U.S. patent application number 09/918549 was filed with the patent office on 2002-02-14 for polymerizable composition.
Invention is credited to Kanemura, Yoshinobu, Kobayashi, Seiichi, Morijiri, Hiroyuki, Okazaki, Koju, Ryu, Akinori, Shimakawa, Chitoshi.
Application Number | 20020019511 09/918549 |
Document ID | / |
Family ID | 26368564 |
Filed Date | 2002-02-14 |
United States Patent
Application |
20020019511 |
Kind Code |
A1 |
Morijiri, Hiroyuki ; et
al. |
February 14, 2002 |
Polymerizable composition
Abstract
An optical resin prepared by curing a polymerizable composition
comprising a (thio)epoxy compound having at least one
intramolecular disulfide bond exhibits a considerably high
refractive index while maintaining good optical properties and a
high Abbe number. In addition, the above polymerizable composition
to which is added primary and/or secondary amines as an yellowing
inhibitor in a proportion of 0.001 to 0.5 of the total molar number
of NH.sub.2 and NH groups in the amines to the total molar number
of thioepoxy and epoxy groups in the (thio)epoxy compound having at
least one intramolecular disulfide bond, can provide a transparent
resin in which yellowing and reduction in heat resistance
associated therewith are adequately prevented while maintaining a
high refractive index.
Inventors: |
Morijiri, Hiroyuki;
(Fukuoka, JP) ; Kobayashi, Seiichi; (Fukuoka,
JP) ; Okazaki, Koju; (Fukuoka, JP) ;
Shimakawa, Chitoshi; (Fukuoka, JP) ; Ryu,
Akinori; (Fukuoka, JP) ; Kanemura, Yoshinobu;
(Fukuoka, JP) |
Correspondence
Address: |
BURNS DOANE SWECKER & MATHIS L L P
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Family ID: |
26368564 |
Appl. No.: |
09/918549 |
Filed: |
August 1, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09918549 |
Aug 1, 2001 |
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09745448 |
Dec 26, 2000 |
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6300464 |
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09745448 |
Dec 26, 2000 |
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09263483 |
Mar 8, 1999 |
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6204311 |
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Current U.S.
Class: |
528/373 ;
528/418 |
Current CPC
Class: |
C08G 75/08 20130101;
G02B 1/04 20130101; C08G 65/22 20130101; C07D 303/34 20130101; C08G
59/302 20130101; C07D 331/02 20130101; G02B 1/04 20130101; C08L
81/00 20130101 |
Class at
Publication: |
528/373 ;
528/418 |
International
Class: |
C08G 075/00; C08G
059/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 13, 1998 |
JP |
63402/1998 |
Feb 8, 1999 |
JP |
30246/1999 |
Claims
What is claimed is:
1. A polymerizable composition comprising a (thio)epoxy compound
having at least one intramolecular disulfide bond.
2. A polymerizable composition as claimed in claim 1 where the
(thio)epoxy compound having at least one intramolecular disulfide
bond is represented by formula (1): 3wherein X and Y are
independently oxygen or sulfur and may be different or the
same.
3. A polymerizable composition as claimed in claim 1 where the
(thio)epoxy compound having at least one intramolecular disulfide
bond is a compound having at least two 2,3-epithiopropyl groups in
its molecule.
4. A polymerizable composition as claimed in claim 1 comprising one
or more compounds selected from the group of compounds having at
least one NH.sub.2 group and/or at least one NH group per a
molecule as a yellowing inhibitor, having a total molar ratio of
0.001 to 0.5 of NH.sub.2 and NH groups in the inhibitor to
thioepoxy and epoxy groups in the (thio)epoxy compound comprising
at least one intramolecular disulfide bond.
5. A polymerizable composition as claimed in claim 4 where the
(thio)epoxy compound having at least one intramolecular disulfide
bond is represented by formula (1): 4wherein X and Y are
independently oxygen or sulfur and may be different or the
same.
6. A polymerizable composition as claimed in claim 4 where the
(thio)epoxy compound having at least one intramolecular disulfide
bond is a compound having at least two 2,3-epithiopropyl groups in
its molecule.
7. A resin prepared by curing a polymerizable composition
comprising a (thio)epoxy compound having at least one
intramolecular disulfide bond.
8. A resin as claimed in claim 7 where the (thio)epoxy compound
having at least one intramolecular disulfide bond is represented by
formula (1): 5wherein X and Y are independently oxygen or sulfur
and may be different or the same.
9. A resin as claimed in claim 7 where the (thio)epoxy compound
having at least one intramolecular disulfide bond is a compound
having at least two 2,3-epithiopropyl groups in its molecule.
10. A resin as claimed in claim 7 prepared by curing a
polymerizable composition comprising one or more compounds selected
from the group of compounds having at least one NH.sub.2 group
and/or at least one NH group per a molecule as a yellowing
inhibitor, having a total molar ratio of 0.001 to 0.5 of NH.sub.2
and NH groups in the inhibitor to thioepoxy and epoxy groups in the
(thio)epoxy compound comprising at least one intramolecular
disulfide bond.
11. A resin as claimed in claim 10 where the (thio)epoxy compound
having at least one intramolecular disulfide bond is represented by
formula (1): 6wherein X and Y are independently oxygen or sulfur
and may be different or the same.
12. A resin as claimed in claim 10 where the (thio)epoxy compound
having at least one intramolecular disulfide bond is a compound
having at least two 2,3-epithiopropyl groups in its molecule.
13. An optical device consisting of a resin prepared by curing a
polymerizable composition comprising a (thio)epoxy compound having
at least one intramolecular disulfide bond.
14. An optical device as claimed in claim 13 consisting of a resin
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is represented by formula (1): 7wherein X and Y are
independently oxygen or sulfur and may be different or the
same.
15. An optical device as claimed in claim 13 consisting of a resin
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is a compound having at least two 2,3-epithiopropyl
groups in its molecule.
16. An optical device as claimed in claim 13 consisting of a resin
prepared by curing a polymerizable composition comprising one or
more compounds selected from the group of compounds having at least
one NH.sub.2 group and/or at least one NH group per a molecule as a
yellowing inhibitor, having a total molar ratio of 0.001 to 0.5 of
NH.sub.2 and NH groups in the inhibitor to thioepoxy and epoxy
groups in the (thio)epoxy compound comprising at least one
intramolecular disulfide bond.
17. An optical device as claimed in claim 16 consisting of a resin
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is represented by formula (1): 8wherein X and Y are
independently oxygen or sulfur and may be different or the
same.
18. An optical device as claimed in claim 16 consisting of a resin
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is a compound having at least two intramolecular
2,3-epithiopropyl groups.
19. Use of an optical device as claimed in claim 13, as a plastic
lens.
20. Use of an optical device as claimed in claim 14, as a plastic
lens.
21. Use of an optical device as claimed in claim 15, as a plastic
lens.
22. Use of an optical device as claimed in claim 16, as a plastic
lens.
23. Use of an optical device as claimed in claim 17, as a plastic
lens.
24. Use of an optical device as claimed in claim 18, as a plastic
lens.
25. A process for manufacturing a resin comprising casting
polymerization of a polymerizable composition comprising a
(thio)epoxy compound having at least one intramolecular disulfide
bond.
26. A process for manufacturing a resin as claimed in claim 25
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is represented by formula (1): 9wherein X and Y are
independently oxygen or sulfur and may be different or the
same.
27. A process for manufacturing a resin as claimed in claim 25
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is a compound having at least two 2,3-epithiopropyl
groups in its molecule.
28. A process for manufacturing a resin as claimed in claim 25
comprising a polymerizable composition comprising one or more
compounds selected from the group of compounds having at least one
NH.sub.2 group and/or at least one NH group per a molecule as a
yellowing inhibitor, having a total molar ratio of 0.001 to 0.5 of
NH.sub.2 and NH groups in the inhibitor to thioepoxy and epoxy
groups in the (thio)epoxy compound comprising at least one
intramolecular disulfide bond.
29. A process for manufacturing a resin as claimed in claim 28
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is represented by formula (1): 10wherein X and Y are
independently oxygen or sulfur and may be different or the
same.
30. A process for manufacturing a resin as claimed in claim 28
where the (thio)epoxy compound having at least one intramolecular
disulfide bond is a compound having at least two 2,3-epithiopropyl
groups in its molecule.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to a (thio)epoxy compound suitably
used in the field of resins such as optical materials including
plastic lenses, prisms, optical fibers, information recording media
and light emitting diodes which are required to have a high
refractive index and a high transparency, as well as resins
therefrom.
[0003] This invention also relates to a polymerizable composition
suitably used as a starting material for a plastic lens for
eyeglasses.
[0004] 2. Description of the Related Art
[0005] A plastic lens is lighter and less brittle than an inorganic
lens, and dyeable, which has been therefore rapidly prevailing in
the areas of optical devices such as a lens of eyeglasses and a
camera lens. Such a plastic lens is required to exhibit optical
properties including a high refractive index and a high Abbe number
and physical properties including high heat resistance and a low
specific gravity.
[0006] Among these, high heat resistance and a low specific gravity
have been considerably achieved by a current plastic lens with a
high refractive index. Currently, the resins which may be widely
used for these applications, include those prepared by radical
polymerization of diethylene glycol bis(allylcarbonate) (referred
to as "D.A.C."). These resins have various features such as
excellent impact resistance, lightness, excellent dye-affinity, and
good processability including machinability and abradability. These
resins, however, have a low refractive index (nd) of about 1.50,
leading to a lens with thick center and margin. Thus, there is a
need for a resin for a lens with a higher refractive index.
[0007] Resins with a higher refractive index than D.A.C. resin are
known; for example, polythiourethane resins (e.g., JP-A 63-46213);
sulfur-containing O-(meth)acrylate resins (e.g., JP-A 1-128966,
3-217412 and 4-16141); and thio(meth)acrylate resins (e.g., JP-A
63-188660 and JP-B 3-59060), in which sulfur atoms are introduced.
A polythiourethane resin is well-balanced in its properties, that
is, having suitable properties such as a high refractive index and
good impact resistance.
[0008] A refractive index and an Abbe number are, however,
conflicting properties; as the refractive index increases, the Abbe
number decreases. It is, therefore, quite difficult to
simultaneously improve these properties. Thus, it has been
intensively investigated to achieve a high refractive index,
preventing an Abbe number from being decreased.
[0009] Most typical suggestions of these attempts are processes
using a (thio)epoxy compound as described in JP-As 9-110979,
9-71580 and 9-255781.
[0010] According to the processes, a high refractive index can be
achieved while maintaining a relatively high Abbe number. A resin
prepared according to these processes exhibits a refractive index
of nd=about 1.70. Thus, it cannot be considered to meet the need
for an improved refractive index sufficient to make a margin of an
eyeglass significantly thinner while maintaining a high Abbe
number, compared with a commercially available common lens with
nd=1.67. An thioepoxy resin prepared from an thioepoxy compound
tends to turn yellow during heating in a secondary process,
long-term storage or its use. Such yellowing may cause tone
alteration of an eyeglass which is required to be fashionable.
Thus, it may not meet the needs of routine users of eyeglasses. A
procedure for solving the problem has been suggested in, e.g., JP-A
10-298287, where a thiol compound is added to an thioepoxy compound
to prevent yellowing. Although such a process can prevent
yellowing, addition of a thiol compound, especially a mono- or
bis-functional thiol, may cause significant deterioration of heat
resistance, resulting in a lens which cannot give sufficient
properties for an application requiring higher heat resistance.
SUMMARY OF THE INVENTION
[0011] An objective of this invention is to provide a polymerizable
composition which can be used to prepare a resin having a very high
refractive index and a high transparency, specifically having nd of
1.71 or higher, maintaining a high Abbe number.
[0012] Another objective of this invention is to provide a
polymerizable composition which can give a resin maintaining a high
refractive index and a high heat resistance, and which can prevent
yellowing.
[0013] The inventors have intensely investigated to solve the above
problems and finally have found that a higher refractive index can
be provided by using a (thio)epoxy compound having at least one
intramolecular disulfide bond which has been believed to be
unstable (e.g., Reld. E. E., Organic Chemistry of Bivalent Sulfur
Vol.3).
[0014] Specifically, one aspect of this invention is a
polymerizable composition comprising a (thio)epoxy compound having
at least one intramolecular disulfide bond. We have found that the
polymerizable composition can be cured to give a resin with a high
refractive index of nd=1.71 or higher.
[0015] There have been no information for physical properties or
other characteristics of a polysulfide polymer prepared by curing a
polymerizable composition containing a (thio)epoxy compound
comprising at least one intramolecular disulfide bond.
[0016] The second aspect of this invention is a polymerizable
composition comprising one or more compounds selected from the
group of compounds having at least one NH.sub.2 group and/or at
least one NH group per a molecule as a yellowing inhibitor, having
a total molar ratio of 0.001 to 0.5 of NH.sub.2 and NH groups in
the inhibitor to thioepoxy and epoxy groups in the (thio)epoxy
compound comprising at least one intramolecular disulfide bond. We
have found that a resin from the second polymerizable composition
of this invention exhibits a high refractive index and a high Abbe
number without heat resistance reduction or yellowing.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] The first aspect of this invention will be described in
detail.
[0018] A polymerizable composition comprising a (thio)epoxy
compound having at least one intramolecular disulfide bond
according to the first aspect of this invention contains at least
one epoxy or thioepoxy compound having a disulfide bond and an
epoxy or thioepoxy group. The composition may contain inorganic
and/or organic compounds including polyether or polysulfide
oligomers such as dimers, trimers and tetramers thereof, inorganic
and organic acids added as a polymerization retarder, solvents or
other byproducts as long as they are not harmful.
[0019] In the specification, the term "(thio)epoxy" means thioepoxy
or epoxy. Thioepoxy is represented by the following structure:
1
[0020] A (thio)epoxy compound having at least one intramolecular
disulfide bond includes (thio)epoxy compound having one
intramolecular disulfide bond such as bis(2,3-epoxypropyl)disulfide
and bis(2,3-epithiopropyl)disu- lfide; (thio)epoxy compounds having
two or more intramolecular disulfide bond such as
bis(2,3-epithiopropyldithio)methane, bis(2,3-epithiopropyldi-
thio)ethane, bis(6,7-epithio-3,4-dithiaheptane)sulfide,
1,4-dithian-2,5-bis(2,3-epitiopropyldithiomethyl),
1,3-bis(2,3-epithiopropyldithiomethyl)benzene,
1,6-bis(2,3-epithiopropyld-
ithio)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane and
1,2,3-tris(2,3-epithiopropyldithio)propane. Among the compounds,
(thio)epoxy compounds having one intramolecular disulfide bond
represented by formula (1) are preferred. Besides the process
described in the document, bis(2,3-epithiopropyl)disulfide can be
prepared by reacting bis(2,3-epoxypropyl)disulfide with a
sulfurating agent such as a thiocyanate, thiourea,
triphenylphosphine sulfide and 3-methylbenzothiazol-2-thione,
preferably a thiocyanate and thiourea. 2
[0021] wherein X and Y are independently oxygen or sulfur and may
be different or the same.
[0022] A most preferred (thio)epoxy compound having at least one
intramolecular disulfide bond is
bis(2,3-epithiopropyl)disulfide.
[0023] The (thio)epoxy compound having at least one intramolecular
disulfide bond may be used to improve a refractive index of a resin
prepared by curing a polymerizable composition comprising the
(thio)epoxy compound.
[0024] A polymerizable composition comprising a (thio)epoxy
compound having at least one intramolecular disulfide bond
according to the first aspect of this invention may contain resin
modifiers for mainly improving resin properties, e.g., adjusting
optical properties such as a refractive index; and physical
properties such as impact resistance and a specific gravity, as
well as handling properties such as the viscosity of the
composition.
[0025] Resin modifiers which may be used include (thio)epoxy
compounds other than those contained in the (thio)epoxy compound
having at least one intramolecular disulfide bond according to the
first aspect of this invention, thiols, organic mercapto acids,
organic acids and acid anhydrides, amino acids, mercaptoamines,
amines and olefins including (meth)acrylates.
[0026] Specific examples of the thioepoxy compound as a modifier
are, but not limited to, linear aliphatic 2,3-epithiopropylthio
compounds such as bis(2,3-epithiopropyl)sulfide,
bis(2,3-epithiopropyl-thio)methane,
1,2-bis(2,3-epithiopropylthio)ethane,
1,2-bis(2,3-epithiopropylthio)propa- ne,
1,3-bis(2,3-epithiopropylthio)propane,
1,3-bis(2,3-epithiopropylthio)-- 2-methylpropane,
1,4-bis(2,3-epithiopropylthio)butane,
1,4-bis(2,3-epithiopropylthio)-2-methylbutane,
1,3-bis(2,3-epithiopropylt- hio)butane,
1,5-bis(2,3-epithio-propylthio)pentane,
1,5-bis(2,3-epithiopropyl-thio)-2-methylpentane,
1,5-bis(2,3-epithio-prop- ylthio)-3-thiapentane,
1,6-bis(2,3-epithio-propylthio)hexane,
1,6-bis(2,3-epithiopropyl-thio)-2-methylhexane,
1,8-bis(2,3-epithiopropyl- -thio)-3,6-dithiaoctane,
1,2,3-tris(2,3-epithio-propylthio)propane,
2,2-bis(2,3-epithiopropyl-thio)-1,3-bis(2,3-epithiopropylthiomethyl)propa-
ne,
2,2-bis(2,3-epithiopropylthiomethyl)-1-(2,3-epithiopropylthio)butane,
1,5-bis(2,3-epithiopropyl-thio)-2-(2,3-epithiopropylthiomethyl)-3-thia-pe-
ntane,
1,5-bis(2,3-epithiopropylthio)-2,4-bis(2,3-epithiopropylthiomethyl)-
-3-thiapentane,
1-(2,3-epithiopropylthio)-2,2-bis(2,3-epithio-propylthiome-
thyl)-4-thiahexane,
1,5,6-tris(2,3-epithiopropylthio)-4-(2,3-epithiopropyl-
thio-methyl)-3-thiahexane,
1,8-bis(2,3-epithiopropyl-thio)-4-(2,3-epithiop-
ropylthiomethyl)-3,6-dithia-octane,
1,8-bis(2,3-epithiopropylthio)-4,5-bis-
-(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,
1,8-bis(2,3-epithiopropyl-
thio)-4,4-bis(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,
1,8-bis-(2,3-epithiopropylthio)-2,5-bis(2,3-epithiopropylthiomethyl)-3,6--
dithiaoctane,
1,8-bis(2,3-epithiopropylthio)-2,4,5-tris(2,3-epithiopropylt-
hiomethyl)-3,6-dithiaoctane,
1,1,1-tris{[2-(2,3-epithiopropylthio)ethyl]th-
iomethyl}-2-(2,3-epithiopropylthio)ethane,
1,1,2,2-tetrakis{[2-(2,3-epithi-
opropylthio)ethyl]thiomethyl}ethane,
1,11-bis(2,3-epithiopropylthio)-4,8-b-
is(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-epithiop-
ropylthiomethyl)-3,6,9-trithiaundecane; 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-epithiopropylthiom- ethyl)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;
aromatic 2,3-epithiopropylthio compounds such as
1,2-bis(2,3-epithiopropylthio)ben- zene,
1,3-bis-(2,3-epithiopropylthio)benzene,
1,4-bis(2,3-epithiopropylthi- o)benzene,
1,2-bis(2,3-epithiopropylthiomethyl)benzene,
1,3-bis(2,3-epithiopropylthiomethyl)benzene,
1,4-bis(2,3-epithiopropylthi- omethyl)benzene,
bis[4-(2,3-epithiopropylthio)phenyl]methane,
2,2-bis[4-(2,3-epithiopropylthio)phenyl]propane,
bis[4-(2,3-epithiopropyl- thio)phenyl]sulfide,
bis[4-(2,3-epithiopropylthio)phenyl]sulfone and
4,4'-bis(2,3-epithiopropylthio)biphenyl; monofunctional epithio
compounds such as ethylene sulfide and propylene sulfide; and
epithio compounds comprising a mercapto group such as
3-mercaptopropylene sulfide and 4-mercaptobutene sulfide.
[0027] Specific epoxy compounds which may be used include, but are
not limited to, phenolic epoxy compounds prepared by condensation
of an epihalohydrin with a polyphenol including bisphenol-A
glycidyl ether; alcoholic epoxy compounds prepared by condensation
of an epihalohydrin with a polyalcohol including hydrogenated
bisphenol-A glycidyl ether; glycidyl ester epoxy compounds prepared
by condensation of an epihalohydrin with an organic polyacid
derivatives including
3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate and
diglycidyl 1,2-hexahydrophthalate; amino epoxy compounds prepared
by condensation of an epihalohydrin with a secondary amine; and
aliphatic polyepoxy compounds such as vinylcyclohexene
diepoxide.
[0028] Specific thiols which may be used include, but are not
limited to, aliphatic thiols such as methyl mercaptan, ethyl
mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol,
1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol,
1,2,3-trimercaptopropane, tetrakis(mercaptomethyl)methane,
1,2-dimercaptocyclohexane, bis(2-mercaptoethyl)sulfide,
2,3-dimercapto-1-propanol, ethyleneglycol
bis(3-mercaptopropionate), diethyleneglycol
bis(3-mercaptopropionate), diethyleneglycol
bis(2-mercaptoglycolate), pentaerythritol
tetrakis(2-mercaptothioglycolate), pentaerythritol
tetrakis(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptothioglycolate), trimethylolpropane
tris(3-mercaptopropiona- te), 1,1,1-trimethylmercaptoethane,
1,1,1-trimethylmercaptopropane, 2,5-dimercaptomethylthiophane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithia- octane,
2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis[(2-mercaptoethyl)thiome-
thyl]-1,4-dithiane, 1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and
aromatic thiols such as benzylthiol, thiophenol,
1,2-dimercaptobenzene, 1,3-dimercaptobenzene,
1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benz- ene,
1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene,
2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl,
bis(4-mercaptophenyl)me- thane, bis(4-mercaptophenyl)sulfide,
bis(4-mercaptophenyl)sulfone, 2,2-bis(4-mercaptophenyl)propane,
1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene and
1,2,5-trimercaptobenzene.
[0029] Organic mercapto acids which may be used include, but are
not limited to, thioglycolic acid, 3-mercaptopropionic acid,
thioacetic acid, thiolactic acid, thiomalic acid and thiosalicylic
acid. Organic acids and their anhydrides which may be used include,
but are not limited to, the above polymerization retarders as well
as thiodiglycolic acid, thiodipropionic acid, dithiodipropionic
acid, phthalic anhydride, hexahydrophthalic anhydride,
methylhexahydrophthalic anhydride, methyltetrahydrophthalic
anhydride, methylnorbornenoic anhydride, methylnorbornanoic
anhydride, maleic anhydride, trimellite anhydride and pyromellitic
dianhydride.
[0030] Olefins which may be used include, but are not limited to,
(meth)acrylates such as benzyl acrylate, benzyl methacrylate,
butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl
acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl
methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate,
phenyl methacrylate, 3-phenoxy-2-hydroxypropyl acrylate,
ethyleneglycol diacrylate, ethyleneglycol dimethacrylate,
diethyleneglycol diacrylate, diethyleneglycol dimethacrylate,
triethyleneglycol diacrylate, triethyleneglycol dimethacrylate,
tetraethyleneglycol diacrylate, tetraethyleneglycol direthacrylate,
polyethyleneglycol diacrylate, polyethyleneglycol dimethacrylate,
neopentylglycol diacrylate, neopentylglycol dimethacrylate,
ethyleneglycolbisglycidyl diacrylate, ethyleneglycolbisglycidyl
dimethacrylate, bisphenol-A diacrylate, bisphenol-A dimethacrylate,
2,2-bis(4-acryloxyethoxyphenyl)propane,
2,2-bis(4-methacryloxyethoxypheny- l)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-acryloxydiethoxyphe- nyl)methane,
1,1-bis(4-methacryloxydiethoxyphenyl)methane,
dimethyloltricyclodecane diacrylate, trimethylolpropane
triacrylate, trimethylolpropane trimethacrylate, glycerol
diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate,
methylthio acrylate, methylthio methacrylate, phenylthio acrylate,
benzylthio methacrylate, xylenedithiol diacrylate, xylenedithiol
dimethacrylate, mercaptoethylsulfide diacrylate and
mercaptoethylsulfide dimethacrylate; allyl compounds such as allyl
glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl
isophthalate, diallyl carbonate and diethyleneglycol-bisallyl
carbonate; vinyl compounds such as styrene, chlorostyrene,
methylstyrene, bromostyrene, dibromostyrene, divinylbenzene and
3,9-divinyl-spiro-bis(m-dioxane); and diisopropenylbenzene.
[0031] These resin modifiers may be used alone or in combination of
two or more thereof.
[0032] Curing catalysts which may be used in the first aspect of
this invention may be typically tertiary amines, phosphines, Lewis
acids, radical polymerization catalysts and cationic polymerization
catalysts.
[0033] The preferable curing catalysts include, but are not limited
to, 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-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-dimethylamino-methy- l)phenol; 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; Lewis acids such as dimethyltin
dichloride, dibutyltin dichloride, dibutyltin dilaurate,
tetrachlorotin, dibutyltin oxide, zinc chloride, zinc
acetylacetonate, aluminum chloride, aluminum fluoride,
triphenylaluminum, titanium tetrachloride and calcium acetate;
radical polymerization catalysts such as 2,2'-azobis(2-cycloprop-
ylpropionitrile), 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; and cationic polymerization catalysts such as
diphenyliodonium hexafluorophosphate, diphenyliodonium
hexafluoroarsenate, diphenyliodonium hexafluoroantimony,
triphenylsulfonium tetrafluoroborate, triphenylsulfonium
hexafluorophosphate and triphenylsulfonium hexafluoroarsenate.
[0034] These curing catalysts may be used alone or in combination
of two or more thereof.
[0035] A curing catalyst may be preferably added in a proportion of
0.001 to 10 wt %, more preferably 0.01 to 5 wt % to the total
amount of the polymerizable composition comprising a (thio)epoxy
compound. If the proportion is less than 0.001 wt %, polymerization
may be insufficient due to a too small effect of the catalyst. On
the other hand, the catalyst may be contained in a proportion of
more than 10 wt %, but it may cause problems such as a shorter pot
life and deterioration in transparency, optical properties or
weatherproof.
[0036] A typical polymerization process for preparing the resin
according to the first aspect of this invention (e.g., a plastic
lens) is casting polymerization. Specifically, a polymerizable
composition comprising a (thio)epoxy compound and a curing
catalyst, which may be also referred to as a monomer mixture, is
poured between molds held by a fixing means, such as a gasket and
tapes, during which some treatments such as defoaming may be, if
necessary, conducted.
[0037] Then, it may be subject to curing by heating in a heating
apparatus such as an oven or in water, and then a polymerization
product may be took out from the mold.
[0038] A polymerization method or polymerization conditions for
preparing a resin according to the first aspect of this invention
cannot be generalized since they depend on the amounts and types of
ingredients such as curing catalysts as well as types and
proportions of monomers.
[0039] Heat curing conditions for a polymerizable composition
according the first aspect of this invention poured into the mold
significantly vary depending on various factors such as a type of a
composition comprising a (thio)epoxy compound, a type of a curing
catalyst and the shape of the mold and therefore cannot be
specifically limited, but the composition may be typically cured at
-50 to 200.degree. C. for 1 to 100 hours. It may be cured keeping
or gradually raising a temperature within a range of 10.degree. C.
to 150.degree. C. for 1 to 80 hours, providing good results.
[0040] In addition, a composition comprising a (thio)epoxy compound
having at least one intramolecular disulfide bond, especially a
(thio)epoxy compound having an intramolecular disulfide bond, may
be cured in a reduced time by UV irradiation, where a curing
catalyst such as a radical polymerization catalyst may be
necessary.
[0041] For molding a resin according to the first aspect of this
invention, a variety of substances such as chain extenders,
crosslinking agents, photostabilizers, UV absorbents, antioxidants,
anti-coloring agents, dyes, fillers and internal mold release
agents, may be added, depending on a purpose, as in the known
molding methods.
[0042] The resin, which has been taken out from the mold, may be,
if necessary, annealed.
[0043] A resin obtained by curing a polymerizable composition
comprising a (thio)epoxy compound having at least one
intramolecular disulfide bond according to the first aspect of this
invention has a high refractive index, a reduced dispersibility and
a high thermal resistance, especially an extremely high refractive
index. It is a transparent resin having a refractive index of
preferably nd.gtoreq.1.71, more preferably nd.gtoreq.1.72, most
preferably nd.gtoreq.1.73. Furthermore, the resin of this invention
can be formed in various forms by altering a mold in the casting
polymerization, and be thus used as optical device materials for an
eyeglass lens, a camera lens and a light emitting diode (LED), as
well as a transparent resin for a variety of applications. In
particular, it is suitable for an optical device material for an
eyeglass lens and a camera lens.
[0044] Furthermore, a lens from the resin according to the first
aspect of this invention may be, if necessary, subject to physical
or chemical post-treatments such as surface abrasion, antistatic
treatment, hard coating, non-reflection coating and dyeing, for
improvements such as prevention of reflection; improvement in
hardness, abrasion resistance or chemical resistance; and
impartation of antifoggy or cosmetic property.
[0045] Next, the second aspect of this invention will be described
in detail.
[0046] JP-As 9-110979, 9-71580, 9-255781 and 10-298287 describing
thioepoxy resins list primary and secondary amines corresponding to
Compound (b) according to the second aspect of this invention as a
curing catalyst, but they have disclosed only hydrogenated
4,4'-diaminodiphenylmethane in their examples and comparative
examples. In our investigation, when hydrogenated
4,4'-diaminodiphenylmethane was used as a curing catalyst, a
reaction mixture became cloudy and lost transparency due to local
polymerization immediately after adding 4,4'-diaminodiphenylmethane
to an thioepoxy compound. In addition, polymerization could not be
completed even after heating and thus a satisfactory resin was not
obtained. Among the other amines listed except tertiary amines,
primary and secondary amines corresponding to a compound having an
amino group and/or an imino group of this invention did not exhibit
satisfactory effects as a curing catalyst, so that the
polymerization was not completed and a viscous liquid or a gummy
resin was provided. Thus, we have found that primary and secondary
amines can be used not as a curing catalyst for an thioepoxy resin,
but as an yellowing inhibitor which may prevent deterioration in
heat resistance.
[0047] In the second aspect of this invention, the composition has
a proportion of 0.001 to 0.5, preferably equal to or more 0.01 and
less than 0.3 of the total molar number of NH.sub.2 and NH groups
in the above primary and secondary amines (referred to as Compound
(b)) to the total molar number of thioepoxy and epoxy groups in a
(thio)epoxy compound having at least one intramolecular disulfide
bond (referred to as Compound (a)).
[0048] If the total molar ratio is more than 0.5, a resulting resin
after polymerization has reduced heat resistance and a lower
refractive index. If the ratio is less than 0.001, yellowing cannot
be adequately prevented as intended in the second aspect of this
invention.
[0049] A polymerizable composition according to the second aspect
of this invention comprises Compounds (a) and (b), and may contain
inorganic and/or organic compounds including polyether or
polysulfide oligomers such as dimers, trimers and tetramers
thereof, inorganic and organic acids added as a polymerization
retarder, solvents or other byproducts as long as they are not
harmful.
[0050] A polymerizable composition according to the second aspect
of this invention may contain resin modifiers for mainly improving
resin properties, e.g., adjusting optical properties such as a
refractive index; and physical properties such as impact resistance
and a specific gravity, as well as improving handling properties as
the viscosity of the composition.
[0051] Resin modifiers which may be used are as described
above.
[0052] Preferable examples of Compound (b) in the second aspect of
this invention are, but not limited to,
[0053] (1) monofunctional primary amines such as ethylamine,
n-propylamine, isopropylamine, n-butylamine, sec-butylamine,
tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine,
decylamine, laurylamine, myristylamine, 3-pentylamine,
2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine,
aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine,
2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline,
benzylamine, phenethylamine, 2-, 3- or 4-methylbenzylamine, o-, m-
or p-methylaniline, o-, m- or p-ethylaniline, aminomorpholine,
naphthylamine, furfurylamine, .alpha.-aminodiphenylmetha- ne,
toluidine, aminopyridine, aminophenol, aminoethanol,
1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol,
aminohexanol, methoxyethylamine, 2-(2-aminoethoxy)ethanol,
3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine,
3-isopropoxypropylamine, 3-isobutoxypropylamine and
2,2-diethoxyethylamine; and primary polyamines such as
ethylenediamine, 1,2- or 1,3-diaminopropane, 1,2-, 1,3- or
1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-,
1,3- or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4- or
4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'- or
4,4'-diaminodiphenyl sulfone, 2,7-diaminofluorene, 1,5-, 1,8- or
2,3-diaminonaphthalene, 2,3-, 2,6- or 3,4-diaminopyridine, 2,4- or
2,6-diaminotoluene, m- or p-xylylenediamine, isophoronediamine,
diaminomethylbicycloheptane, 1,3- or 1,4-diaminomethylcyclohexane,
2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or
4-aminoethylpiperidine, N-aminoethylmorpholine and
N-aminopropylmorpholine;
[0054] (2) monofunctional secondary amines such as diethylamine,
dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine,
di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine,
di(2-ethylhexyl)amine, methylhexylamine, diallylamine,
N-methylallylamine, piperidine, pyrrolidine, diphenylamine,
N-methylphenylamine, N-ethylphenylamine, dibenzylamine,
N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine,
N-methylaniline, N-ethylaniline, dinaphthylamine,
1-methylpiperazine and morpholine; and secondary polyamines such as
N,N'-dimethylethylenediamine- , N,N'-dimethyl-1,2-diaminopropane,
N,N'-dimethyl-1,3-diaminopropane, N,N'-dimethyl-1,2-diaminobutane,
N,N'-dimethyl-1,3-diaminobutane, N,N'-dimethyl-1,4-diaminobutane,
N,N'-dimethyl-1,5-diaminopentane, N,N'-dimethyl-1,6-diaminohexane,
N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine,
N,N'-diethyl-1,2-diaminopropane, N,N'-diethyl-1,3-diaminopropane,
N,N'-diethyl-1,2-diaminobutane, N,N'-diethyl-1,3-diaminobutane,
N,N'-diethyl-1,4-diaminobutane, N,N'-diethyl-1,5-diaminopentane,
N,N'-diethyl-1,6-diaminohexane, N,N'-diethyl-1,7-diaminoheptane,
piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine,
2,6-dimethylpiperazine, homopiperazine,
1,1-di-(4-piperidyl)methane, 1,2-di-(4-piperidyl)ethane,
1,3-di-(4-piperidyl)propane, 1,4-di-(4-piperidyl)butane and
tetramethylguanidine. These may be used alone or in combination of
two or more thereof. More preferable compounds are benzylamine and
piperazines.
[0055] A polymerizable composition according to the second aspect
of this invention may be cured by heating or being left at an
ambient temperature in the presence or absence of a curing
catalyst, to provide a resin. It may be preferable to use a curing
catalyst since curing may not proceed adequately or at all in the
absence of the catalyst. Typical curing catalysts which may be used
for the second aspect of this invention include amines other than
Compound (b) in the second aspect of this invention, phosphines,
Lewis acids, radical polymerization catalysts and cation
polymerization catalysts as described in terms of the first aspect
of this invention.
[0056] A curing catalyst may be preferably added in a proportion of
0.001 to 10 wt %, more preferably 0.01 to 1 wt % to the total
amount of the polymerizable composition comprising Compound (a)
having an epoxy or thioepoxy group. If its proportion is less than
0.001 wt %, polymerization may be insufficient due to a too small
effect of the catalyst. On the other hand, the catalyst may be
contained in a proportion of more than 10 wt %, but it may cause
problems such as a shorter pot life and deterioration in
transparency, optical properties or weatherproof.
[0057] A typical polymerization process for preparing the resin
according to the second aspect of this invention (e.g., a plastic
lens) is casting polymerization. Specifically, a polymerizable
composition according to the second aspect of this invention, after
mixing, if necessary, with a curing catalyst and/or a resin
modifier, is poured between molds held by a fixing means such as a
gasket and tapes. Before or after pouring, some treatments such as
defoaming may be, if necessary, conducted.
[0058] Then, it may be subject to curing by heating in a heating
apparatus such as an oven or in water, and then a polymerization
product may be took out from the mold.
[0059] A polymerization method and polymerization conditions for
preparing a resin according to the second aspect of this invention
cannot be generalized since they depend on the amounts and types of
ingredients such as curing catalysts as well as types and
proportions of monomers.
[0060] Heat curing conditions for a polymerizable composition
according the second aspect of this invention poured into the mold
significantly vary depending on various factors such as Compounds
(a) and (b) in the second aspect of this invention, a type of a
resin modifier, a type of a curing catalyst and the shape of the
mold and therefore cannot be specifically limited, but the
composition may be typically cured at -50 to 200.degree. C. for 1
to 100 hours.
[0061] It may be cured keeping or gradually raising a temperature
within a range of 10.degree. C. to 150.degree. C. for 1 to 80
hours, providing good results.
[0062] In addition, the polymerizable composition according to the
second aspect of this invention may be cured in a reduced time by
UV irradiation, where a curing catalyst such as a radical
polymerization catalyst may be added.
[0063] For molding a resin according to the second aspect of this
invention, a variety of substances such as chain extenders,
crosslinking agents, photostabilizers, UV absorbents, antioxidants,
anti-coloring agents other than those in the second aspect of this
invention, dyes, fillers, internal and external mold release
agents, internal and external adherence improver and compounds
having a hydroxy group as a dye-affinity improver may be added,
depending on a purpose, as in the known molding methods.
[0064] The resin, which has been took out from the mold, may be, if
necessary, annealed. Furthermore, the resin of the second aspect of
this invention can be formed in various forms by altering a mold in
the casting polymerization, and be thus used as an optical material
for an eyeglass lens, a camera lens and a light emitting diode
(LED), as well as a transparent resin for a variety of
applications. In particular, it is suitable for an optical material
for an eyeglass lens and a camera lens.
[0065] Furthermore, a lens from the optical material according to
the second aspect of this invention may be, if necessary, subject
to physical or chemical post-treatments such as surface abrasion,
antistatic treatment, hard coating, non-reflection coating and
dyeing, for improvements such as prevention of reflection;
improvement in hardness, abrasion resistance or chemical
resistance; and impartation of antifoggy or cosmetic property.
[0066] This invention will be specifically described by the
following examples and preparation examples. The properties
relevant to performance of a resin obtained, that is, a refractive
index, an Abbe number, a specific gravity and heat resistance were
evaluated as follows.
[0067] (1) A refractive index (nd) and Abbe number (.nu.d):
measured at 20.degree. C. using a Pulfrich refractometer.
[0068] (2) Specific gravity: measured by Archimedes' method.
[0069] (3) Heat resistance: Tg was measured by TMA penetration
method (load: 50 g, pinpoint: 0.5 mm.PHI., temperature-programming
rate: 10.degree. C./min.).
Preparation Example 1
Bis(2,3-epoxypropyl)disulfide
[0070] In a reaction flask equipped with an agitator, a
thermometer, a gas cylinder and a condenser were placed 190 g of
epichlorohydrin (2 mol), 500 mL of methanol and 1.0 g of calcium
hydroxide. Keeping the internal temperature at 0 to 5.degree. C.,
into the reaction system was introduced 75 g of hydrogen sulfide
gas (2.2 mol) from the gas cylinder, and then the reaction was
matured at 5.degree. C. for 3 hours.
[0071] After filtration of the reaction mixture and evaporation of
methanol, the residue was distilled to give chloromercaptopropanol
with a purity of 99%. In a reaction vessel were placed the
chloromercaptopropanol, 1000 mL of purified water and 168 g of
sodium hydrogen carbonate (2 mol). Keeping the internal temperature
at 5 to 10.degree. C., to the mixture was added portionwise 254 g
of solid iodine (1 mol) over 1 hour, and then the reaction mixture
was aged at 10.degree. C. for 12 hours. After aging, the reaction
mixture was filtered to give white crystals, which were then dried
in vacuo.
[0072] The dried white crystals, 250 mL of methanol and 500 mL of
toluene were placed in a reaction vessel. Keeping the internal
temperature at 3 to 5.degree. C., 240 g of 47 wt % sodium hydroxide
(2.8 mol) was added dropwise over 1 hour, and the reaction mixture
was aged for 30 min. After completion of the reaction, 100 mL of
toluene was added. The organic layer was washed with water three
times, dried over anhydrous magnesium sulfate and filtered. The
filtrate was evaporated.
[0073] The residue was filtered to give 171 g of
bis(2,3-epoxypropyl)disul- fide (referred to as Compound (A)) with
a purity of 96 wt % (yield after calculation based on the purity:
92%). Its elemental analysis results are shown below.
1 C H O S Measured (%) 39.0 5.4 18.5 37.1 Calculated (%) 40.4 5.7
17.9 36.0
Preparation Example 2
Bis(2,3-epithiopropyl)disulfide (Procedure 1)
[0074] In a reaction flask equipped with an agitator, a thermometer
and a condenser were placed 100 g of Compound (A) prepared as
described in Preparation Example 1 with a purity of 96 wt % (0.54
mol), 100 g of thiourea (1.3 mol), 2 g of acetic acid, 250 mL of
toluene and 200 mL of methanol. Keeping the internal temperature at
15.degree. C., the mixture was stirred for 16 hours.
[0075] After completion of the reaction and then adding 150 mL of
toluene, the mixture was sequentially washed with sodium chloride
aq., 1% sulfuric acid and again sodium chloride aq. The organic
layer was dried over anhydrous magnesium sulfate, filtered and
evaporated. The residue was dissolved in 600 mL of acetonitrile and
the supernatant was filtered. The filtrate was evaporated to give a
residue, which was then filtered to give 77.5 g of composition of a
thioepoxy compound comprising bis(2,3-epithiopropyl) disulfide
(referred to as Compound (B)) in 85 wt % (yield after calculation
based on the purity: 58%). Its elemental analysis results are shown
below.
2 C H S Measured (%) 32.6 4.6 62.8 Calculated (%) 34.2 4.8 61.0
Preparation Example 3
Compound (B)(Procedure 2)
[0076] In a reaction flask equipped with an agitator, a thermometer
and a condenser were placed 100 g of 2,3-dimercaptopropan-1-ol (0.8
mol) and 450 mL of dichloromethane. Keeping the internal
temperature at 0.degree. C., to the stirred mixture was added
dropwise 73 g of phosphorous tribromide (0.27 mol) using a dropping
funnel over 1 hour, and then the reaction mixture was aged for 1
hour. After aging, to the mixture were added 134.4 g of sodium
hydrogen carbonate (1.6 mol) and 1000 mL of water. The organic
layer was washed with an alkaline solution, neutralized with 35%
hydrochloric acid and evaporated. The residue was distilled and 50
g of fraction was collected at 26.degree. C./0.2 mmHg. The
collected product was 3-mercapto-1,2-propylene sulfide with a
purity of 99 wt % (yield after calculated based on the purity:
59%).
[0077] In a reaction vessel were placed 53 g of the distillation
fraction (0.5 mol), 250 mL of toluene, 250 mL of methanol and 84 g
of potassium iodide (0.5 mol). Keeping the internal temperature at
-20.degree. C., to the mixture was added portionwise 127 g of solid
iodine (0.5 mol) over 1 hour, and the reaction mixture was aged for
6 hours. The mixture was worked up as described in Preparation
Example 2 to give a composition of a thioepoxy compound comprising
Compound (B) in 81 wt % after evaporation. Its elemental analysis
results are shown below.
3 C H S Measured (%) 32.6 4.8 62.8 Calculated (%) 34.2 4.8 61.0
Purification Example 1
[0078] The crude thioepoxy compound with a purity of 85 wt %
prepared as described in Preparation Example 2 (50 g) was purified
by silica gel chromatography to provide 38 g of polymerizable
composition comprising Compound (B) with a purity of 94 wt %.
EXAMPLE 1
[0079] To 50 g of the composition of the thioepoxy compound with a
purity of 85 wt % prepared as described in Preparation Example 2
was added 0.1 g of N,N-dimethylcyclohexylamine. After defoaming for
0.4 hours under a reduced pressure, the mixture was poured into a
mold template consisting of glass molds and a gasket. The mold was
gradually warmed from 0.degree. C. to 120.degree. C. and at the
temperature the mixture was polymerized for 24 hours. After
completion of the polymerization, the mold was gradually cooled and
the molding was took out from the mold. The physical properties of
the molding (lens) are shown in Table 1.
EXAMPLE 2
[0080] Compound (B) with a purity of 94 wt % prepared as described
in Purification Example 1 (30 g) was tested as described in Example
1. The physical properties of the molding (lens) are shown in Table
1.
EXAMPLE 3
[0081] Compound (B) with a purity of 94 wt % prepared as described
in Purification Example 1 (30 g) was tested as described in Example
1 except that 1.5 g of bis(2-mercaptoethyl)sulfide (referred to as
Compound (C)) was added to Compound (B) and
N,N-dimethylcyclohexylamine was replaced with 0.06 g of
N,N-dimethylbenzylamine. The physical properties of the molding
(lens) are shown in Table 1.
EXAMPLE 4
[0082] Compound (B) with a purity of 94 wt % prepared as described
in Purification Example 1 (30 g) was tested as described in Example
1 except that 1.5 g of 4,8-, 4,7- or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tr- ithiaundecane
(referred to as Compound (D)) was added to Compound (B) and 0.06 g
of N,N-dimethylcyclohexylamine. The physical properties of the
molding (lens) are shown in Table 1.
EXAMPLE 5
[0083] Compound (B) with a purity of 94 wt % prepared as described
in Purification Example 1 (30 g) was tested as described in Example
1 except that 1.5 g of Compound (A) was added to Compound (B) and
0.06 g of N,N-diethylethanolamine was added. The physical
properties of the molding (lens) are shown in Table 1.
EXAMPLE 6
[0084] Compound (B) with a purity of 94 wt % prepared as described
in Purification Example 1 (30 g) was tested as described in Example
1 except that 1.5 g of cyclohexene vinyl diepoxide (referred to as
Compound (E)) was added to Compound (B) and 0.06 g of
N,N-dimethylcyclohexylamine was added. The physical properties of
the molding (lens) are shown in Table 1.
EXAMPLE 7
[0085] Compound (B) with a purity of 94 wt % prepared as described
in Purification Example 1 (30 g) was tested as described in Example
1 except that 1.5 g of 1,1-bis(4-acryloxydiethoxyphenyl)methane
(referred to as Compound (F)) was added to Compound (B) and 0.06 g
of N,N-dimethylcyclohexylamine was added. The physical properties
of the molding (lens) are shown in Table 1.
EXAMPLE 8
[0086] Compound (B) with a purity of 94 wt % prepared as described
in Purification Example 1 (30 g) was tested as described in Example
1 except that 1.5 g of divinylbenzene (referred to as Compound (G))
was added to Compound (B) and 0.06 g of
N,N-dimethyl-cyclohexylamine was added. The physical properties of
the molding (lens) are shown in Table 1.
Comparative Example 1
[0087] Bis(2,3-epithiopropyl)sulfide with a purity of 89 wt %
(referred to as Compound (H))(50 g) was tested as described in
Example 5. The physical properties of the molding (lens) are shown
in Table 1.
4 TABLE 1 Polymerizable Refractive Abbe Specific Tg Composition
Index(nd) No. Gravity (.degree. C.) Exam. 1 Compd. (B) 85% 1.737 33
1.47 84 Composition Exam. 2 Compd. (B) 94% 1.740 33 1.47 95
Composition Exam. 3 Compds. (B) + (C) 1.734 33 1.46 81 Composition
Exam. 4 Compds. (B) + (D) 1.736 33 1.46 88 Composition Exam. 5
Compds. (B) + (A) 1.729 33 1.46 92 Composition Exam. 6 Compds. (B)
+ (E) 1.725 33 1.46 78 Composition Exam. 7 Compds. (B) + (F) 1.722
33 1.46 79 Composition Exam. 8 Compds. (B) + (G) 1.728 32 1.46 77
Composition Comp. Compd. (H) 89% 1.701 36 1.41 82 Exam. 1
Composition
[0088] Thus, according to the first aspect of this invention a
polymerizable composition for an optical resin can provide a
transparent resin having excellent optical properties such as a
considerably high refractive index, which may contribute to
achieving a thinner lens, especially in the field of
eyeglasses.
[0089] Examples of the second aspect of this invention will be
described. The properties relevant to performance of a resin
obtained, that is, a refractive index, an Abbe number, and heat
resistance were evaluated as described in the above Examples for
the first aspect of this invention. Change in tone was rated as
follows.
[0090] Change rate of tone: A resin was heated in the air at
120.degree. C. for 3 hours, and the rate was determined on the
basis of the difference between its b* values before and after
heating. Each compound (a) was cured in the presence of only a
curing catalyst without compound (b). The resin product was heated
in the air at 120.degree. C. for 3 hours. The difference between
its b* values before and after heating was used as a reference
value for tone change.
[0091] Change rate of tone={(b* after heating)-(b* before heating)}
in the system with Compound (b)/{(b* after heating)-(b* before
heating)} in the system without Compound (b)
EXAMPLE 9
[0092] N,N-dimethylcyclohexylamine (referred to as DCA) (0.2 g) as
a curing catalyst was added to 100 g of Compound (B) as Compound
(a) and 5 g of n-propylamine as Compound (b). The mixture was
stirred, defoamed 0.4 hours under a reduced pressure, filtered
through a 3 .mu.m fluororesin (Teflon.RTM.) filter and poured into
a mold template consisting of glass molds and a gasket. The mold
was gradually warmed from 30.degree. C. to 100.degree. C. and at
the temperature the mixture was polymerized for 10 hours. After
completion of the polymerization, the mold was gradually cooled and
the resin was took out from the mold. The resin was annealed at
100.degree. C. for 2 hours. The resin (lens) was further heated at
120.degree. C. for 3 hours, and then its physical properties were
determined. Its physical properties and tone change results are
shown in Table 2.
EXAMPLE 10
[0093] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
isopropylamine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 11
[0094] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
n-butylamine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 12
[0095] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
sec-butylamine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 13
[0096] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
tert-butylamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 14
[0097] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
n-hexylamine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 15
[0098] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
n-octylamine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 16
[0099] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
n-laurylamine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 17
[0100] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
methoxyethylamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 18
[0101] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
cyclohexylamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 19
[0102] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
2-aminoethanol. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 20
[0103] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
benzylamine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 21
[0104] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
.beta.-phenethylamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 22
[0105] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
aniline. The physical properties and the tone change results for
the resin are shown in Table 2.
EXAMPLE 23
[0106] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
o-toluidine. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 24
[0107] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
2-methylbenzylamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 25
[0108] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 5 g of
.alpha.-naphthylamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 26
[0109] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
ethylenediamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 27
[0110] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
diaminopropane. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 28
[0111] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
diaminobutane. The physical properties and the tone change results
for the resin are shown in Table 2.
EXAMPLE 29
[0112] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
diaminomethylbicycloheptane. The physical properties and the tone
change results for the resin are shown in Table 2.
EXAMPLE 30
[0113] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
m-xylylenediamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 31
[0114] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
1,3-diaminomethylcyclohexylamine. The physical properties and the
tone change results for the resin are shown in Table 2.
EXAMPLE 32
[0115] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
naphthalenediamine. The physical properties and the tone change
results for the resin are shown in Table 2.
EXAMPLE 33
[0116] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
N,N'-dimethylethylenediamine. The physical properties and the tone
change results for the resin are shown in Table 2.
EXAMPLE 34
[0117] The procedure as described in Example 9 was repeated, except
that n-propylamine as Compound (b) was replaced with 3 g of
piperazine. The physical properties and the tone change results for
the resin are shown in Table 2.
Reference Example 1
[0118] Compound (B) (100 g) as Compound (a) was mixed with 5 g of
thiophenol as a yellowing inhibitor. To the mixture was added DCA
as a curing catalyst and then the mixture was stirred. The
subsequent lens molding procedure was conducted as described in
Example 9. The physical properties and the tone change results for
the resin are shown in Table 3.
Reference Example 2
[0119] Compound (B) (100 g) as Compound (a) was mixed with 5 g of
bis(mercaptoethyl)sulfide as a yellowing inhibitor. To the mixture
was added DCA as a curing catalyst and then the mixture was
stirred. The subsequent lens molding procedure was conducted as
described in Example 9. The physical properties and the tone change
results for the resin are shown in Table 3.
5TABLE 2 Heat Ex. Composition Amino/ Change rate Refractive Abbe
No. resist- No. (a) (b) Thioepoxy of tone Index(nd) (vd)
ance(Tg,.degree. C.) 9 Compd. (B) n-Propylamine 0.089 0.500 1.723
34 81 10 Compd. (B) Isopropylamine 0.089 0.516 1.720 34 78 11
Compd. (B) n-Butylamine 0.072 0.500 1.722 34 79 12 Compd. (B)
sec-Butylamine 0.072 0.548 1.722 34 79 13 Compd. (B)
tert-Butylamine 0.072 0.500 1.723 34 80 14 Compd. (B) n-Hexylamine
0.052 0.468 1.722 34 79 15 Compd. (B) n-Octylamine 0.041 0.435
1.719 34 78 16 Compd. (B) n-Laurylamine 0.028 0.468 1.720 34 77 17
Compd. (B) Methoxyethylamine 0.070 0.532 1.722 33 79 18 Compd. (B)
Cyclohexylamine 0.053 0.532 1.718 34 78 19 Compd. (B)
2-Aminoethanol 0.043 0.468 1.723 33 80 20 Compd. (B) Benzylamine
0.049 0.484 1.727 33 78 21 Compd. (B) .beta.-Phenethylamine 0.043
0.532 1.727 33 79 22 Compd. (B) Aniline 0.056 0.581 1.729 33 79 23
Compd. (B) o-Toluidine 0.049 0.581 1.728 33 78 24 Compd. (B)
2-Methylbenzylamine 0.043 0.565 1.728 33 78 25 Compd. (B)
.alpha.-Naphthylamine 0.037 0.887 1.725 33 78 26 Compd. (B)
Ethylenediamine 0.105 0.532 1.724 33 77 27 Compd. (B)
Diaminopropane 0.085 0.532 1.725 33 77 28 Compd. (B) Diaminobutane
0.072 0.548 1.724 33 77 29 Compd. (B) Diaminomethyl-bicycloheptane
0.048 0.500 1.720 34 81 30 Compd. (B) m-Xylylenediamine 0.046 0.565
1.726 33 80 31 Compd. (B) 1,3-Diaminomethyl-cyclohexylamine 0.044
0.484 1.722 33 79 32 Compd. (B) Naphthalenediamine 0.040 0.935
1.728 33 79 33 Compd. (B) N,N'-dimethylethyl-enediamine 0.071 0.532
1.722 33 83 34 Compd. (B) Piperazine 0.073 0.323 1.732 33 96
[0120]
6 TABLE 3 Functional Composition group/ Change Heat Ref. Curing
Thioepoxy rate of Refractive Abbe resistance Ex. No. (a) Yellowing
inhibitor catalyst group tone Index(nd) No.(.nu.d) (Tg,.degree. C.)
1 Compd. (B) Thiophenol DCA 0.048 0.581 1.732 33 72 2 Compd. (B)
Bis(mercaptoethyl)- DCA 0.068 0.516 1.733 33 74 sulfide
* * * * *