulfur atom or an oxygen atom. In consideration of a high
refractive index as a desired effect of the present invention,
X.sub.1 and X.sub.2 are each preferably a sulfur atom.
[0077] In General Formula (1), R.sub.1 represents a divalent
organic group.
[0078] Examples of such the divalent organic group include a
chained or alicyclic group, an aromatic group or an
aromatic-aliphatic group, preferably a chained aliphatic group
having 1 to 20 carbon atom(s), an alicyclic group having 3 to 20
carbon atoms, an aromatic group having 5 to 20 carbon atoms and an
aromatic-aliphatic group having 6 to 20 carbon atoms.
[0079] More specifically, as R.sub.1, this divalent organic group
is a chained or alicyclic group, an aromatic group or an
aromatic-aliphatic group, preferably a substituted or unsubstituted
chained or alicyclic group having 1 to 20 carbon atom(s) such as a
methylene group, an ethylene group, a 1,2-dichloroethylene group, a
trimethylene group, a tetramethylene group, a pentamethylene group,
a cyclopentylene group, a hexamethylene group, a cyclohexylene
group, a heptamethylene group, an octamethylene group, a
nonamethylene group, a decamethylene group, an undecamethylene
group, a dodecamethylene group, a tridecamethylene group, a
tetradecamethylene group, and a pentadecamethylene group;
[0080] a substituted or unsubstituted aromatic group having 5 to 20
carbon atoms such as a phenylene group, a chlorophenylene group, a
naphthylene group, an indenylene group, an anthracenylene group,
and a fluorenylene group; and
[0081] a substituted or unsubstituted aromatic-aliphatic group
having 6 to 20 carbon atoms such as a --C.sub.6H.sub.4--CH.sub.2--
group, a --CH.sub.2--C.sub.6H.sub.4--CH.sub.2-- group, a
--CH.sub.2--C.sub.6H.sub.3 (Cl)--CH.sub.2-- group, a
--C.sub.10H.sub.6--CH.sub.2-- group, a
--CH.sub.2--C.sub.10H.sub.6--CH.sub.2-- group, and a
--CH.sub.2CH.sub.2--C.sub.6H.sub.4--CH.sub.2CH.sub.2-- group.
[0082] R.sub.1 is more preferably a substituted or unsubstituted
chained or alicyclic group having 1 to 6 carbon atom(s) such as a
methylene group, an ethylene group, a 1,2-dichloroethylene group, a
trimethylene group, a cyclopentylene group, and a cyclohexylene
group;
[0083] a substituted or unsubstituted aromatic group having 5 to 15
carbon atoms such as a phenylene group, a chlorophenylene group, a
naphthylene group, an indenylene group, an anthracenylene group,
and a fluorenylene group; or
[0084] a substituted or unsubstituted aromatic-aliphatic group
having 6 to 15 carbon atoms such as a --C.sub.6H.sub.4--CH.sub.2
group, a --CH.sub.2--C.sub.6H.sub.4--CH.sub.2-- group, a
--CH.sub.2--C.sub.6H.sub.3 (Cl)--CH.sub.2-- group, a
--C.sub.10H.sub.6--CH.sub.2-- group, a
--CH.sub.2--C.sub.10H.sub.6--CH.sub.2-- group, and a
--CH.sub.2CH.sub.2--C.sub.6H.sub.4--CH.sub.2CH.sub.2-- group.
[0085] This divalent organic group may contain a heteroatom except
for a carbon atom or a hydrogen atom in the group. Examples of the
heteroatom include an oxygen atom or a sulfur atom. Considering the
desired effect of the present invention, a sulfur atom is
preferable.
[0086] In General Formula (1), m represents an integer of 0 or 1 or
greater. Examples of this m are preferably an integer of 0 to 4,
more preferably an integer of 0 to 2, and further more preferably
an integer of 0 or 1.
[0087] Furthermore, for the group containing a thietanyl group and
bonding to M in General Formula (1), it is more preferable that m
is 0, and X.sub.1 is a sulfur atom. Herein, General Formula (1) is
represented by the following General Formula (12).
##STR00005##
[0088] (in General Formula (12), M, Y, p and n are each the same as
M, Y, p and n, respectively, in General Formula (1)).
[0089] Furthermore, in General Formula (12), preferably n is p, and
more preferably n is p, and M is Sn.
[0090] Next, in General Formula (1), the --(Y).sub.n-p group
bonding to M will be described.
[0091] In General Formula (1), n represents a valence of a metal
atom M.
[0092] Furthermore, p represents an integer of 1 to n. This p is
preferably n, n-1, or n-2, and more preferably n or n-1.
[0093] In General Formula (1), Y's each independently represents an
inorganic or organic residue.
[0094] If the compound represented by General Formula (1) contains
a plurality of Y's, the plurality of Y's each independently
represents an inorganic or organic residue. That is, the plurality
of Y's may be the same as or different from each other. More
specifically, the plurality of Y's may be different from each
other, some of the plurality of Y's may be the same as each other,
or all of the plurality of Y's may be the same.
[0095] Examples of the inorganic or organic residue that
constitutes Y include, without any particular limitation, a
hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted aralkyl
group, a substituted or unsubstituted alkoxy group, a substituted
or unsubstituted alkylthio group, a substituted or unsubstituted
aryloxy group, and a substituted or unsubstituted arylthio
group.
[0096] Among these, the halogen atom, the substituted or
unsubstituted alkyl group, the substituted or unsubstituted aryl
group, the substituted or unsubstituted aralkyl group, the
substituted or unsubstituted alkoxy(alkyloxy) group, the
substituted or unsubstituted alkylthio group, the substituted or
unsubstituted aryloxy group, and the substituted or unsubstituted
arylthio group will be each described.
[0097] Specific examples of the halogen atom include a fluorine
atom, a chlorine atom, a bromine atom, and an iodine atom.
[0098] Specific examples of the substituted or unsubstituted alkyl
group include a linear alkyl group having 1 to 10 carbon atom(s) in
total such as a methyl group, an ethyl group, an n-propyl group, an
n-butyl group, an n-pentyl group, and an n-hexyl group; a branched
alkyl group having 3 to 10 carbon atoms in total such as an
isopropyl group, an isobutyl group, a sec-butyl group, an isopentyl
group, a sec-pentyl group, a 1-methylpentyl group, a 2-methylpentyl
group, a 3-methylpentyl group, a 4-methylpentyl group, a
1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylhexyl group, a
2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group,
a 5-methylhexyl group, a 1-ethylpentyl group, a 2-ethylpentyl
group, a 3-ethylpentyl group, a 1-n-propylbutyl group, a
1-iso-propylbutyl group, a 1-iso-propyl-2-methylpropyl group, a
1-methylheptyl group, a 2-methylheptyl group, a 3-methylheptyl
group, a 4-methylheptyl group, a 5-methylheptyl group, a
6-methylheptyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a
3-ethylhexyl group, a 4-ethylhexyl group, a 1-n-propylpentyl group,
a 2-n-propylpentyl group, a 1-iso-propylpentyl group, a
2-iso-propylpentyl group, a 1-n-butylbutyl group, a
1-iso-butylbutyl group, a 1-sec-butylbutyl group, a
1-tert-butylbutyl group, a 2-tert-butylbutyl group, a tert-butyl
group, a tert-pentyl group, a 1,1-dimethylbutyl group, a
1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a
2,3-dimethylbutyl group, a 1-ethyl-2-methylpropyl group, a
1,1-dimethylpentyl group, a 1,2-dimethylpentyl group, a
1,3-dimethylpentyl group, a 1,4-dimethylpentyl group, a
2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a
2,4-dimethylpentyl group, a 3,3-dimethylpentyl group, a
3,4-dimethylpentyl group, a 1-ethyl-1 ethylbutyl group, a
1-ethyl-2-methylbutyl group, a 1-ethyl-3-methylbutyl group, a
2-ethyl-1-methylbutyl group, a 2-ethyl-3-methylbutyl group, a
1,1-dimethylhexyl group, a 1,2-dimethylhexyl group, a
1,3-dimethylhexyl group, a 1,4-dimethylhexyl group, a
1,5-dimethylhexyl group, a 2,2-dimethylhexyl group, a
2,3-dimethylhexyl group, a 2,4-dimethylhexyl group, a
2,5-dimethylhexyl group, a 3,3-dimethylhexyl group, a
3,4-dimethylhexyl group, a 3,5-dimethylhexyl group, a
4,4-dimethylhexyl group, a 4,5-dimethylhexyl group, a
1-ethyl-2-methylpentyl group, a 1-ethyl-3-methylpentyl group, a
1-ethyl-4-methylpentyl group, a 2-ethyl-1-methylpentyl group, a
2-ethyl-2-methylpentyl group, a 2-ethyl-3-methylpentyl group, a
2-ethyl-4-methylpentyl group, a 3-ethyl-1-methylpentyl group, a
3-ethyl-2-methylpentyl group, a 3-ethyl-3-methylpentyl group, a
3-ethyl-4-methylpentyl group, a 1-n-propyl-1-methylbutyl group, a
1-n-propyl-2-methylbutyl group, a 1-n-propyl-3-methylbutyl group, a
1-iso-propyl-1-methylbutyl group, a 1-iso-propyl-2-methylbutyl
group, a 1-iso-propyl-3-methylbutyl group, a 1,1-diethylbutyl
group, a 1,2-diethylbutyl group, a 1,1,2-trimethylpropyl group, a
1,2,2-trimethylpropyl group, a 1,1,2-trimethylbutyl group, a
1,1,3-trimethylbutyl group, a 1,2,3-trimethylbutyl group, a
1,2,2-trimethylbutyl group, a 1,3,3-trimethyl-butyl group, a
2,3,3-trimethylbutyl group, a 1,1,2-trimethylpentyl group, a
1,1,3-trimethylpentyl group, a 1,1,4-trimethylpentyl group, a
1,2,2-trimethylpentyl group, a 1,2,3-trimethylpentyl group, a
1,2,4-trimethylpentyl group, a 1,3,4-trimethylpentyl group, a
2,2,3-trimethylpentyl group, a 2,2,4-trimethylpentyl group, a
2,3,4-trimethylpentyl group, a 1,3,3-trimethylpentyl group, a
2,3,3-trimethylpentyl group, a 3,3,4-trimethylpentyl group, a
1,4,4-trimethylpentyl group, a 2,4,4-trimethylpentyl group, a
3,4,4-trimethylpentyl group, a 1-ethyl-1,2-dimethylbutyl group, a
1-ethyl-1,3-dimethylbutyl group, a 1-ethyl-2,3-dimethylbutyl group,
a 2-ethyl-1,1-dimethylbutyl group, a 2-ethyl-1,2-dimethylbutyl
group, a 2-ethyl-1,3-dimethylbutyl group, and a
2-ethyl-2,3-dimethylbutyl group; and
[0099] a saturated cyclic alkyl group having 5 to 10 carbon atoms
in total such as a cyclopentyl group, a cyclohexyl group, a
methylcyclopentyl group, a methoxycyclopentyl group, a
methoxycyclohexyl group, a methylcyclohexyl group, a
1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a
1,4-dimethylcyclohexyl group, and an ethylcyclohexyl group.
[0100] Specific examples of the substituted or unsubstituted aryl
group include aromatic hydrocarbons having not more than 20 carbon
atoms in total such as a phenyl group, a naphthyl group, an
anthranyl group, and a cyclopentadienyl group;
[0101] an alkyl-substituted aryl group having not more than 20
carbon atoms in total such as a 2-methylphenyl group, a
3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl
group, a propylphenyl group, a butylphenyl group, a hexylphenyl
group, a cyclohexylphenyl group, an octylphenyl group, a
2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, a
4-methyl-1-naphthyl group, a 5-methyl-1-naphthyl group, a
6-methyl-1-naphthyl group, a 7-methyl-1-naphthyl group, a
8-methyl-1-naphthyl group, a 1-methyl-2-naphthyl group, a
3-methyl-2-naphthyl group, a 4-methyl-2-naphthyl group, a
5-methyl-2-naphthyl group, a 6-methyl-2-naphthyl group, a
7-methyl-2-naphthyl group, a 8-methyl-2-naphthyl group, a
2-ethyl-1-naphthyl group, a 2,3-dimethylphenyl group, a
2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a
2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a
3,5-dimethylphenyl group, a 3,6-dimethylphenyl group, a
2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a
2,3,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a
2,4,6-trimethylphenyl group, and a 3,4,5-trimethylphenyl group;
[0102] a monoalkoxyaryl group having not more than 20 carbon atoms
in total wherein a substituted or unsubstituted alkyloxy group
having not more than 10 carbon atoms is substituted, such as a
2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl
group, a 2-ethoxyphenyl group, a propoxyphenyl group, a
butoxyphenyl group, a hexyloxyphenyl group, a cyclohexyloxyphenyl
group, an octyloxyphenyl group, a 2-methoxy-1-naphthyl group, a
3-methoxy-1-naphthyl group, a 4-methoxy-1-naphthyl group, a
5-methoxy-1-naphthyl group, a 6-methoxy-1-naphthyl group, a
7-methoxy-1-naphthyl group, a 8-methoxy-1-naphthyl group, a
1-methoxy-2-naphthyl group, a 3-methoxy-2-naphthyl group, a
4-methoxy-2-naphthyl group, a 5-methoxy-2-naphthyl group, a
6-methoxy-2-naphthyl group, a 7-methoxy-2-naphthyl group, a
8-methoxy-2-naphthyl group, and a 2-ethoxy-1-naphthyl group;
[0103] a dialkoxyaryl group having not more than 20 carbon atoms in
total wherein a substituted or unsubstituted alkyloxy group having
not more than 10 carbon atoms is substituted, such as a
2,3-dimethoxyphenyl group, a 2,4-dimethoxyphenyl group, a
2,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a
3,4-dimethoxyphenyl group, a 3,5-dimethoxyphenyl group, a
3,6-dimethoxyphenyl group, a 4,5-dimethoxy-1-naphthyl group, a
4,7-dimethoxy-1-naphthyl group, a 4,8-dimethoxy-1-naphthyl group, a
5,8-dimethoxy-1-naphthyl group, and a 5,8-dimethoxy-2-naphthyl
group;
[0104] a trialkoxyaryl group having not more than 20 carbon atoms
in total wherein a substituted or unsubstituted alkyloxy group
having not more than 10 carbon atoms is substituted, such as a
2,3,4-trimethoxyphenyl group, a 2,3,5-trimethoxyphenyl group, a
2,3,6-trimethoxyphenyl group, a 2,4,5-trimethoxyphenyl group, a
2,4,6-trimethoxyphenyl group, and a 3,4,5-trimethoxyphenyl group;
and
[0105] an aryl group having not more than 20 carbon atoms in total
wherein a halogen atom is substituted, such as a chlorophenyl
group, a dichlorophenyl group, a trichlorophenyl group, a
bromophenyl group, a dibromophenyl group, an iodophenyl group, a
fluorophenyl group, a chloronaphthyl group, a bromonaphthyl group,
a difluorophenyl group, a trifluorophenyl group, a
tetrafluorophenyl group, and a pentafluorophenyl group.
[0106] Specific examples of the substituted or unsubstituted
aralkyl group include a benzyl group, a phenethyl group, a
phenylpropyl group, a naphthylethyl group, or a methyl group, an
ethyl group and a propyl group having an aryl group specifically
mentioned as examples of the substituted or unsubstituted aryl
group beforehand in a side chain.
[0107] Specific examples of the substituted or unsubstituted
alkyloxy group include a linear or branched alkoxy group having 1
to 10 carbon atom (s) in total such as a methoxy group, an ethoxy
group, an n-propoxy group, an iso-propoxy group, an n-butoxy group,
an iso-butoxy group, a tert-butoxy group, an n-pentyloxy group, an
iso-pentyloxy group, an n-hexyloxy group, an iso-hexyloxy group, a
2-ethylhexyloxy group, a 3,5,5-trimethylhexyloxy group, an
n-heptyloxy group, an n-octyloxy group, and an n-nonyloxy
group;
[0108] a cycloalkoxy group having 5 to 10 carbon atoms in total
such as a cyclopentyloxy group, and a cyclohexyloxy group;
[0109] an alkoxyalkoxy group having 2 to 10 carbon atoms in total
such as a methoxymethoxy group, an ethoxymethoxy group, an
ethoxyethoxy group, an n-propoxymethoxy group, an
iso-propoxymethoxy group, an n-propoxyethoxy group, an
iso-propoxyethoxy group, an n-butoxyethoxy group, an
iso-butoxyethoxy group, a tert-butoxyethoxy group, an
n-pentyloxyethoxy group, an iso-pentyloxyethoxy group, an
n-hexyloxyethoxy group, an iso-hexyloxyethoxy group, and an
n-heptyloxyethoxy group; and
[0110] an aralkyloxy group such as a benzyloxy group.
[0111] Specific examples of the substituted or unsubstituted
alkylthio group include a linear or branched alkylthio group having
1 to 10 carbon atom (s) in total such as a methylthio group, an
ethylthio group, an n-propylthio group, an iso-propylthio group, an
n-butylthio group, an iso-butylthio group, a sec-butylthio group, a
t-butylthio group, an n-pentylthio group, an iso-pentylthio group,
an n-hexylthio group, an iso-hexylthio group, a 2-ethylhexylthio
group, a 3,5,5-trimethylhexylthio group, an n-heptylthio group, an
n-octylthio group, and an n-nonylthio group;
[0112] a cycloalkylthio group having 5 to 10 carbon atoms in total
such as a cyclopentylthio group, and a cyclohexylthio group;
[0113] an alkoxyalkylthio group having 2 to 10 carbon atoms in
total such as a methoxyethylthio group, an ethoxyethylthio group,
an n-propoxyethylthio group, an iso-propoxyethylthio group, an
n-butoxyethylthio group, an iso-butoxyethylthio group, a
tert-butoxyethylthio group,
[0114] an n-pentyloxyethylthio group, an iso-pentyloxyethylthio
group, an n-hexyloxyethylthio group, an iso-hexyloxyethylthio
group, and an n-heptyloxyethylthio group;
[0115] an aralkylthio group such as a benzylthio group; and
[0116] an alkylthioalkylthio group having 2 to 10 carbon atoms in
total such as a methylthioethylthio group, an ethylthioethylthio
group, an n-propylthioethylthio group, an iso-propylthioethylthio
group, an n-butylthioethylthio group, an iso-butylthioethylthio
group, a tert-butylthioethylthio group, an n-pentylthioethylthio
group, an iso-pentylthioethylthio group, an n-hexylthioethylthio
group, an iso-hexylthioethylthio group, and an
n-heptylthioethylthio group.
[0117] Specific examples of the substituted or unsubstituted
aryloxy group include an unsubstituted or alkyl-substituted aryloxy
group having not more than 20 carbon atoms in total such as a
phenyloxy group, a naphthyloxy group, an anthranyloxy group, a
2-methylphenyloxy group, a 3-methylphenyloxy group, a
4-methylphenyloxy group, a 2-ethylphenyloxy group, a
propylphenyloxy group, a butylphenyloxy group, a hexylphenyloxy
group, a cyclohexylphenyloxy group, an octylphenyloxy group, a
2-methyl-1-naphthyloxy group, a 3-methyl-1-naphthyloxy group, a
4-methyl-1-naphthyloxy group, a 5-methyl-1-naphthyloxy group, a
6-methyl-1-naphthyloxy group, a 7-methyl-1-naphthyloxy group, a
8-methyl-1-naphthyloxy group, a 1-methyl-2-naphthyloxy group, a
3-methyl-2-naphthyloxy group, a 4-methyl-2-naphthyloxy group, a
5-methyl-2-naphthyloxy group, a 6-methyl-2-naphthyloxy group, a
7-methyl-2-naphthyloxy group, a 8-methyl-2-naphthyloxy group, a
2-ethyl-1-naphthyloxy group, a 2,3-dimethylphenyloxy group, a
2,4-dimethylphenyloxy group, a 2,5-dimethylphenyloxy group, a
2,6-dimethylphenyloxy group, a 3,4-dimethylphenyloxy group, a
3,5-dimethylphenyloxy group, a 3,6-dimethylphenyloxy group, a
2,3,4-trimethylphenyloxy group, a 2,3,5-trimethylphenyloxy group, a
2,3,6-trimethylphenyloxy group, a 2,4,5-trimethylphenyloxy group, a
2,4,6-trimethylphenyloxy group, and a 3,4,5-trimethylphenyloxy
group;
[0118] a monoalkoxyaryloxy group having not more than 20 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 10 carbon atoms is substituted, such as
a 2-methoxyphenyloxy group, a 3-methoxyphenyloxy group, a
4-methoxyphenyloxy group, a 2-ethoxyphenyloxy group, a
propoxyphenyloxy group, a butoxyphenyloxy group, a
hexyloxyphenyloxy group, a cyclohexyloxyphenyloxy group, an
octyloxyphenyloxy group, a 2-methoxy-1-naphthyloxy group, a
3-methoxy-1-naphthyloxy group, a 4-methoxy-1-naphthyloxy group, a
5-methoxy-1-naphthyloxy group, a 6-methoxy-1-naphthyloxy group, a
7-methoxy-1-naphthyloxy group, a 8-methoxy-1-naphthyloxy group, a
1-methoxy-2-naphthyloxy group, a 3-methoxy-2-naphthyloxy group, a
4-methoxy-2-naphthyloxy group, a 5-methoxy-2-naphthyloxy group, a
6-methoxy-2-naphthyloxy group, a 7-methoxy-2-naphthyloxy group, a
8-methoxy-2-naphthyloxy group, and a 2-ethoxy-1-naphthyloxy
group;
[0119] a dialkoxyaryloxy group having not more than 20 carbon atoms
in total wherein a substituted or unsubstituted alkyloxy group
having not more than 10 carbon atoms is substituted, such as a
2,3-dimethoxyphenyloxy group, a 2,4-dimethoxyphenyloxy group, a
2,5-dimethoxyphenyloxy group, a 2,6-dimethoxyphenyloxy group, a
3,4-dimethoxyphenyloxy group, a 3,5-dimethoxyphenyloxy group, a
3,6-dimethoxyphenyloxy group, a 4,5-dimethoxy-1-naphthyloxy group,
a 4,7-dimethoxy-1-naphthyloxy group, a 4,8-dimethoxy-1-naphthyloxy
group, a 5,8-dimethoxy-1-naphthyloxy group, and a
5,8-dimethoxy-2-naphthyloxy group;
[0120] a trialkoxyaryloxy group having not more than 20 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 10 carbon atoms is substituted, such as
a 2,3,4-trimethoxyphenyloxy group, a 2,3,5-trimethoxyphenyloxy
group, a 2,3,6-trimethoxyphenyloxy group, a
2,4,5-trimethoxyphenyloxy group, a 2,4,6-trimethoxyphenyloxy group,
and a 3,4,5-trimethoxyphenyloxy group; and
[0121] an aryloxy group having not more than 20 carbon atoms in
total wherein a halogen atom is substituted, such as a
chlorophenyloxy group, a dichlorophenyloxy group, a
trichlorophenyloxy group, a bromophenyloxy group, a
dibromophenyloxy group, an iodophenyloxy group, a fluorophenyloxy
group, a chloronaphthyloxy group, a bromonaphthyloxy group, a
difluorophenyloxy group, a trifluorophenyloxy group, a
tetrafluorophenyloxy group, and a pentafluorophenyloxy group.
[0122] Specific examples of the substituted or unsubstituted
arylthio group include an unsubstituted or alkyl-substituted
arylthio group having not more than 20 carbon atoms in total such
as a phenylthio group, a naphthylthio group, an anthranylthio
group, a 2-methylphenylthio group, a 3-methylphenylthio group, a
4-methylphenylthio group, a 2-ethylphenylthio group, a
propylphenylthio group, a butylphenylthio group, a hexylphenylthio
group, a cyclohexylphenylthio group, an octylphenylthio group, a
2-methyl-1-naphthylthio group, a 3-methyl-1-naphthylthio group, a
4-methyl-1-naphthylthio group, a 5-methyl-1-naphthylthio group, a
6-methyl-1-naphthylthio group, a 7-methyl-1-naphthylthio group, a
8-methyl-1-naphthylthio group, a 1-methyl-2-naphthylthio group, a
3-methyl-2-naphthylthio group, a 4-methyl-2-naphthylthio group, a
5-methyl-2-naphthylthio group, a 6-methyl-2-naphthylthio group, a
7-methyl-2-naphthylthio group, a 8-methyl-2-naphthylthio group, a
2-ethyl-1-naphthylthio group, a 2,3-dimethylphenylthio group, a
2,4-dimethylphenylthio group, a 2,5-dimethylphenylthio group, a
2,6-dimethylphenylthio group, a 3,4-dimethylphenylthio group, a
3,5-dimethylphenylthio group, a 3,6-dimethylphenylthio group, a
2,3,4-trimethylphenylthio group, a 2,3,5-trimethylphenylthio group,
a 2,3,6-trimethylphenylthio group, a 2,4,5-trimethylphenylthio
group, a 2,4,6-trimethylphenylthio group, and a
3,4,5-trimethylphenylthio group;
[0123] a monoalkoxyarylthio group having not more than 20 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 10 carbon atoms is substituted, such as
a 2-methoxyphenylthio group, a 3-methoxyphenylthio group, a
4-methoxyphenylthio group, a 2-ethoxyphenylthio group, a
propoxyphenylthio group, a butoxyphenylthio group, a
hexyloxyphenylthio group, a cyclohexyloxyphenylthio group, an
octyloxyphenylthio group, a 2-methoxy-1-naphthylthio group, a
3-methoxy-1-naphthylthio group, a 4-methoxy-1-naphthylthio group, a
5-methoxy-1-naphthylthio group, a 6-methoxy-1-naphthylthio group, a
7-methoxy-1-naphthylthio group, a 8-methoxy-1-naphthylthio group, a
1-methoxy-2-naphthylthio group, a 3-methoxy-2-naphthylthio group, a
4-methoxy-2-naphthylthio group, a 5-methoxy-2-naphthylthio group, a
6-methoxy-2-naphthylthio group, a 7-methoxy-2-naphthylthio group, a
8-methoxy-2-naphthylthio group, and a 2-ethoxy-1-naphthylthio
group;
[0124] a dialkoxyarylthio group having not more than 20 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 10 carbon atoms is substituted, such as
a 2,3-dimethoxyphenylthio group, a 2,4-dimethoxyphenylthio group, a
2,5-dimethoxyphenylthio group, a 2,6-dimethoxyphenylthio group, a
3,4-dimethoxyphenylthio group, a 3,5-dimethoxyphenylthio group, a
3,6-dimethoxyphenylthio group, a 4,5-dimethoxy-1-naphthylthio
group, a 4,7-dimethoxy-1-naphthylthio group, a
4,8-dimethoxy-1-naphthylthio group, a 5,8-dimethoxy-1-naphthylthio
group, and a 5,8-dimethoxy-2-naphthylthio group;
[0125] a trialkoxyarylthio group having not more than 20 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 10 carbon atoms is substituted, such as
a 2,3,4-trimethoxyphenylthio group, a 2,3,5-trimethoxyphenylthio
group, a 2,3,6-trimethoxyphenylthio group, a
2,4,5-trimethoxyphenylthio group, a 2,4,6-trimethoxyphenylthio
group, and a 3,4,5-trimethoxyphenylthio group; and
[0126] an arylthio group having not more than 20 carbon atoms in
total wherein a halogen atom is substituted, such as a
chlorophenylthio group, a dichlorophenylthio group, a
trichlorophenylthio group, a bromophenylthio group, a
dibromophenylthio group, an iodophenylthio group, a
fluorophenylthio group, a chloronaphthylthio group, a
bromonaphthylthio group, a difluorophenylthio group, a
trifluorophenylthio group, a tetrafluorophenylthio group, and a
pentafluorophenylthio group. However, Y is not restricted
thereto.
[0127] Preferred examples of Y are as follows.
[0128] A preferred example thereof includes a hydrogen atom.
[0129] Furthermore, preferred examples of Y include a chlorine
atom, a bromine atom, and an iodine atom as a halogen atom.
[0130] Preferred examples of the substituted or unsubstituted alkyl
group include a linear alkyl group having 1 to 6 carbon atom(s) in
total such as a methyl group, an ethyl group, an n-propyl group, an
n-butyl group, an n-pentyl group, and an n-hexyl group;
[0131] a branched alkyl group having 3 to 6 carbon atoms in total
such as an isopropyl group, an isobutyl group, a sec-butyl group,
an isopentyl group, a sec-pentyl group, a 1-methylpentyl group, a
2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl
group, a 1-ethylbutyl group, a 2-ethylbutyl group, a tert-butyl
group, a tert-pentyl group, a 1,1-dimethylbutyl group, a
1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, and a
2,3-dimethylbutyl group; and
[0132] a saturated cyclic alkyl group having 5 to 6 carbon atoms in
total such as a cyclopentyl group, and a cyclohexyl group.
[0133] Preferred examples of the substituted or unsubstituted aryl
group include aromatic hydrocarbons having not more than 12 carbon
atoms in total such as a phenyl group, a naphthyl group, and a
cyclopentadienyl group;
[0134] an alkyl-substituted aryl group having not more than 12
carbon atoms in total such as a 2-methylphenyl group, a
3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl
group, a propylphenyl group, a butylphenyl group, a
2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a
2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a
3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a
3,6-dimethylphenyl group, a 2,3,4-trimethylphenyl group, a
2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a
2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, and a
3,4,5-trimethylphenyl group;
[0135] a monoalkoxyaryl group having not more than 12 carbon atoms
in total wherein a substituted or unsubstituted alkyloxy group
having not more than 6 carbon atoms is substituted, such as a
2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl
group, a 2-ethoxyphenyl group, a propoxyphenyl group, and a
butoxyphenyl group;
[0136] a dialkoxyaryl group having not more than 12 carbon atoms in
total wherein a substituted or unsubstituted alkyloxy group having
not more than 6 carbon atoms is substituted, such as a
2,3-dimethoxyphenyl group, a 2,4-dimethoxyphenyl group, a
2,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a
3,4-dimethoxyphenyl group, a 3,5-dimethoxyphenyl group, and a
3,6-dimethoxyphenyl group; and
[0137] an aryl group having not more than 12 carbon atoms in total
wherein a halogen atom is substituted, such as a chlorophenyl
group, a dichlorophenyl group, a trichlorophenyl group, a
bromophenyl group, a dibromophenyl group, an iodophenyl group, a
fluorophenyl group, a chloronaphthyl group, a bromonaphthyl group,
a difluorophenyl group, a trifluorophenyl group, a
tetrafluorophenyl group, and a pentafluorophenyl group.
[0138] Preferred examples of the substituted or unsubstituted
aralkyl group include an aralkyl group having not more than 12
carbon atoms in total such as a benzyl group, a phenethyl group,
and a phenylpropyl group.
[0139] Preferred examples of the substituted or unsubstituted
alkyloxy group include a linear or branched alkoxy group having 1
to 6 carbon atom(s) in total such as a methoxy group, an ethoxy
group, an n-propoxy group, an iso-propoxy group, an n-butoxy group,
an iso-butoxy group, a tert-butoxy group, an n-pentyloxy group, an
iso-pentyloxy group, an n-hexyloxy group, and an iso-hexyloxy
group;
[0140] a cycloalkoxy group having 5 to 6 carbon atoms in total such
as a cyclopentyloxy group, and a cyclohexyloxy group; and
[0141] an alkoxyalkoxy group having 2 to 6 carbon atoms in total
such as a methoxymethoxy group, an ethoxymethoxy group, an
ethoxyethoxy group, an n-propoxymethoxy group, an
iso-propoxymethoxy group, an n-propoxyethoxy group, an
iso-propoxyethoxy group, an n-butoxyethoxy group, an
iso-butoxyethoxy group, and a tert-butoxyethoxy group.
[0142] Preferred examples of the substituted or unsubstituted
alkylthio group include a linear or branched alkylthio group having
1 to 6 carbon atom (s) in total such as a methylthio group, an
ethylthio group, an n-propylthio group, an iso-propylthio group, an
n-butylthio group, an iso-butylthio group, a sec-butylthio group, a
t-butylthio group, an n-pentylthio group, an iso-pentylthio group,
an n-hexylthio group, and an iso-hexylthio group;
[0143] a cycloalkylthio group having 5 to 6 carbon atoms in total
such as a cyclopentylthio group and a cyclohexylthio group;
[0144] an alkoxyalkylthio group having 2 to 6 carbon atoms in total
such as a methoxyethylthio group, an ethoxyethylthio group, an
n-propoxyethylthio group, an iso-propoxyethylthio group, an
n-butoxyethylthio group, an iso-butoxyethylthio group, and a
tert-butoxyethylthio group; and
[0145] an alkylthioalkylthio group having 2 to 6 carbon atoms in
total such as a methylthioethylthio group, an ethylthioethylthio
group, an n-propylthioethylthio group, an iso-propylthioethylthio
group, an n-butylthioethylthio group, an iso-butylthioethylthio
group, and a tert-butylthioethylthio group.
[0146] Preferred examples of the substituted or unsubstituted
aryloxy group include an unsubstituted or alkyl-substituted aryloxy
group having not more than 12 carbon atoms in total such as a
phenyloxy group, a naphthyloxy group, a 2-methylphenyloxy group, a
3-methylphenyloxy group, a 4-methylphenyloxy group, a
2-ethylphenyloxy group, a propylphenyloxy group, a butylphenyloxy
group, a hexylphenyloxy group, a cyclohexylphenyloxy group, a
2,4-dimethylphenyloxy group, a 2,5-dimethylphenyloxy group, a
2,6-dimethylphenyloxy group, a 3,4-dimethylphenyloxy group, a
3,5-dimethylphenyloxy group, a 3,6-dimethylphenyloxy group, a
2,3,4-trimethylphenyloxy group, a 2,3,5-trimethylphenyloxy group, a
2,3,6-trimethylphenyloxy group, a 2,4,5-trimethylphenyloxy group, a
2,4,6-trimethylphenyloxy group, and a 3,4,5-trimethylphenyloxy
group;
[0147] a monoalkoxyaryloxy group having not more than 12 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 6 carbon atoms is substituted, such as a
2-methoxyphenyloxy group, a 3-methoxyphenyloxy group, a
4-methoxyphenyloxy group, a 2-ethoxyphenyloxy group, a
propoxyphenyloxy group, a butoxyphenyloxy group, a
hexyloxyphenyloxy group, a cyclohexyloxyphenyloxy group;
[0148] a dialkoxyaryloxy group having not more than 12 carbon atoms
in total wherein a substituted or unsubstituted alkyloxy group
having not more than 6 carbon atoms is substituted, such as a
2,3-dimethoxyphenyloxy group, a 2,4-dimethoxyphenyloxy group, a
2,5-dimethoxyphenyloxy group, a 2,6-dimethoxyphenyloxy group, a
3,4-dimethoxyphenyloxy group, a 3,5-dimethoxyphenyloxy group, and a
3,6-dimethoxyphenyloxy group; and
[0149] an aryloxy group having not more than 12 carbon atoms in
total wherein a halogen atom is substituted, such as a
chlorophenyloxy group, a dichlorophenyloxy group, a
trichlorophenyloxy group, a bromophenyloxy group, a
dibromophenyloxy group, an iodophenyloxy group, a fluorophenyloxy
group, a chloronaphthyloxy group, a bromonaphthyloxy group, a
difluorophenyloxy group, a trifluorophenyloxy group, a
tetrafluorophenyloxy group, and a pentafluorophenyloxy group.
[0150] Preferred examples of the substituted or unsubstituted
arylthio group include an unsubstituted or alkyl-substituted
arylthio group having not more than 12 carbon atoms in total such
as a phenylthio group, a naphthylthio group, a 2-methylphenylthio
group, a 3-methylphenylthio group, a 4-methylphenylthio group, a
2-ethylphenylthio group, a propylphenylthio group, a
butylphenylthio group, a hexylphenylthio group, a
cyclohexylphenylthio group, a 2,4-dimethylphenylthio group, a
2,5-dimethylphenylthio group, a 2,6-dimethylphenylthio group, a
3,4-dimethylphenylthio group, a 3,5-dimethylphenylthio group, a
3,6-dimethylphenylthio group, a 2,3,4-trimethylphenylthio group, a
2,3,5-trimethylphenylthio group, a 2,3,6-trimethylphenylthio group,
a 2,4,5-trimethylphenylthio group, a 2,4,6-trimethylphenylthio
group, and a 3,4,5-trimethylphenylthio group;
[0151] a monoalkoxyarylthio group having not more than 12 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 6 carbon atoms is substituted, such as a
2-methoxyphenylthio group, a 3-methoxyphenylthio group, a
4-methoxyphenylthio group, a 2-ethoxyphenylthio group, a
propoxyphenylthio group, a butoxyphenylthio group, a
hexyloxyphenylthio group, and a cyclohexyloxyphenylthio group;
[0152] a dialkoxyarylthio group having not more than 12 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 6 carbon atoms is substituted, such as a
2,3-dimethoxyphenylthio group, a 2,4-dimethoxyphenylthio group, a
2,5-dimethoxyphenylthio group, a 2,6-dimethoxyphenylthio group, a
3,4-dimethoxyphenylthio group, a 3,5-dimethoxyphenylthio group, a
3,6-dimethoxyphenylthio group, a 4,5-dimethoxy-1-naphthylthio
group, a 4,7-dimethoxy-1-naphthylthio group, a
4,8-dimethoxy-1-naphthylthio group, a 5,8-dimethoxy-1-naphthylthio
group, and a 5,8-dimethoxy-2-naphthylthio group; and
[0153] an arylthio group having not more than 12 carbon atoms in
total wherein a halogen atom is substituted, such as a
chlorophenylthio group, a dichlorophenylthio group, a
trichlorophenylthio group, a bromophenylthio group, a
dibromophenylthio group, an iodophenylthio group, a
fluorophenylthio group, a chloronaphthylthio group, a
bromonaphthylthio group, a difluorophenylthio group, a
trifluorophenylthio group, a tetrafluorophenylthio group, and a
pentafluorophenylthio group.
[0154] More preferred examples of Y are as follows.
[0155] More preferred example includes a hydrogen atom.
[0156] Further, examples of the halogen atom include a chlorine
atom and a bromine atom.
[0157] More preferred examples of the substituted or unsubstituted
alkyl group include a linear or branched alkyl group having 1 to 3
carbon atom(s) in total such as a methyl group, an ethyl group, and
an iso-propyl group.
[0158] More preferred examples of the substituted or unsubstituted
aryl group include aromatic hydrocarbons having not more than 12
carbon atoms in total such as a phenyl group, a naphthyl group, and
a cyclopentadienyl group;
[0159] an alkyl-substituted aryl group having not more than 9
carbon atoms in total such as a 2-methylphenyl group, a
3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl
group, a propylphenyl group, a 2,3-dimethylphenyl group, a
2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a
2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a
3,5-dimethylphenyl group, and a 3,6-dimethylphenyl group;
[0160] a monoalkoxyaryl group having not more than 9 carbon atoms
in total wherein a substituted or unsubstituted alkyloxy group
having not more than 3 carbon atoms is substituted, such as a
2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl
group, a 2-ethoxyphenyl group, and a propoxyphenyl group; and
[0161] an aryl group having not more than 12 carbon atoms in total
wherein a halogen atom is substituted, such as a chlorophenyl
group, a dichlorophenyl group, a trichlorophenyl group, a
bromophenyl group, a dibromophenyl group, a chloronaphthyl group,
and a bromonaphthyl group.
[0162] More preferred examples of the substituted or unsubstituted
aralkyl group include an aralkyl group having not more than 9
carbon atoms in total such as a benzyl group, a phenethyl group,
and a phenylpropyl group.
[0163] More preferred examples of the substituted or unsubstituted
alkyloxy group include a linear or branched alkoxy group having 1
to 3 carbon atom(s) in total such as a methoxy group, an ethoxy
group, and an iso-propoxy group; and
[0164] a cycloalkoxy group having 5 to 6 carbon atoms in total such
as a cyclopentyloxy group, and a cyclohexyloxy group.
[0165] More preferred examples of the substituted or unsubstituted
alkylthio group include a linear or branched alkylthio group having
1 to 3 carbon atom(s) in total such as a methylthio group, an
ethylthio group, an n-propylthio group, and an iso-propylthio
group;
[0166] a cycloalkylthio group having 5 to 6 carbon atoms in total
such as a cyclopentylthio group, and a cyclohexylthio group;
and
[0167] an alkylthioalkylthio group having 2 to 6 carbon atoms in
total such as a methylthioethylthio group, an ethylthioethylthio
group, an n-propylthioethylthio group, an iso-propylthioethylthio
group, an n-butylthioethylthio group, an iso-butylthioethylthio
group, and a tert-butylthioethylthio group.
[0168] More preferred examples of the substituted or unsubstituted
aryloxy group include an unsubstituted or alkyl-substituted aryloxy
group having not more than 9 carbon atoms in total such as a
phenyloxy group, a naphthyloxy group, a 2-methylphenyloxy group, a
3-methylphenyloxy group, a 4-methylphenyloxy group, a
2-ethylphenyloxy group, a propylphenyloxy group, a
2,4-dimethylphenyloxy group, a 2,5-dimethylphenyloxy group, a
2,6-dimethylphenyloxy group, a 3,4-dimethylphenyloxy group, a
3,5-dimethylphenyloxy group, and a 3,6-dimethylphenyloxy group;
[0169] a monoalkoxyaryloxy group having not more than 9 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 3 carbon atoms is substituted, such as a
2-methoxyphenyloxy group, a 3-methoxyphenyloxy group, a
4-methoxyphenyloxy group, a 2-ethoxyphenyloxy group, and a
propoxyphenyloxy group; and
[0170] an aryloxy group having not more than 12 carbon atoms in
total wherein a halogen atom is substituted, such as a
chlorophenyloxy group, a dichlorophenyloxy group, a
trichlorophenyloxy group, a bromophenyloxy group, a
dibromophenyloxy group, a chloronaphthyloxy group, and a
bromonaphthyloxy group.
[0171] More preferred examples of the substituted or unsubstituted
arylthio group include an unsubstituted or alkyl-substituted
arylthio group having not more than 9 carbon atoms in total such as
a phenylthio group, a 2-methylphenylthio group, a
3-methylphenylthio group, a 4-methylphenylthio group, a
2-ethylphenylthio group, a propylphenylthio group, a
2,4-dimethylphenylthio group, a 2,5-dimethylphenylthio group, a
2,6-dimethylphenylthio group, a 3,4-dimethylphenylthio group, a
3,5-dimethylphenylthio group, and a 3,6-dimethylphenylthio
group;
[0172] a monoalkoxyarylthio group having not more than 9 carbon
atoms in total wherein a substituted or unsubstituted alkyloxy
group having not more than 3 carbon atoms is substituted, such as a
2-methoxyphenylthio group, a 3-methoxyphenylthio group, a
4-methoxyphenylthio group, a 2-ethoxyphenylthio group, and a
propoxyphenylthio group; and
[0173] an arylthio group having not more than 12 carbon atoms in
total wherein a halogen atom is substituted, such as a
chlorophenylthio group, a dichlorophenylthio group, a
trichlorophenylthio group, a bromophenylthio group, a
dibromophenylthio group, a chloronaphthylthio group, and a
bromonaphthylthio group.
[0174] Furthermore, if n-p is an integer of 2 or greater, Y's may
be bonded to each other to form a ring structure with the
intermediary of a metal atom M. That is, a plurality of Y's may be
bonded to each other to form a ring containing a metal atom M.
[0175] In General Formula (1), Y in the --(Y).sub.n-p group bonding
to M is preferably (S--R.sub.2) (wherein S is a sulfur atom, and
R.sub.2 is the same as R.sub.2 in the following General Formula
(5)), and p is an integer of 2 to (n-1). In this constitution, it
is preferable that m=0 and X.sub.1 is a sulfur atom. Furthermore,
in this constitution, it is more preferable that m=0, X.sub.1 is
sulfur atom, and M is a Group 14 element. Thus, the compound of
General Formula (1) is a compound represented by the following
General Formula (13).
[0176] Furthermore, preferred examples of the thietane compound
wherein Y is (S--R.sub.2) in General Formula (1) include a compound
represented by the following General Formula (5).
##STR00006##
[0177] (in General Formula (5), M is a Group 14 element in a long
form of the Periodic Table. X.sub.1 and n are each the same as
X.sub.1 and n, respectively, in General Formula (1). P is an
integer of 2 to (n-1).
[0178] If n-p is 1, R.sub.2 represents an optionally substituted,
linear or branched alkyl group having 1 to 3 carbon atom(s).
[0179] If n-p is 2 or greater, a plurality of R.sub.2's each
independently represents an optionally substituted, linear or
branched alkyl group having 1 to 3 carbon atom(s). Furthermore, a
plurality of R.sub.2's may be bonded to each other to form an
M-containing ring, and in this case, the alkyl chain forming the
ring has 1 to 3 carbon atom(s), and the moiety constituting the
ring contains no sulfur atom).
[0180] In General Formula (5), M represents a Group 14 element such
as a Sn atom, a Si atom, a Ge atom, and a Pb atom. M is preferably
a higher-periodic Group 14 metal element such as a Sn atom and a Pb
atom, more preferably a Sn atom.
[0181] In General Formula (5), from the viewpoint of improvement in
the refractive index of the resin, X.sub.1 is preferably a sulfur
atom. Here, General Formula (5) would be the following General
Formula (13).
##STR00007##
[0182] (in General Formula (13), M, p, n and R.sub.2 are each the
same as M, p, n and R.sub.2, respectively, in General Formula
(5)).
[0183] In General Formula (13), M is preferably a Sn atom as in
General Formula (5)
[0184] In General Formula (5), n represents a valence of a metal
atom M. Furthermore, in General Formula (5), p is a positive
integer of (the valence of M-1) or less. That is, p is an integer
of 2 to (n-1).
[0185] In General Formula (5), R.sub.2 represents an optionally
substituted, linear or branched alkyl group having 1 to 3 carbon
atom(s)
[0186] If n-p is 2 or greater, R.sub.2's each independently
represents an optionally substituted, linear or branched alkyl
group having 1 to 3 carbon atom(s). A plurality of R.sub.2's may be
the same group, or all or a part thereof may be different.
Furthermore, a plurality of R.sub.2's may be bonded to each other
to form a ring containing M. In this case, the alkyl chain forming
the ring has 1 to 3 carbon atom(s), and any sulfur atom is directed
bonded to M. That is, in R.sub.2, the moiety constituting the ring
contains no sulfur atom.
[0187] One preferred example of the compound represented by General
Formula (5) includes the following embodiment. That is, if
R.sub.2's do not form a ring, specific examples of R.sub.2 include
an alkyl group having 1 to 3 carbon atom (s), such as a methyl
group, an ethyl group, a propyl group, and an isopropyl group.
Further, if they form a ring, examples of the alkyl chain forming a
ring include an alkylene group having 1 to 3 carbon atom(s), such
as a methylene group, an ethylene group, and a propylene group. The
ring containing M is specifically a 4- to 6-membered ring.
Furthermore, if the ring containing M is a 4-membered ring, one of
two R.sub.2's is specifically a single bond.
[0188] More specifically, if they do not form a ring, R.sub.2 is a
methyl group, and if they do form ring, the alkyl chain forming a
ring is an ethylene group.
[0189] Next, specific examples of the compound represented by
General Formula (1) will be described. Specific examples of the
compound represented by General Formula (1) are presented in the
following Tables 1 to 17, but not limited thereto. Tables 1 to 17
show specific examples of the compound represented by General
Formula (1) Furthermore, in Tables 1 to 17, "CMPD. No." refers to
Compound No.
[0190] Furthermore, in Tables 1 to 17, Y.sub.1, Y.sub.2, and
Y.sub.3 each represent Y in the case where the total number of Y's
bonding to M is 3 or less, that is, the value of n-p is 3 or less.
Specifically, in the case of n-p=1, Y is only Y.sub.1. In the case
of n-p=2, the compound contains Y.sub.1 and Y.sub.2 as Y, which may
be the same as or different from each other. Furthermore, in the
case of n-p=3, the compound contains Y.sub.1, Y.sub.2, and Y.sub.3
as Y, which may be the same as or different from each other.
[0191] Furthermore, in Tables, in the case where n-p is 2, two Y's,
in the compound in which one group is depicted in Y.sub.1 through
Y.sub.2, may be bonded to each other to form a ring containing
metal atom M.
TABLE-US-00001 TABLE 1 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-1 Sn 4 4 0 0 S -- -- -- -- -- 1-2
Sn 4 4 0 0 O -- -- -- -- -- 1-3 Sn 4 4 0 1 S S CH.sub.2 -- -- --
1-4 Sn 4 4 0 1 O S CH.sub.2 -- -- -- 1-5 Sn 4 4 0 1 S O CH.sub.2 --
-- -- 1-6 Sn 4 4 0 1 O O CH.sub.2 -- -- -- 1-7 Sn 4 4 0 1 S S
C.sub.2H.sub.4 -- -- -- 1-8 Sn 4 4 0 1 O S C.sub.2H.sub.4 -- -- --
1-9 Sn 4 4 0 1 S O C.sub.2H.sub.4 -- -- -- 1-10 Sn 4 4 0 1 O O
C.sub.2H.sub.4 -- -- -- 1-11 Sn 4 4 0 1 S S ##STR00008## -- -- --
1-12 Sn 4 4 0 1 O S ##STR00009## -- -- -- 1-13 Sn 4 4 0 1 S O
##STR00010## -- -- -- 1-14 Sn 4 4 0 1 O O ##STR00011## -- -- --
1-15 Sn 4 4 0 1 S S ##STR00012## -- -- -- 1-16 Sn 4 4 0 1 O S
##STR00013## -- -- -- 1-17 Sn 4 4 0 1 S O ##STR00014## -- -- --
TABLE-US-00002 TABLE 2 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-18 Sn 4 4 0 1 O O ##STR00015## --
-- -- 1-19 Sn 4 4 0 1 S S ##STR00016## -- -- -- 1-20 Sn 4 4 0 1 O S
##STR00017## -- -- -- 1-21 Sn 4 4 0 1 S O ##STR00018## -- -- --
1-22 Sn 4 4 0 1 O O ##STR00019## -- -- -- 1-23 Sn 4 4 0 1 S S
##STR00020## -- -- -- 1-24 Sn 4 4 0 1 O S ##STR00021## -- -- --
1-25 Sn 4 4 0 1 S O ##STR00022## -- -- -- 1-26 Sn 4 4 0 1 O O
##STR00023## -- -- -- 1-27 Sn 4 4 0 1 S S ##STR00024## -- -- --
1-28 Sn 4 4 0 1 O S ##STR00025## -- -- -- 1-29 Sn 4 4 0 1 S O
##STR00026## -- -- -- 1-30 Sn 4 4 0 1 O O ##STR00027## -- -- --
TABLE-US-00003 TABLE 3 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-31 Sn 4 4 0 1 S S ##STR00028## --
-- -- 1-32 Sn 4 4 0 1 O S ##STR00029## -- -- -- 1-33 Sn 4 4 0 1 S O
##STR00030## -- -- -- 1-34 Sn 4 4 0 1 O O ##STR00031## -- -- --
1-35 Sn 4 3 1 0 S -- -- CH.sub.3 -- -- 1-36 Sn 4 3 1 0 O -- --
CH.sub.3 -- -- 1-37 Sn 4 3 1 0 S -- -- C.sub.2H.sub.5 -- -- 1-38 Sn
4 3 1 0 O -- -- C.sub.2H.sub.5 -- -- 1-39 Sn 4 3 1 0 S -- --
C.sub.3H.sub.7 -- -- 1-40 Sn 4 3 1 0 O -- -- C.sub.3H.sub.7 -- --
1-41 Sn 4 3 1 0 S -- -- C.sub.4H.sub.9 -- -- 1-42 Sn 4 3 1 0 O --
-- C.sub.4H.sub.9 -- -- 1-43 Sn 4 3 1 0 S -- -- C.sub.6H.sub.5 --
-- 1-44 Sn 4 3 1 0 O -- -- C.sub.6H.sub.5 -- -- 1-45 Sn 4 2 2 0 S
-- -- CH.sub.3 CH.sub.3 -- 1-46 Sn 4 2 2 0 O -- -- CH.sub.3
CH.sub.3 -- 1-47 Sn 4 2 2 0 S -- -- C.sub.2H.sub.5 C.sub.2H.sub.5
-- 1-48 Sn 4 2 2 0 O -- -- C.sub.2H.sub.5 C.sub.2H.sub.5 -- 1-49 Sn
4 2 2 0 S -- -- C.sub.3H.sub.7 C.sub.3H.sub.7 -- 1-50 Sn 4 2 2 0 O
-- -- C.sub.3H.sub.7 C.sub.3H.sub.7 --
TABLE-US-00004 TABLE 4 CMPD. No. M n p n - p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-51 Sn 4 2 2 0 S -- --
C.sub.4H.sub.9 C.sub.4H.sub.9 -- 1-52 Sn 4 2 2 0 O -- --
C.sub.4H.sub.9 C.sub.4H.sub.9 -- 1-53 Sn 4 2 2 0 S -- --
C.sub.6H.sub.5 C.sub.6H.sub.5 -- 1-54 Sn 4 2 2 0 O -- --
C.sub.6H.sub.5 C.sub.6H.sub.5 -- 1-55 Sn 4 1 3 0 S -- -- CH.sub.3
CH.sub.3 CH.sub.3 1-56 Sn 4 1 3 0 O -- -- CH.sub.3 CH.sub.3
CH.sub.3 1-57 Sn 4 1 3 0 S -- -- C.sub.2H.sub.5 C.sub.2H.sub.5
C.sub.2H.sub.5 1-58 Sn 4 1 3 0 O -- -- C.sub.2H.sub.5
C.sub.2H.sub.5 C.sub.2H.sub.5 1-59 Sn 4 1 3 0 S -- --
C.sub.3H.sub.7 C.sub.3H.sub.7 C.sub.3H.sub.7 1-60 Sn 4 1 3 0 O --
-- C.sub.3H.sub.7 C.sub.3H.sub.7 C.sub.3H.sub.7 1-61 Sn 4 1 3 0 S
-- -- C.sub.4H.sub.9 C.sub.4H.sub.9 C.sub.4H.sub.9 1-62 Sn 4 1 3 0
O -- -- C.sub.4H.sub.9 C.sub.4H.sub.9 C.sub.4H.sub.9 1-63 Sn 4 1 3
0 S -- -- C.sub.6H.sub.5 C.sub.6H.sub.5 C.sub.6H.sub.5 1-64 Sn 4 1
3 0 O -- -- C.sub.6H.sub.5 C.sub.6H.sub.5 C.sub.6H.sub.5 1-65 Sn 4
3 1 0 S -- -- SCH.sub.3 -- -- 1-66 Sn 4 3 1 0 O -- -- SCH.sub.3 --
-- 1-67 Sn 4 3 1 0 S -- -- SC.sub.2H.sub.5 -- -- 1-68 Sn 4 3 1 0 O
-- -- SC.sub.2H.sub.5 -- -- 1-69 Sn 4 3 1 0 S -- -- SC.sub.6H.sub.5
-- -- 1-70 Sn 4 3 1 0 O -- -- SC.sub.6H.sub.5 -- -- 1-71 Sn 4 2 2 0
S -- -- SC.sub.2H.sub.4S -- 1-72 Sn 4 2 2 0 O -- --
SC.sub.2H.sub.4S -- 1-73 Sn 4 2 2 0 S -- -- SC.sub.3H.sub.6S --
TABLE-US-00005 TABLE 5 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-74 Sn 4 2 2 0 O -- --
SC.sub.3H.sub.6S -- 1-75 Sn 4 2 2 0 S -- --
SC.sub.2H.sub.4SC.sub.2H.sub.4S -- 1-76 Sn 4 2 2 0 O -- --
SC.sub.2H.sub.4SC.sub.2H.sub.4S -- 1-77 Sn 4 3 1 1 S S CH.sub.2
CH.sub.3 -- -- 1-78 Sn 4 3 1 1 O S CH.sub.2 CH.sub.3 -- -- 1-79 Sn
4 3 1 1 S O CH.sub.2 CH.sub.3 -- -- 1-80 Sn 4 3 1 1 O O CH.sub.2
CH.sub.3 -- -- 1-81 Sn 4 3 1 1 S S C.sub.2H.sub.4 CH.sub.3 -- --
1-82 Sn 4 3 1 1 O S C.sub.2H.sub.4 CH.sub.3 -- -- 1-83 Sn 4 3 1 1 S
O C.sub.2H.sub.4 CH.sub.3 -- -- 1-84 Sn 4 3 1 1 O O C.sub.2H.sub.4
CH.sub.3 -- -- 1-85 Sn 4 3 1 1 S S ##STR00032## CH.sub.3 -- -- 1-86
Sn 4 3 1 1 O S ##STR00033## CH.sub.3 -- -- 1-87 Sn 4 3 1 1 S O
##STR00034## CH.sub.3 -- -- 1-88 Sn 4 3 1 1 O O ##STR00035##
CH.sub.3 -- -- 1-89 Sn 4 3 1 1 S S ##STR00036## CH.sub.3 -- -- 1-90
Sn 4 3 1 1 O S ##STR00037## CH.sub.3 -- -- 1-91 Sn 4 3 1 1 S O
##STR00038## CH.sub.3 -- --
TABLE-US-00006 TABLE 6 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-92 SN 4 3 1 1 O O ##STR00039##
CH.sub.3 -- -- 1-93 Sn 4 3 1 1 S S ##STR00040## CH.sub.3 -- -- 1-94
Sn 4 3 1 1 O S ##STR00041## CH.sub.3 -- -- 1-95 Sn 4 3 1 1 S O
##STR00042## CH.sub.3 -- -- 1-96 Sn 4 3 1 1 O O ##STR00043##
CH.sub.3 -- -- 1-97 Sn 4 3 1 1 S S ##STR00044## CH.sub.3 -- -- 1-98
Sn 4 3 1 1 O S ##STR00045## CH.sub.3 -- -- 1-99 Sn 4 3 1 1 S O
##STR00046## CH.sub.3 -- -- 1-100 Sn 4 3 1 1 O O ##STR00047##
CH.sub.3 -- -- 1-101 Sn 4 3 1 1 S S ##STR00048## CH.sub.3 -- --
1-102 Sn 4 3 1 1 O S ##STR00049## CH.sub.3 -- -- 1-103 Sn 4 3 1 1 S
O ##STR00050## CH.sub.3 -- -- 1-104 Sn 4 3 1 1 O O ##STR00051##
CH.sub.3 -- --
TABLE-US-00007 TABLE 7 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-105 Sn 4 3 1 1 S S ##STR00052##
CH.sub.3 -- -- 1-106 Sn 4 3 1 1 O S ##STR00053## CH.sub.3 -- --
1-107 Sn 4 3 1 1 S O ##STR00054## CH.sub.3 -- -- 1-108 Sn 4 3 1 1 O
O ##STR00055## CH.sub.3 -- -- 1-109 Sn 4 3 1 1 S S CH.sub.2
C.sub.6H.sub.5 -- -- 1-110 Sn 4 3 1 1 O S CH.sub.2 C.sub.6H.sub.5
-- -- 1-111 Sn 4 3 1 1 S O CH.sub.2 C.sub.6H.sub.5 -- -- 1-112 Sn 4
3 1 1 O O CH.sub.2 C.sub.6H.sub.5 -- -- 1-113 Sn 4 3 1 1 S S
C.sub.2H.sub.4 C.sub.6H.sub.5 -- -- 1-114 Sn 4 3 1 1 O S
C.sub.2H.sub.4 C.sub.6H.sub.5 -- -- 1-115 Sn 4 3 1 1 S O
C.sub.2H.sub.4 C.sub.6H.sub.5 -- -- 1-116 Sn 4 3 1 1 O O
C.sub.2H.sub.4 C.sub.6H.sub.5 -- -- 1-117 Sn 4 3 1 1 S S
##STR00056## C.sub.6H.sub.5 -- -- 1-118 Sn 4 3 1 1 O S ##STR00057##
C.sub.6H.sub.5 -- -- 1-119 Sn 4 3 1 1 S O ##STR00058##
C.sub.6H.sub.5 -- -- 1-120 Sn 4 3 1 1 O O ##STR00059##
C.sub.6H.sub.5 -- --
TABLE-US-00008 TABLE 8 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-121 Sn 4 3 1 1 S S ##STR00060##
C.sub.6H.sub.5 -- -- 1-122 Sn 4 3 1 1 O S ##STR00061##
C.sub.6H.sub.5 -- -- 1-123 Sn 4 3 1 1 S O ##STR00062##
C.sub.6H.sub.5 -- -- 1-124 Sn 4 3 1 1 O O ##STR00063##
C.sub.6H.sub.5 -- -- 1-125 Sn 4 3 1 1 S S ##STR00064##
C.sub.6H.sub.5 -- -- 1-126 Sn 4 3 1 1 O S ##STR00065##
C.sub.6H.sub.5 -- -- 1-127 Sn 4 3 1 1 S O ##STR00066##
C.sub.6H.sub.5 -- -- 1-128 Sn 4 3 1 1 O O ##STR00067##
C.sub.6H.sub.5 -- -- 1-129 Sn 4 3 1 1 S S ##STR00068##
C.sub.6H.sub.5 -- -- 1-130 Sn 4 3 1 1 O S ##STR00069##
C.sub.6H.sub.5 -- -- 1-131 Sn 4 3 1 1 S O ##STR00070##
C.sub.6H.sub.5 -- -- 1-132 Sn 4 3 1 1 O O ##STR00071##
C.sub.6H.sub.5 -- -- 1-133 Sn 4 3 1 1 S S ##STR00072##
C.sub.6H.sub.5 -- --
TABLE-US-00009 TABLE 9 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-134 Sn 4 3 1 1 O S ##STR00073##
C.sub.6H.sub.5 -- -- 1-135 Sn 4 3 1 1 S O ##STR00074##
C.sub.6H.sub.5 -- -- 1-136 Sn 4 3 1 1 O O ##STR00075##
C.sub.6H.sub.5 -- -- 1-137 Sn 4 3 1 1 S S ##STR00076##
C.sub.6H.sub.5 -- -- 1-138 Sn 4 3 1 1 O S ##STR00077##
C.sub.6H.sub.5 -- -- 1-139 Sn 4 3 1 1 S O ##STR00078##
C.sub.6H.sub.5 -- -- 1-140 Sn 4 3 1 1 O O ##STR00079##
C.sub.6H.sub.5 -- -- 1-141 Si 4 4 0 0 S -- -- -- -- -- 1-142 Si 4 4
0 0 O -- -- -- -- -- 1-143 Si 4 4 0 1 S S CH.sub.2 -- -- -- 1-144
Si 4 4 0 1 O S CH.sub.2 -- -- -- 1-145 Si 4 4 0 1 S O CH.sub.2 --
-- -- 1-146 Si 4 4 0 1 O O CH.sub.2 -- -- -- 1-147 Si 4 4 0 1 S S
C.sub.2H.sub.4 -- -- -- 1-148 Si 4 4 0 1 O S C.sub.2H.sub.4 -- --
-- 1-149 Si 4 4 0 1 S O C.sub.2H.sub.4 -- -- -- 1-150 Si 4 4 0 1 O
O C.sub.2H.sub.4 -- -- --
TABLE-US-00010 TABLE 10 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-151 Si 4 4 0 1 S S ##STR00080##
-- -- -- 1-152 Si 4 4 0 1 O S ##STR00081## -- -- -- 1-153 Si 4 4 0
1 S O ##STR00082## -- -- -- 1-154 Si 4 4 0 1 O O ##STR00083## -- --
-- 1-155 Si 4 4 0 1 S S ##STR00084## -- -- -- 1-156 Si 4 4 0 1 O S
##STR00085## -- -- -- 1-157 Si 4 4 0 1 S O ##STR00086## -- -- --
1-158 Si 4 4 0 1 O O ##STR00087## -- -- -- 1-159 Si 4 4 0 1 S S
##STR00088## -- -- -- 1-160 Si 4 4 0 1 O S ##STR00089## -- -- --
1-161 Si 4 4 0 1 S O ##STR00090## -- -- -- 1-162 Si 4 4 0 1 O O
##STR00091## -- -- -- 1-163 Si 4 4 0 1 S S ##STR00092## -- --
--
TABLE-US-00011 TABLE 11 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-164 Si 4 4 0 1 O S ##STR00093##
-- -- -- 1-165 Si 4 4 0 1 S O ##STR00094## -- -- -- 1-166 Si 4 4 0
1 O O ##STR00095## -- -- -- 1-167 Si 4 4 0 1 S S ##STR00096## -- --
-- 1-168 Si 4 4 0 1 O S ##STR00097## -- -- -- 1-169 Si 4 4 0 1 S O
##STR00098## -- -- -- 1-170 Si 4 4 0 1 O O ##STR00099## -- -- --
1-171 Si 4 4 0 1 S S ##STR00100## -- -- -- 1-172 Si 4 4 0 1 O S
##STR00101## -- -- -- 1-173 Si 4 4 0 1 S O ##STR00102## -- -- --
1-174 Si 4 4 0 1 O O ##STR00103## -- -- -- 1-175 Si 4 3 1 0 S -- --
CH.sub.3 -- -- 1-176 Si 4 3 1 0 O -- -- CH.sub.3 -- -- 1-177 Si 4 3
1 0 S -- -- C.sub.2H.sub.5 -- --
TABLE-US-00012 TABLE 12 CMPD. No. M n p n - p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-178 Si 4 3 1 0 O -- --
C.sub.2H.sub.5 -- -- 1-179 Si 4 3 1 0 S -- -- C.sub.6H.sub.5 -- --
1-180 Si 4 3 1 0 O -- -- C.sub.6H.sub.5 -- -- 1-181 Si 4 2 2 0 S --
-- CH.sub.3 CH.sub.3 -- 1-182 Si 4 2 2 0 O -- -- CH.sub.3 CH.sub.3
-- 1-183 Si 4 2 2 0 S -- -- C.sub.6H.sub.5 C.sub.6H.sub.5 -- 1-184
Si 4 2 2 0 O -- -- C.sub.6H.sub.5 C.sub.6H.sub.5 -- 1-185 Si 4 1 3
0 S -- -- C.sub.6H.sub.5 C.sub.6H.sub.5 C.sub.6H.sub.5 1-186 Si 4 1
3 0 O -- -- C.sub.6H.sub.5 C.sub.6H.sub.5 C.sub.6H.sub.5 1-187 Si 4
2 2 0 S -- -- SC.sub.2H.sub.4S -- 1-188 Si 4 2 2 0 O -- --
SC.sub.2H.sub.4S -- 1-189 Si 4 2 2 0 S -- -- SC.sub.3H.sub.6S --
1-190 Si 4 2 2 0 O -- -- SC.sub.3H.sub.6S -- 1-191 Si 4 2 2 0 S --
-- SC.sub.2H.sub.4SC.sub.2H.sub.4S -- 1-192 Si 4 2 2 0 O -- --
SC.sub.2H.sub.4SC.sub.2H.sub.4S -- 1-193 Ge 4 4 0 0 S -- -- -- --
-- 1-194 Ge 4 4 0 0 O -- -- -- -- -- 1-195 Ge 4 4 0 1 S S CH.sub.2
-- -- -- 1-196 Ge 4 4 0 1 O S CH.sub.2 -- -- -- 1-197 Ge 4 4 0 1 S
O CH.sub.2 -- -- -- 1-198 Ge 4 4 0 1 O O CH.sub.2 -- -- -- 1-199 Ge
4 4 0 1 S S C.sub.2H.sub.4 -- -- -- 1-200 Ge 4 4 0 1 O S
C.sub.2H.sub.4 -- -- --
TABLE-US-00013 TABLE 13 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-201 Ge 4 4 0 1 S O C.sub.2H.sub.4
-- -- -- 1-202 Ge 4 4 0 1 O O C.sub.2H.sub.4 -- -- -- 1-203 Ge 4 4
0 1 S S ##STR00104## -- -- -- 1-204 Ge 4 4 0 1 O S ##STR00105## --
-- -- 1-205 Ge 4 4 0 1 S O ##STR00106## -- -- -- 1-206 Ge 4 4 0 1 O
O ##STR00107## -- -- -- 1-207 Ge 4 4 0 1 S S ##STR00108## -- -- --
1-208 Ge 4 4 0 1 O S ##STR00109## -- -- -- 1-209 Ge 4 4 0 1 S O
##STR00110## -- -- -- 1-210 Ge 4 4 0 1 O O ##STR00111## -- -- --
1-211 Ge 4 4 0 1 S S ##STR00112## -- -- -- 1-212 Ge 4 4 0 1 O S
##STR00113## -- -- -- 1-213 Ge 4 4 0 1 S O ##STR00114## -- -- --
1-214 Ge 4 4 0 1 O O ##STR00115## -- -- --
TABLE-US-00014 TABLE 14 CMPD. No. M n p n-p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-215 Ge 4 4 0 1 S S ##STR00116##
-- -- -- 1-216 Ge 4 4 0 1 O S ##STR00117## -- -- -- 1-217 Ge 4 4 0
1 S O ##STR00118## -- -- -- 1-218 Ge 4 4 0 1 O O ##STR00119## -- --
-- 1-219 Ge 4 4 0 1 S S ##STR00120## -- -- -- 1-220 Ge 4 4 0 1 O S
##STR00121## -- -- -- 1-221 Ge 4 4 0 1 S O ##STR00122## -- -- --
1-222 Ge 4 4 0 1 O O ##STR00123## -- -- -- 1-223 Ge 4 4 0 1 S S
##STR00124## -- -- -- 1-224 Ge 4 4 0 1 O S ##STR00125## -- -- --
1-225 Ge 4 4 0 1 S O ##STR00126## -- -- -- 1-226 Ge 4 4 0 1 O O
##STR00127## -- -- -- 1-227 Ge 4 3 1 0 S -- -- CH.sub.3 -- -- 1-228
Ge 4 3 1 0 O -- -- CH.sub.3 -- --
TABLE-US-00015 TABLE 15 CMPD. No. M n p n - p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-229 Ge 4 3 1 0 S -- --
C.sub.2H.sub.5 -- -- 1-230 Ge 4 3 1 0 O -- -- C.sub.2H.sub.5 -- --
1-231 Ge 4 3 1 0 S -- -- C.sub.6H.sub.5 -- -- 1-232 Ge 4 3 1 0 O --
-- C.sub.6H.sub.5 -- -- 1-233 Ge 4 2 2 0 S -- -- CH.sub.3 CH.sub.3
-- 1-234 Ge 4 2 2 0 O -- -- CH.sub.3 CH.sub.3 -- 1-235 Ge 4 2 2 0 S
-- -- C.sub.6H.sub.5 C.sub.6H.sub.5 -- 1-236 Ge 4 2 2 0 O -- --
C.sub.6H.sub.5 C.sub.6H.sub.5 -- 1-237 Ge 4 1 3 0 S -- --
C.sub.6H.sub.5 C.sub.6H.sub.5 C.sub.6H.sub.5 1-238 Ge 4 1 3 0 O --
-- C.sub.6H.sub.5 C.sub.6H.sub.5 C.sub.6H.sub.5 1-239 Ge 4 2 2 0 S
-- -- SC.sub.2H.sub.4S -- 1-240 Ge 4 2 2 0 O -- -- SC.sub.2H.sub.4S
-- 1-241 Ge 4 2 2 0 S -- -- SC.sub.3H.sub.6S -- 1-242 Ge 4 2 2 0 O
-- -- SC.sub.3H.sub.6S -- 1-243 Ge 4 2 2 0 S -- --
SC.sub.2H.sub.4SC.sub.2H.sub.4S -- 1-244 Ge 4 2 2 0 O -- --
SC.sub.2H.sub.4SC.sub.2H.sub.4S -- 1-245 Zn 2 2 0 0 S -- -- -- --
-- 1-246 Zn 2 2 0 0 O -- -- -- -- -- 1-247 Zr 4 4 0 0 S -- -- -- --
-- 1-248 Zr 4 4 0 0 O -- -- -- -- -- 1-249 Zr 4 2 2 0 S -- --
CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-250 Zr 4 2 2 0 O -- --
CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-251 Zr 4 4 0 1 S S CH.sub.2
-- -- --
TABLE-US-00016 TABLE 16 CMPD. No. M n p n - p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-252 Zr 4 4 0 1 O S CH.sub.2 -- --
-- 1-253 Zr 4 4 0 1 S O CH.sub.2 -- -- -- 1-254 Zr 4 4 0 1 O O
CH.sub.2 -- -- -- 1-255 Zr 4 4 0 1 S S C.sub.2H.sub.4 -- -- --
1-256 Zr 4 4 0 1 O S C.sub.2H.sub.4 -- -- -- 1-257 Zr 4 4 0 1 S O
C.sub.2H.sub.4 -- -- -- 1-258 Zr 4 4 0 1 O O C.sub.2H.sub.4 -- --
-- 1-259 Zr 4 2 2 1 S S CH.sub.2 CYCLOPENTADIENYL CYCLOPENTADIENYL
-- 1-260 Zr 4 2 2 1 O S CH.sub.2 CYCLOPENTADIENYL CYCLOPENTADIENYL
-- 1-261 Zr 4 2 2 1 S O CH.sub.2 CYCLOPENTADIENYL CYCLOPENTADIENYL
-- 1-262 Zr 4 2 2 1 O O CH.sub.2 CYCLOPENTADIENYL CYCLOPENTADIENYL
-- 1-263 Zr 4 2 2 1 S S C.sub.2H.sub.4 CYCLOPENTADIENYL
CYCLOPENTADIENYL -- 1-264 Zr 4 2 2 1 O S C.sub.2H.sub.4
CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-265 Zr 4 2 2 1 S O
C.sub.2H.sub.4 CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-266 Zr 4 2 2
1 O O C.sub.2H.sub.4 CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-267 Ti
4 4 0 0 S -- -- -- -- -- 1-268 Ti 4 4 0 0 O -- -- -- -- -- 1-269 Ti
4 2 2 0 S -- -- CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-270 Ti 4 2 2
0 O -- -- CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-271 Ti 4 4 0 1 S S
CH.sub.2 -- -- -- 1-272 Ti 4 4 0 1 O S CH.sub.2 -- -- -- 1-273 Ti 4
4 0 1 S O CH.sub.2 -- -- -- 1-274 Ti 4 4 0 1 O O CH.sub.2 -- -- --
1-275 Ti 4 4 0 1 S S C.sub.2H.sub.4 -- -- --
TABLE-US-00017 TABLE 17 CMPD. No. M n p n - p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-276 Ti 4 4 0 1 O S C.sub.2H.sub.4
-- -- -- 1-277 Ti 4 4 0 1 S O C.sub.2H.sub.4 -- -- -- 1-278 Ti 4 4
0 1 O O C.sub.2H.sub.4 -- -- -- 1-279 Ti 4 2 2 1 S S CH.sub.2
CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-280 Ti 4 2 2 1 O S CH.sub.2
CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-281 Ti 4 2 2 1 S O CH.sub.2
CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-282 Ti 4 2 2 1 O O CH.sub.2
CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-283 Ti 4 2 2 1 S S
C.sub.2H.sub.4 CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-284 Ti 4 2 2
1 O S C.sub.2H.sub.4 CYCLOPENTADIENYL CYCLOPENTADIENYL -- 1-285 Ti
4 2 2 1 S O C.sub.2H.sub.4 CYCLOPENTADIENYL CYCLOPENTADIENYL --
1-286 Ti 4 2 2 1 O O C.sub.2H.sub.4 CYCLOPENTADIENYL
CYCLOPENTADIENYL -- 1-287 Pb 4 4 0 0 S -- -- -- -- -- 1-288 Pb 4 4
0 0 O -- -- -- -- -- 1-289 Al 3 3 0 0 S -- -- -- -- -- 1-290 Al 3 3
0 0 O -- -- -- -- -- 1-291 Al 3 2 1 0 S -- -- SCH.sub.3 -- -- 1-292
Al 3 2 1 0 O -- -- SCH.sub.3 -- -- 1-293 Al 3 2 1 0 S -- --
SC.sub.2H.sub.5 -- -- 1-294 Al 3 2 1 0 O -- -- SC.sub.2H.sub.5 --
-- 1-295 Al 3 2 1 0 S -- -- SC.sub.6H.sub.5 -- -- 1-296 Al 3 2 1 0
O -- -- SC.sub.6H.sub.5 -- -- 1-297 Al 3 1 2 0 S -- --
SC.sub.2H.sub.4S -- 1-298 Al 3 1 2 0 O -- -- SC.sub.2H.sub.4S --
1-299 Al 3 1 2 0 S -- -- SC.sub.2H.sub.4SC.sub.2H.sub.4S -- 1-300
Al 3 1 2 0 O -- -- SC.sub.2H.sub.4SC.sub.2H.sub.4S --
[0192] Furthermore, specific examples of the compound represented
by General Formula (1) include the compounds shown in the following
Table 18. The compounds in Table 18 are all the compounds
represented by General Formula (5)
TABLE-US-00018 TABLE 18 CMPD. No. M n p n - p m X.sub.1 X.sub.2
R.sub.1 Y.sub.1 Y.sub.2 Y.sub.3 1-301 Sn 4 3 1 0 S -- --
S--C.sub.3H.sub.7 -- -- 1-302 Sn 4 3 1 0 S -- --
S-(iso-C.sub.3H.sub.7) -- -- 1-303 Sn 4 2 2 0 S -- -- SCH.sub.3
SCH.sub.3 -- 1-304 Sn 4 2 2 0 S -- -- SC.sub.2H.sub.5
SC.sub.2H.sub.5 -- 1-305 Sn 4 2 2 0 S -- -- S--C.sub.3H.sub.7
S--C.sub.3H.sub.7 -- 1-306 Sn 4 2 2 0 S -- --
S-(iso-C.sub.3H.sub.7) S-(iso-C.sub.3H.sub.7) -- 1-307 Sn 4 2 2 0 S
-- -- SCH.sub.3 SC.sub.2H.sub.5 -- 1-308 Sn 4 2 2 0 S -- --
SCH.sub.3 S--C.sub.3H.sub.7 -- 1-309 Sn 4 2 2 0 S -- -- SCH.sub.3
S-(iso-C.sub.3H.sub.7) -- 1-310 Sn 4 2 2 0 S -- -- SC.sub.2H.sub.5
S--C.sub.3H.sub.7 -- 1-311 Sn 4 2 2 0 S -- -- SC.sub.2H.sub.5
S-(iso-C.sub.3H.sub.7) -- 1-312 Sn 4 2 2 0 S -- --
S--C.sub.3H.sub.7 S-(iso-C.sub.3H.sub.7) -- 1-313 Sn 4 2 2 0 S --
-- SCH.sub.2S --
[0193] Among the compounds shown in Tables 1 to 18, specifically,
the compound represented by General Formula (1) wherein m is 0 is
used.
[0194] Furthermore, more specifically, the compound wherein m is 0,
and X.sub.1 is a sulfur atom is used. As such the compound, for
example, there are compounds of CMPD. Nos. 1-1, 1-35, 1-37, 1-39,
1-41, 1-43, 1-45, 1-47, 1-49, 1-51, 1-53, 1-55, 1-57, 1-59, 1-61,
1-63, 1-65, 1-67, 1-69, 1-71, 1-7.3, 1-75, 1-141, 1-175, 1-177,
1-179, 1-181, 1-183, 1-185, 1-187, 1-189, 1-191, 1-193, 1-227,
1-229, 1-231, 1-233, 1-235, 1-237, 1-239, 1-241, 1-243, 1-245,
1-247, 1-249, 1-267, 1-269, 1-287, 1-289, 1-291, 1-293, 1-295,
1-297, 1-299, and 1-301 through 1-313 among the compounds shown in
Tables 1 to 18.
[0195] Furthermore, preferred examples of the compounds shown in
Tables 1 to 18 include the compounds of General Formula (1) with
n=p, more preferably, the compounds of General Formula (1), wherein
n=p, m=0, and X.sub.i is a sulfur atom. As such the compounds, for
example, there are compounds of CMPD. Nos. 1-1, 1-141, 1-193,
1-245, 1-247, 1-267, 1-287, and 1-289 among the compounds shown in
Tables 1 to 17. Furthermore, among these, more preferred are those
in which the metal atom M is any element selected from Groups 4,
12, 13, 14 and 15 elements in a long form of the Periodic Table,
and even more preferred are those in which the metal atom M is a Sn
atom.
[0196] Furthermore, other preferred examples among the compounds
shown in Tables 1 to 18 include the compound represented by General
Formula (5). As such the compounds, there are compounds of CMPD.
Nos. 1-65, 67, 71 and 73 among the compounds shown in Table 4, and
compounds of CMPD. Nos. 1-301 through 1-313 among the compounds
shown in Table 18.
[0197] Furthermore, examples of the compound of General Formula (1)
wherein n-p is 2 or greater, that is, the compound represented by
General Formula (1), containing 2 or more Y's in the molecule
further include the compounds represented by the following Formula.
In the following compound, three Y's are different groups from each
other.
##STR00128##
[0198] Next, the method for preparing the compound represented by
General Formula (1) will be described.
[0199] The compound represented by General Formula (1) is typically
prepared by reaction of a halide of the metal atom M represented by
the following General Formula (2) with a thiol compound or hydroxy
compound having a thietane group represented by the following
General Formula (3).
##STR00129##
[0200] (in General Formula (2), M, n, p, and Y are each the same as
M, n, p, and Y, respectively, in General Formula (1), and Z
represents a halogen atom).
##STR00130##
[0201] (in General Formula (3), X.sub.1, X.sub.2, R.sub.1, and m
are each the same as X.sub.1, X.sub.2, R.sub.1 and m, respectively,
in General Formula (1)).
[0202] Furthermore, the compound represented by General Formula (5)
can be also prepared in accordance with the method for preparing
the compound represented by General Formula (1).
[0203] For example, the compound is prepared by reaction of a
halide represented by the following General Formula (6) with a
thiol compound or hydroxy compound having a thietane group
represented by General Formula (3).
##STR00131##
[0204] (in General Formula (6), M, p, n, and R.sub.2 are each the
same as M, p, n, and R.sub.2, respectively, in General Formula (5),
and Z represents a halogen atom).
[0205] Furthermore, the compound is prepared by reacting the halide
represented by the following General Formula (6) with n=p, with the
thiol compound or hydroxy compound having a thietane group
represented by General Formula (3), and at the same time with the
thiol compound represented by the following Chemical Formula
(7).
R.sub.2--SH (7)
[0206] (in General Formula (7), R.sub.2 is the same as R.sub.2 in
General Formula (5)).
[0207] Furthermore, the compound is also prepared by reaction of
the compound, which has been obtained by preliminary reaction of
the halide represented by the following General Formula (6) with
n=p, with the thiol compound or hydroxy compound having a thietane
group represented by General Formula (3), with a thiol compound
represented by General Formula (7).
[0208] The compounds represented by General Formulae (2), (6), and
(7) are available as raw materials in the industry, or as
laboratory reagents.
[0209] Furthermore, the compound represented by General Formula (3)
is a known compound, and prepared, for example, in accordance with
the method as described in Patent Document 3(Japanese Patent
Laid-Open No. 2003-327583).
[0210] The reaction of the halide of the metal atom M represented
by General Formula (2) with the thiol compound or hydroxy compound
having a thietane group represented by General Formula (3) may be
carried out without or with a solvent, which is inert to the
reaction.
[0211] The solvents are not particularly limited as long as they
are inert to the reaction. Examples thereof include hydrocarbon
solvents such as petroleum ether, hexane, benzene, toluene, xylene,
and mesitylene;
[0212] ether solvents such as diethyl ether, tetrahydrofuran, and
diethylene glycol dimethyl ether;
[0213] ketone solvents such as acetone, methyl ethyl ketone, and
methyl isobutyl ketone;
[0214] ester solvents such as ethyl acetate, butyl acetate, and
amyl acetate;
[0215] chlorine-containing solvents such as methylene chloride,
chloroform, chlorobenzene, and dichlorobenzene;
[0216] polar aprotic solvents such as N,N-dimethylformamide,
N,N-dimethylacetamide, N,N-dimethylimidazolidinone, and dimethyl
sulfoxide;
[0217] sulfur-containing solvents such as tetrahydrothiophene,
thiophene, sulfolane, trimethylenesulfide, diethylsulfide,
di-n-propylsulfide, di-t-butylsulfide, 3-mercaptothiethane, and
bis(2-mercaptoethyl)sulfide; and water.
[0218] The reaction temperature for the compounds represented by
General Formulae (2) and (3) is not particularly limited, but it is
usually in the range of -78.degree. C. to 200.degree. C.,
preferably from -78.degree. C. to 100.degree. C.
[0219] The reaction time varies depending on the reaction
temperature, but it is usually from several minutes to 100
hours.
[0220] For the reaction of the compounds represented by above
General Formulae (2) and (3), the use amount of the compound
represented by General Formula (2) and the compound represented by
General Formula (3) is not particularly limited, but the amount of
the compound represented by General Formula (3) is usually from
0.01 to 100 mole, preferably from 0.1 to 50 moles, more preferably
from 0.5 to 20 moles, based on 1 mole of the halogen atom contained
in the compound represented by General Formula (2).
[0221] When carrying out the reaction with the compounds
represented by General Formulae (2) and (3), it is preferable to
use a basic compound as a capturing agent of the produced hydrogen
halide for effectively carrying out the reaction.
[0222] Examples of the basic compound include inorganic bases such
as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium
carbonate, potassium carbonate, lithium carbonate, sodium
bicarbonate, potassium bicarbonate, lithium bicarbonate, magnesium
hydroxide, and calcium hydroxide; and
[0223] organic bases such as pyridine, triethylamine,
dimethylaniline, diethylaniline, and
1,8-diazabicyclo[5,4,0]-7-undecene.
[0224] Next, specific examples of the thiol compound will be
described.
[0225] As used in the present invention, the thiol compound refers
a compound containing one or more thiol groups (SH groups) in the
molecule. As the thiol compound, for example, the compounds having
any structure that is compatible with the compound represented by
General Formula (1) can be used.
[0226] As the thiol compounds, examples of a monofunctional thiol
compound include aliphatic mercaptan compounds such as methyl
mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan,
octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan,
hexadecyl mercaptan, octadecyl mercaptan, cyclohexyl mercaptan,
benzyl mercaptan, ethylphenyl mercaptan,
2-mercaptomethyl-1,3-dithiolane, 2-mercaptomethyl-1,4-dithiane,
1-mercapto-2,3-epithiopropane,
1-mercaptomethylthio-2,3-epithiopropane,
1-mercaptoethylthio-2,3-epithiopropane, 3-mercaptothietane,
2-mercaptothietane, 3-mercaptomethylthiothietane,
2-mercaptomethylthiothietane, 3-mercaptoethylthiothietane, and
2-mercaptoethylthiothietane; aromatic mercaptan compounds such as
thiophenol, and mercaptotoluene; and compounds each containing a
hydroxyl group in addition to a mercapto group, such as
2-mercaptoethanol, and 3-mercapto-1,2-propanediol.
[0227] Furthermore, examples of polyfunctional thiol(polythiol)
compounds include aliphatic polythiol compounds such as
1,1-methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol,
1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol,
1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol,
1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol,
3,4-dimethoxy butane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol,
1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid
bis(2-mercaptoethylester),
2,3-dimercapto-1-propanol(2-mercaptoacetate),
2,3-dimercapto-1-propanol(3-mercaptopropionate), diethyleneglycol
bis(2-mercaptoacetate), diethyleneglycol bis(3-mercaptopropionate),
1,2-dimercaptopropylmethylether, 2,3-dimercaptopropylmethylether,
2,2-bis(mercaptomethyl)-1,3-propanedithiol,
bis(2-mercaptoethyl)ether, ethyleneglycol bis(2-mercaptoacetate),
ethyleneglycol bis(3-mercaptopropionate), trimethylolpropane
bis(2-mercaptoacetate), trimethylolpropane
bis(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), tetrakis(mercaptomethyl)methane,
and 1,1,1,1-tetrakis(mercaptomethyl)methane;
[0228] aromatic polythiol compounds, such as 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene,
1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene,
1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene,
1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene,
1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene,
1,2,4-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyl)benzene,
1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene,
1,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol,
3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol,
1,3-diphenyl propane-2,2-dithiol, phenylmethane-1,1-dithiol, and
2,4-di(p-mercaptophenyl)pentane;
[0229] aromatic polythiol compounds each containing a sulfur atom
in addition to a mercapto group, such as
1,2-bis(mercaptoethylthio)benzene,
1,3-bis(mercaptoethylthio)benzene,
1,4-bis(mercaptoethylthio)benzene,
1,2,3-tris(mercaptomethylthio)benzene,
1,2,4-tris(mercaptomethylthio)benzene,
1,3,5-tris(mercaptomethylthio)benzene,
1,2,3-tris(mercaptoethylthio)benzene,
1,2,4-tris(mercaptoethylthio)benzene, and
1,3,5-tris(mercaptoethylthio)benzene, and nuclear alkylated
products thereof;
[0230] aliphatic polythiol compounds each containing a sulfur group
in addition to a mercapto group, such as
bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide,
bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide,
bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane,
bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane,
1,2-bis(mercaptomethylthio)ethane,
1,2-bis(2-mercaptoethylthio)ethane,
1,2-bis(3-mercaptopropyl)ethane,
1,3-bis(mercaptomethylthio)propane,
1,3-bis(2-mercaptoethylthio)propane,
1,3-bis(3-mercaptopropylthio)propane,
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
5,7-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
tetrakis(3-mercaptopropylthiomethyl)methane,
bis(2,3-dimercaptopropyl)sulfide, bis(1,3-dimercaptopropyl)sulfide,
2,5-dimercapto-1,4-dithiane, 2,5-bis(mercaptomethyl)-1,4-dithiane,
2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane,
bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide,
bis(mercaptopropyl)disulfide, and
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and an ester
thereof with thioglycolic acid and mercaptopropionic acid;
[0231] aliphatic polythiol compounds each containing an ester bond
with a sulfur group in addition to a mercapto group, such as
hydroxymethylsulfidebis(2-mercaptoacetate), hydroxymethylsulfide
bis(3-mercaptopropionate), hydroxyethylsulfide
bis(2-mercaptoacetate),
hydroxyethylsulfidebis(3-mercaptopropionate),
hydroxypropylsulfidebis(2-mercaptoacetate),
hydroxypropylsulfidebis(3-mercaptopropionate),
hydroxymethyldisulfidebis(2-mercaptoacetate),
hydroxymethyldisulfidebis(3-mercaptopropionate),
hydroxyethyldisulfidebis(2-mercaptoacetate),
hydroxyethyldisulfidebis(3-mercaptopropionate),
hydroxypropyldisulfidebis(2-mercaptoacetate),
hydroxypropyldisulfidebis(3-mercaptopropionate),
2-mercaptoethylether bis(2-mercaptoacetate), 2-mercaptoethylether
bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol
bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol
bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl
ester), thiodipropionic acid bis(2-mercaptoethyl ester),
4,4-thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic
acid bis(2-mercaptoethyl ester), dithiodipropionic acid
bis(2-mercaptoethyl ester), 4,4-dithiodibutyric acid
bis(2-mercaptoethyl ester), thiodiglycolic acid
bis(2,3-dimercaptopropylester), thiodipropionic acid
bis(2,3-dimercaptopropylester), dithioglycolic acid
bis(2,3-dimercaptopropylester), and dithiodipropionic acid
bis(2,3-dimercaptopropylester);
[0232] heterocyclic compounds each containing a sulfur atom in
addition to a mercapto group, such as 3,4-thiophenedithiol, and
2,5-dimercapto-1,3,4-thiadiazole;
[0233] compounds each containing hydroxyl group in addition to a
mercapto group, such as glycerin di(mercaptoacetate),
1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol,
2-mercaptohydroquinone, 4-mercaptophenol,
3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol,
2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol,
pentaerythritol tris(3-mercaptopropionate), pentaerythritol
mono(3-mercaptopropionate), pentaerythritol
bis(3-mercaptopropionate), pentaerythritoltris(thioglycolate),
dipentaerythritolpentakis(3-mercaptopropionate),
hydroxymethyltris(mercaptoethylthiomethyl)methane, and 1-hydroxy
ethylthio-3-mercaptoethylthio benzene;
[0234] compounds each having a dithioaectal or dithioketal
skeleton, such as 1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane,
1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane,
1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane,
2,2-bis(mercaptomethylthio)ethane thiol,
2-(4,5-dimercapto-2-thiapentyl)-1,3-dithiacyclopentane,
2,2-bis(mercaptomethyl)-1,3-dithiacyclopentane,
2,5-bis(4,4-bis(mercaptomethylthio)-2-thiabutyl)-1,4-dithiane,
2,2-bis(mercaptomethylthio)-1,3-propanedithiol,
3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane,
3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane,
4,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane,
3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane,
1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thi-
apropyl) 3,7-dithianonane,
tris(2,2-bis(mercaptomethylthio)ethyl)methane,
tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane,
tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane,
tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane,
3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiam-
idecane,
3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,-
12,14,18-hexathianonadecane,
9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercapto
methylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane,
3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaun-
decane,
3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10-
,12,15-hexathiahexadecane,
8-{bis(mercaptomethylthio)methyl}-3,4,12,13-tetrakis(mercaptomethylthio)--
1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane,
4,6-bis{3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthiol}-1,3-
-dithiane,
4-{3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthiol-
}-6-mercaptomethylthio-1,3-dithiane,
1,1-bis{4-(6-mercaptomethylthio)-1,3-dithianylthio}-3,3-bis(mercaptomethy-
lthio)propane,
1,3-bis{4-(6-mercaptomethylthio)-1,3-dithianylthio}-1,3-bis(mercaptomethy-
lthio)propane,
1-{4-(6-mercaptomethylthio)-1,3-dithianylthio}-3-{2,2-bis(mercaptomethylt-
hio)ethyl}-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane,
1-{4-(6-mercaptomethylthio)-1,3-dithianylthio}-3-{2-(1,3-dithietanyl)}met-
hyl-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane,
1,5-bis{-4-(6-mercaptomethylthio)-1,3-dithianylthio}-3-{2-(1,3-dithietany-
l)}methyl-2,4-dithiapentane,
4,6-bis[3-{2-(1,3-dithietanyl)}methyl-5-mercapto-2,4-dithiapentylthio]-1,-
3-dithiane,
4,6-bis{4-(6-mercaptomethylthio)-1,3-dithianylthio}-1,3-dithiane,
4-{4-(6-mercaptomethylthio)-1,3-dithianylthio}-6-{4-(6-mercaptomethylthio-
)-1,3-dithianylthio}-1,3-dithiane,
3-{2-(1,3-dithietanyl)}methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-
-2,4,6,10-tetrathiaundecane,
9-{2-(1,3-dithietanyl)}methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-
-dimercapto-2,6,8,10,12,16-hexathiaheptadecane,
3-{2-(1,3-dithietanyl)}methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-
-dimercapto-2,4,6,10,12,16-hexathiaheptadecane,
3,7-bis{2-(1,3-dithietanyl)}methyl-1,9-dimercapto-2,4,6,8-tetrathianonane-
,
4-{3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaun-
decyl}-5-mercaptomethylthio-1,3-dithiolane,
4,5-bis{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthiol}-1,3--
dithiolane,
4-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}-5-mercapto-
methylthio-1,3-dithiolane,
4-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-
-2,4,7-trithiaoctyl}-5-mercaptomethylthio-1,3-dithiolane,
2-[bis{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}methyl]-
-1,3-dithietane,
2-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}mercaptomet-
hylthiomethyl-1,3-dithietane,
2-{3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaund-
ecylthio}mercaptomethylthiomethyl-1,3-dithietane,
2-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-
-2,4,7-trithiaoctyl}mercaptomethylthiomethyl-1,3-dithietane,
4,5-bis[1-{2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiola-
ne,
4-[1-{2-(1,3-dithietanyl)}-3-mercapto-2-thiapropylthio]-5-{1,2-bis(mer-
captomethylthio)-4-mercapto-3-thiabutylthio}-1,3-dithiolane,
2-[bis{4-(5-mercaptomethylthio-1,3-dithiolanyl)thio}]methyl-1,3-dithietan-
e, and 4-{4-(5-mercaptomethylthio-1,3-dithiolanyl)
thio}-5-[1-{2-(1,3-dithietanyl)}-3-mercapto-2-thiapropylthio]-1,3-dithiol-
ane, and an oligomer thereof;
[0235] compounds each having an orthotrithio formic acid ester
skeleton, such as tris(mercaptomethylthio)methane,
tris(mercaptoethylthio)methane,
1,1,5,5-tetrakis(mercaptomethylthio)-2,4-dithiapentane,
bis[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl](mercaptomethylthio)metha-
ne, tris[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl]methane,
2,4,6-tris(mercaptomethylthio)-1,3,5-trithiacyclohexane,
2,4-bis(mercaptomethylthio)-1,3,5-trithiacyclohexane,
1,1,3,3-tetrakis(mercaptomethylthio)-2-thiapropane,
bis(mercaptomethyl)methylthio-1,3,5-trithiacyclohexane,
tris[(4-mercaptomethyl-2,5-dithiacyclohexyl
1-yl)methylthio]methane,
2,4-bis(mercaptomethylthio)-1,3-dithiacyclopentane,
2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane,
2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane,
4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane,
4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiacyclopentane,
tris[2,2-bis(mercaptomethylthio)-1-thia ethyl]methane,
tris[3,3-bis(mercaptomethylthio)-2-thiapropyl]methane,
tris[4,4-bis(mercaptomethylthio)-3-thia butyl]methane,
2,4,6-tris[3,3-bis(mercaptomethylthio)-2-thiapropyl]-1,3,5-trithiacyclohe-
xane, and
tetrakis[3,3-bis(mercaptomethylthio)-2-thiapropyl]methane, and an
oligomer thereof; and
[0236] compounds each having an orthotetrathiocarbonic acid ester
skeleton, such as
3,3'-di(mercaptomethylthio)-1,5-dimercapto-2,4-dithiapentane,
2,2'-di(mercaptomethylthio)-1,3-dithiacyclopentane,
2,7-di(mercaptomethyl)-1,4,5,9-tetrathiaspiro[4,4]nonane,
3,9-dimercapto-1,5,7,11-tetrathiaspiro[5,5]undecane, and an
oligomer thereof, but not limited to these exemplary compounds.
These exemplary compounds are used alone, or in a mixture of two or
more kinds thereof.
[0237] Among these thiol compounds, from the viewpoint of the
optical properties, in particular Abbe's numbers, of the obtained
resin, aliphatic thiol compounds are preferably selected rather
than aromatic thiol compounds. Further, from the viewpoint of
optical properties, in particular, requirements in refractive
indices, a compound containing a sulfur atom, such as a sulfide
bond and/or a disulfide bond, in addition to a thiol group is more
preferably selected. From the viewpoint of heat resistance of the
obtained resin, and improvement in a 3-dimensional
crosslinkability, at least one selected from the compounds each
having a polymerizable group such as an epithio group and a
thietanyl group, or three or more thiol groups is more preferably
selected.
[0238] From the above-described viewpoints, examples of preferable
thiols include 3-mercaptothietane, 1-mercapto-2,3-epithiopropane,
1-mercaptomethylthio-2,3-epithiopropane,
1-mercaptoethylthio-2,3-epithiopropane, 3-mercaptothietane,
2-mercaptothietane, 3-mercaptomethylthiothietane,
2-mercaptomethylthiothietane, 3-mercaptoethylthiothietane,
2-mercaptoethylthiothietane, 2,5-bis(mercaptomethyl)-1,4-dithiane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
5,7-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
1,1,1,1-tetrakis(mercaptomethyl)methane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.
[0239] More preferred examples of thiols include
3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
2,5-bis(mercaptomethyl)-1,4-dithiane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
5,7-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane,
1,1,1,1-tetrakis(mercaptomethyl)methane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane. Furthermore,
if a divalent thiol compound is selected, it is preferable to use a
mixture of a thiol compound containing a polymerizable group and/or
a trivalent or higher thiol compound.
[0240] More specifically, the thiol compound is at least one
selected from the group consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane.
[0241] Furthermore, preferable combinations of the thiol compound
and the compound represented by General Formula (1) include, for
example, the followings.
[0242] (i) A combination in which the compound represented by
General Formula (1) is the compound represented by General Formula
(13), and further, the thiol compound is at least one selected from
the group consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0243] (ii) a combination in which, for the compound represented by
General Formula (1), n=p, m=0, and X.sub.1 is a sulfur atom, and
further, the thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane; and
[0244] (iii) a combination in which, for the compound represented
by General Formula (1), said metal atom is a Sn atom, and further,
the thiol compound is at least one selected from the group
consisting of 3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,1'-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane.
[0245] As for the amount of the thiol compound used, based on 100
parts by weight of the total weight of the compound represented by
General Formula (1) and the thiol compound, if the amount of the
thiol compound used is too low, improvement in color and mechanical
strength is unfavorably reduced in some cases. Furthermore, if the
amount of the thiol compound used is too high, based on 100 parts
by weight of the total weight of the compound represented by
General Formula (1) and the thiol compound, reduction in the heat
resistance is unfavorably significant, in some cases.
[0246] Thus, it is preferable that the thiol compound is used in an
amount of 1 to 50 part(s) by weight based on 100 parts by weight of
the total weight of the compound represented by General Formula (1)
and the thiol compound. It is further more preferable that the
thiol compound is used in an amount of 1 to 25 part(s) by weight
based on 100 parts by weight of the total weight of the compound
represented by General Formula (1) and the thiol compound.
[0247] Since the polymerizable composition of the present invention
contains the compound represented by General Formula (1) and the
thiol compound, the obtained resin can have improved mechanical
properties and color, for example.
[0248] Furthermore, as the polymerizable composition of the present
invention, the compound represented by General Formula (1) may be
used singly, or a plurality of the different compounds represented
by General Formula (1) may be used together.
[0249] Furthermore, the polymerizable composition of the present
invention contains the compound represented by General Formula (1)
and the thiol compound as essential components, and further, it may
contain sulfur as a monomer. Further addition of sulfur as a
monomer to the polymerizable composition composed of the compound
represented by General Formula (1) and the thiol compound is one
preferable embodiment that facilitates further high refractive
indices. Here, if necessary, a polymerization catalyst can be
further contained. Furthermore, the compound may be represented by
General Formula (1), wherein m=0, and X.sub.1 is a sulfur atom.
[0250] Sulfur as a monomer, used in the polymerizable composition
according to the invention, refers to inorganic sulfur, and if used
for the resin composition in the present invention or a transparent
resin employing the composition, the purity is preferably 98% or
more, more preferably 99% or more, and even more preferably 99.5%
or more. In order to increase the purity, a method for removing
volatile components is preferably used in some cases.
[0251] Furthermore, the form of sulfur as a monomer is in any form,
for example, that can be dissolved in the compound represented by
General Formula (1), and preferably in the form of powders, and
more preferably in the form of fine powders.
[0252] In the present invention, if the polymerizable composition
containing the compound represented by General Formula (1) and the
thiol compound is used, for example, to provide a resin having a
higher refractive index, sulfur as a monomer may be added to the
polymerizable composition.
[0253] As for the amount of sulfur added to the polymerizable
composition, from the viewpoint of a high refractive index, based
on 100 parts by weight of the total weight of the compound
represented by General Formula (1), the thiol compound, and sulfur,
if the amount of sulfur added as a monomer is too low, the effect
of improvement in the refractive indices is unfavorably low in some
cases. Furthermore, if the amount of sulfur added as a monomer is
too high based on 100 parts by weight of the total weight of the
compound represented by General Formula (1), the thiol compound,
and sulfur, fogging unfavorably occurs in some cases.
[0254] Thus, from the viewpoint as above, the amount of sulfur
added as a monomer, based on 100 parts by weight of the total
weight of the compound represented by General Formula (1), the
thiol compound, and sulfur, is preferably 5 to 50 parts by weight.
The amount of sulfur added as a monomer, based on 100 parts by
weight of the total weight of the compound represented by General
Formula (1), is more preferably 5 to 25 parts by weight.
[0255] One of preferable methods for mixing the compound
represented by General Formula (1) of the present invention and
sulfur as a monomer is, for example, a method in which sulfur as a
monomer is added to a mixture of the compound represented by
General Formula (1) and the thiol compound, and then dissolved
under stirring, and if necessary, the temperature is increased.
Furthermore, the method as described below, for example, in which
sulfur as a monomer is added to other polymerizable compounds or
polymerization catalysts, and then dissolved; simultaneously mixed
under stirring in one vessel; stepwise added, and mixed; or some
components are separately added and then mixed together in the same
vessel.
[0256] The polymerizable composition of the present invention
includes the compound represented by General Formula (1), the thiol
compound, and the compound having a carbon-carbon double bond, and
if necessary, a polymerization catalyst. Furthermore, the compound
may be represented by General Formula (1), wherein m=0, and X.sub.1
is a sulfur atom.
[0257] The compound having a carbon-carbon double bond used in the
present invention is a compound containing one or more
carbon-carbon double bonds in the molecule. The compound having a
carbon-carbon double bond can be, for example, a compound having
any structure that is compatible with the compound represented by
General Formula (1), and it is preferably a compound having two or
more carbon-carbon double bonds.
[0258] Specific examples of the compound having a carbon-carbon
double bond include (meth)acrylate compounds such as benzyl
acrylate, benzyl methacrylate, butoxy ethyl acrylate, butoxymethyl
methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl
acrylate, glycidyl methacrylate, phenoxyethyl acrylate,
phenoxyethyl methacrylate, phenyl methacrylate, ethyleneglycol
diacrylate, ethyleneglycol dimethacrylate, diethyleneglycol
diacrylate, diethyleneglycol dimethacrylate, triethyleneglycol
diacrylate, triethyleneglycoldimethacrylate, tetraethyleneglycol
diacrylate, tetraethyleneglycoldimethacrylate, polyethyleneglycol
diacrylate, polyethyleneglycoldimethacrylate, neopentyl glycol
diacrylate, neopentylglycol dimethacrylate, ethyleneglycol
bisglycidylacrylate, ethyleneglycol bisglycidylmethacrylate,
bisphenol A diacrylate, bisphenol A dimethacrylate,
2,2-bis(4-acryloxyethoxyphenyl)propane,
2,2-bis(4-methacryloxyethoxyphenyl)propane,
2,2-bis(4-acryloxydiethoxyphenyl)propane,
2,2-bis(4-methacryloxydiethoxyphenyl)propane, bisphenol F
diacrylate, bisphenol F dimethacrylate,
1,1-bis(4-acryloxyethoxyphenyl)methane,
1,1-bis(4-methacryloxyethoxyphenyl)methane,
1,1-bis(4-acryloxydiethoxyphenyl)methane,
1,1-bis(4-methacryloxydiethoxyphenyl)methane,
dimethyloltricyclodecane diacrylate, trimethylolpropane
triacrylate, trimethylolpropane trimethacrylate, glycerol
diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate,
methylthioacrylate, methylthiomethacrylate, phenylthioacrylate,
benzylthiomethacrylate, xylenedithiol diacrylate, xylenedithiol
dimethacrylate, mercaptoethyl sulfide diacrylate, and
mercaptoethylsulfide dimethacrylate;
[0259] allyl compounds such as allyl glycidyl ether, diallyl
phthalate, diallyl terephthalate, diallyl isophthalate, diallyl
carbonate, diethyleneglycol-bisallyl carbonate, and triallyl
isocyanurate;
[0260] vinyl compounds such as styrene, chlorostyrene,
methylstyrene, bromostyrene, dibromostyrene, divinylbenzene,
3,9-divinyl-spiro-bi(m-dioxane), divinylsulfide, and
divinyldisulfide;
[0261] diisopropenylbenzene; and the like, but not limited to these
exemplary compounds. Further, these may be used alone or in
combination of two or more thereof. As the compound having a
carbon-carbon double bond, triallyl isocyanurate may be preferably
used.
[0262] The amount of the compound having a carbon-carbon double
bond added depends on the structure of the compound used and the
structure or amount of the thiol compound used, but it is
preferably 25% by weight or less based on the total amount of the
polymerizable composition, from the viewpoint of the refractive
index of the obtained resin. It is more preferably 23% by weight or
less, and even more preferably 20% by weight or less. From the
viewpoint of the color of the obtained resin, it is preferably 2.5%
by weight or more.
[0263] Furthermore, as for the ratio of the thiol compound used and
the compound having a carbon-carbon double bond used, the ratio of
the functional groups (that is, SH groups/carbon-carbon double
bonds) that is the ratio of the thiol groups in the thiol compound
and the carbon-carbon double bonds in the compound having a
carbon-carbon double bond is preferably 0.7 or more from the
viewpoint of the color of the resin. It is more preferably from 0.9
to 5, and even more preferably from 0.9 to 3. If the ratio of the
functional groups is too low, the obtained resin unfavorably has
reduction in transparency in some cases, whereas if the ratio is
too high, the obtained resin unfavorably has reduction in heat
resistance in some cases.
[0264] If the polymerizable composition further includes the
compound having a carbon-carbon double bond, the content of the
compound represented by General Formula (1) in the total weight of
the polymerizable compounds contained in the polymerizable
composition of the present invention is not particularly limited,
but it is usually 10% by weight or more.
[0265] As the content of the compound represented by General
Formula (1) is increased, there is a tendency that materials having
higher refractive indices are obtained. Thus, the content is
preferably 30% by weight or more, more preferably 50% by weight or
more, and even more preferably 70% by weight or more.
[0266] However, if the content of the compound represented by
General Formula (1) is too high, it relatively reduces the content
of the thiol compound and the compound having a carbon-carbon
double bond. From the viewpoint of improving the color of the resin
and suppressing the reduction in mechanical strength, the content
of the compound represented by General Formula (1) in the
polymerizable composition is preferably 95% by weight or less.
[0267] Furthermore, if the polymerizable composition further
includes the compound having a carbon-carbon double bond, the
amount of the thiol compound used depends on the structure of the
compound used and the structure or amount of the compound having a
carbon-carbon double bond. However, since the compound represented
by General Formula (1) provides a resin having a high refractive
index, generally addition of a thiol compound leads to reduction in
the refractive index of the obtained resin. Thus, from the
viewpoint of the refractive index of the obtained resin, it is
contained in an amount of preferably 35% by weight or less based on
the total amount of the polymerizable composition of the present
invention, more preferably 30% by weight or less, and even more
preferably 25% by weight or less. From the viewpoint of the color
of the obtained resin, the amount is preferably 2.5% by weight or
more.
[0268] The polymerizable composition of the present invention
includes the compound represented by General Formula (1), the thiol
compound, and a compound including an iso(thio)cyanate compound,
and if necessary, a polymerization catalyst. Furthermore, the
compound may be represented by General Formula (1), wherein m=0,
and X.sub.1 is a sulfur atom.
[0269] The iso(thio)cyanate compound used in the present invention
is a compound containing one or more iso(thio)cyanate groups (NCO
groups and/or NCS groups) in the molecule. The iso(thio)cyanate
compound more specifically represents one that is compatible with
the compound represented by General Formula (1), and it is
preferably a compound having two or more iso(thio)cyanate
groups.
[0270] Specific examples of the isocyanate compound include
aliphatic polyisocyanate compounds such as hexamethylene
diisocyanate, 2,2-dimethylpentane diisocyanate,
2,2,4-trimethylhexane diisocyanate, butene diisocyanate,
1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene
diisocyanate, 1,6,11-undecatriisocyanate,
1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato
4-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate,
bis(isocyanatoethyl)ether, lisine diisocyanatomethylester, lisine
triisocyanate, m-xylene diisocyanate, p-xylene diisocyanate,
bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethyl xylene diisocyanate,
bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene,
bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate,
mesitylene triisocyanate, and 2,6-di(isocyanatomethyl)furan;
[0271] alicyclic polyisocyanate compounds such as isophorone
diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexyl
methane diisocyanate, cyclohexane diisocyanate, methyl cyclohexane
diisocyanate, dicyclohexyl dimethyl methane diisocyanate,
2,2-dimethyl dicyclohexyl methane diisocyanate,
2,5-bis(isocyanatomethyl)bicyclo[2,2,1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo[2,2,1]-heptane,
3,8-bis(isocyanatomethyl)tricyclodecane,
3,9-bis(isocyanatomethyl)tricyclodecane,
4,8-bis(isocyanatomethyl)tricyclodecane,
4,9-bis(isocyanatomethyl)tricyclodecane, and
1,1'-methylenebis(4-isocyanatocyclohexane);
[0272] aromatic polyisocyanate compounds such as phenylene
diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate,
isopropylphenylene diisocyanate, dimethylphenylene diisocyanate,
diethylphenylene diisocyanate, diisopropylphenylene diisocyanate,
trimethylbenzenetriisocyanate, benzenetriisocyanate,
biphenyldiisocyanate, toluidine diisocyanate, 4,4-diphenyl methane
diisocyanate, 3,3-dimethyl diphenyl methane-4,4-diisocyanate,
bibenzyl-4,4-diisocyanate, bis(isocyanatophenyl)ethylene,
3,3-dimethoxybiphenyl-4,4-diisocyanate,
phenylisocyanatoethylisocyanate, hexahydrobenzene diisocyanate, and
hexahydrodiphenyl methane-4,4-diisocyanate;
[0273] sulfur-containing aliphatic polyisocyanate compounds such as
bis(isocyanatomethyl)sulfide, bis(isocyanatoethyl)sulfide,
bis(isocyanatopropyl)sulfide, bis(isocyanatohexyl)sulfide,
bis(isocyanatomethyl)sulfone, bis(isocyanatomethyl)disulfide,
bis(isocyanatoethyl)disulfide, bis(isocyanatopropyl)disulfide,
bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane,
bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane,
and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane;
[0274] aromatic sulfide-based polyisocyanate compounds such as
diphenyl sulfide-2,4-diisocyanate, diphenyl
sulfide-4,4-diisocyanate,
3,3-dimethoxy-4,4-diisocyanatodibenzylthioether,
bis(4-isocyanatomethylbenzene)sulfide, and 4,4-methoxybenzene
thioethyleneglycol-3,3-diisocyanate;
[0275] aromatic disulfide-based isocyanate compounds such as
diphenyldisulfide-4,4-diisocyanate,
2,2-dimethyldiphenyldisulfide-5,5-diisocyanate,
3,3-dimethyldiphenyldisulfide-5,5-diisocyanate,
3,3-dimethyldiphenyldisulfide 6,6-diisocyanate,
4,4-dimethyldiphenyldisulfide-5,5-diisocyanate,
3,3-dimethoxydiphenyldisulfide-4,4-diisocyanate, and
4,4-dimethoxydiphenyldisulfide 3,3-diisocyanate; and
[0276] sulfur-containing heterocyclic compounds such as
2,5-diisocyanatothiophene, and
2,5-bis(isocyanatomethyl)thiophene.
[0277] Other examples of the isocyanate compound include
2,5-diisocyanatotetrahydrothiophene,
2,5-bis(isocyanatomethyl)tetrahydrothiophene,
3,4-bis(isocyanatomethyl)tetrahydrothiophene,
2,5-diisocyanato-1,4-dithiane,
2,5-bis(isocyanatomethyl)-1,4-dithiane,
4,5-diisocyanato-1,3-dithiolane,
4,5-bis(isocyanatomethyl)-1,3-dithiolane, and
4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane, but not limited
to these exemplary compounds.
[0278] Also, there may be used a halogen substitute such as a
chlorine substitute or a bromine substitute, an alkyl substitute,
an alkoxy substitute, a nitro substitute, polyhydric alcohol
prepolymer-type modified products, carbodiimide-modified products,
urea-modified products, burette-modified products, or dimerization
or trimerization reaction products, of those compounds.
[0279] Specific examples of the isothiocyanate compound include
monofunctional isothiocyanate compounds (compounds each containing
one isothiocyanate group), such as methyl isothiocyanate, ethyl
isothiocyanate, n-propylthioisocyanate, isopropyl isothiocyanate,
n-butyl isothiocyanate, sec-butyl isothiocyanate, tert-butyl
isothiocyanate, pentyl isothiocyanate, hexyl isothiocyanate, heptyl
isothiocyanate, octyl isothiocyanate, decyl isothiocyanate, lauryl
isothiocyanate, myristyl isothiocyanate, octadecyl isothiocyanate,
3-pentyl isothiocyanate, 2-ethylhexyl isothiocyanate,
2,3-dimethylcyclohexyl isothiocyanate, 2-methoxyphenyl
isothiocyanate, 4-methoxyphenyl isothiocyanate, a-methylbenzyl
isothiocyanate, phenylethyl isothiocyanate, phenyl isothiocyanate,
o-, m-, or p-tolyl isothiocyanate, cyclohexyl isothiocyanate,
benzyl isothiocyanate, and isothiocyanatemethylbicycloheptane;
[0280] aliphatic polyisothiocyanate compounds such as
1,6-diisothiocyanatohexane, and
p-phenyleneisopropylidenediisothiocyanate;
[0281] alicyclic polyisothiocyanate compounds such as
cyclohexanediisothiocyanate, and
diisothiocyanatomethylbicycloheptane;
[0282] aromatic polyisothiocyanate compounds such as
1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene,
1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene,
2,5-diisothiocyanato-m-xylene, 4,4-diisothiocyanato-1,1-biphenyl,
1,1-methylenebis(4-isothiocyanatobenzene),
1,1-methylenebis(4-isothiocyanato 2-methylbenzene),
1,1-methylenebis(4-isothiocyanato-3-methylbenzene),
1,1-(1,2-ethanediyl)bis(isothiocyanatobenzene),
4,4-diisothiocyanatobenzophenone,
4,4-diisothiocyanato-3,3-dimethylbenzophenone, diphenyl
ether-4,4-diisothiocyanate, and diphenylamine-4,4-diisothiocyanate;
and
[0283] carbonyl polyisothiocyanate compounds such as
1,3-benzenedicarbonyl diisothiocyanate,
1,4-benzenedicarbonyldiisothiocyanate, and
(2,2-pyridine)-4,4-dicarbonyldiisothiocyanate, but not limited to
these exemplary compounds.
[0284] Furthermore, specific examples of the isothiocyanate
compound having one or more sulfur atoms in addition to an
isothiocyanato group include sulfur-containing aliphatic
polyisothiocyanate compounds such as
thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane),
and dithiobis(2-isothiocyanatoethane);
[0285] sulfur-containing aromatic polyisothiocyanate compounds such
as 1-isothiocyanato-4-[(2-isothiocyanato)sulfonyl]benzene,
thiobis(4-isothiocyanatobenzene),
sulfonylbis(4-isothiocyanatobenzene), and
dithiobis(4-isothiocyanatobenzene);
[0286] sulfur-containing heterocyclic polyisothiocyanate compounds
such as 2,5-diisothiocyanatothiophene, and
2,5-diisothiocyanato-1,4-dithiane, but not limited to these
exemplary compounds.
[0287] Also, there may be used a halogen substitute such as a
chlorine substitute or a bromine substitute, an alkyl substitute,
an alkoxy substitute, a nitro substitute, polyhydric alcohol
prepolymer-type modified products, carbodiimide-modified products,
urea-modified products, burette-modified products, or dimerization
or trimerization reaction products, of those compounds.
[0288] Furthermore, isothiocyanate compounds having isocyanate
groups can be included. Specific examples thereof include aliphatic
or alicyclic compounds such as 1-isocyanato-6-isothiocyanatohexane,
and 1-isocyanato-4-isothiocyanatocyclohexane;
[0289] aromatic compounds such as
1-isocyanato-4-isothiocyanatobenzene, and
4-methyl-3-isocyanato-1-isothiocyanatobenzene;
[0290] heterocyclic compounds such as
2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine; and
[0291] compounds each containing a sulfur atom in addition to an
isothiocyanato group, such as
4-isocyanato-4'-isothiocyanatodiphenyl sulfide, and
2-isocyanato-2'-isothiocyanatodiethyl disulfide, but not limited to
these exemplary compounds.
[0292] Also, there may be used a halogen substitute such as a
chlorine substitute or a bromine substitute, an alkyl substitute,
an alkoxy substitute, a nitro substitute, polyhydric alcohol
prepolymer-type modified products, carbodiimide-modified products,
urea-modified products, burette-modified products, or dimerization
or trimerization reaction products.
[0293] Among these compounds, from the viewpoint of the strength of
the obtained resin, the compound that is preferably at least one
selected from the group consisting of
2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane,
2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane,
bis(isocyanatomethyl)cyclohexane, cyclohexane diisocyanate,
isophorone diisocyanate,
1,1'-methylenebis(4-isocyanatocyclohexane), m-xylenediisocyanate,
and 2,5-bis(isocyanatomethyl)-1,4-dithiane, and the compound is
more preferably 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, and
2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane.
[0294] The amount of the iso(thio)cyanate compound added of the
present invention depends on the structure of the compound used and
the structure or amount of the thiol compound, but it is preferably
25% by weight or less based on the total amount of the
polymerizable composition of the invention, from the viewpoint of
the refractive index of the obtained resin. It is more preferably
23% by weight or less, and even more preferably 20% by weight or
less. From the viewpoint of the color of the obtained resin, it is
preferably 2.5% by weight or more.
[0295] Furthermore, as for the ratio of the thiol compound used and
the iso(thio)cyanate compound, the ratio of the functional groups
(that is, SH groups/(NCO groups+NCS groups)) that is the ratio of
the thiol groups in the thiol compound and the iso(thio)cyanate
groups in the iso(thio)cyanate compound is preferably 0.7 or more
from the viewpoint of the color of the resin. It is more preferably
from 0.9 to 5, and even more preferably from 0.9 to 3. If the ratio
of the functional groups is too low, the obtained resin unfavorably
has the reduced mechanical strength in some cases, whereas if the
ratio is too high, the obtained resin unfavorably has the reduced
heat resistance in some cases.
[0296] If the polymerizable composition further includes the
iso(thio)cyanate compound, the content of the compound represented
by General Formula (1) in the total weight of the polymerizable
compounds contained in the polymerizable composition of the present
invention is not particularly limited, but it is usually 10% by
weight or more.
[0297] As the content of the compound represented by General
Formula (1) is increased, there is a tendency that materials having
higher refractive indice are obtained. Thus, the content is
preferably 30% by weight or more, more preferably 50% by weight or
more, and even more preferably 70% by weight or more.
[0298] However, if the content of the compound represented by
General Formula (1) is too high, it relatively reduces the content
of the thiol compound and the iso(thio)cyanate compound. Thus, from
the viewpoints for improving the color of the resin and suppressing
the reduction in mechanical strength, the content of the compound
represented by General Formula (1) in the polymerizable composition
is preferably 95% by weight or less.
[0299] Furthermore, if the polymerizable composition further
includes the iso(thio)cyanate compound, the amount of the thiol
compound used depends on the structure of the compound used and the
structure or amount of the iso(thio)cyanate compound. However,
since the compound represented by General Formula (1) provides a
resin having a high refractive index, generally addition of a thiol
compound leads to reduction in the refractive index of the obtained
resin. Thus, considering the refractive index of the obtained
resin, it is contained in an amount of preferably 35% by weight or
less based on the total amount of the polymerizable composition of
the present invention, more preferably 30% by weight or less, and
even more preferably 25% by weight or less. From the viewpoint of
the color and the mechanical strength of the obtained resin, the
amount is preferably 2.5% by weight or more.
[0300] The polymerizable composition of the present invention
includes the compound represented by General Formula (1), the thiol
compound, and a compound including an epoxy compound and/or an
episulfide compound, and if necessary, a polymerization catalyst.
Furthermore, the compound may be represented by General Formula
(1), wherein m=0, and X.sub.1 is a sulfur atom.
[0301] The epoxy compound and the episulfide compound contain one
or more epoxy groups and episulfide groups in the molecule,
respectively. As each of the epoxy compound and the episulfide
compound, any one having a structure that is compatible with the
compound represented by General Formula (1) can be used, and they
are preferably compounds each containing two or more epoxy groups
and/or episulfide groups in total.
[0302] Specifically, examples of the epoxy compound include
phenolic epoxy compounds obtained by condensation of an
epihalohydrin compound with a polyphenol compound such as bisphenol
A/glycidyl ether, and bisphenol F/glycidyl ether;
[0303] alcoholic epoxy compounds obtained by condensation of an
epihalohydrin compound with a polyalcohol compound such as
hydrogenated bisphenol A/glycidyl ether, hydrogenated bisphenol
F/glycidyl ether, and cyclohexanedimethanol;
[0304] glycidyl ester epoxy compounds obtained by condensation of
an epihalohydrin compound with a polyorganic acid compound such as
3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, and
diglycidyl 1,2-hexahydrophthalate; and
[0305] amine epoxy compounds obtained by condensation of an
epihalohydrin compound with a primary/secondary amine; as well
as
[0306] aliphatic polyepoxy compounds such as vinylcyclohexene
diepoxide which includes 4-vinyl-1-cyclohexanedipoxide and the
like.
[0307] Specific examples of the sulfide group-containing epoxy
compound and the ether group-containing epoxy compound include
chained aliphatic 2,3-epoxypropylthio compounds such as
bis(2,3-epoxypropyl)sulfide, bis(2,3-epoxypropyl)disulfide,
bis(2,3-epoxypropylthio)methane,
1,2-bis(2,3-epoxypropylthio)ethane,
1,2-bis(2,3-epoxypropylthio)propane,
1,3-bis(2,3-epoxypropylthio)propane,
1,3-bis(2,3-epoxypropylthio)-2-methyl propane,
1,4-bis(2,3-epoxypropylthio)butane,
1,4-bis(2,3-epoxypropylthio)-2-methylbutane,
1,3-bis(2,3-epoxypropylthio)butane,
1,5-bis(2,3-epoxypropylthio)pentane,
1,5-bis(2,3-epoxypropylthio)-2-methylpentane,
1,5-bis(2,3-epoxypropylthio)-3-thiapentane,
1,6-bis(2,3-epoxypropylthio)hexane,
1,6-bis(2,3-epoxypropylthio)-2-methylhexane,
3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane,
1,2,3-tris(2,3-epoxypropylthio)propane,
2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane,
2,2-bis(2,3-epoxypropylthiomethyl)-1-(2,3-epoxypropylthio)butane,
1,5-bis(2,3-epoxypropylthio)-2-(2,3-epoxypropylthiomethyl)-3-thiapentane,
1,5-bis(2,3-epoxypropylthio)-2,4-bis(2,3-epoxypropylthiomethyl)-3-thiapen-
tane,
1-(2,3-epoxypropylthio)-2,2-bis(2,3-epoxypropylthiomethyl)-4-thiahex-
ane,
1,5,6-tris(2,3-epoxypropylthio)-4-(2,3-epoxypropylthiomethyl)-3-thiah-
exane,
1,8-bis(2,3-epoxypropylthio)-4-(2,3-epoxypropylthiomethyl)-3,6-dith-
iaoctane,
1,8-bis(2,3-epoxypropylthio)-4,5-bis(2,3-epoxypropylthiomethyl)--
3,6-dithiaoctane,
1,8-bis(2,3-epoxypropylthio)-4,4-bis(2,3-epoxypropylthiomethyl)-3,6-dithi-
aoctane,
1,8-bis(2,3-epoxypropylthio)-2,5-bis(2,3-epoxypropylthiomethyl)-3-
,6-dithiaoctane,
1,8-bis(2,3-epoxypropylthio)-2,4,5-tris(2,3-epoxypropylthiomethy
1)-3,6-dithiaoctane,
1,1,1-tris[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]-2-(2,3-epoxypropylth-
io)ethane,
1,1,2,2-tetrakis[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]ethan- e,
1,11-bis(2,3-epoxypropylthio)-4,8-bis(2,3-epoxypropylthiomethyl)-3,6,9--
trithiaundecane,
1,11-bis(2,3-epoxypropylthio)-4,7-bis(2,3-epoxypropylthiomethyl)-3,6,9-tr-
ithiaundecane, and
1,11-bis(2,3-epoxypropylthio)-5,7-bis(2,3-epoxypropylthiomethyl)-3,6,9-tr-
ithiaundecane;
[0308] alicyclic 2,3-epoxypropylthio compounds such as
1,3-bis(2,3-epoxypropylthio)cyclohexane,
1,4-bis(2,3-epoxypropylthio)cyclohexane,
1,3-bis(2,3-epoxypropylthiomethyl)cyclohexane,
1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane,
2,5-bis(2,3-epoxypropylthiomethyl)-1,4-dithiane,
2,5-bis[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]-1,4-dithiane, and
2,5-bis(2,3-epoxypropylthiomethyl)-2,5-dimethyl-1,4-dithiane;
[0309] aromatic 2,3-epoxypropylthio compounds such as
1,2-bis(2,3-epoxypropylthio)benzene,
1,3-bis(2,3-epoxypropylthio)benzene,
1,4-bis(2,3-epoxypropylthio)benzene,
1,2-bis(2,3-epoxypropylthiomethyl)benzene,
1,3-bis(2,3-epoxypropylthiomethyl)benzene,
1,4-bis(2,3-epoxypropylthiomethyl)benzene,
bis[4-(2,3-epoxypropylthio)phenyl]methane,
2,2-bis[4-(2,3-epoxypropylthio)phenyl]propane,
bis[4-(2,3-epoxypropylthio)phenyl]sulfide,
bis[4-(2,3-epoxypropylthio)phenyl]sulfone, and
4,4'-bis(2,3-epoxypropylthio)biphenyl;
[0310] monofunctional epoxy compounds (compounds having one epoxy
group) such as ethylene oxide, propylene oxide, glycidol, and
epichlorohydrin;
[0311] chained aliphatic 2,3-epoxypropyloxy compounds such as
bis(2,3-epoxypropyl)ether, bis(2,3-epoxypropyloxy)methane,
1,2-bis(2,3-epoxypropyloxy)ethane,
1,2-bis(2,3-epoxypropyloxy)propane,
1,3-bis(2,3-epoxypropyloxy)propane,
1,3-bis(2,3-epoxypropyloxy)-2-methyl propane,
1,4-bis(2,3-epoxypropyloxy)butane,
1,4-bis(2,3-epoxypropyloxy)-2-methylbutane,
1,3-bis(2,3-epoxypropyloxy)butane,
1,5-bis(2,3-epoxypropyloxy)pentane,
1,5-bis(2,3-epoxypropyloxy)-2-methylpentane,
1,5-bis(2,3-epoxypropyloxy)-3-thiapentane,
1,6-bis(2,3-epoxypropyloxy)hexane,
1,6-bis(2,3-epoxypropyloxy)-2-methylhexane,
3,8-bis(2,3-epoxypropyloxy)-3,6-dithiaoctane,
1,2,3-tris(2,3-epoxypropyloxy)propane,
2,2-bis(2,3-epoxypropyloxy)-1,3-bis(2,3-epoxypropyloxy
methyl)propane, 2,2-bis(2,3-epoxypropyloxy
methyl)-1-(2,3-epoxypropyloxy)butane,
1,5-bis(2,3-epoxypropyloxy)-2-(2,3-epoxypropyloxy
methyl)-3-thiapentane,
1,5-bis(2,3-epoxypropyloxy)-2,4-bis(2,3-epoxypropyloxy
methyl)-3-thiapentane,
1-(2,3-epoxypropyloxy)-2,2-bis(2,3-epoxypropyloxy
methyl)-4-thiahexane,
1,5,6-tris(2,3-epoxypropyloxy)-4-(2,3-epoxypropyloxy
methyl)-3-thiahexane,
1,8-bis(2,3-epoxypropyloxy)-4-(2,3-epoxypropyloxy
methyl)-3,6-dithiaoctane,
1,8-bis(2,3-epoxypropyloxy)-4,5-bis(2,3-epoxypropyloxy
methyl)-3,6-dithiaoctane,
1,8-bis(2,3-epoxypropyloxy)-4,4-bis(2,3-epoxypropyloxy
methyl)-3,6-dithiaoctane,
1,8-bis(2,3-epoxypropyloxy)-2,5-bis(2,3-epoxypropyloxy
methyl)-3,6-dithiaoctane,
1,8-bis(2,3-epoxypropyloxy)-2,4,5-tris(2,3-epoxypropyloxy
methyl)-3,6-dithiaoctane,
1,1,1-tris[[2-(2,3-epoxypropyloxy)ethyl]thiomethyl]-2-(2,3-epoxypropyloxy-
)ethane,
1,1,2,2-tetrakis[[2-(2,3-epoxypropyloxy)ethyl]thiomethyl]ethane,
1,11-bis(2,3-epoxypropyloxy)-4,8-bis(2,3-epoxypropyloxy
methyl)-3,6,9-trithiaundecane,
1,11-bis(2,3-epoxypropyloxy)-4,7-bis(2,3-epoxypropyloxy
methyl)-3,6,9-trithiaundecane, and
1,11-bis(2,3-epoxypropyloxy)-5,7-bis(2,3-epoxypropyloxymethyl)-3,6,9-trit-
hiaundecane;
[0312] alicyclic 2,3-epoxypropyloxy compounds such as
1,3-bis(2,3-epoxypropyloxy)cyclohexane,
1,4-bis(2,3-epoxypropyloxy)cyclohexane, 1,3-bis(2,3-epoxypropyloxy
methyl)cyclohexane, 1,4-bis(2,3-epoxypropyloxy methyl)cyclohexane,
2,5-bis(2,3-epoxypropyloxy methyl)-1,4-dithiane,
2,5-bis[[2-(2,3-epoxypropyloxy)ethyl]thiomethyl]-1,4-dithiane, and
2,5-bis(2,3-epoxypropyloxy methyl)-2,5-dimethyl-1,4-dithiane;
and
[0313] aromatic 2,3-epoxypropyloxy compounds such as
1,2-bis(2,3-epoxypropyloxy)benzene,
1,3-bis(2,3-epoxypropyloxy)benzene,
1,4-bis(2,3-epoxypropyloxy)benzene, 1,2-bis(2,3-epoxypropyloxy
methyl)benzene, 1,3-bis(2,3-epoxypropyloxy methyl)benzene,
1,4-bis(2,3-epoxypropyloxy methyl)benzene,
bis[4-(2,3-epoxypropyloxy)phenyl]methane,
2,2-bis[4-(2,3-epoxypropyloxy)phenyl]propane,
bis[4-(2,3-epoxypropyloxy)phenyl]sulfide,
bis[4-(2,3-epoxypropyloxy)phenyl]sulfone, and
4,4'-bis(2,3-epoxypropyloxy)biphenyl, but not limited to these
exemplary compounds.
[0314] Among these exemplified epoxy compounds, preferred examples
thereof include bis(2,3-epoxypropyl)disulfide,
4-vinyl-1-cyclohexanediepoxide, and phenolic epoxy compounds
obtained by condensation of an epihalohydrin compound with a
polyphenol compound such as and bisphenol A/bisphenol F/glycidyl
ether;
[0315] alcoholic epoxy compounds obtained by condensation of an
epihalohydrin compound with a polyalcohol compound such as
hydrogenated bisphenol A/bisphenol F/glycidyl ether;
[0316] glycidyl ester epoxy compounds prepared by condensation of
an epihalohydrin compound with a polyorganic acid compound such as
3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, and
diglycidyl 1,2-hexahydrophthalate; and
[0317] amine epoxy compounds prepared by condensation of an
epihalohydrin compound with a primary or secondary amine.
Furthermore, examples include aliphatic polyfunctional epoxy
compounds such as vinylcyclohexene diepoxide, more preferably
bis(2,3-epoxypropyl)disulfide, cyclohexanedimethanol diglycidyl
ether, bisphenol A/glycidyl ether, and bisphenol F/glycidyl ether,
and even more preferably cyclohexanedimethanol diglycidyl ether and
bisphenol F/glycidyl ether.
[0318] Specific examples of the episulfide compound include
epithioethylthio compounds such as bis(1,2-epithioethyl)sulfide,
bis(1,2-epithioethyl)disulfide, bis(epithioethylthio)methane,
bis(epithioethylthio)benzene,
bis[4-(epithioethylthio)phenyl]sulfide, and
bis[4-(epithioethylthio)phenyl]methane;
[0319] chained aliphatic 2,3-epithiopropylthio compounds such as
bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide,
bis(2,3-epithiopropylthio)methane,
1,2-bis(2,3-epithiopropylthio)ethane,
1,2-bis(2,3-epithiopropylthio)propane,
1,3-bis(2,3-epithiopropylthio)propane,
1,3-bis(2,3-epithiopropylthio)-2-methyl propane,
1,4-bis(2,3-epithiopropylthio)butane,
1,4-bis(2,3-epithiopropylthio)-2-methylbutane,
1,3-bis(2,3-epithiopropylthio)butane,
1,5-bis(2,3-epithiopropylthio)pentane,
1,5-bis(2,3-epithiopropylthio)-2-methylpentane,
1,5-bis(2,3-epithiopropylthio)-3-thiapentane,
1,6-bis(2,3-epithiopropylthio)hexane,
1,6-bis(2,3-epithiopropylthio)-2-methylhexane,
3,8-bis(2,3-epithiopropylthio)-3,6-dithiaoctane,
1,2,3-tris(2,3-epithiopropylthio)propane,
2,2-bis(2,3-epithiopropylthio)-1,3-bis(2,3-epithiopropylthiomethyl)propan-
e,
2,2-bis(2,3-epithiopropylthiomethyl)-1-(2,3-epithiopropylthio)butane,
1,5-bis(2,3-epithiopropylthio)-2-(2,3-epithiopropylthiomethyl)-3-thiapent-
ane,
1,5-bis(2,3-epithiopropylthio)-2,4-bis(2,3-epithiopropylthiomethyl)-3-
-thiapentane,
1-(2,3-epithiopropylthio)-2,2-bis(2,3-epithiopropylthiomethyl)-4-thiahexa-
ne,
1,5,6-tris(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl)-3-th-
iahexane,
1,8-bis(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl)-3-
,6-dithiaoctane,
1,8-bis(2,3-epithiopropylthio)-4,5-bis(2,3-epithiopropylthiomethyl)-3,6-d-
ithiaoctane,
1,8-bis(2,3-epithiopropylthio)-4,4-bis(2,3-epithiopropylthiomethyl)-3,6-d-
ithiaoctane,
1,8-bis(2,3-epithiopropylthio)-2,5-bis(2,3-epithiopropylthiomethyl)-3,6-d-
ithiaoctane,
1,8-bis(2,3-epithiopropylthio)-2,4,5-tris(2,3-epithiopropylthiomethyl)-3,-
6-dithiaoctane,
1,1,1-tris[[2-(2,3-epithiopropylthio)ethyl]thiomethyl]-2-(2,3-epithioprop-
ylthio)ethane,
1,1,2,2-tetrakis[[2-(2,3-epithiopropylthio)ethyl]thiomethyl]ethane,
1,11-bis(2,3-epithiopropylthio)-4,8-bis(2,3-epithiopropylthiomethyl)-3,6,-
9-trithiaundecane,
1,11-bis(2,3-epithiopropylthio)-4,7-bis(2,3-epithiopropylthiomethyl)-3,6,-
9-trithiaundecane, and
1,11-bis(2,3-epithiopropylthio)-5,7-bis(2,3-epithiopropylthiomethyl)-3,6,-
9-trithiaundecane;
[0320] alicyclic 2,3-epithiopropylthio compounds such as
1,3-bis(2,3-epithiopropylthio)cyclohexane,
1,4-bis(2,3-epithiopropylthio)cyclohexane,
1,3-bis(2,3-epithiopropylthiomethyl)cyclohexane,
1,4-bis(2,3-epithiopropylthiomethyl)cyclohexane,
2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane,
2,5-bis[[2-(2,3-epithiopropylthio)ethyl]thiomethyl]-1,4-dithiane,
and
2,5-bis(2,3-epithiopropylthiomethyl)-2,5-dimethyl-1,4-dithiane;
[0321] aromatic 2,3-epithiopropylthio compounds such as
1,2-bis(2,3-epithiopropylthio)benzene,
1,3-bis(2,3-epithiopropylthio)benzene,
1,4-bis(2,3-epithiopropylthio)benzene,
1,2-bis(2,3-epithiopropylthiomethyl)benzene,
1,3-bis(2,3-epithiopropylthiomethyl)benzene,
1,4-bis(2,3-epithiopropylthiomethyl)benzene,
bis[4-(2,3-epithiopropylthio)phenyl]methane,
2,2-bis[4-(2,3-epithiopropylthio)phenyl]propane,
bis[4-(2,3-epithiopropylthio)phenyl]sulfide,
bis[4-(2,3-epithiopropylthio)phenyl]sulfone, and
4,4'-bis(2,3-epithiopropylthio)biphenyl;
[0322] monofunctional episulfide compounds (compounds each
containing one episulfide group) such as ethylene sulfide,
propylene sulfide, mercaptopropylene sulfide, and
mercaptobutenesulfide, epithiochlorohydrin;
[0323] chained aliphatic 2,3-epithiopropyloxy compounds such as
bis(2,3-epithiopropyl)ether, bis(2,3-epithiopropyloxy)methane,
1,2-bis(2,3-epithiopropyloxy)ethane,
1,2-bis(2,3-epithiopropyloxy)propane,
1,3-bis(2,3-epithiopropyloxy)propane,
1,3-bis(2,3-epithiopropyloxy)-2-methyl propane,
1,4-bis(2,3-epithiopropyloxy)butane,
1,4-bis(2,3-epithiopropyloxy)-2-methylbutane,
1,3-bis(2,3-epithiopropyloxy)butane,
1,5-bis(2,3-epithiopropyloxy)pentane,
1,5-bis(2,3-epithiopropyloxy)-2-methylpentane,
1,5-bis(2,3-epithiopropyloxy)-3-thiapentane,
1,6-bis(2,3-epithiopropyloxy)hexane,
1,6-bis(2,3-epithiopropyloxy)-2-methylhexane,
3,8-bis(2,3-epithiopropyloxy)-3,6-dithiaoctane,
1,2,3-tris(2,3-epithiopropyloxy)propane,
2,2-bis(2,3-epithiopropyloxy)-1,3-bis(2,3-epithiopropyloxymethyl)propane,
2,2-bis(2,3-epithiopropyloxymethyl)-1-(2,3-epithiopropyloxy)butane,
1,5-bis(2,3-epithiopropyloxy)-2-(2,3-epithiopropyloxymethyl)-3-thiapentan-
e,
1,5-bis(2,3-epithiopropyloxy)-2,4-bis(2,3-epithiopropyloxymethyl)-3-thi-
apentane,
1-(2,3-epithiopropyloxy)-2,2-bis(2,3-epithiopropyloxymethyl)-4-t-
hiahexane,
1,5,6-tris(2,3-epithiopropyloxy)-4-(2,3-epithiopropyloxymethyl)-
-3-thiahexane,
1,8-bis(2,3-epithiopropyloxy)-4-(2,3-epithiopropyloxymethyl)-3,6-dithiaoc-
tane,
1,8-bis(2,3-epithiopropyloxy)-4,5-bis(2,3-epithiopropyloxymethyl)-3,-
6-dithiaoctane,
1,8-bis(2,3-epithiopropyloxy)-4,4-bis(2,3-epithiopropyloxymethyl)-3,6-dit-
hiaoctane,
1,8-bis(2,3-epithiopropyloxy)-2,5-bis(2,3-epithiopropyloxymethy-
l)-3,6-dithiaoctane,
1,8-bis(2,3-epithiopropyloxy)-2,4,5-tris(2,3-epithiopropyloxymethyl)-3,6--
dithiaoctane,
1,1,1-tris[[2-(2,3-epithiopropyloxy)ethyl]thiomethyl]-2-(2,3-epithio
propyloxy)ethane,
1,1,2,2-tetrakis[[2-(2,3-epithiopropyloxy)ethyl]thiomethyl]ethane,
1,11-bis(2,3-epithiopropyloxy)-4,8-bis(2,3-epithiopropyloxymethyl)-3,6,9--
trithiaundecane,
1,1'-bis(2,3-epithiopropyloxy)-4,7-bis(2,3-epithiopropyloxymethyl)-3,6,9--
trithiaundecane, and
1,11-bis(2,3-epithiopropyloxy)-5,7-bis(2,3-epithiopropyloxymethyl)-3,6,9--
trithiaundecane;
[0324] cyclic aliphatic 2,3-epithiopropyloxy compounds such as
1,3-bis(2,3-epithiopropyloxy)cyclohexane,
1,4-bis(2,3-epithiopropyloxy)cyclohexane,
1,3-bis(2,3-epithiopropyloxymethyl)cyclohexane,
1,4-bis(2,3-epithiopropyloxymethyl)cyclohexane,
2,5-bis(2,3-epithiopropyloxymethyl)-1,4-dithiane,
2,5-bis[[2-(2,3-epithiopropyloxy)ethyl]thiomethyl]-1,4-dithiane,
and 2,5-bis(2,3-epithiopropyloxymethyl)-2,5-dimethyl-1,4-dithiane;
and
[0325] aromatic 2,3-epithiopropyloxy compounds such as
1,2-bis(2,3-epithiopropyloxy)benzene,
1,3-bis(2,3-epithiopropyloxy)benzene,
1,4-bis(2,3-epithiopropyloxy)benzene,
1,2-bis(2,3-epithiopropyloxymethyl)benzene,
1,3-bis(2,3-epithiopropyloxymethyl)benzene,
1,4-bis(2,3-epithiopropyloxymethyl)benzene,
bis[4-(2,3-epithiopropyloxy)phenyl]methane,
2,2-bis[4-(2,3-epithiopropyloxy)phenyl]propane,
bis[4-(2,3-epithiopropyloxy)phenyl]sulfide,
bis[4-(2,3-epithiopropyloxy)phenyl]sulfone, and
4,4'-bis(2,3-epithiopropyloxy)biphenyl, but not limited to these
the exemplified compounds.
[0326] Among these exemplified compounds, examples of preferred
compounds include bis(1,2-epithioethyl)sulfide,
bis(1,2-epithioethyl)disulfide, bis(2,3-epithiopropyl)sulfide,
bis(2,3-epithiopropylthio)methane and
bis(2,3-epithiopropyl)disulfide, and examples of more preferable
compound include bis(1,2-epithioethyl)sulfide,
bis(1,2-epithioethyl)disulfide, bis(2,3-epithiopropyl)sulfide, and
bis(2,3-epithiopropyl)disulfide. Furthermore, examples of even more
preferable compound include bis(2,3-epithiopropyl)sulfide and
bis(2,3-epithiopropyl)disulfide.
[0327] The used amount of the epoxy compound and/or the episulfide
compound varies depending on the structure of the compound to be
used and the structure or used amount of the thiol compound, but it
is preferably 25% by weight or less based on the total amount of
the polymerizable composition of the invention, from the viewpoint
of a refractive index of the resin to be obtained. It is more
preferably 23% by weight or less, and even more preferably 20% by
weight or less. From the viewpoint of color and mechanical strength
of the resin to be obtained, it is preferably 2.5% by weight or
more.
[0328] The epoxy compound and/or the episulfide compound can be
used singly or in combination thereof, and the ratio thereof is not
particularly limited. Furthermore, a plurality of the same epoxy
compounds or the different epoxy compounds, or the same episulfide
compounds or the different episulfide compounds may also be used in
combination. However, in order to obtain a resin having a high
refractive index, it is preferable to use an episulfide
compound.
[0329] As for the ratio of the thiol compound used and the
episulfide compound used, the ratio of the functional groups (SH
groups/(epoxy groups+episulfide groups)) that is the ratio of the
thiol groups in the thiol compound and the epoxy groups and/or
episulfide groups in the epoxy compound and/or the episulfide
compound is preferably 0.7 or more from the viewpoint of resin
color. It is more preferably from 0.9 to 5, and even more
preferably from 0.9 to 3. If the ratio of the functional groups is
too low, the obtained resin may be unfavorable due to the reduced
transparency, whereas if the ratio is too high, the obtained resin
may also be unfavorable due to the reduced heat resistance.
[0330] If the polymerizable composition further includes the epoxy
compound and/or the episulfide compound, the content of the
compound represented by General Formula (1) in the total weight of
the polymerizable compounds contained in the polymerizable
composition of the present invention is not particularly limited,
but it is usually 10% by weight or more.
[0331] As the content of the compound represented by General
Formula (1) is increased, there is a tendency that materials having
higher refractive indice are obtained. Thus, the content is
preferably 30% by weight or more, more preferably 50% by weight or
more, and even more preferably 70% by weight or more.
[0332] However, if the content of the compound represented by
General Formula (1) is too high, it relatively reduces the content
of the thiol compound and the epoxy compound and/or the episulfide
compound. From the viewpoint of improving the color of the resin
and suppressing the reduction in mechanical strength, the content
of the compound represented by General Formula (1) in the
polymerizable composition is preferably 95% by weight or less.
[0333] Furthermore, if the polymerizable composition further
includes the epoxy compound and/or the episulfide compound, the
amount of the thiol compound used depends on the structure of the
compound used and the structure or amount of the epoxy compound
and/or the episulfide compound. However, since the compound
represented by General Formula (1) provides a resin having a high
refractive index, generally addition of a thiol compound leads to
reduction in the refractive index of the obtained resin. Thus, from
the viewpoint of the refractive index of the obtained resin, it is
contained in an amount of preferably 35% by weight or less based on
the total amount of the polymerizable composition of the present
invention, more preferably 30% by weight or less, and even more
preferably 25% by weight or less. From the viewpoint of the color
and the mechanical strength of the obtained resin, the amount is
preferably 2.5% by weight or more.
[0334] The polymerizable composition of the present invention
includes the compound represented by General Formula (1), the thiol
compound, and a compound including a thietane compound containing
no metal, and if necessary, a polymerization catalyst. Furthermore,
the compound may be represented by General Formula (1), wherein
m=0, and X.sub.1 is a sulfur atom.
[0335] The thietane compound containing no metal used in the
present invention is a compound containing no metal in the
molecule. The thietane compound containing no metal more
specifically represents the compound represented by the following
General Formula (8), having one or more thietanyl groups in the
molecule, and it can be any one having a structure that is
compatible with the compound represented by General Formula
(1).
##STR00132##
[0336] (in General Formula (8), Q represents a reactive terminal
group, a straight, branched or cyclic alkyl group having 1 to 10
carbon atom(s) that has a reactive terminal group, or its thia
derivative, an aryl group, or an aralkyl group, R.sub.3 represents
a substituted or unsubstituted bivalent hydrocarbon group having 1
to 10 carbon atom(s), which may be thianated, and n represents an
integer of 0 to 3).
[0337] Hereinbelow, the compound represented by General Formula (8)
will be described.
[0338] In General Formula (8), Q represents a straight, branched or
cyclic alkyl group having 1 to 10 carbon atom(s) that has a
reactive terminal group, or its thia derivative, an aryl group, or
an aralkyl group.
[0339] In General Formula (8), R.sub.3 represents a substituted or
unsubstituted bivalent hydrocarbon group having 1 to 10 carbon
atom(s), which may be thianated.
[0340] In General Formula (8), n represents an integer of 0 to 3.
Furthermore, if n is 2 or greater, a plurality of R.sub.3's each
independently represents a substituted or unsubstituted bivalent
hydrocarbon group having 1 to 10 carbon atom(s), which may be
thianated.
[0341] Specific examples of the compound represented by General
Formula (8) include sulfur-containing cyclic sulfide or disulfide
compounds such as bis(3-thietanyl)sulfide, and
bis(3-thietanylthiomethyl)sulfide, bis(3-thietanyl)disulfide;
[0342] chained aliphatic 3-thietanylthio compounds such as
1,1-bis(3-thietanylthio)methane, 1,2-bis(3-thietanylthio)ethane,
1,2-bio(1-thietanylthio)propane, 1,3-bis(3-thietanylthio)propane,
1,2,3-tris(3-thietanylthio)propane,
1,3-bis(3-thietanylthio)-2-methyl propane,
1,4-bis(3-thietanylthio)butane,
1,4-bis(3-thietanylthio)-2-methylbutane,
1,3-bis(3-thietanylthio)butane, 1,5-bis(3-thietanylthio)pentane,
1,5-bis(3-thietanylthio)-2-methylpentane,
1,5-bis(3-thietanylthio)-3-thiapentane,
1,6-bis(3-thietanylthio)hexane,
1,6-bis(3-thietanylthio)-2-methylhexane,
3,8-bis(3-thietanylthio)-3,6-dithiaoctane,
1,2,3-tris(1-thietanylthio)propane,
2,2-bis(3-thietanylthio)-1,3-bis(3-thietanylthiomethyl)propane,
2,2-bis(3-thietanylthio)-1-(3-thietanylthiomethyl)butane,
1,5-bis(3-thietanylthio)-2-(3-thietanylthiomethyl)-3-thiapentane,
1,5-bis(3-thietanylthio)-2,4-bis(3-thietanylthiomethyl)-3-thiapentane,
1-(3-thietanylthio)-2,2-bis(3-thietanylthiomethyl)-4-thiahexane,
1,5,6-tris(3-thietanylthio)-4-(3-thietanylthiomethyl)-3-thiahexane,
1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane,
1,8-bis(3-thietanylthio)-4,5-bis(3-thietanylthiomethyl)-3,6-dithiaoctane,
1,8-bis(3-thietanylthio)-4,4-bis(3-thietanylthiomethyl)-3,6-dithiaoctane,
1,8-bis(3-thietanylthio)-2,5-bis(3-thietanylthiomethyl)-3,6-dithiaoctane,
1,8-bis(3-thietanylthio)-2,4,5-tris(3-thietanylthiomethyl)-3,6-dithiaocta-
ne,
1,1,1-tris[[2-(3-thietanylthio)ethyl]thiomethyl]-2-(3-thietanylthio)et-
hane, 1,1,2,2-tetrakis[[2-(3-thietanylthio)ethyl]thiomethyl]ethane,
1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiaund-
ecane,
1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trit-
hiaundecane,
1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaund-
ecane, 1,1,3,3-tetrakis(3-thietanylthiomethylthio)propane,
1,1,2,2-tetrakis(3-thietanylthiomethylthio)ethane, and
3-(3-thietanylthiomethyl)-1,5-di(3-thietanylthio)-2,4-dithiapentane;
[0343] alicyclic 3-thietanylthio compounds such as
1,3-bis(3-thietanylthio)cyclohexane,
1,4-bis(3-thietanylthio)cyclohexane,
1,3-bis(3-thietanylthiomethyl)cyclohexane,
1,4-bis(3-thietanylthiomethyl)cyclohexane,
2,5-bis(1-thietanylthiomethyl)-1,4-dithiane,
4,6-bis(3-thietanylthiomethyl)-1,3-dithiane,
4,5-bis(3-thietanylthiomethyl)-1,3-dithiolane,
2,4-bis(3-thietanylthiomethyl)-1,3-dithietane,
2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane,
2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, and
2,2-bis(3-thietanylthiomethyl)-1,3-dithiolane; and
[0344] aromatic 3-thietanylthio compounds such as
1,2-bis(3-thietanylthio)benzene, 1,3-bis(3-thietanylthio)benzene,
1,4-bis(3-thietanylthio)benzene,
1,2-bis(3-thietanylthiomethyl)benzene,
1,3-bis(3-thietanylthiomethyl)benzene,
1,4-bis(3-thietanylthiomethyl)benzene,
bis[4-(3-thietanylthio)phenyl]methane,
2,2-bis[4-(3-thietanylthio)phenyl]propane,
bis[4-(3-thietanylthio)phenyl]sulfide,
bis[4-(3-thietanylthio)phenyl]sulfone, and
4,4'-bis(3-thietanylthio)biphenyl.
[0345] Furthermore, examples of the asymmetric compound include
1,3-bis(3-thietanylthio)propane-1-one, and
1,3-bis(3-thietanylthio)-2-methyl propane-1-one, but not limited
these exemplified compounds.
[0346] Among the exemplified compounds, examples of the preferable
compounds include bis(3-thietanyl)sulfide,
bis(3-thietanylthiomethyl)sulfide, bis(3-thietanyl)disulfide,
1,1-bis(3-thietanylthio)methane, 1,2-bis(3-thietanylthio)ethane,
1,2,3-tris(3-thietanylthio)propane,
1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane,
1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiaund-
ecane,
1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trit-
hiaundecane,
1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaund-
ecane, 2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,
2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane,
2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane,
4,5-bis(3-thietanylthiomethyl)-1,3-dithiolane,
2,4-bis(3-thietanylthiomethyl)-1,3-dithietane, and
2,2-bis(3-thietanylthiomethyl)-1,3-dithiolane; examples of more
preferable compounds include bis(3-thietanyl)sulfide,
bis(3-thietanylthiomethyl)sulfide, bis(3-thietanyl)disulfide,
1,1-bis(3-thietanylthio)methane, and
2,2-bis(3-thietanylthiomethyl)-1,3-dithiolane; and examples of even
more preferable compounds include bis(3-thietanyl)disulfide.
[0347] The amount of the thietane compound containing no metal used
depends on the structure of the compound used and the structure or
amount of the thiol compound used, but it is preferably 25% by
weight or less based on the total amount of the polymerizable
composition, from the viewpoint of the refractive index of the
obtained resin. It is more preferably 23% by weight or less, and
even more preferably 20% by weight or less. From the viewpoint of
the color and the mechanical strength of the obtained resin, it is
preferably 2.5% by weight or more.
[0348] As the thietane compound containing no metal, the thietane
compounds containing no metal may be used singly, or a plurality of
the different the thietane compounds containing no metal may also
be used together. However, the amount ratio is not particularly
limited.
[0349] As for the ratio of the thiol compound used and the thietane
compound containing no metal used, the ratio of the functional
groups (SH groups/thietanyl groups), that is the ratio of the thiol
groups in the thiol compound and the thietanyl groups in the
thietane compound containing no metal, is preferably 0.7 or more
from the viewpoint of the color of the resin. It is more preferably
from 0.9 to 5, and even more preferably from 0.9 to 3. If the ratio
of the functional groups is too low, the obtained resin unfavorably
has the reduced transparency in some cases, whereas if the ratio is
too high, the obtained resin unfavorably has the reduced heat
resistance in some cases.
[0350] If the polymerizable composition further includes the
thietane compound containing no metal, the content of the compound
represented by General Formula (1) in the total weight of the
polymerizable compounds contained in the polymerizable composition
of the present invention is not particularly limited, but it is
usually 10% by weight or more.
[0351] As the content of the compound represented by General
Formula (1) is increased, there is a tendency that materials having
higher refractive indice are obtained. Thus, the content is
preferably 30% by weight or more, more preferably 50% by weight or
more, and even more preferably 70% by weight or more.
[0352] However, if the content of the compound represented by
General Formula (1) is too high, it relatively reduces the content
of the thiol compound and the thietane compound containing no
metal. From the viewpoint of improving the color of the resin and
suppressing the reduction in mechanical strength, the content of
the compound represented by General Formula (1) in the
polymerizable composition is preferably 95% by weight or less.
[0353] Furthermore, if the polymerizable composition further
includes the thietane compound containing no metal, the amount of
the thiol compound used depends on the structure of the compound
used and the structure or amount of the thietane compound
containing no metal. However, since the compound represented by
General Formula (1) provides a resin having a high refractive
index, generally addition of a thiol compound leads to reduction in
the refractive index of the obtained resin. Thus, from the
viewpoint of the refractive index of the obtained resin, it is
contained in an amount of preferably 35% by weight or less based on
the total amount of the polymerizable composition of the present
invention, more preferably 30% by weight or less, and even more
preferably 25% by weight or less. From the viewpoint of the color
of the obtained resin, the amount is preferably 2.5% by weight or
more.
[0354] Furthermore, the polymerizable composition of the present
invention may include one or two or more kinds of said components.
For example, the polymerizable composition may include at least one
of the compound having a carbon-carbon double bond, the
iso(thio)cyanate compound, the epoxy compound and/or the episulfide
compound, and the thietane compound containing no metal atom in the
molecular structure, and sulfur as a monomer. In this case, the
polymerizable composition can be polymerized to provide the
obtained resin with a higher refractive index.
[0355] As for the amount of sulfur added, from the viewpoint of a
high refractive index, if the amount of sulfur added is too low,
the effect of improvement in the refractive indices is unfavorably
low in some cases. Furthermore, if the amount of sulfur added as a
monomer is too high fogging unfavorably occurs in some cases. Thus,
the amount of sulfur added based on the total amount of the
polymerizable composition of the present invention is preferably 5
to 50 parts by weight, and preferably 5 to 25 parts by weight.
[0356] Furthermore, from the viewpoint of better balance among the
refractive index, the mechanical properties, and the color of the
polymerizable composition of the present invention, the molar ratio
of the thiol groups in the polymerizable composition may be 1 or
more, based on the total the iso(thio)cyanate groups, the epoxy
groups, the episulfide groups, the carbon-carbon double bonds, and
the thietanyl groups in the thietane compound containing no metal
atom. That is, the molar ratio expressed by SH groups/(NCO groups
and/or NCS groups+epoxy groups+episulfide groups+carbon-carbon
double bonds+thietanyl groups) may be 1 or more.
[0357] The polymerizable composition of the present invention
includes the compound represented by General Formula (1) and the
thiol compound as essential components, and further, it may contain
a polymerization catalyst as described later.
[0358] In the present invention, since the compound represented by
General Formula (1) includes a compound that does not require
particularly a polymerization catalyst, and auto-catalytically
proceeds polymerization reaction, the polymerization catalyst may
be used, if desired.
[0359] In this case, as the compound represented by General Formula
(1), the compound represented by General Formula (1) may be used
singly, or a plurality of the different compounds may be used
together.
[0360] The content of the compound represented by General Formula
(1) in the total weight of the polymerizable compounds contained in
the polymerizable composition of the present invention is not
particularly limited, but it is usually 10% by weight or more, and
from the viewpoint of the high refractive index, it is preferably
30% by weight or more, more preferably 50% by weight or more, and
even more preferably 70% by weight or more.
[0361] Furthermore, the components other than the compound
represented by General Formula (1) often decrease the refractive
index of the resin obtained by using the polymerizable composition,
and as a result, in order to obtain a resin having a high
refractive index, it is preferable that the content of the compound
represented by General Formula (1) in the total weight of the
polymerizable compounds is 50% by weight or more.
[0362] The polymerization catalyst that is used, if necessary, in
the present invention, can be cured usually by using a method as in
the polymerization of a known thietane group-containing compound.
The kind and amount of the polymerization catalyst, or the like to
obtain a cured resin, and the kind and ratio of the monomers depend
on the structure of the compound constituting the polymerizable
composition. But, while not clearly defined, the kinds of the
polymerization catalyst include amines, phosphines, organic acids
and salts, esters, anhydrides thereof, inorganic acids, quaternary
ammonium salts, quaternary phosphonium salts, tertiary sulfonium
salts, secondary iodonium salts, Lewis acids, radical
polymerization catalysts, and cationic polymerization catalysts are
conventionally used.
[0363] Specific examples of the polymerization catalyst include
aliphatic and aromatic tertiary amines such as triethylamine,
tri-n-butylamine, tri-n-hexylamine, N,N-diisopropylethylamine,
triethylenediamine, triphenylamine, N,N-dimethylethanolamine,
N,N-diethylethanolamine, N,N-dibutylethanolamine, triethanolamine,
N-ethyldiethanolamine, N,N-dimethylbenzylamine,
N,N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine,
N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine,
N,N-dimethylbutylamine, N-methyldicyclohexylamine,
N,N-dicyclohexylmethylamine, N-methylmorpholine,
N-isopropylmorpholine, pyridine, quinoline, N,N-dimethylaniline,
N,N-diethylaniline, .alpha.-, .beta.- or .gamma.-picoline,
2,2'-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide,
tetramethylethylenediamine, hexamethylenetetramine,
1,8-diazabicyclo(5,4,0)-7-undecene, and
2,4,6-tris(N,N-dimethylaminomethyl)phenol;
[0364] phosphines such as trimethylphosphine, triethylphosphine,
tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,
triphenylphosphine, tribenzylphosphine,
1,2-bis(diphenylphosphino)ethane, and
1,2-bis(dimethylphosphino)ethane;
[0365] trihalogenoacetic acids, and esters, anhydrides and salts
thereof, such as trifluoroacetic acid, trichloroacetic acid,
trifluoroacetic anhydride, ethyl trifluoroacetate, and sodium
trifluoroacetate;
[0366] p-toluenesulfonic acid;
[0367] methanesulfonic acid; trihalogenomethanesulfonic acids, and
esters, anhydrides and salts thereof, such as
trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride,
ethyl trifluoromethanesulfonate, and sodium
trifluoromethanesulfonate;
[0368] inorganic acids such as hydrochloric acid, sulfuric acid,
and nitric acid;
[0369] quaternary ammonium salts such as tetramethylammonium
chloride, tetrabutylammonium chloride, and tetrabutylammonium
bromide;
[0370] quaternary phosphonium salts such as tetramethylphosphonium
chloride, tetrabutylphosphonium chloride, and tetrabutylphosphonium
bromide;
[0371] tertiary sulfonium salts, such as trimethylsulfonium
bromide, and tributylsulfonium bromide;
[0372] secondary iodonium salts such as diphenyliodonium
bromide;
[0373] dimethyltin dichloride, dibutyltin dichloride, dibutyltin
dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide,
diacetoxytetrabutyldistannoxane, zinc chloride, acetylacetone zinc,
aluminum chloride, aluminum fluoride, triphenyl aluminum,
acetylacetone aluminum, isopropoxide aluminum, tetrachlorotitanium
and complexes thereof, tetraiodotitanium, titanium alkoxides such
as dichlorotitanium diisopropoxide, and titanium isopropoxide;
calcium acetate;
Lewis acids such as boron trihalides and complexes thereof, such as
boron trifluoride, boron trifluoride complexes such as boron
trihalide compounds such as boron trifluoride, boron trifluoride
diethyl ether complex, boron trifluoride piperidine complex, boron
trifluoride ethyleneamine complex, boron trifluoride acetic acid
complex, boron trifluoride phosphoric acid complex, boron
trifluoride t-butyl methyl ether complex, boron trifluoride dibutyl
ether complex, boron trifluoride THF complex, boron trifluoride
methyl sulfide complex, boron trifluoride phenol complex, and boron
trichloride complexes;
[0374] radial polymerization catalysts such as
2,2'-azobis(2-cyclopropylpropionitrile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
t-butylperoxy-2-ethylhexanoate,
n-butyl-4,4'-bis(t-butylperoxy)valerate, and t-butylperoxybenzoate
and;
[0375] cationic polymerization catalysts such as diphenyliodonium
hexafluorophosphate, diphenyliodonium hexafluoroarsenate,
diphenyliodonium hexafluoroantimony, triphenylsulfonium
tetrafluoroborate, triphenylsulfonium hexafluorophosphate,
triphenylsulfonium hexafluoroarsenate, and (tolylcumyl)iodonium
tetrakis(pentafluorophenyl)borate. However, the polymerization
catalysts are not limited to these the exemplary compounds.
[0376] The polymerization catalyst may be used alone or in a
mixture of two or more kinds thereof. A mixture of at least two
types of polymerization catalysts having different reactivities is
preferably used for improving the monomer handleability, and the
optical physical properties, hue, transparency, and optical strain
(striation) of the resultant resin in some cases.
[0377] Among the above compounds exemplified as the polymerization
catalyst, preferred examples include organotin compounds such as
dimethyltin dichloride, dibutyltin dichloride, dibutyltin
dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide,
and diacetoxytetrabutylstannoxane;
[0378] trihalogenoacetic acids, and esters, anhydrides and salts
thereof, such as trifluoroacetic acid, trichloroacetic acid,
trifluoroacetic anhydride, and ethyl trifluoroacetate, sodium
trifluoroacetate;
[0379] p-toluenesulfonic acid, methanesulfonic acid,
trihalogenomethanesulfonic acids, and esters, anhydrides and salts
thereof, such as trifluoromethanesulfonic acid,
trifluoromethanesulfonic anhydride, ethyl
trifluoromethanesulfonate, and sodium
trifluoromethanesulfonate;
[0380] Lewis acids such as boron trihalides and complexes thereof,
such as boron trifluoride, boron trifluoride complexes such as
boron trifluoride, boron trifluoride diethyl ether complex, boron
trifluoride piperidine complex, boron trifluoride ethylamine
complex, boron trifluoride acetic acid complex, boron trifluoride
phosphoric acid complex, boron trifluoride t-butyl methyl ether
complex, boron trifluoride dibutyl ether complex, boron trifluoride
THF complex, boron trifluoride methyl sulfide complex, and boron
trifluoride phenol complex, and boron trichloride and complexes
thereof, and preferably dimethyltin dichloride, trifluoromethane,
and esters, anhydrides and salts thereof, and various
borotrifluoride complexes; and
[0381] radical polymerization catalysts such as
2,2'-azobis(2-cyclopropylpropionitrile),
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile), t-butylperoxy-2-ethyl
hexanoate, n-butyl-4,4'-bis(t-butylperoxy)valerate, and t-butyl
peroxybenzoate.
[0382] The polymerization catalyst of the polymerizable composition
according to the present invention is added in a proportion of
0.0001 to 10% by weight, preferably 0.001 to 10% by weight, more
preferably 0.01% by weight to 5% by weight, and most preferably
0.01% by weight to 1% by weight, based on the total amount of the
polymerizable composition.
[0383] With the amount of the polymerization catalyst added in this
range, a sufficiently cured resin can be produced, and a pot life
can be maintained. Also, the obtained resin has good transparency
and optical physical properties in some cases.
[0384] The polymerization catalyst may be added directly to the
polymerizable compositions or some of the compounds thereof, or may
be dissolved or dispersed in another compound and then added. In
some cases, the polymerization catalyst is preferably dissolved or
dispersed in another compound and then added, for obtaining good
results in some cases. Furthermore, the polymerization catalyst is
preferably added under a nitrogen atmosphere or a dry gas
atmosphere for obtaining good results in some cases. In order to
improve the performance of the resultant resin, the amount of the
unreactive groups remaining in the resin is preferably 0.5% by
weight or less, and more preferably 0.4% by weight or less, based
on the total weight of the resin.
[0385] The polymerizable composition of the present invention may
include other polymerizable compounds, in addition to the compound
represented by General Formula (1), within the range not
interfering with the desired effects of the present invention.
[0386] Examples of the polymerizable compound include various
polymerizable monomers or polymerizable oligomers, known in the
art. Examples thereof include a (meth) acrylic acid ester compound,
a vinyl compound, an epoxy compound, an episulfide compounds, an
oxetane compound, a thietane compound and the like.
[0387] The amount of the other polymerizable compounds occupied in
the total weight of the polymerizable compounds contained in the
polymerizable composition of the present invention is not
particularly limited. But usually the refractive index becomes low
by adding the other polymerizable compounds, it is usually not more
than 90% by weight, preferably not more than 70% by weight, more
preferably not more than 50% by weight, and further preferably not
more than 30% by weight. Furthermore, if the polymerizable
composition of the present invention includes other polymerizable
compounds, the content of the other polymerizable compounds is not
particularly limited in their lower limits.
[0388] As essential requirements for the polymerizable composition
according to the present invention, the polymerizable composition
includes the compound represented by General Formula (1) and the
thiol compound.
[0389] For the purpose of following improvement of the resin
obtained by curing the polymerizable composition or following
improvement of handling ability thereof, it may be preferable to
subject the polymerizable composition of the invention to means and
operations that are generally used upon synthesizing organic
compounds, such as purification or washing, thermal insulation,
cold storage, filtration or depressurization treatment, or to add
known compounds or the like as stabilizers or resin modifying
agents. The improvement of the resin or the improvement of handling
ability thereof includes further adjustment of the optical
properties of the resin such as refractive index or Abbe number;
the adjustment of various properties of the resin such as color,
light resistance or weather resistance, heat resistance, impact
resistance, hardness, specific gravity, linear expansion
coefficient, polymerization shrinkage ratio, water absorbability,
hygroscopicity, chemical resistance and viscoelasticity; the
adjustment of transmittance or transparency; and the adjustment of
the viscosity and handling ability of other storage or
transportation method of the polymerizable composition. Examples of
compounds added for improving stability such as long-term
preservation stability, polymerization stability and thermal
stability include a polymerization retardant, a polymerization
inhibitor, a deoxidant, and an antioxidant.
[0390] Purification of the polymerizable composition is a means for
improving the transparency of the resin produced by curing, or
increasing the purity of the resin to improving the hue thereof. As
a method for purifying the polymerizable composition containing the
compound having the structure represented by Formula (1) of the
present invention, any known method, for example, distillation,
recrystallization, column chromatography (a silica gel method, an
activated carbon method, an ion-exchange resin method, or the
like), extraction, or the like, may be performed with any timing as
long as the transparency and hue of the resin obtained by curing
the purified composition are improved.
[0391] As a method for washing the polymerizable composition, a
method for improving the transparency and hue of the resin obtained
by curing may be used with timing when or after the synthesized
polymerizable composition is taken out. In this method, the
composition is washed with a polar and/or nonpolar solvent to
remove or reduce a resin transparency inhibitor, for example, an
inorganic salt used for synthesizing the polymerizable composition
or secondarily produced in synthesizing the composition, such as an
ammonium salt, thiourea, or the like. Although the solvent used
depends upon the polymerizable composition to be cleaned and the
polarity of a solution containing the polymerizable composition,
and is not limited, a solvent which can dissolve a component to be
removed, and which is incompatible with the polymerizable
composition to be cleaned and the solution containing the
polymerizable composition is preferably used. The solvent may be
used singly, or a mixture of at least two solvents may be used.
Although the amount of a component to be removed depends upon the
purpose and application, the amount is preferably as low as
possible. The amount is preferably 5000 ppm or less, and more
preferably 1000 ppm or less.
[0392] As a hot insulation, cold insulation or filtration method
for the polymerizable composition, a method for improving the
transparency and hue of the resin obtained by curing is generally
used with timing when or after the synthesized polymerizable
composition is taken out. In the hot insulation method, for
example, when the polymerizable composition is crystallized to
deteriorate handleability during storage, the polymerizable
composition is melted by heating within a range causing no
deterioration in the performance of the polymerizable composition
and the resin obtained by curing the polymerizable composition.
Although the heating temperature range and heat melting method
depend upon the compound constituting the polymerizable composition
to be handled and are not limited, the heating temperature is
generally in a range of the solidification point+50.degree. C., and
preferably the solidification point+20.degree. C. In this method,
the composition may be melted by mechanically stirring with a
stirring device or bubbling with an inert gas for moving an
internal liquid. The cold insulation method is generally performed
for improving the preservation stability of the polymerizable
composition. However, when the composition has a high melting point
and consideration must be given to the storage temperature in order
to improve handleability after crystallization. Although the cold
insulation temperature depends upon the structure and preservation
stability of the compound constituting the polymerizable
composition to be handled and is not limited, the polymerizable
composition containing a compound having the structure represented
by Formula (1) is typically required to be stored at a temperature
no higher than a temperature that maintains stability of the
polymerizable composition containing the compound represented by
General Formula (1).
[0393] Furthermore, in the case where the polymerizable composition
according to the present invention is a polymerizable composition
used for optical applications, it is required to have high
transparency, and thus typically it is preferable that the
polymerizable composition is filtered with a filter having a small
pore size. Although the pore size of the filter used is usually
0.05 to 10 .mu.m, the pore size is preferably 0.05 to 5 .mu.m, and
more preferably 0.1 to 5 .mu.m, from the viewpoint of
operationality and performance. In many cases, filtration of the
polymerizable composition containing the sulfur-containing cyclic
compound of the present invention produces good results without
exception. Although a low filtration temperature near the
solidification temperature produces more desirable results in some
cases, filtration is preferably performed at a temperature causing
no trouble in the filtration work when solidification proceeds
during filtration.
[0394] The reduced-pressure treatment is a means for removing a
solvent, dissolved gas and odor which deteriorate the performance
of the resin generally produced by curing the polymerizable
composition. Since a dissolved solvent generally decreases the
refractive index of the resultant resin and deteriorates the heat
resistance thereof, the dissolved solvent must be removed as much
as possible. Although the allowable amount of the dissolved solvent
depends upon the structure of the compound constituting the
polymerizable composition to be handled and the structure of the
dissolved solvent and is not limited, the allowable amount is
usually 1% or less, and preferably 5000 ppm or less. The dissolved
gas inhibits polymerization or causes the problem of mixing bubbles
in the resultant resin, and is thus preferably removed.
Particularly, a moisture gas such as water vapor or the like is
preferably removed by bubbling with a dry gas. The amount of the
dissolved gas depends upon the structure of the compound
constituting the polymerizable composition, the physical
properties, structure and type of the dissolved gas.
[0395] Examples of the method for preparing the polymerizable
composition of the present invention typically include a method
including using a compound represented by General Formula (1) and a
thiol compound, and other components such as sulfur as a monomer,
and if necessary, using the above-described various known
polymerizable compounds in combination, and then if necessary,
adding the polymerization catalyst, mixing, and dissolving.
[0396] In curing and molding the polymerizable composition of the
present invention, a known molding method may be used according to
purposes, and various additives in addition to the above-described
additives, such as a stabilizer, a resin modifier, a chain
extender, a crosslinking agent, a photostabilizer including a
HALS-type photostabilizer or the like, an ultraviolet light
absorber including a benzotriazole ultraviolet light absorber or
the like, an antioxidant including a hindered phenol antioxidant or
the like, a coloring inhibitor, a dye or bluing agent including an
anthraquinone disperse dye or the like, a filler, an external mold
releasing agent including a silicone-based external mold releasing
agent, or an internal mold releasing agent including a surfactant
such as acidic phosphate, quaternary ammonium salt or quaternary
phosphonium salt, and an adhesion improving agent may be used.
Here, the internal mold releasing agent includes those that exhibit
releasing effect among various additives as described above.
[0397] Although the amount of each of the additives which can be
added depends upon the type, structure and effect of each additive
and is not limited, the adding amount is usually in the range of
0.001% by weight to 10% by weight, and preferably 0.01 to 5% by
weight, based on the total weight of the polymerizable composition.
The amount of the dye added is preferably in the range of 1 ppb to
100 ppm, not in the above-described range. Within these ranges, a
sufficiently cured resin can be produced, and the obtained resin
has good transparency and optical physical properties in some
cases.
[0398] Next, the resin according to the present invention will be
described.
[0399] The resin and the optical part composed of such a resin
according to the present invention are obtained by polymerization
of said polymerizable composition. Furthermore, the method for
preparing the resin according to the present invention involves a
process for polymerization of the polymerizable composition
according to the present invention. Such polymerization is suitably
carried out according to various methods known in the art, used
when producing plastic lenses. A typical method includes a casting
polymerization.
[0400] Namely, the polymerizable composition of the present
invention produced by the above method is degassed under a reduced
pressure or filtered off, as required, and then the polymerizable
composition is poured into a mold, and heated as required for
carrying out polymerization. In this case, it is preferable to
carry out polymerization by slowly heating from a low temperature
to a high temperature.
[0401] The mold as described above is composed of, for example, two
pieces of mirror surface-ground molds via a gasket made of
polyethylene, an ethylene vinyl acetate copolymer, and polyvinyl
chloride. Typical examples of the mold include, though not
restricted to, combined molds such as glass and glass, glass and
plastic plate, and glass and metal plate. The mold may comprise two
pieces of molds fixed by a tape such as a polyester adhesive tape
or the like. In addition, a known method such as the mold release
process may be performed for the mold, as needed.
[0402] When carrying out casting polymerization, the polymerization
temperature is affected by the polymerization conditions such as
the kind of the polymerization initiator, and the like, and is not
particularly limited. But, it is usually from -50.degree. C. to
200.degree. C., preferably from -20.degree. C. to 170.degree. C.,
and more preferably from 0 to 150.degree. C.
[0403] The polymerization temperature affects the polymerization
time, but it is usually from 0.01 to 200 hours and preferably from
0.05 to 100 hours. Polymerization can also be carried out in
combination of several temperatures by conducting low temperature,
temperature elevation, and temperature dropping as required.
[0404] Furthermore, the polymerizable composition of the present
invention can be polymerized by applying the active energy line
such as an electron beam, ultraviolet light, visible light or the
like. At this time, a radical polymerization catalyst or a cationic
polymerization catalyst for initiating polymerization by the active
energy line is used, as required.
[0405] If the heat resistance of the obtained resin is too low,
some problems, such as thermal deformation, in the use as glass
lens in daily life occur in some cases. On the other hand, if the
heat resistance of the obtained resin is too high, some problems
such as resin intingibility of the resin occur in some cases. In
consideration of tingibility, the heat resistance of the obtained
resin preferably has a glass transition temperature (Tg) of
100.degree. C. to 150.degree. C.
[0406] Here, Tg is a temperature that is measured by a TMA (Thermal
Mechanical Analysis) penetration method, from the cross-points in a
TMA curve, which corresponds a heat distortion beginning
temperature.
[0407] After the thus-obtained resin and the optical lens composed
of the resin are cured, they may be subjected to an annealing
process as required. Furthermore, for purposes of anti-reflection,
high hardness grant, wear resistance improvement, anti-fogging
property grant or fashionability grant, various known physical or
chemical processes such as surface polishing, antistatic treatment,
hard coat treatment, non-reflective coat treatment, anti-reflective
treatment, tinting treatment, and photochromic treatment (for
example, photochromic lens process), may be performed as
needed.
[0408] Furthermore, for the optical lens including the obtained
resin and the optical lens including the resin, if necessary,
coating layers may be formed on either or both of the surfaces and
used. Hereinbelow, the optical lens will be described by way of an
example. Examples of the coating layer include a primer layer, a
hard coat layer, an anti-reflection layer, an anti-fogging coat
film layer, and an anti-fouling layer, a water-repellent layer.
These coating layers may be used alone, respectively, or a
plurality of coating layers may be formed into a multi-layer to be
used. In the case of providing coating layers on both sides, the
coating layers provided on each side may either be the same with or
different from each other.
[0409] For those coating layers, there may be employed in
combination known additive agents for the purpose of improving
properties of lenses. In particular, an UV absorber for the purpose
of protecting lenses or eyes from UV light, an IR absorber for the
purpose of protecting eyes from infrared rays, a light stabilizer
or antioxidant for the purpose of improving the weatherability of
lenses, dye or pigment for the purpose of increasing fashionability
of lenses, photochromic dye or photochromic pigment, an antistatic
agent, and other known additives for improving the properties of
lenses, respectively. Various leveling agents for improving the
coatability may also be used for the layer which to be coated by
application.
[0410] The primer layer is usually formed between after mentioned
the hard coat layer and lenses. The primer layer is typically a
coating layer provided for the purpose of improving the
adhesiveness between the hard coat layer and lenses, and there may
be a case where the impact resistance is also improved.
[0411] For the primer layer, any material can be used as long as it
provides high adhesivity to the obtained optical lens, and usually
employed are an urethane-based resin, an epoxy-based resin, a
polyester-based resin, a melanin-based resin, a primer composition
mainly including polyvinylacetal. For the purpose of adjusting the
viscosity of the composition, an appropriate solvent can be used,
which does not affect the lens, in the primer composition. Of
course, the solvent may not be used.
[0412] The primer composition can be formed by either of an
application process or a dry process. If the application process is
used, a spin coat, a dip coat, or the like is applied on the lens
by means of a known application process, and then solidified to
form a primer layer. If the dry process is used, the primer layer
is formed by means of a CVD process, a vacuum deposition process,
or the like. In order to improve the adhesion when the primer layer
is formed, if necessary, the surfaces of the lens may be subject to
preliminary treatments such as alkali treatment, plasma treatment,
and ultraviolet light treatment.
[0413] The hard coat layer is a coating layer provided for the
purpose of giving functions such as an anti-scratching property,
abrasion resistance, humidity resistance, hot-water resistance,
heat resistance, and weather resistance, to the lens surface.
[0414] For the hard coat layer, an organosilicon compound having
curing property, and a hard coat composition having at least one
particulate oxide of element selected from the group consisting of
Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti and/or at
least one particulate constituted of a composite oxide of two or
more elements selected from the group consisting of those elements,
are generally used. The fine particles composed of the oxide fine
particles and/or the composite oxide may be used singly, or in
combination of two or more kinds thereof in the hard coat
composition. The hard coat composition preferably includes, in
addition to said components, at least one selected from amines,
amino acids, metal acetyl acetate complexes, organic acid salts,
pechloric acids, pechloric acid salts, acids, metal chlorides, and
polyfunctional epoxy compounds. For the hard coat composition, an
appropriate solvent can be used, which does not affect the lens. Of
course, the solvent may not be used.
[0415] The hard coat layer is usually formed by applying a hard
coat composition using a known process such as spin coat, and dip
coat, and then curing it. Examples of the curing process include a
thermal curing process, a curing process using an energy ray such
as an ultraviolet light and a visible light. In order to inhibit
generation of the interference fringe, the refractive index of the
hard coat layer is preferably in the range of the refractive index
of the lens .+-.0.1.
[0416] The antireflection layer is usually formed on said hard coat
layer, if necessary. There are an inorganic type and an organic
type for the antireflection layer, and the inorganic type is
provided by the use of inorganic oxide such as SiO.sub.2 and
TiO.sub.2 in accordance with the dry method such as a vacuum
evaporation technique, a sputtering method, an ion plating method,
an ion beam assist method, and a CVD method. The organic type is
provided by the use of a composition which includes an
organosilicon compound and a silica particle having internal
cavity, in accordance with the wet method.
[0417] The anti-reflection layer may be a mono-layer or a
multi-layer, and if it is used as a mono-layer, it is preferable
that its refractive index is lower than that of the hard coat layer
by at least 0.1 or more. In order to exhibit the anti-reflection
function more effectively, a multi-layer is preferable as the
anti-reflection layer. In this case, a layer having a low
refractive index and a layer having a high refractive index are
stacked alternately. Also, in this case, the difference in the
refractive indices of the layer having a low refractive index and
the layer having a high refractive index ex is preferably 0.1 or
more. Examples of the layer having a high refractive index include
ZnO, TiO.sub.2, CeO.sub.2, Sb.sub.2O.sub.5, SnO.sub.2, ZrO.sub.2,
and Ta.sub.2O.sub.5 layer, and the film having a refractive index
include a SiO.sub.2 layer.
[0418] If necessary, an antifogging coat layer, an anti-staining
layer, and a water-repellent layer may be further formed on the
antireflection layer. As the means for forming the antifogging coat
layer, the anti-staining layer, and the water-repellent layer,
methods and materials for the treatment thereof, or the like are
not particularly limited as long as it is within the scope of not
adversely affecting the antireflection properties, and there may be
employed a generally known antifogging coat treatment method,
anti-staining treatment method, water-repellent treatment method,
and materials.
[0419] For example, examples of the methods for anti-fogging coat
and anti-fouling treatment include a method of covering a surface
with a surfactant, a method of adding a hydrophilic layer on a
surface to give absorptivity, a method of covering a surface with a
fine unevenness to increase absorptivity, a method of using the
activity of a photo-catalyst to give absorptivity, and a method of
performing an ultra-water-repellency treatment to prevent
attachment of water drops.
[0420] Furthermore, examples of the water-repellency treatment
method include a method of forming a water-repellent treatment
layer by deposition or sputtering with a fluorine-containing silane
compound, or the like, and a method of dissolving a
fluorine-containing silane compound in a solvent, and then
performing coating to form a water-repellency treated layer.
[0421] In addition, the obtained resin, and optical lens composed
of the resin may be tinted for a use with the use of a dye
appropriate for the purpose so as to provide fashionability or
photochromic property. Hereinbelow, the tinting of optical lens
will be described by way of an example.
[0422] Tinting of the optical lens can be carried out in accordance
with a generally known tinting method, and is carried out generally
by the following methods: [0423] (a) a method of immersing a lens
in a dye liquid; [0424] (b) a method of subjecting coating with the
use of a coating agent containing a dye, or providing a coating
layer which can be tinted and tinting the provided coating layer;
[0425] (c) a method of polymerizing monomer raw materials in which
materials which can be tinted are contained; [0426] (d) a method of
heating a sublimation dye to allow sublimation; or the like.
[0427] The method (a) is a method including immersing a lens
material finished on a predetermined optical surface in a dye
liquid in which the dye to be used is dissolved or uniformly
dispersed (tinting process), and solidifying the dye on the lens by
heating (annealing process after tinting), if necessary.
[0428] There are no particular limitations on the dye used in the
tinting process and generally known dye can be used, but an
oil-soluble dye or a disperse dye is usually used. The solvent used
in the tinting process is not particularly limited as long as it is
the solvent in which the dye to be used can be dissolved or
uniformly dispersed therein.
[0429] In the tinting process, a surfactant for dispersing the dye
in a dye liquid or a carrier which encourages tinting may also be
employed, if necessary.
[0430] In the tinting process, a colorant and a surfactant that is
added, if necessary, are dispersed in water, or a mixture of water
and an organic solvent, to prepare a tinting bath. An optical lens
is immersed in the tinting bath to perform tinting at a
predetermined temperature for a predetermined time. The tinting
temperature and time vary depending on the color density, but they
are usually 120.degree. C. or lower and several minutes to several
decades, respectively. Tinting is performed at a concentration of
the tinting bath of around 0.01 to 10% by weight. Furthermore, if
it is difficult to tint, the tinting is performed under pressure.
The annealing process, that is performed, if necessary, after
tinting, is a process in which the tinted lens greige is subject to
heat treatment. The heat treatment is, for example, an infrared
heating treatment at an atmosphere, or a resistant heating
treatment, thereby allowing a predetermined retention in an oven,
after removing water remaining on the surface of the tinted lens
greige in the tinting process with a solvent, or the like, or
removing the solvent by blowing air. The annealing process after
tinting prevents the tinted lens greige from decoloration
(decoloration-preventing treatment), as well as remove the moisture
penetrated into the inside of the lens greige upon tinting.
[0431] The method (b) is not for directly tinting a plastic lens
material, and it is the method either including a process of
coating a plastic lens with an organic coating liquid in which a
dye is dispersed or dissolved and subjecting to a curing treatment
to form a tinted coating layer on a lens surface, or a process of
forming a coating layer which can be tinted on a plastic lens
surface, and then performing the method (a), that is, immersing the
plastic lens in a dye liquid, and subjecting to heating to be
tinted.
[0432] The method (c) is a method including preliminarily
dissolving a dye in monomer raw materials for a plastic lens and
thereafter carrying out a polymerization. The dye to be used is not
particularly limited as long as it can be uniformly dissolved or
dispersed to the extent of not deteriorating the optical
properties, in monomer raw materials.
[0433] As the method (d), there may be employed the following (d1)
to (d3):
[0434] (d1) a method which includes sublimating a solid sublimation
dye and tinting a plastic lens;
[0435] (d2) a method which includes facing a plastic lens to a
substrate to which a solution containing a sublimation dye is
applied in a non-contacting manner, and heating the substrate and
the lens to allow tinting; or
[0436] (d3) a method which includes transferring a colored layer
containing a sublimation dye and a transfer layer comprising an
adhesive layer to a plastic lens, and thereafter heating to allow
tinting.
[0437] The resin of the invention and the optical lenses composed
of the resin may be tinted in accordance with any of those methods.
The dye to be used is not particularly limited as long as it is a
dye having a sublimating property.
[0438] Also, the cured resin obtained by polymerization of the
polymerizable composition of the present invention, and the optical
members have high transparency, good heat resistance, and
mechanical strength, while attaining a much higher refractive index
(nd) exceeding 1.7.
[0439] Examples of the optical parts according to the present
invention include various plastic lens such as such as a spectacle
lens for vision correction, a lens for cameras, a fresnel lens for
liquid crystal projectors, a lenticular lens, and a contact
lens;
[0440] a sealing material for light emitting diodes (LED);
[0441] an optical waveguide;
[0442] an optical adhesive used for the junction of an optical lens
or an optical waveguide;
[0443] an anti-reflection film to be used for optical lenses;
[0444] transparent coating or transparent substrate used for liquid
crystal display members such as a substrate, a light guiding plate,
a film, and a sheet.
[0445] As such, the resin obtained by polymerization of the
polymerizable compound of the present invention has good
transparency, and good heat resistance and mechanical strength,
while attaining a very high refractive index (nd) exceeding 1.7,
and is useful as a resin for optical parts such as, for example,
plastic lens. Also, the polymerizable composition of the present
invention is useful for a monomer raw material composition for a
transparent resin having a high refractive index.
[0446] The embodiments of the present invention are described as
above, but these are presented only for the illustrative purpose,
and thus other modified constitutions can be employed.
[0447] For example, in the polymerizable composition of the present
invention, as a metal thietane compound, the compound represented
by General Formula (1) may be a compound represented by the
following General Formula (9).
##STR00133##
[0448] (in General Formula (9), p, X.sub.1, and Y are each the same
as p, X.sub.1, and Y, respectively, in General Formula (1). r
represents an integer of 0 to 4. p+r=5 or 3).
[0449] In General Formula (9), from the viewpoint of the improved
refractive index of the resin, X.sub.1 is preferably a sulfur
atom.
[0450] In General Formula (9), p is an integer of the valence of Bi
or less, and the valence of Bi is 3 or 5. That is, p is an integer
of 1 to 5.
[0451] r is an integer of 0 to 4.
[0452] p+r is the valence of Bi, that is, 5 or 3. From the
viewpoint of increased number of functional groups involving in the
polymerization with the polymerizable compound in the polymerizable
composition, p+r is preferably 5.
[0453] Furthermore, in General Formula (9), specifically, p is 3,
and specifically, X.sub.1 is a sulfur atom, p=3, and r=0. Here, the
compound represented by General Formula (9) would be a compound
represented by the following Formula.
##STR00134##
[0454] In General Formula (9), incase of r=1, Y represents an
inorganic or organic residue. Further, in a case where r is an
integer of 2 or greater, a plurality of Y's each independently
represents an inorganic or organic residue. The plurality of Y may
be the same group, or all or a part thereof may be different. Also,
a plurality of Y's may be bonded to each other to form a ring
containing a Bi atom.
[0455] If Y does not form a ring, specific examples of Y include an
alkyl group having 1 to 3 carbon atom(s), such as a methyl group,
an ethyl group, a propyl group, and an isopropyl group.
[0456] On the other hand, if Y forms a ring, examples of the alkyl
chain forming a ring include an alkylene group having 1 to 3 carbon
atom (s), such as a methylene group, an ethylene group, and a
propylene group. Examples of the ring containing Bi specifically
include 4- to 6-membered rings.
[0457] More specifically, if Y does not form a ring, Y is a methyl
group, and if Y forms a ring, the alkyl chain forming a ring is an
ethylene group.
[0458] The thietane compound represented by General Formula (9) is
typically prepared in accordance with the method for preparing the
compound represented by General Formula (1), in which a halide of
Bi represented by the following General Formula (10) is reacted
with a hydroxy compound containing a thietane group the following
General Formula (11) or a thiol compound.
##STR00135##
[0459] (in General Formula (10), p, r, and Y are the same as p, r
and Y in General Formula (9), and W represents a halogen atom)
##STR00136##
[0460] (in General Formula (11), X.sub.1 is the same as X.sub.1 in
General Formula (9)).
[0461] The present invention also includes the following
embodiments.
[0462] (1-1) A polymerizable composition comprising a compound
represented by General Formula (1'):
##STR00137##
[0463] (wherein M represents a metal atom, X.sub.1 and X.sub.2 each
independently represents a sulfur atom or an oxygen atom, R.sub.1
represents a divalent organic group, m represents an integer of 0
or 1 or greater, p represents an integer of 1 to n, q represents an
integer of 1 to (n-p), n represents a valence of a metal atom M,
Yq's each independently represents an inorganic or organic residue,
and if q is 2 or greater, Yq's may be bonded to each other to form
a ring structure with the intermediary of a metal atom M),
[0464] and a thiol compound;
[0465] (1-2) the polymerizable composition as set forth in (1-1),
wherein the content of the thiol compound is 1 to 50% by
weight;
[0466] (1-3) the polymerizable composition as set forth in (1-1) or
(1-2), further containing sulfur;
[0467] (1-4) the polymerizable composition as set forth in (1-3),
wherein the content of the thiol compound is 1 to 50% by weight,
and the content of sulfur is 5 to 50% by weight;
[0468] (1-5) the polymerizable composition as set forth in any one
of (1-1) to (1-4), wherein the metal atom is a Sn atom, a Si atom,
a Zr atom, a Ge atom, a Ti atom, a Zn atom, an Al atom, a Fe atom,
a Cu atom, a Pt atom, a Pb atom, an Au atom, or an Ag atom;
[0469] (1-6) the polymerizable composition as set forth in any one
of (1-1) to (1-4), wherein the metal atom is a Sn atom, a Si atom,
a Zr atom, a Ti atom, a Ge atom, an Al atom, a Pb atom, or a Zn
atom;
[0470] (1-7) a resin obtained by polymerization of the
polymerizable composition as set forth in any one of (1-1) to
(1-6); and
[0471] (1-8) optical part(s) composed of the resin as set forth in
(1-7).
[0472] (2-1) A polymerizable composition including the compound
represented by General Formula (1)', the thiol compound, and a
compound having a carbon-carbon double bond;
[0473] (2-2) the polymerizable composition as set forth in (2-1),
wherein the content of the compound represented by General Formula
(1)' is 50% by weight or more;
[0474] (2-3) the polymerizable composition as set forth in (2-1) or
(2-2), wherein the ratio of the functional groups (that is, SH
groups/carbon-carbon double bonds) that is the ratio of the thiol
groups in the thiol compound and the carbon-carbon double bonds in
the compound having a carbon-carbon double bond is 1 or more;
[0475] (2-4) the polymerizable composition as set forth in any one
of (2-1) to (2-3), wherein the metal atom is a Sn atom, a Si atom,
a Zr atom, a Ge atom, a Ti atom, a Zn atom, an Al atom, a Fe atom,
a Cu atom, a Pt atom, a Pb atom, an Au atom, or an Ag atom;
[0476] (2-5) the polymerizable composition as set forth in any one
of (2-1) to (2-3), wherein the metal atom is a Sn atom, a Si atom,
a Zr atom, a Ti atom, a Ge atom, an Al atom, a Pb atom, or a Zn
atom;
[0477] (2-6) a resin obtained by polymerization of the
polymerizable composition as set forth in any one of (2-1) to
(2-5); and
[0478] (2-7) an optical part (member) composed of the resin as set
forth in (2-6).
[0479] (3-1) A polymerizable composition including the compound
represented by General Formula (1)', the thiol compound, and an
iso(thio)cyanate compound;
[0480] (3-2) the polymerizable composition as set forth in (3-1),
wherein the content of the compound represented by General Formula
(1)' is 50% by weight or more;
[0481] (3-3) the polymerizable composition as set forth in (3-1) or
(3-2), wherein the ratio of the functional groups (that is, SH
groups/(NCO groups+NCS groups)) that is the ratio of the thiol
groups in the thiol compound and the iso(thio)cyanate groups in the
iso(thio)cyanate compound is 1 or more;
[0482] (3-4) the polymerizable composition as set forth in any one
of (3-1) to (3-3), wherein the metal atom is a Sn atom, a Si atom,
a Zr atom, a Ge atom, a Ti atom, a Zn atom, an Al atom, a Fe atom,
a Cu atom, a Pt atom, a Pb atom, an Au atom, or an Ag atom;
[0483] (3-5) the polymerizable composition as set forth in any one
of (3-1) to (3-3), wherein the metal atom is a Sn atom, a Si atom,
a Zr atom, a Ti atom, a Ge atom, an Al atom, a Pb atom, or a Zn
atom;
[0484] (3-6) a resin obtained by polymerization of the
polymerizable composition as set forth in any one of (3-1) to
(3-5); and
[0485] (3-7) an optical part (member) composed of the resin as set
forth in (3-6).
[0486] (4-1) A polymerizable composition including the compound
represented by General Formula (1)', the thiol compound, and an
epoxy compound and/or an episulfide compound;
[0487] (4-2) the polymerizable composition as set forth in (4-1),
wherein the content of the compound represented by General Formula
(1)' is 50% by weight or more;
[0488] (4-3) the polymerizable composition as set forth in (4-1) or
(4-2), wherein the ratio of the functional groups (SH groups/(epoxy
groups+episulfide groups)) that is the ratio of the thiol groups in
the thiol compound and the epoxy groups and/or episulfide groups in
the epoxy compound and/or the episulfide compound is 1 or more;
[0489] (4-4) the polymerizable composition as set forth in any one
of (4-1) to (4-3), wherein in the compound represented by General
Formula (1)', m is 0;
[0490] (4-5) the polymerizable composition as set forth in any one
of (4-1) to (4-3), wherein in the compound represented by General
Formula (1)', m=0, and X.sub.1 is a sulfur atom;
[0491] (4-6) the polymerizable composition as set forth in any one
of (4-1) to (4-3), wherein in the compound represented by General
Formula (1)', n=p, m=0, and X.sub.1 is a sulfur atom;
[0492] (4-7) the polymerizable composition as set forth in any one
of (4-1) to (4-6), wherein in the compound represented by General
Formula (1)', the metal atom M is a Group 2B, 3B, 4A, or 4B element
in a Periodic Table;
[0493] (4-8) the polymerizable composition as set forth in any one
of (4-1) to (4-6), wherein in the compound represented by General
Formula (1)', the metal atom M is a Sn atom;
[0494] (4-9) the polymerizable composition as set forth in any one
of (4-1) to (4-8), wherein the thiol compound is any one of
3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0495] (4-10) the polymerizable composition as set forth in any one
of (4-1) to (4-9), wherein the epoxy compound is any one of
cyclohexanedimethanol diglycidyl ether, and bisphenol F/glycidyl
ether;
[0496] (4-11) the polymerizable composition as set forth in any one
of (4-1) to (4-9), wherein the episulfide compound is either
bis(2,3-epithiopropyl)sulfide or
bis(2,3-epithiopropyl)disulfide;
[0497] (4-12) a method for preparing a resin, including casting
polymerization of the polymerizable composition as set forth in any
one of (4-1) to (4-11);
[0498] (4-13) a resin obtained by polymerization of the
polymerizable composition as set forth in any one of (4-1) to
(4-11); and
[0499] (4-14) an optical part composed of the resin as set forth in
(4-13).
[0500] (5-1) A polymerizable composition including the compound
represented by General Formula (1)', the thiol compound, and a
thietane compound containing no metal represented by General
Formula (8):
##STR00138##
[0501] (wherein Q represents a reactive terminal group, a straight,
branched or cyclic alkyl group having 1 to 10 carbon atom(s) that
has a reactive terminal group, or its thia derivative, an aryl
group, or an aralkyl group, R.sub.3 represents a substituted or
unsubstituted bivalent hydrocarbon group having 1 to 10 carbon
atom(s), which may be thianated, and n represents an integer of 0
to 3);
[0502] (5-2) the polymerizable composition as set forth in (5-1),
wherein the content of the compound represented by General Formula
(1)' is 50% by weight or more;
[0503] (5-3) the polymerizable composition as set forth in (5-1) or
(5-2), wherein the ratio of the functional groups (SH
groups/thietanyl groups) that is the ratio of the thiol groups in
the thiol compound and the thietanyl groups in the thietane
compound containing no metal is 1 or more;
[0504] (5-4) the polymerizable composition as set forth in any one
of (5-1) to (5-3), wherein in the compound represented by General
Formula (1)', m is 0;
[0505] (5-5) the polymerizable composition as set forth in any one
of (5-1) to (5-3), wherein in the compound represented by General
Formula (1)', m=0, and X.sub.1 is a sulfur atom;
[0506] (5-6) the polymerizable composition as set forth in any one
of (5-1) to (5-3), wherein in the compound represented by General
Formula (1)', n=p, m=0, and X.sub.1 is a sulfur atom;
[0507] (5-7) the polymerizable composition as set forth in any one
of (5-1) to (5-6), wherein in the compound represented by General
Formula (1)', the metal atom M is a Group 2B, 3B, 4A, or 4B element
in a Periodic Table;
[0508] (5-8) the polymerizable composition as set forth in any one
of (5-1) to (5-6), wherein in the compound represented by General
Formula (1)', the metal atom M is a Sn atom;
[0509] (5-9) the polymerizable composition as set forth in any one
of (5-1) to (5-8), wherein the thiol compound is any one of
3-mercaptothietane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
2,5-bis(mercaptomethyl)-1,4-dithiane;
[0510] (5-10) the polymerizable composition as set forth in any one
of (5-1) to (5-9), wherein the thietane compound containing no
metal represented by General Formula (8) is
bis(3-thietanyl)disulfide;
[0511] (5-11) (a method for preparing a resin, including casting
polymerization of the polymerizable composition as set forth in any
one of (5-1) to (5-10);
[0512] (5-12) a resin obtained by polymerization of the
polymerizable composition as set forth in any one of (5-1) to
(5-10); and
[0513] (5-13) an optical part composed of the resin as set forth in
(5-12).
EXAMPLES
[0514] Hereinafter, the present invention will be explained in more
detail with reference to Preparation Examples and Examples, but is
not limited thereto.
[0515] Furthermore, in the following Examples, the glass transition
temperature (Tg) is a temperature that is measured by Ta MA
penetration method, and determined from a cross-points in a TMA
curve, which corresponds a heat distortion beginning
temperature.
Reference Preparative Example 1
[0516] 3-Thietanol was synthesized in accordance with the method as
described in Patent Document 3 (Japanese Patent Laid-Open No.
2003-327583).
[0517] Further, 3-mercaptothietane was synthesized using the
obtained 3-thietanol. That is, 190 g of thiourea, 253 g of a 35%
hydrochloric acid solution and 250 g of water were introduced into
a reactor equipped with a stirrer and a thermometer, and stirred,
while 156 g of 3-thietanol was added dropwise to the reaction
solution over 1 hour. The resulting solution was stirred and
reacted at 30.degree. C. for 24 hours, and then 177 g of 24%
ammonia water was added dropwise thereto over 1 hour. The solution
was further reacted at 30.degree. C. for 15 hours, and then allowed
to stand for taking out an organic layer (lower layer) to obtain
134 g of a crude composition. The resulting crude composition was
distilled off under a reduced pressure to collect a fraction with a
boiling point of 40.degree. C./106 Pa to obtain 3-mercaptothietane,
as the desired product of a colorless transparent liquid.
Reference Preparative Example 2
Preparation of Compound Represented by Compound (CMPD). No. 1-1 in
Table 1
[0518] 11.15 g (0.105 mole) of 3-mercaptothietane was introduced to
50 g of pure water. Subsequently, 41.2 g (0.103 mole) of a 10% NaOH
aqueous solution was introduced dropwise at room temperature over
40 minutes. Then, the reaction solution was subjected to a
temperature elevation to 30.degree. C. and 65.2 g (corresponding to
0.025 mole of tin tetrachloride) of an aqueous solution of 10% tin
tetrachloride was added dropwise at the same temperature over 4
hours. After the dropwise addition was completed, the solution was
further stirred at the same temperature for 2 hours. 100 ml of
chloroform was added to the reaction mixture, and the organic layer
and the water layer were separated. The organic layer was washed
with 100 ml of pure water twice, and then dried over anhydrous
sodium sulfate. The solvent was distilled off from the extract to
obtain 13.40 g (yield: 99%) of a compound represented by the
Compound No. 1-1 in Table 1.
##STR00139##
[0519] (Preparation of Polymerizable Composition, and Preparation
of the Article with Resin Curing by Polymerization)
[0520] The physical properties of the resin or the optical part
(lens) prepared in the following Examples and Comparative Examples
were tested in accordance with the following methods.
[0521] Appearance: Transparency and presence or absence of optical
strain were investigated with naked eyes, and with microscopy.
[0522] Refractive Index (ne): Refractive index was measured with
the use of a Pulfrich refractometer at 20.degree. C.
[0523] Heat Resistance: Glass transition temperature (Tg) was
measured by a TMA penetration method. The case where Tg was
80.degree. C. or higher evaluated as "o", and the case where Tg was
lower than 80.degree. C. evaluated as "x".
[0524] Strength: A steel ball was dropped on a lens having a
central thickness of 1.3 mm. Specifically, 8 g of the steel ball
was dropped on a lens from a height of 127 cm. The lens that was
not scattered was evaluated as "o", and the lens that was scattered
or penetrated with the steel ball was evaluated as "x".
[0525] Color: Yellow index (YI) of a flat plate having a thickness
of 2 mm was measured in accordance with ASTM D1925 using a
Gretagmacbeth spectrophotometer CE-7000 A.
Example 1-1
[0526] 95 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, and 5 parts by weight of 3-mercaptothietane (thiol
compound A) as a thiol compound were charged into a glass beaker at
40.degree. C. The mixture was filtered through a Teflon (trade
name) filter without addition of a polymerization catalyst, and
then sufficiently degassed until all bubbling had ceased under a
reduced pressure of 1.3 kPa or less. The degassed polymerizable
composition was injected into a mold formed by a glass mold and a
tape, and placed in a heating oven to perform polymerization for 20
hours. During the polymerization, the inner temperature of the oven
was gradually increased from 60.degree. C. to 120.degree. C.
[0527] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 18.
Examples 1-2 to 1-11
[0528] The same operation as in Example 1-1 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 18. The composition and the
evaluation results of the obtained resin are presented in Table
18.
Comparative Example 1-1
[0529] 100 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, was charged into a glass beaker at 60.degree. C.,
filtered through a Teflon (trade name) filter without addition of a
polymerization catalyst, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 1.3 kPa or less.
The degassed polymerizable composition was injected into a mold
formed by a glass mold and a tape, and placed in a heating oven to
perform polymerization for 20 hours. During the polymerization, the
inner temperature of the oven was gradually increased from
70.degree. C. to 120.degree. C.
[0530] The molded piece of the obtained resin had good transparency
and good appearance with no strain, but was yellowed. The
evaluation results of the obtained resin are presented in Table
19.
TABLE-US-00019 TABLE 19 Composition (parts by weight) Compound
represented Evaluation Items by General Thiol Refractive Heat
Formula (1) compound Sulfur index (ne) resistance Strength Color
Appearance Example 1-1 No1-1 (95) A (5) 1.792 .smallcircle.
.smallcircle. 12 Transparent, no strain Example 1-2 No1-1 (95) B
(5) 1.788 .smallcircle. .smallcircle. 10 Transparent, no strain
Example 1-3 No1-1 (95) C (5) 1.787 .smallcircle. .smallcircle. 11
Transparent, no strain Example 1-4 No1-1 (90) A 1.786 .smallcircle.
.smallcircle. 8 Transparent, no (10) strain Example 1-5 No1-1 (90)
B 1.783 .smallcircle. .smallcircle. 6 Transparent, no (10) strain
Example 1-6 No1-1 (90) D 1.785 .smallcircle. .smallcircle. 8
Transparent, no (10) strain Example 1-7 No1-1 (90) A (5) B (5)
1.783 .smallcircle. .smallcircle. 7 Transparent, no strain Example
1-8 No1-1 (90) A (5) C (5) 1.783 .smallcircle. .smallcircle. 8
Transparent, no strain Example 1-9 No1-1 (85) A (5) B 1.776
.smallcircle. .smallcircle. 5 Transparent, no (10) strain Example
No1-1 (85) A B (5) 1.776 .smallcircle. .smallcircle. 4 Transparent,
no 1-10 (10) strain Example No1-1 (90) A (5) (5) 1.799
.smallcircle. .smallcircle. 12 Transparent, no 1-11 strain
Comparative No1-1 (100) 1.797 .smallcircle. x 37 Transparent, no
Example 1-1 strain
[0531] Furthermore, Table 19 shows the thiol compounds used in each
Example using the following abbreviations.
[0532] A: 3-Mercaptothietane
[0533] B: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0534] C:
4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
[0535] D: 2,5-Bis(mercaptomethyl)-1,4-dithiane
[0536] The physical properties of the resin and optical parts
(lens) prepared in the following Examples and Comparative Examples
were tested in accordance with the following methods.
[0537] Appearance: Transparency and presence or absence of optical
strain were investigated with naked eyes, and with microscopy.
[0538] Refractive Index: Refractive index was measured with the use
of a Pulfrich refractometer at 20.degree. C.
[0539] Color: Yellow index (YI) of a flat plate having a thickness
of 2 mm was measured in accordance with ASTM D1925 using a
Gretagmacbeth spectrophotometer CE-7000 A.
Example 2-1
[0540] 75 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, 13 parts by weight of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (thiol compound A)
as a thiol compound, 12 parts by weight of triallyl isocyanurate
(TAIC) as a compound having a carbon-carbon double bond, and 0.02
part by weight of t-butylperoxy-2-ethylhexanoate (PBO) as a
polymerization catalyst were charged into a glass beaker at
40.degree. C. The mixture was filtered through a Teflon (trade
name) filter manufactured, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 1.3 kPa or less.
The degassed polymerizable composition was injected into a mold
formed by a glass mold and a tape, and placed in a heating oven to
perform polymerization for 20 hours. During the polymerization, the
inner temperature of the oven was gradually increased from
60.degree. C. to 120.degree. C.
[0541] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 20.
Examples 2-2 to 2-4
[0542] The same operation as in Example 2-1 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 20. The composition and the
evaluation results of the obtained resin are presented in Table
20.
Comparative Example 2-1
[0543] 100 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, was charged into a glass beaker at 60.degree. C.,
filtered through a Teflon (trade name) filter without addition of a
polymerization catalyst, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 1.3 kPa or less.
The degassed polymerizable composition was injected into a mold
formed by a glass mold and a tape, and placed in a heating oven to
perform polymerization for 20 hours. During the polymerization, the
inner temperature of the oven was gradually increased from
70.degree. C. to 120.degree. C.
[0544] The molded piece of the obtained resin had good transparency
and good appearance with no strain, but was yellowed. The
composition and the evaluation results of the obtained resin are
presented in Table 20.
TABLE-US-00020 TABLE 20 Composition (parts by weight) Ratio of
Compound Compound functional Evaluation Items represented having
groups (SH Refractive by General Thiol carbon-carbon Polymerization
groups/double index Heat Formula (1) compound bonds catalyst bonds)
(ne) resistance Color Appearance Example 2-1 No1-1 (75) A (13) TAIC
(12) PBO (0.01) 1/1 1.758 .smallcircle. 12 Transparent, no strain
Example 2-2 No1-1 (75) A (17) TAIC (8) PBO (0.01) 2/1 1.763
.smallcircle. 9 Transparent, no strain Example 2-3 No1-1 (80) A
(14) TAIC (6) PBO (0.01) 2/1 1.767 .smallcircle. 10 Transparent, no
strain Example 2-4 No1-1 (80) B (14) TAIC (6) PBO (0.01) 2/1 1.768
.smallcircle. 10 Transparent, no strain Comparative No1-1 (100) 0 0
0 -- 1.797 .smallcircle. 37 Transparent, Example 2-1 no strain
[0545] Furthermore, in Table 20, the following abbreviations were
used.
[0546] A: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0547] B:
4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
[0548] TAIC: Triallyl isocyanurate
[0549] PBO: t-Butylperoxy-2-ethylhexanoate
[0550] The physical properties of the resin and the optical parts
(lens) prepared in the following Examples and Comparative Examples
were tested in accordance with the following methods.
[0551] Appearance: Transparency and presence or absence of optical
strain were investigated with naked eyes, and with microscopy.
[0552] Refractive Index: Refractive index was measured with the use
of a Pulfrich refractometer at 20.degree. C.
[0553] Strength: A steel ball was dropped on a lens having a
central thickness of 1.3 mm. Specifically, 8 g of the steel ball
was dropped on a lens from a height of 127 cm. The lens that was
not scattered was evaluated as "o", and the lens that was scattered
or penetrated with the steel ball was evaluated as "x".
[0554] Color: Yellow index (YI) of a flat plate having a thickness
of 2 mm was measured in accordance with ASTM D1925 using a
Gretagmacbeth spectrophotometer CE-7000 A.
Example 3-1
[0555] 80 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, 12 parts by weight of 3-mercaptothietane (thiol compound
A) as a thiol compound, and 8 parts by weight of
bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI) as an isocyanate
compound were charged into a glass beaker at 40.degree. C. The
mixture was filtered through a Teflon (trade name) filter without
addition of a polymerization catalyst, and then sufficiently
degassed until all bubbling had ceased under a reduced pressure of
1.3 kPa or less. The degassed polymerizable composition was
injected into a mold formed by a glass mold and a tape, and placed
in a heating oven to perform polymerization for 20 hours. During
the polymerization, the inner temperature of the oven was gradually
increased from 60.degree. C. to 120.degree. C.
[0556] Furthermore, NBDI used in this Example is a mixture of
2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane.
[0557] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 21.
Examples 3-2 to 3-8
[0558] The same operation as in Example 3-1 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 21. The composition and the
evaluation results of the obtained resin were presented in Table
21.
Comparative Example 3-1
[0559] 100 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, was charged into a glass beaker at 60.degree. C.,
filtered through a Teflon (trade name) filter without addition of a
polymerization catalyst, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 1.3 kPa or less.
The degassed polymerizable composition was injected into a mold
formed by a glass mold and a tape, and placed in a heating oven to
perform polymerization for 20 hours. During the polymerization, the
inner temperature of the oven was gradually increased from
70.degree. C. to 120.degree. C.
[0560] The molded piece of the obtained resin had good transparency
and good appearance with no strain, but was yellowed. The
evaluation results of the obtained resin are presented in Table
21.
TABLE-US-00021 TABLE 21 Composition (parts by weight) Ratio of
Compound functional Evaluation Items represented groups (SH
Refractive by General thiol isocyanate groups/NCO index Heat
Formula (1) compound compound groups) (ne) resistance Strength
Color Appearance Example 3-1 No1-1 (80) A NBDI (8) 3/2 1.761
.smallcircle. .smallcircle. 10 Transparent, (12) no strain Example
3-2 No1-1 (80) B NBDI (9) 3/2 1.753 .smallcircle. .smallcircle. 8
Transparent, (11) no strain Example 3-3 No1-1 (80) C NBDI (8) 3/2
1.759 .smallcircle. .smallcircle. 9 Transparent, (12) no strain
Example 3-4 No1-1 (90) A (4) B NBDI (4) 3/2 1.775 .smallcircle.
.smallcircle. 15 Transparent, (2) no strain Example 3-5 No1-1 (90)
A (2) B NBDI (4) 3/2 1.776 .smallcircle. .smallcircle. 14
Transparent, (4) no strain Example 3-6 No1-1 (80) A (7) B NBDI (9)
3/2 1.755 .smallcircle. .smallcircle. 9 Transparent, (4) no strain
Example 3-7 No1-1 (75) A NBDI (10) 3/2 1.751 .smallcircle.
.smallcircle. 12 Transparent, (15) no strain Example 3-8 No1-1 (75)
A (6) B NBDI (10) 3/2 1.755 .smallcircle. .smallcircle. 8
Transparent, (9) no strain Comparative No1-1 (100) 1.797
.smallcircle. x 37 Transparent, Example 3-1 no strain
[0561] Furthermore, in Table 21, the following abbreviations were
used.
[0562] A: 3-Mercaptothietane
[0563] B: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0564] C: 2,5-Bis(mercaptomethyl)-1,4-dithiane
[0565] NBDI: Bis(isocyanatomethyl)bicyclo[2.2.1]heptane (a mixture
of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane).
[0566] The physical properties of the resin and the optical parts
(lens) prepared in the following Examples (Examples 4-1 to 4-8) and
Comparative Examples were tested in accordance with the following
methods.
[0567] Appearance: Transparency and presence or absence of optical
strain were investigated with naked eyes, and with microscopy.
[0568] Refractive Index: Refractive index was measured with the use
of a Pulfrich refractometer at 20.degree. C.
[0569] Heat Resistance: Tg was measured by a TMA penetration
method. The case where Tg was 80.degree. C. or higher evaluated as
"o", and the case where Tg was lower than 80.degree. C. evaluated
as "x".
[0570] Strength: A steel ball was dropped on a lens having a
central thickness of 1.3 mm. Specifically, 8 g of the steel ball
was dropped on a lens from a height of 127 cm. The lens that was
not scattered was evaluated as "o", and the lens that was scattered
or penetrated with the steel ball was evaluated as "x".
[0571] Color: Yellow index (YI) of a flat plate having a thickness
of 2 mm was measured in accordance with ASTM D1925 using a
Gretagmacbeth spectrophotometer CE-7000 A.
Example 4-1
[0572] 85 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, 6 parts by weight of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (thiol compound A)
as a thiol compound, and 9 parts by weight of cyclohexanedimethanol
diglycidyl ether(CHDMDG) as an epoxy compound were charged into a
glass beaker at 40.degree. C. The mixture was filtered through a
Teflon (trade name) filter without addition of a polymerization
catalyst, and then sufficiently degassed until all bubbling had
ceased under a reduced pressure of 1.3 kPa or less. The degassed
polymerizable composition was injected into a mold formed by a
glass mold and a tape, and placed in a heating oven to perform
polymerization for 20 hours. During the polymerization, the inner
temperature of the oven was gradually increased from 60.degree. C.
to 120.degree. C.
[0573] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 22.
Examples 4-2 to 4-8
[0574] The same operation as in Example 4-1 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 22. The composition and the
evaluation results of the obtained resin are presented in Table
22.
Comparative Example 4-1
[0575] 100 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, was charged into a glass beaker at 60.degree. C.,
filtered through a Teflon (trade name) filter without addition of a
polymerization catalyst, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 1.3 kPa or less.
The degassed polymerizable composition was injected into a mold
formed by a glass mold and a tape, and placed in a heating oven to
perform polymerization for 20 hours. During the polymerization, the
inner temperature of the oven was gradually increased from
70.degree. C. to 120.degree. C.
[0576] The molded piece of the obtained resin had good transparency
and good appearance with no strain, but was yellowed. The
evaluation results of the obtained resin are presented in Table
22.
TABLE-US-00022 TABLE 22 Composition (parts by weight) Ratio of
Compound functional Evaluation Items represented groups (SH
Refractive by General Thiol Epoxy groups/epoxy index Heat Formula
(1) compound compound groups) (ne) resistance Strength Color
Appearance Example 4-1 No1-1 (85) A (6) CHDMDG (9) 1/1 1.754
.smallcircle. .smallcircle. 12 Transparent, no strain Example 4-2
No1-1 (80) A (12) CHDMDG (8) 2/1 1.750 .smallcircle. .smallcircle.
10 Transparent, no strain Example 4-3 No1-1 (80) A (11) DGBF (9)
2/1 1.761 .smallcircle. .smallcircle. 11 Transparent, no strain
Example 4-4 No1-1 (80) B (11) DGBF (9) 2/1 1.760 .smallcircle.
.smallcircle. 11 Transparent, no strain Example 4-5 No1-1 (80) A
(10) DGBA (10) 2/1 1.755 .smallcircle. .smallcircle. 12
Transparent, no strain Example 4-6 No1-1 (80) B (12) DGBF (8) 5/2
1.762 .smallcircle. .smallcircle. 10 Transparent, no strain Example
4-7 No1-1 (80) C (10) CHDMDG (10) 2/1 1.758 .smallcircle.
.smallcircle. 11 Transparent, no strain Example 4-8 No1-1 (80) A
(5), B DGBF (10) 2/1 1.760 .smallcircle. .smallcircle. 11
Transparent, (5) no strain Comparative No1-1 (100) 1.797
.smallcircle. x 37 Transparent, Example 4-1 no strain
[0577] Furthermore, in Table 22, the following abbreviations were
used.
[0578] A: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0579] B:
4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
[0580] C: Mercaptoethyl sulfide
[0581] CHDMDG: Cyclohexanedimethanol diglycidyl ether
[0582] DGBF: Bisphenol F/diglycidyl ether
[0583] DGBA: Bisphenol A/diglycidyl ether
[0584] The physical properties (refractive index, Abbe's number),
heat resistance, color, and mechanical properties of the resin
prepared in the following Examples (Examples 4-9 to 4-11) and
Comparative Examples were tested in accordance with the following
methods.
[0585] Refractive Index (ne) and Abbe's Number (ye): Refractive
index and Abbe's number were respectively measured with the use of
a Pulfrich refractometer at 20.degree. C.
[0586] Heat Resistance: Tg (.degree. C.) by a TMA penetration
method (50 g load, pin tip of 0.5 mm.phi., rate of temperature
increase of 10.degree. C./min) was determined as the heat
resistance.
[0587] Color: The YI, a*, and b* values of the resin made into a
flat plate having a thickness of 5 mm was measured by using a
Colorimeter (CR-200) manufactured by Minolta Co., Ltd.
[0588] 3-Point bending test: 3-Point bending strength was measured
by using Autograph AGS-J manufactured by Shimadzu Corporation.
Example 4-9
[0589] 75 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, 12.5 parts by weight of 3-mercaptothietane (thiol
compound A) as a thiol compound, and 12.5 parts by weight of
bis(2,3-epithiopropyl)disulfide as an episulfide compound were
heated, mixed, and dissolved at 75.degree. C. Then, the mixture was
filtered through a PTFA filter, and then sufficiently degassed
until all bubbling had ceased under a reduced pressure of 3.9 kPa
or less. Subsequently, the degassed polymerizable composition was
injected into a mold formed by a glass mold and a tape, and placed
in a heating oven to perform polymerization for 46 hours. During
the polymerization, the inner temperature of the oven was gradually
increased from 70.degree. C. to 130.degree. C.
[0590] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 23.
Examples 4-10 to 4-12
[0591] The same operation as in Example 4-9 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 23. The composition and the
evaluation results of the obtained resin are presented in Table
23.
Comparative Example 4-2
[0592] 100 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, was heated, mixed, dissolved at 85.degree. C., filtered
through a PTFA filter, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 3.9 kPa or less.
Subsequently, the degassed polymerizable composition was injected
into a mold formed by a glass mold and a tape, and placed in a
heating oven to perform polymerization for 22 hours. During the
polymerization, the inner temperature of the oven was gradually
increased from 85.degree. C. to 130.degree. C.
[0593] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 23.
TABLE-US-00023 TABLE 23 Composition (parts by weight) Evaluation
Items Ratio of 3-Point functional bending test groups Heat
resistance Strain Compound (SH Optical Distortion at max.
represented groups/ properties beginning point Max. by General
thiol episulfide episulfide Refractive Abbe's Tg temperature Resin
color (N/ shift Formula (1) compound compound groups) index Number
(.degree. C.) (.degree. C.) YI a* b* mm.sup.2) (mm) Example 4-9
No1-1 (75) D (12.5) ETDS (12.5) 1/1 1.775 26.9 116.9 94.2 25.5
-5.59 15.72 145.3 2.48 Example No1-1 (75) A (12.5) ETDS (12.5)
1.2/1 1.773 27.2 90.0 71.8 19.4 -3.97 11.54 151.0 2.55 4-10 Example
No1-1 (75) B (12.5) ETDS (12.5) 1.1/1 1.773 27.0 94.7 75.2 20.0
-4.10 11.89 125.0 2.09 4-11 Example No1-1 (86) D (7) ETDS (7) 1/1
1.785 25.7 142.7 125.1 28.7 -6.16 17.86 83.2 1.30 4-12 Comparative
No1-1 (100) 1.802 24.1 171.2 155.2 77.8 -15.04 61.19 33.8 0.29
Example 4-2
[0594] Furthermore, in Table 23, the following abbreviations were
used.
[0595] A: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0596] B:
4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
[0597] D: 3-Mercaptothietane
[0598] ETDS: Bis(2,3-epithiopropyl)disulfide
[0599] The physical properties (refractive index, Abbe's number),
heat resistance, color, and mechanical properties of the resin
prepared in the following Examples and Comparative Examples were
tested in accordance with the following methods.
[0600] Refractive Index (ne) and Abbe's Number (.nu.e): Refractive
index and Abbe's number were respectively measured with the use of
a Pulfrich refractometer at 20.degree. C.
[0601] Heat Resistance: Tg (.degree. C.) by a TMA penetration
method (50 g load, pin tip of 0.5 mm.phi., rate of temperature
increase of 10.degree. C./min) was determined as the heat
resistance.
[0602] Color: The YI, a*, and b* values of the resin made into a
flat plate having a thickness of 5 mm was measured by using a
Colorimeter (CR-200) manufactured by Minolta Co., Ltd.
[0603] 3-Point bending test: 3-Point bending strength was measured
by using Autograph AGS-J manufactured by Shimadzu Corporation.
Example 5-1
[0604] 85 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, 7.5 parts by weight of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (thiol compound A)
as a thiol compound, and 7.5 parts by weight of bis(3-thietanyl)
disulfide as a thietane compound containing no metal were heated,
mixed, and dissolved at 75.degree. C. Then, the mixture was
filtered through a PTFA filter, and then sufficiently degassed
until all bubbling had ceased under a reduced pressure of 3.9 kPa
or less. Subsequently, the degassed polymerizable composition was
injected into a mold formed by a glass mold and a tape, and placed
in a heating oven to perform polymerization for 46 hours. During
the polymerization, the inner temperature of the oven was gradually
increased from 70.degree. C. to 130.degree. C.
[0605] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 24.
Examples 5-2 to 5-3
[0606] The same operation as in Example 5-1 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 24. The composition and the
evaluation results of the obtained resin are presented in Table
24.
Comparative Example 5-1
[0607] 100 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, was heated, mixed, dissolved at 85.degree. C., filtered
through a PTFA filter, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 3.9 kPa or less.
Subsequently, the degassed polymerizable composition was injected
into a mold formed by a glass mold and a tape, and placed in a
heating oven to perform polymerization for 22 hours. During the
polymerization, the inner temperature of the oven was gradually
increased from 85.degree. C. to 130.degree. C.
[0608] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 24.
TABLE-US-00024 TABLE 24 Composition (parts by weight) Evaluation
Items Ratio of 3-Point functional bending test groups Heat
resistance Strain Compound thietane (SH Optical Distortion at max.
represented compound groups/ properties beginning point Max. by
General thiol containing episulfide Refractive Abbe's Tg
temperature Resin color (N/ shift Formula (1) compound no metal
groups) index Number (.degree. C.) (.degree. C.) YI a* b* mm.sup.2)
(mm) Example5-1 No1-1 (85) A (7.5) TES (7.5) 1.2/1 1.784 26.1 123.0
101.2 23.2 -3.91 13.37 77.5 0.85 Example5-2 No1-1 (85) A (10) TES
(5) 2.4/1 1.782 26.2 113.2 95.3 19.4 -3.16 11.01 62.2 0.78
Example5-3 No1-1 (85) B (7.5) TES (7.5) 1.1/1 1.785 26.1 131.6
109.9 24.8 -4.47 14.51 77.6 0.87 Comparative No1-1 (100) 1.802 24.1
171.2 155.2 77.8 -15.04 61.19 33.8 0.29 Example5-1
[0609] Furthermore, in Table 24, the following abbreviations were
used.
[0610] A: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0611] B:
4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
[0612] TES: Bis(3-thietanyl)disulfide
[0613] The physical properties (refractive index, Abbe's number),
heat resistance, color, and mechanical properties of the resin
prepared in the following Examples and Comparative Examples were
tested in accordance with the following methods.
[0614] Refractive Index (ne) and Abbe's Number (.nu.e): Refractive
index and Abbe's number were respectively measured with the use of
a Pulfrich refractometer at 20.degree. C.
[0615] Heat Resistance: Tg (.degree. C.) by a TMA penetration
method (50 g load, pin tip of 0.5 mm.phi., rate of temperature
increase of 10.degree. C./min) was determined as the heat
resistance.
[0616] Color: The YI, a*, and b* values of the resin made into a
flat plate having a thickness of 5 mm was measured by using a
Colorimeter (CR-200) manufactured by Minolta Co., Ltd.
[0617] 3-Point bending test: 3-Point bending strength was measured
by using Autograph AGS-J manufactured by Shimadzu Corporation.
Comparative Example 6-1
[0618] 100 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, heated, mixed, dissolved at 85.degree. C., filtered
through a PTFA filter, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 3.9 kPa or less.
Subsequently, the degassed polymerizable composition was injected
into a mold formed by a glass mold and a tape, and placed in a
heating oven to perform polymerization for 22 hours. During the
polymerization, the inner temperature of the oven was gradually
increased from 85.degree. C. to 130.degree. C.
[0619] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 25.
Example 6-1
[0620] 85 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, and 15 parts by weight of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (thiol compound A)
as a thiol compound were heated, mixed, and dissolved at 75.degree.
C. Then, the mixture was filtered through a PTFA filter, and then
sufficiently degassed until all bubbling had ceased under a reduced
pressure of 3.9 kPa or less. Subsequently, the degassed
polymerizable composition was injected into a mold formed by a
glass mold and a tape, and placed in a heating oven to perform
polymerization for 46 hours. During the polymerization, the inner
temperature of the oven was gradually increased from 70.degree. C.
to 130.degree. C.
[0621] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 25.
Examples 6-2 to 6-3
[0622] The same operation as in Example 6-1 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 25. The composition and the
evaluation results of the obtained resin are presented in Table
25.
TABLE-US-00025 TABLE 25 Evaluation Items 3-Point Composition (parts
by weight) Heat resistance bending test Compound Distortion Max.
represented Optical properties beginning strain Max. by General
Thiol Thiol refractive Abbe's Tg temperature Resin color (N/ shift
Formula (1) compound 1 compound 2 catalyst index Number (.degree.
C.) (.degree. C.) YI a* b* mm.sup.2) (mm) Comparative No1-1 (100)
-- -- -- 1.802 24.1 171.2 155.2 77.8 -15.04 61.19 33.8 0.29 Example
6-1 Example 6-1 No1-1 (85) A (15) -- -- 1.777 26.4 86.2 70.9 16.2
-3.03 9.28 41.8 0.60 Example 6-2 No1-1 (85) A (5) B (10) -- 1.780
26.5 113.1 93.5 17.2 -3.39 10.11 56.5 0.80 Example 6-3 No1-1 (85) A
(5) B (10) DCH 1.781 26.5 109.8 91.2 16.0 -3.03 9.29 73.7 0.96
[0623] Furthermore, in Table 25, the following abbreviations were
used.
[0624] No1-1: Tetrakis(3-thietanylthio)tin
[0625] A: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0626] B: 3-Mercaptothietane
[0627] DCH: Dicyclohexylmethylamine
Example 6-4
[0628] 87.4 parts by weight of the compound represented by CMPD.
No. 1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, and 8.7 parts by weight of sulfur were heated, and
molten at 85.degree. C. Subsequently, 3.9 parts by weight of
bis(2-mercaptoethyl)sulfide (thiol compound C) was added to the
mixture and mixed at 85.degree. C., and the mixture was filtered
through a PTFA filter, and then sufficiently degassed until all
bubbling had ceased under a reduced pressure of 3.9 kPa or less.
Subsequently, the degassed polymerizable composition was injected
into a mold formed by a glass mold and a tape, and placed in a
heating oven to perform polymerization for 22 hours. During the
polymerization, the inner temperature of the oven was gradually
increased from 70.degree. C. to 130.degree. C.
[0629] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 26.
Example 6-5
[0630] 91 parts by weight of the compound represented by CMPD. No.
1-1 in Table 1, that had been prepared in Reference Preparative
Example 2, and 9 parts by weight of sulfur were heated, and molten
at 85.degree. C. The mixture was filtered through a PTFA filter,
and then sufficiently degassed until all bubbling had ceased under
a reduced pressure of 3.9 kPa or less. Subsequently, the degassed
polymerizable composition was injected into a mold formed by a
glass mold and a tape, and placed in a heating oven to perform
polymerization for 22 hours. During the polymerization, the inner
temperature of the oven was gradually increased from 70.degree. C.
to 130.degree. C.
[0631] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 26.
TABLE-US-00026 TABLE 26 Evaluation Items Composition (parts by
weight) Heat resistance 3-Point bending Compound Distortion test
represented by Optical properties beginning Max. Max. General thiol
refractive Abbe's Tg temperature Resin color strain shift Formula
(1) Sulfur compound index Number (.degree. C.) (.degree. C.) YI a*
b* (N/mm.sup.2) (mm) Comparative No1-1 (100) -- -- 1.802 24.1 171.2
155.2 77.8 -15.04 61.19 33.8 0.29 Example 6-1 Example 6-4 No1-1
(87.4) (8.7) C (3.9) 1.813 23.5 141.4 121.1 85.2 -13.48 66.27 21.3
0.24 Example 6-5 No1-1 (91) (9) -- 1.822 22.3 158.1 143.9 111.2
0.11 84.02 -- --
[0632] Furthermore, in Table 26, the following abbreviations were
used.
[0633] No1-1: Tetrakis(3-thietanylthio)tin
[0634] C: Bis(2-mercaptoethyl)sulfide
Reference Preparative Example 3
[0635] 13.7 g (0.13 mole) of 3-mercaptothietane was introduced to
21 g of pure water, and then 16.5 g (0.13 mole) of a 31% NaOH
aqueous solution was introduced dropwise at room temperature over
45 minutes. Subsequently, 5.9 g (0.06 mole) of ethandithiol and
36.5 g of pure water were introduced to another reactor, and 16.5 g
(0.13 mole) of a 31% NaOH aqueous solution was introduced dropwise
at room temperature over 45 minutes. This solution of ethanedithiol
sodium and 58.9 g (corresponding to 0.06 mole of tin tetrachloride)
of an aqueous solution of 27.5% tin tetrachloride was added
dropwise to the previous the aqueous solution of a mercaptothietane
sodium salt at the same time over 1.5 hours. After the dropwise
addition was completed, the solution was further stirred at the
same temperature for 2 hours. The reaction mixture was filtered to
separate the solid out, to remove the water layer. The solid was
dissolved in 530 g of dichloromethane, washed with 100 g of pure
water three times, and filtered with a PTFE filter to remove the
insolubles. The solvent was distilled off from the extract to
obtain 24.8 g (yield 65%) of a compound represented by
bis(thietanylthio)dithiastannolane (Sn(EDT)(MTE).sub.2) (Compound
No. 1-71 in Table 4).
Example 6-6
[0636] 90 parts by weight of bis(thietanylthio)dithiastannolane
(Sn(EDT)(MTE).sub.2) that had been prepared in Reference
Preparative Example 3, and 10 parts by weight of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (thiol compound A)
as a thiol compound were mixed at room temperature. The mixture was
filtered through a PTFA filter, and then sufficiently degassed at
an oven at 50.degree. C., avoiding foaming, under a reduced
pressure of 3.9 kPa or less. Subsequently, the degassed
polymerizable composition was injected into a mold formed by a
glass mold and a tape, and placed in a heating oven to perform
polymerization for 18 hours. During the polymerization, the inner
temperature of the oven was gradually increased from 70.degree. C.
to 100.degree. C.
[0637] The molded piece of the obtained resin had good transparency
and good appearance with no strain. The evaluation results of the
obtained resin are presented in Table 27.
Examples 6-7 to 6-8
[0638] The same operation as in Example 6-6 was carried out, except
that the formulation of the polymerizable composition was changed
into the composition as shown in Table 27. The composition and the
evaluation results of the obtained resin are presented in Table
27.
TABLE-US-00027 TABLE 27 Evaluation Items Composition (parts by
weight) Heat resistance 3-Point bending Compound Distortion test
represented by Optical properties beginning Max. Max. General
Formula Thiol Episulfide refractive Abbe's Tg temperature Resin
color strain shift (1) compound compound index Number (.degree. C.)
(.degree. C.) YI a* b* (Nmm.sup.2) (mm) Comparative No1-1 (100) --
-- 1.802 24.1 171.2 155.2 77.8 -15.04 61.19 33.8 0.29 Example 6-1
Example 6-6 Sn(EDT) A (10) -- 1.781 25.5 40.4 33.6 34.6 -2.08 17.63
-- -- (MTE).sub.2 (90) Example 6-7 Sn(EDT) A (15) -- 1.787 26.0
38.7 33.1 -- -- -- -- -- (MTE).sub.2 (85) Example 6-8 Sn(EDT) A
(12.5) D (12.5) 1.785 25.4 54.4 47.0 23.0 -2.81 12.80 16.9 0.09
(MTE).sub.2 (75)
[0639] Furthermore, in Table 27, the following abbreviations were
used.
[0640] A: 3-Mercaptothietane
[0641] D: Bis(.beta.-epithiopropyl)disulfide
Reference Preparative Example 4
[0642] 8.0 g (0.075 mole) of 3-mercaptothietane was introduced to
12.0 g of pure water, and then 9.8 g (0.075 mole) of a 30% NaOH
aqueous solution was introduced dropwise at room temperature over
45 minutes. Subsequently, 57.9 g (corresponding to 0.025 mole
bismuth trichloride) of a 13.6% bismuth trichloride solution in
ethanol was inserted dropwise at the same temperature for 1.5
hours. After the dropwise addition was completed, the solution was
further stirred at the same temperature for 2 hours. This reaction
mixture was filtered to separate the solid out, and the solid was
dissolved in 500 g of dichloromethane, and filtered to removed the
insolubles. The organic layer was washed with 100 g of pure water
twice, and filtered with a PTFE filter to remove the insolubles.
The solvent was distilled off from the extract, and hexane was
introduced for filtration to obtain 10.6 g (yield 81%) of a
compound represented by the following Formula, denoted as
tris(mercaptothietanyl)bismuth.
##STR00140##
[0643] Hereinafter, the identification data of the compounds are
shown.
[0644] .sup.1H-NMR (solvent: DMSOd-6, Internal standard: TMS);
.sigma. 3.28 (12 H), .sigma. 5.77 (3H).
[0645] .sup.13C-NMR (solvent: DMSOd-6); .sigma. 41.5.
[0646] IR (Universal ATR method); 2919, 1410, 1196, 931
cm.sup.-1.
[0647] FDMS; m/e Calculated C.sub.9H.sub.15S.sub.6Bi (M.sup.+) 524,
Found 524.
Example 7-1
[0648] 75 parts by weight of tris(mercaptothietanyl)bismuth that
had been prepared in Reference Preparative Example 4, and 25 parts
by weight 3-mercaptothietane as a thiol compound were heated,
mixed, and dissolved at 85.degree. C. Then, the mixture was
sufficiently degassed until all bubbling had ceased under a reduced
pressure of 3.9 kPa or less. Subsequently, the degassed
polymerizable composition was injected into a mold formed by a
glass mold and a tape, and placed in a heating oven to perform
polymerization at 70.degree. C. for 46 hours.
[0649] The molded piece of the obtained resin had good transparency
and good appearance with no strain.
[0650] Also, the refractive index of the obtained resin was
measured, and the refractive index ne was found to be 1.855.
* * * * *