U.S. patent application number 13/509015 was filed with the patent office on 2012-09-06 for film and uses thereof.
This patent application is currently assigned to Mitsui Chemicals, Inc.. Invention is credited to Hisako Ishikawa, Akifumi Kagayama, Toshinori Matsuda, Yosuke Ono, Kazuo Yagi.
Application Number | 20120225274 13/509015 |
Document ID | / |
Family ID | 43991420 |
Filed Date | 2012-09-06 |
United States Patent
Application |
20120225274 |
Kind Code |
A1 |
Ishikawa; Hisako ; et
al. |
September 6, 2012 |
FILM AND USES THEREOF
Abstract
Disclosed is a film composed of a resin having a thiourethane
bond, wherein the molar ratio (S/N) of sulfur to nitrogen contained
in the resin is equal to or more than 0.8 and less than 3.
According to the present invention, the film is excellent in a
balance among high refractive index, low birefringence and light
transmittance, and further excellent in a balance of mechanical
characteristics such as toughness, hardness and dimensional
stability, so that effects of deformation and the like during
processing are very small, and the film is further excellent in
solvent resistance as well.
Inventors: |
Ishikawa; Hisako;
(Ichihara-shi, JP) ; Matsuda; Toshinori;
(Ichihara-shi, JP) ; Ono; Yosuke; (Ichihara-shi,
JP) ; Yagi; Kazuo; (Hiroshima-shi, JP) ;
Kagayama; Akifumi; (Chiba-shi, JP) |
Assignee: |
Mitsui Chemicals, Inc.
Minato-ku
JP
|
Family ID: |
43991420 |
Appl. No.: |
13/509015 |
Filed: |
November 11, 2010 |
PCT Filed: |
November 11, 2010 |
PCT NO: |
PCT/JP2010/006635 |
371 Date: |
May 10, 2012 |
Current U.S.
Class: |
428/220 ;
264/299; 264/328.1; 428/423.1; 528/77 |
Current CPC
Class: |
C08G 18/7671 20130101;
C08G 18/7621 20130101; G02B 5/045 20130101; G02B 5/0841 20130101;
B29L 2011/00 20130101; C09D 175/04 20130101; C08G 18/3876 20130101;
G02B 1/111 20130101; B29D 11/00788 20130101; C08G 18/7642 20130101;
G02B 5/208 20130101; G02B 5/3083 20130101; C08J 2375/04 20130101;
C08J 5/18 20130101; B29K 2075/00 20130101; G02B 1/18 20150115; G02B
5/021 20130101; Y10T 428/31551 20150401; B29C 41/003 20130101; G02B
5/3033 20130101 |
Class at
Publication: |
428/220 ;
264/299; 264/328.1; 428/423.1; 528/77 |
International
Class: |
B32B 27/40 20060101
B32B027/40; B29C 45/00 20060101 B29C045/00; C08G 18/38 20060101
C08G018/38; B29C 39/00 20060101 B29C039/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 13, 2009 |
JP |
2009-260449 |
Mar 24, 2010 |
JP |
2010-067563 |
Claims
1. A film comprising a resin having a thiourethane bond, wherein
the molar ratio (S/N) of sulfur to nitrogen contained in said resin
is equal to or more than 0.8 and less than 3.
2. The film according to claim 1, wherein the refractive index in a
sodium D line is equal to or more than 1.6, the in-plane
birefringence .DELTA.n.sub.n of a film having a film thickness of 1
to 200 .mu.m at a wavelength 590 nm is equal to or less than
1.0.times.10.sup.-2, the birefringence .DELTA.n in the thickness
direction is equal to or less than 1.0.times.10.sup.-3, and the
mean value of the light transmittance to the light having a
wavelength 400 to 800 nm is equal to or more than 80%.
3. The film according to claim 1, wherein the resin having a
thiourethane bond has an aromatic group, a heterocyclic group or an
alicyclic group in the structure.
4. The film according to claim 1, obtained by a casting method.
5. The film according to claim 1, containing partially a
thiourethane bond, and further obtained by a casting method from a
mixture of a compound having an isocyanate group and a compound
having a thiol group which are capable of forming thiourethane.
6. The film according to claim 1, containing partially a
thiourethane bond, and further obtained by injecting a mixture of a
compound having an isocyanate group and a compound having a thiol
group, which is capable of forming a thiourethane between surfaces
of a space of equal to or less than 200 .mu.m and polymerizing and
curing the mixture.
7. The film according to claim 5, wherein said compound having a
thiol group contains at least one kind of compounds having three or
more mercapto groups.
8. An optical film comprising the film according to claim 1.
9. An optical member, wherein the optical film according to claim 8
is formed inside or outside thereof.
10. A display equipped with the optical film according to claim
8.
11. A light emitting device, wherein the optical film according to
claim 8 is formed inside or outside thereof.
12. A lighting device using the light emitting device according to
claim 11.
13. An image display device using the light emitting device
according to claim 11.
Description
TECHNICAL FIELD
[0001] The present invention relates to a film and uses of the
film.
BACKGROUND ART
[0002] Patent Document 1 discloses an optical material composed of
a thiourethane resin. Furthermore, Patent Document 2 discloses an
optical material composed of polythiourethane produced by the use
of a prescribed catalyst. According to the documents, these resins
have a high refractive index and high transparency, and can be
suitably used for optical lenses among optical materials.
[0003] However, the documents do not disclose physical properties
when a thiourethane resin is formed into a film at a thickness of
equal to or less than 1 mm, and a method of controlling
transmission of light as a whole by the use in contact with other
materials in a thin film form. Furthermore, when these resins are
made into a thin film, there are difficulties in coating from the
viewpoint of reactivity of a raw material, and a method of
obtaining a stable film or thin film is not reviewed either.
[0004] Patent Document 3 discloses an optical material having a
structure in which a polythiourethane skeleton is introduced into a
polythiocarbonate skeleton. According to the document, the
resulting film from the optical material is excellent in optical
properties such as high refractive index, high Abbe's number and
the like, and further excellent in mechanical properties such as
tensile properties, high elasticity and the like. The document
discloses a case in which a film is formed from the aforementioned
optical material by a casting (solution casting) method of a resin
solution.
RELATED DOCUMENT
Patent Document
[0005] Patent Document 1: Japanese Laid-open Patent Publication No.
1990-270859
[0006] Patent Document 2: International Publication (WO) No.
2007/97116
[0007] Patent Document 3: Japanese Laid-open Patent Publication No.
2005-336476
DISCLOSURE OF THE INVENTION
[0008] However, the resin as disclosed in the above document 3
involves many steps in synthesis, so that there are problems in
maintenance of a quality and the cost when the resin is made into a
film. Furthermore, a method of forming a film from the resin
described in the above document 3 also requires extra effort and
the cost for removing the solvent at the time of production thereof
due to cast (solution casting) with a solution after completion of
polymerization, there are difficulties in controlling the degree of
polymerization and thickness, and there are many rooms for
improvement in a balance among refractive index, birefringence and
light transmittance of the formed film.
[0009] That is, the present invention is specified by matters
described in below:
[0010] (1) A film comprising a resin having a thiourethane bond,
wherein the molar ratio (S/N) of sulfur to nitrogen contained in
said resin is equal to or more than 0.8 and less than 3.
[0011] (2) The film according to (1), wherein the refractive index
in a sodium D line is equal to or more than 1.6, the in-plane
birefringence .DELTA.n.sub.xy of a film having a film thickness of
1 to 200 .mu.m at a wavelength 590 nm is equal to or less than
1.0.times.10.sup.-2, the birefringence .DELTA.n.sub.xz in the
thickness direction is equal to or less than 1.0.times.10.sup.-3,
and the mean value of the light transmittance to the light having a
wavelength 400 to 800 nm is equal to or more than 80%.
[0012] (3) The film according to (1) or (2), wherein the resin
having a thiourethane bond has an aromatic group, a heterocyclic
group or an alicyclic group in the structure.
[0013] (4) The film according to any one of (1) to (3), obtained by
a casting (thin film coating--polymerization curing) method.
[0014] (5) The film according to any one of (1) to (3), containing
partially a thiourethane bond, and further obtained by a casting
method from a mixture of a compound having an isocyanate group and
a compound having a thiol group, which is capable of forming a
thiourethane.
[0015] (6) The film according to any one of (1) to (3), containing
partially a thiourethane bond, and further obtained by injecting a
mixture of a compound having an isocyanate group and a compound
having a thiol group, which is capable of forming a thiourethane
between surfaces of a space of equal to or less than 200 .mu.m and
polymerizing and curing the mixture.
[0016] (7) The film according to (5) or (6), wherein said compound
having a thiol group contains at least one kind of compounds having
three or more mercapto groups.
[0017] (8) An optical film composed of the film according to any
one of (1) to (7).
[0018] (9) An optical member, wherein the optical film according to
(8) is formed inside or outside thereof.
[0019] (10) A display equipped with the optical film according to
(8).
[0020] (11) Alight emitting device, wherein the optical film
according to (8) is formed inside or outside thereof.
[0021] (12) A lighting device using the light emitting device
according to (11).
[0022] (13) An image display device using the light emitting device
according to (11).
[0023] Incidentally, the film of the present invention also
includes a sheet-like film, and further includes the case that a
thin film obtained by coating and curing on a substrate is used
with the substrate.
[0024] The film of the present invention is excellent in a balance
among high refractive index, low birefringence and light
transmittance, and further excellent in a balance of mechanical
characteristics toughness, hardness, dimensional stability and the
like, so that effects of deformation and the like during processing
are very small, while the film is further excellent in solvent
resistance as well, so that the film can be used as various optical
films.
DESCRIPTION OF EMBODIMENTS
[0025] The present invention will be described in more detail
below.
Film
[0026] The film of the present invention is composed of a resin
having a thiourethane bond. The resin constituting the film of the
present invention has the number of sulfur atoms which is
relatively smaller than the number of thiourethane bonds, that is,
polymerization reaction bonds, and consequently the polymerization
process is made in a relatively simple manner. The molar ratio
(S/N) of sulfur to nitrogen contained in the resin is equal to or
more than 0.8 and less than 3, preferably equal to or more than 0.8
and equal to or less than 2.8, and further preferably equal to or
more than 0.9 and equal to or less than 2.2.
[0027] When the molar ratio (S/N) of sulfur to nitrogen is in the
aforementioned range, the film of the present invention is
excellent in a balance of optical properties such as high
refractive index, low birefringence, light transmittance and the
like, and further excellent in mechanical characteristics such as
toughness and solvent resistance as well.
[0028] Specifically, the film has the properties as described
below.
[0029] The refractive index in a sodium D line is equal to or more
than 1.6 and preferably equal to or more than 1.64.
[0030] The in-plane birefringence .DELTA.n.sub.xy of a film having
a film thickness of 1 to 200 .mu.m at a wavelength 590 nm is equal
to or less 1.0.times.10.sup.-2, preferably equal to or less than
1.0.times.10.sup.-3, more preferably equal to or less than
2.0.times.10.sup.-5, and further preferably equal to or less than
1.1.times.10.sup.-5. Furthermore, the birefringence .DELTA.n.sub.x,
in the thickness direction is equal to or less than
1.0.times.10.sup.-3 and further preferably equal to or less than
8.0.times.10.sup.-4.
[0031] The average light transmittance to the light having a
wavelength 400 to 800 nm is equal to or more than 80%, preferably
equal to or more than 85%, and further preferably equal to or more
than 88%.
[0032] The front birefringence .DELTA.n.sub.xy is defined by nx-ny,
while the in-plane retardation Re is defined by
.DELTA.n.sub.xy.times.d (wherein n.sub.x represents the refractive
index in the in-plane delayed-phase direction of the resin film;
n.sub.y represents the refractive index in the in-plane
advanced-phase direction of the resin film (unit: nm)).
[0033] Meanwhile, the birefringence in the thickness direction,
.DELTA.n.sub.xz, is defined by (nx+ny)/2-nz, while the retardation
in the thickness direction, Rth, is defined by
.DELTA.n.sub.xz.times.d (wherein n.sub.x represents the refractive
index in the in-plane delayed-phase direction of the resin film;
n.sub.y represents the refractive index in the in-plane
advanced-phase direction of the resin film, n.sub.z represents the
refractive index in the film thickness direction, and d is a film
thickness (unit: nm)).
[0034] The film of the present invention is excellent in a balance
among high refractive index, low birefringence and light
transmittance, so that the film can be suitably used for optical
applications. Furthermore, the film of the present invention is
excellent in strong toughness, and also excellent in solvent
resistance because the film is composed of a thermosetting resin.
Incidentally, the above numerical range may be used in any
combination.
[0035] For the film of the present invention, the breaking
elongation is from 3 to 6%. Furthermore, the tensile modulus
measured by a test for tensile strength is equal to or more than 3
GPa. Since the film is excellent in these mechanical
characteristics, for the products obtained by using the film of the
present invention, the yield rate thereof is improved and at the
same time product reliability is improved. Thus, the film can be
further suitably used for various optical films.
[0036] Meanwhile, the film of the present invention has a thickness
of from 0.1 to 1,000 .mu.m, and a film having a thickness of 1 to
1,000 .mu.m can also be used. From the viewpoint of low
birefringence, the thickness is preferably from 0.1 to 200 .mu.m.
In case of a self-support film used by peeling off from the base
material after coating, polymerizing and curing a thin film on a
base material, or used by peeling off from the mold after cast
polymerization, the thickness is particularly preferably from 10 to
200 .mu.m.
[0037] Because of excellent barrier properties of various gases
such as water vapor, oxygen and the like, particularly water vapor
barrier properties, the film can be used as a transparent base
material of a liquid crystal display, a solar cell, an organic
electroluminescence device and the like.
[0038] When the water vapor transmittance rate of the film of the
present invention is measured under the conditions of a temperature
of 60 degrees centigrade, a humidity of 90% RH and a film thickness
of 100 .mu.m in accordance with JIS Z0208, the value is equal to or
less than 10 g/m.sup.224 hr.
[0039] Hereinafter, the resin having a thiourethane bond
constituting the film of the present invention will be
described.
[0040] Resin having a Thiourethane Bond
[0041] A sulfur atom-containing resin having a thiourethane bond
used in the present invention is obtained by polymerizing the
following polymerizable composition.
[0042] The polymerizable composition is mainly composed of one or
more kinds of isocyanates selected from the group consisting of an
isocyanate compound and an isothiocyanate compound, and one or more
kinds of active hydrogen compounds having a mercapto group.
[0043] However, for the purpose of modifying the polythiourethane
resin, a hydroxy compound may further be added.
[0044] In the present invention, concrete examples of the
isocyanate compound which is preferably used as a raw material of
the resin having a thiourethane bond include monofunctional
isocyanate compounds such as methyl isocyanate, ethyl isocyanate,
n-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate,
sec-butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate,
hexyl isocyanate, heptyl isocyanate, octyl isocyanate, decyl
isocyanate, lauryl isocyanate, myristyl isocyanate, octadecyl
isocyanate, 3-pentyl isocyanate, 2-ethylhexyl isocyanate,
2,3-dimethylcyclohexyl isocyanate, 2-methoxyphenyl isocyanate,
4-methoxyphenyl isocyanate, .alpha.-methylbenzyl isocyanate,
phenylethyl isocyanate, phenyl isocyanate, o-, m-, or p-tolyl
isocyanate, cyclohexyl isocyanate, benzyl isocyanate,
isocyanatomethylbicycloheptane and the like; 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-hexamethylene triisocyanate,
1,8-diisocyanato-4-isocyanatomethyloctane,
bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, lysine
diisocyanatomethyl ester, lysine triisocyanate and the like;
alicyclic polyisocyanate compounds such as isophorone diisocyanate,
1,3-bis(isooyanatomethyl)cyclohexane,
1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane
diisocyanate, cyclohexane diisocyanate, methylcyclohexane
diisocyanate, dicyclohexyldimethylmethane isocyanate,
2,2-dimethyldicyclohexylmethane isocyanate,
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 the like; aromatic
polyisocyanate compounds such as phenylene diisocyanate, o-xylylene
diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate,
bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethylxylylene diisocyanate,
bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene,
bis(isocyanatomethyl)diphenyl ether, phenylene diisocyanate,
tolylene diisocyanate, ethylphenylene diisocyanate,
isopropylphenylene diisocyanate, dimethylphenylene diisocyanate,
diethylphenylene diisocyanate, diisopropylphenylene diisocyanate,
trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl
diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane
diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate,
bibenzyl-4,4-diisocyanate, bis(isocyanatophenyl)ethylene,
3,3-dimethoxybiphenyl-4,4-diisocyanate, phenylisocyanatoethyl
isocyanate, hexahydrobenzene diisocyanate,
hexahydrodiphenylmethane-4,4-diisocyanate,
bis(isocyanatoethyl)phthalate, mesitylylene triisocyanate,
2,6-di(isocyanatomethyl)furan and the like; sulfur-containing
aliphatic polyisocyanate compounds such as
bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide,
bis(isocyanatohexyl)sulfide, bis(isocyanatomethyl)sulfone,
bis(isocyanatomethyl)disulfide, bis(isocyanatopropyl)disulfide,
bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane,
bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane,
1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane and the like;
sulfur-containing aromatic polyisocyanate compounds such as
diphenyl sulfide-2,4-diisocyanate, diphenyl
sulfide-4,4-diisocyanate,
3,3-dimethoxy-4,4-diisocyanatodibenzylthioether,
bis(4-isocyanatomethylbenzene)sulfide,
4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl
disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl
disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl
disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl
disulfide-6,6-diisocyanate, 4,4-dimethyldiphenyl
disulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyl
disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl
disulfide-3,3-diisocyanate and the like; and sulfur-containing
heterocyclic polyisocyanate compounds such as
2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene,
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,
4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane and the like.
However, the present invention is not limited to these exemplified
compounds.
[0045] Their halogen substituted compounds such as chlorine
substituted compounds, bromine substituted compounds and the like,
alkyl substituted compounds, alkoxy substituted compounds, nitro
substituted compounds, prepolymer type modified products modified
with polyhydric alcohols, carbodiimide modified products, urea
modified products, biuret modified products, dimerization or
trimerization reaction products, and the like may be employed.
These isocyanate compounds maybe used singly, or two or more kinds
thereof may be used in combination.
[0046] In the present invention, an isothiocyanate compound which
is used as a raw material of the resin having a thiourethane bond
is selected from an isothiocyanate compound and an isothiocyanate
compound having an isocyanate group.
[0047] Concrete examples of the isothiocyanate compound which is
preferably used in the present invention include monofunctional
isothiocyanate compounds such as methyl isothiocyanate, ethyl
isothiocyanate, n-propyl isothiocyanate, 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,
.alpha.-methylbenzyl isothiocyanate, phenylethyl isothiocyanate,
phenyl isothiocyanate, o-, m-, or p-tolyl isothiocyanate,
cyclohexyl isothiocyanate, benzyl isothiocyanate,
isothiocyanatomethylbicycloheptane and the like; aliphatic
polyisothiocyanate compounds such as hexamethylene
diisothiocyanate, 2,2-dimethylpentane diisothiocyanate,
2,2,4-trimethylhexane diisothiocyanate, butene diisothiocyanate,
1,3-butadiene-1,4-diisothiocyanate, 2,4,4-trimethylhexamethylene
diisothiocyanate, 1,6,11-undecatriisothiocyanate,
1,3,6-hexamethylene triisothiocyanate,
1,8-diisothiocyanato-4-isothiocyanatomethyloctane,
bis(isothiocyanatoethyl)carbonate, bis(isothiocyanatoethyl)ether,
lysine diisothiocyanatomethyl ester, lysine triisothiocyanate,
xylylene diisothiocyanate, bis(isothiocyanatoethyl)benzene,
bis(isothiocyanatopropyl)benzene,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethylxylylene
diisothiocyanate, bis(isothiocyanatobutyl)benzene,
bis(isothiocyanatomethyl)naphthalene,
bis(isothiocyanatomethyl)diphenyl ether,
bis(isothiocyanatoethyl)phthalate, mesitylylene triisothiocyanate,
2,6-di(isothiocyanatomethyl)furan and the like; alicyclic
polyisothiocyanate compounds such as isophorone diisothiocyanate,
bis(isothiocyanatomethyl)cyclohexane, dicyclohexylmethane
diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane
diisothiocyanate, dicyclohexyldimethylmethane isothiocyanate,
2,2-dimethyldicyclohexylmethane isothiocyanate,
2,5-bis(isothiocyanatomethyl)bicyclo-[2,2,1]-heptane,
2,6-bis(isothiocyanatomethyl)bicyclo-[2,2,1]-heptane,
3,8-bis(isothiocyanatomethyl)tricyclodecane,
3,9-bis(isothiocyanatomethyl)tricyclodecane,
4,8-bis(isothiocyanatomethyl)tricyclodecane,
4,9-bis(isothiocyanatomethyl)tricyclodecane and the like; aromatic
polyisothiocyanate compounds such as phenylene diisothiocyanate,
tolylene diisothiocyanate, ethylphenylene diisothiocyanate,
isopropylphenylene diisothiocyanate, dimethylphenylene
diisothiocyanate, diethylphenylene diisothiocyanate,
diisothiopropylphenylene diisothiocyanate, trimethylbenzene
triisothiocyanate, benzene triisothiocyanate, biphenyl
diisothiocyanate, toluidine diisothiocyanate, 4,4-diphenylmethane
diisothiocyanate, 3,3-dimethyldiphenylmethane-4,4-diisothiocyanate,
bibenzyl-4,4-diisothiocyanate,
bis(isothiocyanatophenyl)ethylene.sub.r
3,3-dimethoxybiphenyl-4,4-diisothiocyanate,
phenylisothiocyanatoethyl isothiocyanate, hexahydrobenzene
diisothiocyanate, hexahydrodiphenylmethane-4,4-diisothiocyanate and
the like; sulfur-containing aliphatic polyisothiocyanate compounds
such as bis(isothiocyanatoethyl)sulfide,
bis(isothiocyanatopropyl)sulfide, bis(isothiocyanatohexyl)sulfide,
bis(isothiocyanatomethyl)sulfone,
bis(isothiocyanatomethyl)disulfide,
bis(isothiocyanatopropyl)disulfide,
bis(isothiocyanatomethylthio)methane,
bis(isothiocyanatoethylthio)methane,
bis(isothiocyanatoethylthio)ethane,
bis(isothiocyanatomethylthio)ethane,
1,5-diisothiocyanato-2-isothiocyanatomethyl-3-thiapentane and the
like; sulfur-containing aromatic polyisothiocyanate compounds such
as diphenyl sulfide-2,4-diisothiocyanate, diphenyl
sulfide-4,4-diisothiocyanate,
3,3-dimethoxy-4,4-diisothiocyanatodibenzylthioether,
bis(4-isothiocyanatomethylbenzene)sulfide,
4,4-methoxybenzenethioethylene glycol-3,3-diisothiocyanate,
diphenyl disulfide-4,4-diisothiocyanate, 2,2-dimethyldiphenyl
disulfide-5,5-diisothiocyanate, 3,3-dimethyldiphenyl
disulfide-5,5-diisothiocyanate, 3,3-dimethyldiphenyl
disulfide-6,6-diisothiocyanate, 4,4-dimethyldiphenyl
disulfide-5,5-diisothiocyanate, 3,3-dimethoxydiphenyl
disulfide-4,4-diisothiocyanate, 4,4-dimethoxydiphenyl
disulfide-3,3-diisothiocyanate and the like; sulfur-containing
heterocyclic polyisothiocyanate compounds such as
2,5-diisothiocyanatothiophene,
2,5-bis(isothiocyanatomethyl)thiophene,
2,5-diisothiocyanatotetrahydrothiophene,
2,5-bis(isothiocyanatomethyl)tetrahydrothiophene,
3,4-bis(isothiocyanatomethyl)tetrahydrothiophene,
2,5-diisothiocyanato-1,4-dithiane,
2,5-bis(isothiocyanatomethyl)-1,4-dithiane,
4,5-diisothiocyanato-1,3-dithiolane,
4,5-bis(isothiocyanatomethyl)-1,3-dithiolane,
4,5-bis(isothiocyanatomethyl)-2-methyl-1,3-dithiolane and the like.
However, the present invention is not limited to these exemplified
compounds.
[0048] Their halogen substituted compounds such as chlorine
substituted compounds, bromine substituted compounds and the like,
alkyl substituted compounds, alkoxy substituted compounds, nitro
substituted compounds, prepolymer type modified products modified
with polyhydric alcohols, carbodiimide modified products, urea
modified products, biuret modified products, dimerization or
trimerization reaction products, and the like may be employed.
These isothiocyanate compounds may be used singly, or two or more
kinds thereof may be used in combination.
[0049] Examples of the isothiocyanate compound having an isocyanate
group which is used as a raw material in the present invention
include aliphatic or alicyclic compounds such as
1-isocyanato-3-isothiocyanatopropane,
1-isocyanato-5-isothiocyanatopentane,
1-isocyanato-6-isothiocyanatohexane, isocyanatocarbonyl
isothiocyanate, 1-isocyanato-4-isothiocyanatocyclohexane and the
like; aromatic compounds such as
1-isocyanato-4-isothiocyanatobenzene,
4-methyl-3-isocyanato-1-isothiocyanatobenzene and the like;
heterocyclic compounds such as
2-isocyanato-4,5-diisothiocyanato-1,3,5-triazine and the like; and
isothiocyanate groups such as
4-isocyanato-4'-isothiocyanatodiphenyl sulfide, 2-isocyanato-2'
-isothiocyanatodiethyl disulfide and the like, and their sulfur
substituted compounds.
[0050] Furthermore, their halogen substituted compounds such as
chlorine substituted compounds, bromine substituted compounds and
the like, alkyl substituted compounds, alkoxy substituted
compounds, nitro substituted compounds, prepolymer type modified
products modified with polyhydric alcohols, carbodiimide modified
products, urea modified products, biuret modified products,
dimerization or trimerization reaction products, and the like may
be employed.
[0051] In the present invention, from the viewpoints of improvement
of a refractive index and improvement of heat resistance, it is
preferable that a resin having a thiourethane bond has an aromatic
group, a heterocyclic group or an alicyclic group in the structure.
Namely, it is preferable to use a compound having an aromatic
group, a heterocyclic group or an alicyclic group as
isocyanates.
[0052] These isocyanates may be used singly, or two or more kinds
thereof may be used in combination. As isocyanates, more preferably
used are phenylene diisocyanate, m-xylylene diisocyanate, 2,5-bis
(isocyanatomethyl) -bicyclo[2.2.1] heptane, 2,6-bis
(isocyanatomethyl) -bicyclo [2.2.1] heptane, 1,3-bis
(isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl)
cyclohexane, hexamethylene diisocyanate, tolylene diisocyanate and
4,4-diphenylmethane diisocyanate, while particularly preferably
used are phenylene diisocyanate, m-xylylene diisocyanate, tolylene
diisocyanate, 4,4-diphenylmethane diisocyanate, 2,5-bis
(isocyanatomethyl) -bicyclo [2.2.1] heptane and 2,6-bis
(isocyanatomethyl) -bicyclo [2.2.1] heptane.
[0053] In the present invention, from the viewpoint of improvement
of a refractive index, it is preferable that a resin having a
thiourethane bond has an aromatic group, a heterocyclic group or an
alicyclic group in the structure. Namely, it is preferable to use a
compound having an aromatic group, a heterocyclic group or an
alicyclic group as isocyanates.
[0054] In the present invention, among the aforementioned
isocyanates, with the use of isocyanates having an aromatic ring, a
resin having a high refractive index is obtained.
[0055] An active hydrogen compound having a mercapto group which is
used as a raw material of the resin having a thiourethane bond is
selected from a mercapto compound and a mercapto compound having a
hydroxy group.
[0056] Examples of the mercapto compound used in the present
invention include aliphatic polythiol compounds such as
methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol,
1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol,
1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol,
1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol,
1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol,
3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol,
1,1-bis(mercaptomethyl)cyclohexane, 1,2-dimercaptopropylmethyl
ether, 2,3-dimercaptopropylmethyl ether,
2,2-bis(mercaptomethyl)-1,3-propanedithiol,
bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane and the
like; aliphatic polythiol compounds containing an ester bond such
as 2,3-dimercaptosuccinic acid(2-mercaptoethylester), thiomalic
acid bis(2-mercaptoethylester),
2,3-dimercapto-1-propanol(2-mercaptoacetate),
2,3-dimercapto-1-propanol(3-mercaptopropionate),
3-mercapto-1,2-propanediol bis(2-mercaptoacetate),
3-mercapto-1,2-propanediol bis(3-mercaptopropionate), diethylene
glycol bis(2-mercaptoacetate), diethylene glycol
bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate),
ethylene glycol bis(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolethane
tris(2-mercaptoacetate), trimethylolethane
tris(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), glycerine tris(2-mercaptoacetate),
glycerine tris(3-mercaptopropionate), 1,4-cyclohexanediol
bis(2-mercaptoacetate), 1,4-cyclohexanediol
bis(3-mercaptopropionate) and the like; 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-bis(mercaptomethyleneoxy)benzene,
1,3-bis(mercaptomethyleneoxy)benzene,
1,4-bis(mercaptomethyleneoxy)benzene,
1,2-bis(mercaptoethyleneoxy)benzene,
1,3-bis(mercaptoethyleneoxy)benzene,
1,4-bis(mercaptoethyleneoxy)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,
1,2,3-tris(mercaptomethyleneoxy)benzene,
1,2,4-tris(mercaptomethyleneoxy)benzene,
1,3,5-tris(mercaptomethyleneoxy)benzene,
1,2,3-tris(mercaptoethyleneoxy)benzene,
1,2,4-tris(mercaptoethyleneoxy)benzene,
1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol,
3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol,
1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol,
2,4-di(p-mercaptophenyl)pentane, 1,4-naphthalenedithiol,
1,5-naphthalenedithiol, 2,6-naphthalenedithiol,
2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol,
4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol,
1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene,
1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis(mercaptomethyl)benzene,
1,2,3,5-tetrakis(mercaptomethyl)benzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene,
1,2,3,4-tetrakis(mercaptoethyl)benzene,
1,2,3,5-tetrakis(mercaptoethyl)benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene,
1,2,3,4-tetrakis(mercaptomethyleneoxy)benzene,
1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene,
1,2,4,5-tetrakis(mercaptomethyleneoxy)benzene,
1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene,
1,2,3,5-tetrakis(mercaptoethyleneoxy)benzene,
1,2,4,5-tetrakis(mercaptoethyleneoxy)benzene,
2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl,
4,4'-dimercaptobibenzyl, 2,5-dichlorobenzene-1,3-dithiol,
1,3-di(p-chlorophenyl)propane-2,2-dithiol,
3,4,5-tribromo-1,2-dimercaptobenzene,
2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene and the like;
heterocyclic thiol compounds such as
2-methylamino-4,6-dithiol-sym-triazine,
2-ethylamino-4,6-dithiol-sym-triazine,
2-amino-4,6-dithiol-sym-triazine,
2-morpholino-4,6-dithiol-sym-triazine,
2-cyclohexylamino-4,6-dithiol-sym-triazine,
2-methoxy-4,6-dithiol-sym-triazine,
2-phenoxy-4,6-dithiol-sym-triazine,
2-thiobenzeneoxy-4,6-dithiol-sym-triazine,
2-thiobutyloxy-4,6-dithiol-sym-triazine and the like; and their
halogen substituted compounds. However, the present invention is
not limited to these exemplified compounds.
[0057] Furthermore, their halogen substituted compounds such as
chlorine substituted compounds, bromine substituted compounds and
the like may be employed. These mercapto compounds may be used
singly, or two or more kinds thereof may be used in
combination.
[0058] Examples of the mercapto compound having one or more sulfide
bonds in one molecule include aliphatic polythiol compounds 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-mercaptopropylthio)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,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
tetrakis(3-mercaptopropylthiomethyl)methane,
bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane,
2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane and the like;
aliphatic polythiol compounds containing an ester bond such as
esters of thioglycolic acid and mercaptopropionic acid with these
compounds, hydroxymethyl sulfide bis(2-mercaptoacetate),
hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl
sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide
bis(3-mercaptopropionate), hydroxypropyl sulfide
bis(2-mercaptoacetate), hydroxypropyl sulfide
bis(3-mercaptopropionate), hydroxymethyl disulfide
bis(2-mercaptoacetate), hydroxymethyl disulfide
bis(3-mercaptopropionate), hydroxyethyl disulfide
bis(2-mercaptoacetate), hydroxyethyl disulfide
bis(3-mercaptopropionate), hydroxypropyl disulfide
bis(2-mercaptoacetate), hydroxypropyl disulfide
bis(3-mercaptopropionate), 2-mercaptoethyl ether
bis(2-mercaptoacetate), 2-mercaptoethyl ether
bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol
bis(3-mercaptopropionate), thiodiglycolic acid
bis(2-mercaptoethylester), thiodipropionic acid
bis(2-mercaptoethylester), 4,4-thiodibutyric acid
bis(2-mercaptoethylester), dithiodiglycolic acid
bis(2-mercaptoethylester), dithiodipropionic acid
bis(2-mercaptoethylester), 4,4-dithiodibutyric acid
bis(2-mercaptoethylester), thiodiglycolic acid
bis(2,3-dimercaptopropylester), thiodipropionic acid
bis(2,3-dimercaptopropylester), dithiodiglycolic acid
bis(2,3-dimercaptopropylester), thiodipropionic acid
bis(2,3-dimercaptopropylester), dithiodipropionic acid
bis(2,3-dimercaptopropylester) and the like; heterocyclic polythiol
compounds such as 3,4-thiophenedithiol, bismuthiol and the like;
polythiol compounds having a dithioacetal 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-dithiane,
1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane,
1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane,
2,2-bis(mercaptomethylthio)ethanethiol,
2-(4,5-dimercapto-2-thiapentyl)-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,
3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane,
2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiethane,
1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethyl
thio)-1-thiapropyl)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
-tetrathiatridecane,
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(mercap
tomethylthio)-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(mercaptom
ethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane,
4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiahepty
lthio]-1,3-dithiane,
4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercapt-
omethylthio-1,3-dithiane,
1,1-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,
1,5-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2-(1,3-dithietanyl-
)]methyl-2,4-dithiapentane,
4,6-bis{3-[2-(1,3-dithietanyl)]methyl-5-mercapto-2,4-dithiapen
tylthio}-1,3-dithiane,
4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethy-
lthio)-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(mercaptomethy
lthio)-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-dithiahexylthio]-1,3-d-
ithiolane,
4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]--
5-mercaptomethylthio-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-dithiethane,
2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]
mercaptomethylthiomethyl-1,3-dithiethane,
2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaund-
ecylthio]mercaptomethylthiomethyl-1,3-dithiethane,
2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)
8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane,
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-dithioranyl)thio]methyl}-1,
3-dithiethane,
4-[4-(5-mercaptomethylthio-1,3-dithioranyl)thio]-5-{1-[2-(1,3-dithietanyl-
)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane, their oligomers,
and the like; and polythiol compounds having an orthotrithioformic
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)meth-
ane, 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.sup.-2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane-
,
4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiacyclopentane,
tris[2,2-bis(mercaptomethylthio)-2-thiapropyl]methane,
tris[4,4-bis(mercaptomethylthio)-3-thiabutyl]methane,
2,4,6-tris[3,3-bis(mercaptomethylthio)-2-thiapropyl]-1,3,5-trithiacyclohe-
xane, tetrakis[3,3-bis(mercaptomethylthio)-2-thiapropyl]methane,
their oligomers, and the like. However, the present invention is
not limited to these exemplified compounds. Furthermore, their
halogen substituted compounds such as chlorine substituted
compounds, bromine substituted compounds and the like may be
employed. These mercapto compounds having a sulfide bond may be
used singly, or two or more kinds thereof may be used in
combination.
[0059] Furthermore, examples of the mercapto compound having a
hydroxy group include 2-mercaptoethanol,
3-mercapto-1,2-propanediol, glycerine di(mercaptoacetate),
1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol,
2-mercaptohydroquinone, 4-mercaptophenol,
1,3-dimercapto-2-propanol, 2,3-dimercapto-l-propanol,
1,2-dimercapto-1,3-butanediol, pentaerythritol
tris(3-mercaptopropionate), pentaerythritol
mono(3-mercaptopropionate), pentaerythritol
bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate),
pentaerythritol pentakis(3-mercaptopropionate),
hydroxymethyl-tris(mercaptoethylthiomethyl)methane,
1-hydroxyethylthio-3-mercaptoethylthiobenzene,
4-hydroxy-4'-mercaptodiphenylsulfone,
2-(2-mercaptoethylthio)ethanol, dihydroxyethyl sulfide
mono(3-mercaptopropionate), dimercaptoethane mono(salicylate),
hydroxyethylthiomethyl-tris(mercaptoethylthio)methane and the like.
However, the present invention is not limited to these exemplified
compounds. Furthermore, their halogen substituted compounds such as
chlorine substituted compounds, bromine substituted compounds and
the like may be employed. These mercapto compounds having a hydroxy
group may be used singly, or two or more kinds thereof may be used
in combination.
[0060] These active hydrogen compounds may be used singly, or two
or more kinds thereof may be used in combination. As the active
hydrogen compound, preferably used are
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
pentaerythritol tetrakis(3-mercaptopropionate),
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(mercaptodimethylthio)ethyl)-1,3-dithiethane, while
further preferably are
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and
pentaerythritol tetrakis(3-mercaptopropionate).
[0061] In the present invention, it is preferable that the active
hydrogen compounds contain at least one kind of compound having
three or more mercapto groups which is selected from the above
compounds, and it is more preferable that all compounds have three
or more mercapto groups. The refractive index of the thus obtained
resin is improved, the birefringence is also reduced because
optical anisotropy is hardly caused, and mechanical properties such
as impact resistance and the like are improved.
[0062] On the other hand, according to Japanese Laid-open Patent
Publication No. 2005-336476, only a compound having two mercapto
groups is used, which is different from the present invention
employing at least one compound having three or more mercapto
groups. There are many rooms for improvement in optical properties
such as refractive index and the like, and mechanical properties
such as impact resistance and the like of the obtained resin.
[0063] The resin having a thiourethane bond is mainly composed of
one or more kinds of isocyanates selected from the group consisting
of an isocyanate compound and an isothiocyanate compound, and one
or more kinds of active hydrogen compounds having a mercapto group.
However, for the purpose of modifying the polythiourethane resin, a
resin modifier such as a hydroxy compound, an amine compound, an
epoxy compound, an episulfide compound, an organic acid and its
anhydride, an olefin compound containing a (meth)acrylate compound
or the like may be added. Herein, the resin modifier is a compound
which adjusts or improves physical properties such as refractive
index, Abbe's number, heat resistance, specific gravity and the
like, and mechanical strength such as impact resistance of a
polythiourethane resin.
[0064] Examples of the hydroxy compound which may be added as the
resin modifier include diethylene glycol, triethylene glycol,
1,3-propanediol, dipropylene glycol, tripropylene glycol,
1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-pentanediol,
1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol,
1,3-hexanediol, 1,7-heptanediol, 1,8-octanediol, thiodiethanol,
dithiodiethanol, thiodipropanol, dithiodipropanol, their oligomers,
and the like. However, the present invention is not limited to
these exemplified compounds. These alcohol compounds may be used
singly, or two or more kinds thereof may be used in
combination.
[0065] Examples of the amine compound which may be added as the
resin modifier include monofunctional primary amine compounds 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.-aminodiphenylmethane, 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, 2,2-diethoxyethylamine and the like;
primary polyamine compounds 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'-diaminodiphenylsulfone, 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,
N-aminopropylmorpholine and the like; monofunctional secondary
amine compounds 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-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine,
N-ethylbenzylamine, dicyclohexylamine, N-methylaniline,
N-ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine and
the like; and secondary polyamine compounds 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,
tetramethylguanidine and the like. However, the present invention
is not limited to these exemplified compounds. These amine
compounds may be used singly, or two or more kinds thereof may be
used in combination.
[0066] Examples of the epoxy resin which may be added as the resin
modifier include a phenol type epoxy compound obtained by the
condensation reaction of a polyhydric phenol compound such as
bisphenol A glycidyl ether with an epihalohydrin compound, an
alcohol type epoxy compound obtained by condensation of a
polyhydric alcohol compound such as hydrogenated bisphenol A
glycidyl ether with an epihalohydrin compound, a glycidyl ester
type epoxy compound obtained by condensation of a multivalent
organic acid compound such as
3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate or
1,2-hexahydrophthalic acid diglycidyl ester with an epihalohydrin
compound, an amine type epoxy compound obtained by condensation of
a primary or secondary diamine compound with an epihalohydrin
compound, and an aliphatic multivalent epoxy compound such as
vinylcyclohexene diepoxide, and the like. However, the present
invention is not limited to these exemplified compounds. These
epoxy compounds may be used singly, or two or more kinds thereof
may be used in combination.
[0067] Examples of the episulfide compound which may be added as
the resin modifier include chain aliphatic 2,3-epithiopropylthio
compounds such as bis(2,3-epithiopropylthio)sulfide,
bis(2,3-epithiopropylthio)disulfide,
bis(2,3-epithiopropylthio)methane,
1,2-bis(2,3-epithiopropylthio)ethane,
1,5-bis(2,3-epithiopropylthio)-3-thiapentane and the like;
2,3-epithiopropylthio compounds having an alicyclic or heterocyclic
ring such as 1,3-bis(2,3-epithiopropylthio)cyclohexane,
2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane and the like; and
aromatic 2,3-epithiopropylthio compounds such as
1,3-bis(2,3-epithiopropylthio)benzene,
1,4-bis(2,3-epithiopropylthio)benzene and the like. However, the
present invention is not limited to these exemplified
compounds.
[0068] These episulfide compounds maybe used singly, or two or more
kinds thereof may be used in combination.
[0069] Examples of the organic acid and its anhydride which may be
added as the resin modifier include thiodiglycolic acid,
thiodipropionic acid, dithiodipropionic acid, phthalic anhydride,
hexahydrophthalic anhydride, methylhexahydrophthalic anhydride,
methyltetrahydrophthalic anhydride, methylnorbornene anhydride,
methylnorbornene anhydride, maleic anhydride, trimellitic
anhydride, pyromellitic anhydride and the like. However, the
present invention is not limited to these exemplified compounds.
These organic acids and anhydrides thereof may be used singly, or
two or more kinds thereof may be used in combination.
[0070] Examples of the olefin compound which may be added as the
resin modifier include (meth)acrylate compounds such as benzyl
acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl
methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl
acrylate, glycidyl methacrylate, phenoxyethyl acrylate,
phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol
diacrylate, ethylene glycol dimethacrylate, diethylene glycol
diacrylate, diethylene glycol dimethacrylate, triethylene glycol
diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol
diacrylate, tetraethylene glycol dimethacrylate, polyethylene
glycol diacrylate, polyethylene glycol dimethacrylate,
neopentylglycol diacrylate, neopentylglycol dimethacrylate,
ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl
methacrylate, 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, xylylenedithiol diacrylate, xylylenedithiol
dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl
sulfide dimethacrylate and the like; allyl compounds such as allyl
glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl
isophthalate, diallyl carbonate, diethylene glycol
bisallylcarbonate and the like; and vinyl compounds such as
styrene, chlorostyrene, methylstyrene, bromostyrene,
dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane) and
the like. However, the present invention is not limited to these
exemplified compounds. These olefin compounds may be used singly,
or two or more kinds thereof may be used in combination.
[0071] Next, a method for preparing a resin having a thiourethane
bond will be described.
[0072] In the present invention, the proportion of isocyanates used
as a raw material, the active hydrogen compound and the hydroxy
compound as the resin modifier in terms of the molar ratio of
functional groups (NCO+NCS)/(SH+OH) is usually in the range of 0.5
to 3.0, preferably in the range of 0.6 to 2.0, and further
preferably in the range of 0.8 to 1.3.
[0073] At the time of molding the film of the resin having a
thiourethane bond, a variety of substances may be added in the same
manner as in a known molding method depending on the purposes.
Examples of the substance include a catalyst such as dibutyltin
dichloride, dimethyltin dichloride or the like, an ultraviolet
absorber such as a benzotriazole ultraviolet absorber or the like,
an external or internal mold release agent, a light stabilizer, a
chain extender, a cross-linking agent, an anti-oxidant, an
anti-coloring agent, an anti-oxidant, a reaction initiator such as
a radical reaction initiator or the like, a chain extender, a
cross-linking agent, an anti-coloring agent, an oil-soluble dye, a
filler, an adhesion improving agent and the like. These additives
may be added to the polymerizable composition in advance.
[0074] In case of the resin having a thiourethane bond, an
inorganic compound having a sulfur atom or a selenium atom easily
causes remarkable deterioration of color or turbidity, so that the
content of these inorganic compounds in the polymerizable
composition is preferably equal to or less than 1 weight %.
[0075] Next, a method for preparing the monomer will be described.
In the present invention, when isocyanates, the active hydrogen
compound, a reaction catalyst, a mold release agent and other
additives are mixed before the polymerization to prepare a
polymerizable composition, the order of addition of the catalyst,
the mold release agent and other additives will vary depending on
their solubility into the monomers. However, they may be added to
isocyanates and dissolved therein in advance, added to the active
hydrogen compounds and dissolved therein in advance, or added to a
mixture of isocyanates and the active hydrogen compounds and
dissolved therein. Alternatively, the catalyst, the mold release
agent and other additives may be dissolved in a part of the
monomers in use to prepare a master solution, and then the master
solution may be added to the monomer mixture. The order of addition
is not restricted to these exemplified methods, and is properly
selected on the basis of operability, safety, expediency and the
like.
[0076] To add the catalyst, the catalyst may be added as it is, or
the catalyst maybe dissolved in a part of the monomers in use to
prepare a master solution, and then the master solution may be
added to the monomer mixture.
[0077] When the isocyanates, the active hydrogen compound and the
reaction catalyst, the mold release agent and other additives are
mixed to prepare a polymerizable composition, the temperature at
this time is usually equal to or less than 25 degrees centigrade.
From the viewpoint of pot life of the composition, it is sometimes
preferable to employ a lower temperature than 25 degrees
centigrade. However, when the solubility of the reaction catalyst,
the mold release agent and the additives into the monomers is
insufficient, it is also possible to heat them in advance and then
to dissolve them in the isocyanates or the active hydrogen
compounds that are the monomers, or a monomer mixture.
Method for Producing Film
[0078] The film of the present invention can be produced by a usual
method, and can be obtained by the use of the aforementioned
polymerizable composition according to a casting (thin film
coating--polymerization curing) method, a spin
coating--polymerization curing method, a cast molding
polymerization method or the like.
[0079] The casting method or the spin coating--polymerization
curing method refers to a method involving extruding a
viscosity-adjusted polymerizable composition which is a mixture of
a compound having an isocyanate group and a compound having a thiol
group, which is capable of forming a thiourethane, from a cast
coating equipment and casting it on a base material, or rotating a
base material with the composition placed thereon at a high speed
to form a thin film, and then polymerizing and curing it to obtain
a film containing partially a thiourethane bond. Incidentally, the
viscosity at the time of casting (coating) of the mixture is
properly selected by the coating method and uses thereof.
[0080] The cast molding polymerization method refers to a method
involving injecting a polymerizable composition which is a mixture
of a compound having an isocyanate group and a compound having a
thiol group containing partially a thiourethane bond and further
capable of forming thiourethane between surfaces of a mold having a
space of equal to or less than 200 .mu.m composed of a pair of
inorganic glasses, metals or resin plates with four sealed sides,
and polymerizing it to obtain a film. Incidentally, the viscosity
at the time of injecting the mixture is properly selected by the
injection method, curing process and the like.
[0081] Incidentally, in the present invention, the resulting film
may be subjected to annealing. Also, the polymerizable composition
may be mixed with fine particles of a metal oxide, a filler or the
like to form a film.
Uses of Film
[0082] The film of the present invention is excellent in a balance
among high refractive index, low birefringence and light
transmittance, and further excellent in a balance of mechanical
characteristics such as toughness, hardness, dimensional stability
and the like, so that effects of deformation and the like during
processing are very small, while the film is further excellent in
solvent resistance as well, so that the film can be used as various
optical films.
[0083] Examples of the optical film include a polarizing film, a
polarizing element and a polarizing plate protective film
constituting the polarizing film, a phase difference film, an
alignment film, a viewing angle improving (compensation) film, a
diffused plate (film), a prism sheet, a light-guiding plate, a
luminance improving film, a near-infrared absorption film, a
reflection film, an anti-reflection (AR) film, a low reflection
(LR) film, an anti-glare (AG) film, a transparent conductive (ITO)
film, a base material for transparent conductive films, an
anisotropic conductive film (ACF), an electromagnetic wave
shielding (EMI) film, a film for electrode substrates, a film for
color filter substrates, a barrier film, a color filter layer, a
black matrix layer and the like. The optical film of the present
invention may be formed inside or outside of various optical
members of a liquid crystal display, an organic EL display, a
plasma display, a solar cell and the like. The present invention
provides such an optical member.
[0084] Meanwhile, the optical film of the present invention is
particularly positioned on a surface of a light emitting surface or
a light capturing surface, whereby light can be taken out or
captured with good efficiency and the optical film is most suitably
used for applications that require these actions. For example, one
surface of the film is processed into a concavo-convex pattern and
the other surface is attached to the light emitting surface of a
light emitting device, whereby it is possible to provide a light
emitting device having improved luminous efficiency by taking out
light that is reflected inside a luminous body to the outside.
Furthermore, this film itself is used as a substrate and a light
emitting element is directly formed on a surface of the film,
whereby it is possible to provide a light emitting device having
improved luminous efficiency by reducing reflection inside the
element. According to the present invention, it is also possible to
provide a light emitting device in which the optical film is formed
inside or outside thereof, and further a lighting device using the
light emitting device (a LED lamp, a back light of a display, and a
flashlight of a camera or a cellular phone or the like) and an
image display device using the light emitting device (a flat panel
display or the like).
[0085] The optical film of the present invention may be composed of
one film having two or more functions of such an optical film, or
may constitute a part or the whole of a film (a composite film)
having two or more of such optical films. These optical films
formed on a base material such as glass, other resin films or the
like are used without peeling off, whereby it is also possible to
provide a laminated member, and a multi-layer structure.
EXAMPLES
[0086] Hereinafter, the present invention will be illustrated in
more detail with reference to Examples. However, the present
invention is not restricted to these Examples.
[0087] Performances of the films obtained in Examples were
evaluated according to the following test methods. [0088]
Refractive Index and Abbe's Number: These were measured at 20
degrees centigrade using a multiwavelength Abbe refractometer
manufactured by Atago Co., Ltd. (sodium D line: 589 nm). [0089]
Birefringence: The in-plane retardation Re and the in-plane
birefringence .DELTA.n.sub.xy were measured at a wavelength 590 nm
using KOBRA-CCD/X manufactured by Oji Scientific Instruments. The
measurement of the retardation in the thickness direction, Rth and
the birefringence in the thickness direction, .DELTA.n.sub.x, was
conducted in the wavelength range from 400 to 800 nm using a
retardation measuring apparatus, RETS-100, a product of Otsuka
Electronics Co., Ltd. according to a rotation analyzer method (Rth
and .DELTA.n in the Table were values at 590 nm). [0090]
Coefficient of Linear Expansion: It was measured at a temperature
elevation rate of 5 degrees centigrade/min using a test piece
processed into a shape having a length of 15 mm and a width of 5 mm
with a thermomechanical analyzer (TMA-50, a product of Shimadzu
Corporation). Furthermore, a TMA softening temperature was obtained
from the intersection of the tangents of the TMA curves before and
after the glass transition temperature. [0091] Mechanical Strength:
A dumbbell test specimen processed into a shape having a length of
50 mm and a width of 5 mm was pulled from both ends of the test
specimen at a tensile speed of 30 mm/min (thickness: 80 to 100
.mu.m) using a universal testing machine (201-5 model, a product of
Intesco Co., Ltd.). [0092] Impact Strength: It was measured using a
pendulum hammer having a tip diameter of 1 inch with a film impact
tester (a product of Toyo Seiki Seisaku-sho, Ltd.). [0093] Total
Light Transmittance (Transmittance-1): It was measured in
accordance with JIS-K7105 using a haze meter (NDH2000, a product of
Nippon Denshoku Industries Co., Ltd.). [0094] 550 nm Transmittance
(Transmittance-2): The transmittance was measured at a wavelength
550 nm using a spectrophotometer (U-3010, a product of Hitachi,
Ltd.). [0095] Water Vapor Transmission: The amount of water vapor
transmission was measured in accordance with JIS Z0208 under the
conditions of a temperature of 60 degrees centigrade, a humidity of
90% RH and a film thickness of 100 .mu.m. [0096] Solvent
Resistance: Respective solvents (acetone, ethanol, cyclohexanone
and toluene) were respectively added dropwise on the film, and then
the film was rubbed with a bemcot to visually observe the dissolved
state on the surface.
Production Example 1
[0097] A polythiol compound (B-2) containing
5,7-dimercaptomethyl-1,11-dimercapto-3,6-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6-trithiaundecane and
4,8-dimercaptomethyl-1,11-dimercapto-3,6-trithiaundecane was
synthesized in accordance with the method described in Example 1 of
Japanese Laid-open Patent Publication No. 1995-252207.
Production Example 2
[0098] A polythiol compound (B-3) containing 1, 1, 3, 3-tetrakis
(mercaptomethylthio) propane, 4, 6-bis (mercaptomethylthio) -1,
3-dithiane and 2-(2, 2-bis (mercaptomethylthio) ethyl) -1,
3-dithiethane was synthesized in accordance with the method
described in Production Example 2 of Japanese Laid-open Patent
Publication No. 2004-2820.
Example 1
[0099] 10.5 mg of dibutyltin dichloride as a catalyst and 70 mg of
Zelec UN (product name, acid phosphoric acid alkyl ester, a product
of Stepan Company) as an internal release agent were added to 36.4
g of m-xylylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 33.6 g of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was added thereto,
and the contents were well mixed to give a monomer mixed solution.
The monomer mixed solution was degassed under reduced pressure for
1 hour. A Kapton tape of 80 .mu.m was affixed to four sides of a
blue plate glass in a frame shape to build a wall, the monomer
mixed solution was added dropwise to the inside of the wall, and a
plate glass of the same size was further placed from the top. It
was confirmed that the inside of the Kapton tape wall was filled
with the monomer mixed solution, and then two plates of glasses
with the solution sandwiched between them were fixed with a clip.
The resulting material was subjected to a temperature elevation
from 20 to 120 degrees centigrade slowly and cured over 20 hours.
After cooling, a film was obtained by peeling it off from the
glass.
The resulting film was colorless and transparent.
Example 2
[0100] 10.5 mg of dibutyltin dichloride as a catalyst and 70 mg of
Zelec UN (product name, acid phosphoric acid alkyl ester, a product
of
[0101] Stepan Company) as an internal release agent were added to
36.4 g of m-xylylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 33.6 g of 4
-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was added thereto,
and the contents were well mixed to give a monomer mixed solution.
The monomer mixed solution was degassed under reduced pressure for
1 hour, and then applied to a polyethylene naphthalate film (Teonex
Q51, a product of Teijin Ltd.) using an applicator (a product of
Coating Tester Industries Co., Ltd.) with a coating gap set at 70
.mu.m. The monomer mixed solution was uniformly wet spread on the
base material. The resulting material was subjected to a
temperature elevation from 20 to 120 degrees centigrade slowly and
cured over 13 hours. After cooling, a film was obtained by peeling
off the base material. The resulting film was colorless and
transparent. Respective physical properties of the film were as
follows: [0102] Refractive Index: 1.66 (sodium D line: 589 nm)
[0103] Abbe's Number: 32 [0104] Transmittance (average
transmittance at a wavelength 400 to 800 nm): 88.7% (film
thickness: 80 .mu.m)
[0105] Incidentally, it was 88.0% (film thickness: 80 .mu.m) at a
wavelength 430 nm. [0106] Birefringence: In-plane Retardation Re
(wavelength: 590 nm): 0.8 nm (film thickness: 80 .mu.m)
[0107] Birefringence .DELTA.n.sub.xy (wavelength: 590 nm):
1.0.times.10.sup.-5
[0108] Retardation in the thickness direction, Rth (wavelength: 590
nm): 49 nm
[0109] Birefringence .DELTA.n.sub.xz (wavelength: 590 nm):
6.3.times.10.sup.-4 [0110] Water Vapor Transmission Rate: 7
g/m.sup.224 hr (film thickness: 100 .mu.m conversion) [0111]
Solvent Resistance: Dissolution with respect to any of solvents
such as acetone, ethanol, cyclohexanone and toluene was not
recognized. [0112] Coefficient of Linear Expansion:
8.times.10.sup.-5/K (thickness: 80 .mu.m) [0113] Mechanical
strength: [0114] Tensile Modulus: 3.8 to 4.1 GPa [0115] Breaking
stress: 120 MPa [0116] Breaking elongation: 3.1 to 5.7% [0117]
Impact Strength: 2 to 4 kJ/m (thickness: 45 to 55 .mu.m)
Example 3
[0118] 2. 5 mg of dibutyltin dichloride as a catalyst and 12.4 mg
of Zelec UN (product name, acid phosphoric acid alkyl ester, a
product of Stepan Company) as an internal release agent were added
to 6.1 g of 2,4-tolylene diisocyanate in advance, and the contents
were dissolved to give a monomer mixed solution. Next, 6.3 g of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was added thereto,
and the contents were well mixed to give a monomer mixed solution.
The monomer mixed solution was degassed under reduced pressure for
1 hour. A Kapton tape of 80 .mu.m was affixed to four sides of a
blue plate glass in a frame shape to build a wall, the monomer
mixed solution was added dropwise to the inside of the wall, and a
plate glass of the same size was further placed from the top. It
was confirmed that the inside of the Kapton tape wall was filled
with the monomer mixed solution, and then two plates of glasses
with the solution sandwiched between them were fixed with a clip.
The resulting material was subjected to a temperature elevation
from 20 to 120 degrees centigrade slowly and cured over 13 hours.
After cooling, a film was obtained by peeling it off from the
glass. The resulting film was colorless and transparent.
Example 4
[0119] 2.4 mg of dibutyltin dichloride as a catalyst and 11.9 mg of
Zelec UN (product name, acid phosphoric acid alkyl ester, a product
of Stepan Company) as an internal release agent were added to 5.6 g
of 2,4-tolylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 6.3 g of the
polythiol compound (B-2) synthesized according to the method
described in Production Example 1 was added thereto, and the
contents were well mixed to give a monomer mixed solution. The
monomer mixed solution was degassed under reduced pressure for 1
hour. A Kapton tape of 80 .mu.m was affixed to four sides of a blue
plate glass in a frame shape to build a wall, the monomer mixed
solution was added dropwise to the inside of the wall, and a plate
glass of the same size was further placed from the top. It was
confirmed that the inside of the Kapton tape wall was filled with
the monomer mixed solution, and then two plates of glasses with the
solution sandwiched between them were fixed with a clip. The
resulting material was subjected to a temperature elevation from 20
to 120 degrees centigrade slowly and cured over 13 hours. After
cooling, a film was obtained by peeling it off from the glass. The
resulting film was colorless and transparent.
Example 5
[0120] In a water bath at 50 degrees centigrade, 10.0 mg of
dibutyltin dichloride as a catalyst and 100 mg of Zelec UN (product
name, acid phosphoric acid alkyl ester, a product of Stepan
Company) as an internal release agent were added to 41.3 g of
2,4-tolylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 58.7 g of the
polythiol compound (B-3) synthesized according to the method
described in Production Example 2 was added thereto, and the
contents were well mixed to give a monomer mixed solution. The
monomer mixed solution was degassed at 50 degrees centigrade under
reduced pressure for 15 minutes. A Kapton tape of 80 .mu.m was
affixed to four sides of a blue plate glass in a frame shape to
build a wall, the monomer mixed solution was added dropwise to the
inside of the wall, and a plate glass of the same size was further
placed from the top. It was confirmed that the inside of the Kapton
tape wall was filled with the monomer mixed solution, and then two
plates of glasses with the solution sandwiched between them were
fixed with a clip. The resulting material was subjected to a
temperature elevation from 50 to 120 degrees centigrade slowly and
cured over 22 hours. After cooling, a film was obtained by peeling
it off from the glass. The resulting film was colorless and
transparent.
Example 6
[0121] In a water bath at 60 degrees centigrade, 2.3 g of
hexamethylene diisocyanate, 5 mg of dibutyltin dichloride as a
catalyst, 225 mg of dibutyl phosphate as an internal release agent
and 25 mg of monobutyl phosphate were added to 35 g of heat-melted
m-phenylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 62.7 g of the
polythiol compound (B-3) synthesized according to the method
described in Production Example 2 was added thereto, and the
contents were well mixed to give a monomer mixed solution. The
monomer mixed solution was degassed at 60 degrees centigrade under
reduced pressure for 5 minutes. A Kapton tape of 80 .mu.m was
affixed to four sides of a blue plate glass in a frame shape to
build a wall, the monomer mixed solution was added dropwise to the
inside of the wall, and a plate glass of the same size was further
placed from the top. It was confirmed that the inside of the Kapton
tape wall was filled with the monomer mixed solution, and then two
plates of glasses with the solution sandwiched between them were
fixed with a clip. The resulting material was subjected to a
temperature elevation from 50 to 120 degrees centigrade slowly and
cured over 24 hours. After cooling, a film was obtained by peeling
it off from the glass. The resulting film was colorless and
transparent.
Example 7
[0122] 10.0 mg of dibutyltin dichloride as a catalyst and 100 mg of
Zelec UN (product name, acid phosphoric acid alkyl ester, a product
of Stepan Company) as an internal release agent were added to 44.5
g of m-xylylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 55.5 g of the
polythiol compound (B-3) synthesized according to the method
described in Production Example 2 was added thereto, and the
contents were well mixed to give a monomer mixed solution. The
monomer mixed solution was degassed under reduced pressure for 1
hour. A Kapton tape of 80 .mu.m was affixed to four sides of a blue
plate glass in a frame shape to build a wall, the monomer mixed
solution was added dropwise to the inside of the wall, and a plate
glass of the same size was further placed from the top. It was
confirmed that the inside of the Kapton tape wall was filled with
the monomer mixed solution, and then two plates of glasses with the
solution sandwiched between them were fixed with a clip. The
resulting material was subjected to a temperature elevation from 20
to 120 degrees centigrade slowly and cured over 22 hours. After
cooling, a film was obtained by peeling it off from the glass. The
resulting film was colorless and transparent.
[0123] Respective physical properties of respective resulting films
are shown in Table 1.
TABLE-US-00001 TABLE 1 Example 1 Example 3 Example 4 Example 5
Example 6 Example 7 Monomer composition (g) A-1 (36.4) A-2 (6.1)
A-2 (5.6) A-2 (41.3) A-3 (35.0) A-1 (44.5) B-1 (33.6) B-1 (6.3) B-2
(6.3) B-3 (58.7) A-4 (2.3) B-3 (55.5) B-3 (62.7) Film thickness
(.mu.m) 80 80 80 100 90 90 S/N 1.67 1.67 1.75 2.00 2.00 2.67
Refractive index (D line) 1.66 1.68 1.68 1.71 1.73 1.69 Refractive
index (e line) 1.67 1.69 1.69 1.72 1.74 1.70 Abbe's number (.nu.d)
31 25.4 24.6 25.5 24.5 31.1 Transmittance-1 (Total 89 89 89 89 88
88 light transmittance, haze meter) Transmittance-2 (550 nm) 89 89
88 88 88 88 In-plane retardation (Re) 0.8 0.6 0.5 0.5 0.4 0.7 (nm)
Solvent resistance Not Not Not Not Not Not (acetone, ethanol,
dissolved dissolved dissolved dissolved dissolved dissolved
cyclohexanone, toluene) Coefficient of linear 62 76 69 80 60 61
expansion (50 to 90 degrees centigrade) TMA softening temperature
98 118 127 121 102 88 (degrees centigrade) Tensile modulus (GPa)
3.8-4.1 2.7-3.2 2.9-3.3 2.0-3.4* 3.4-3.8 4.1-4.6 Breaking stress
(MPa) 90-120 15-116 15-31 14-90* 116-125 133-136 Breaking
elongation (%) 3.1-5.7 0.6-7 0.6-1.1 0.6-3.8* 4.4-5.4 5.2-5.3 *A
strip having a size of 5 cm .times. 5 mm was used for the
measurement. Abbreviations used in monomer compositions of Table 1
are shown below: A-1: m-xylylene diisocyanate A-2: 2,4-tolylene
diisocyanate A-3: m-phenylene diisocyanate A-4: hexamethylene
diisocyanate B-1: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
B-2: Polythiol compound synthesized in Production Example 1 B-3:
Polythiol compound synthesized in Production Example 2
Example 8
[0124] A film was obtained in the same manner as in Example 1,
except that the height of the Kapton tape wall was changed to 400
.mu.m. The resulting film was colorless and transparent.
Example 9
[0125] A film was obtained in the same manner as in Example 1,
except that the height of the Kapton tape wall was changed to 700
.mu.m. The resulting film was colorless and transparent.
Example 10
[0126] A film was obtained in the same manner as in Example 5,
except that the height of the Kapton tape wall was changed to 200
.mu.m. The resulting film was colorless and transparent.
Example 11
[0127] A film was obtained in the same manner as in Example 6,
except that the height of the Kapton tape wall was changed to 200
.mu.m. The resulting film was colorless and transparent.
TABLE-US-00002 TABLE 2 Film Birefringence in the thickness
thickness direction Monomer combination (.mu.m) (.DELTA.n.sub.xz)
Example 1 A-1 B-1 80 7.5 .times. 10.sup.-4 Example 2 A-1 B-1 80 6.3
.times. 10.sup.-4 Example 8 A-1 B-1 350 8.5 .times. 10.sup.-4
Example 9 A-1 B-1 670 9.3 .times. 10.sup.-4 Example 3 A-2 B-1 80
5.1 .times. 10.sup.-4 Example 4 A-2 B-2 80 6.0 .times. 10.sup.-4
Example 5 A-2 B-3 100 4.8 .times. 10.sup.-4 Example 6 A-3, A-4 B-3
90 6.1 .times. 10.sup.-4 Example 10 A-2 B-3 180 5.6 .times.
10.sup.-4 Example 11 A-3, A-4 B-3 190 6.6 .times. 10.sup.-4 Example
7 A-1 B-3 90 4.6 .times. 10.sup.-4
Example 12
[0128] 10.5 mg of dibutyltin dichloride as a catalyst was added to
36.4 g of m-xylylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 33.6 g of 4
-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was added
thereto, and the contents were well mixed to give a monomer mixed
solution. The monomer mixed solution was degassed under reduced
pressure for 1 hour, and then applied to a borosilicate glass with
its surface cleaned by means of a UV ozone cleaning equipment using
an applicator with a coating gap set at 60 .mu.m. The monomer mixed
solution was uniformly wet spread on the glass base material. The
resulting material was subjected to a temperature elevation from 20
to 120 degrees centigrade slowly and cured over 13 hours. After
curing was completed, the cured product was annealed at 120 degrees
centigrade for 2 hours under a nitrogen atmosphere and placed under
reduced pressure overnight. The thickness of the cured resin film
was 50 .mu.m. Thereafter, an ITO sputtered film was formed on the
cured resin film. Using a target of SnO.sub.2 (10 wt %), in a mixed
atmosphere of argon and oxygen, the substrate temperature was set
at room temperature to form an ITO film having a thickness of 150
nm on the cured resin film (sputtering apparatus for forming thin
film, a product of ULVAC, Inc.). Furthermore, ITO directly formed
into a film on the borosilicate glass was also prepared.
Example 13
[0129] 10.5 mg of dibutyltin dichloride as a catalyst was added to
36.4 g of m-xylylene diisocyanate in advance, and the contents were
dissolved to give a monomer mixed solution. Next, 33.6 g of 4
-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was added
thereto, and the contents were well mixed to give a monomer mixed
solution. The monomer mixed solution was degassed under reduced
pressure for 1 hour, and then applied to the frosted surface of a
Tempax one-side frosted glass plate (grit # 320: concavo-convex
height of 1 to 4 .mu.m) cleaned by means of a UV ozone cleaning
equipment using an applicator with a coating gap set at 120 .mu.m.
The monomer mixed solution was uniformly wet spread on the glass
base material. The resulting material was subjected to a
temperature elevation from 20 to 120 degrees centigrade slowly and
cured over 13 hours. After curing was completed, the cured product
was annealed at 120 degrees centigrade for 2 hours under a nitrogen
atmosphere and placed under reduced pressure overnight. The
thickness of the cured resin film was 120 .mu.m. Thereafter, an ITO
sputtered film was formed on the cured resin film. Using a target
of SnO.sub.2 (10 wt %), in a mixed atmosphere of argon and oxygen,
the substrate temperature was set at room temperature to form an
ITO film having a thickness of 150 nm on the cured resin film
(sputtering apparatus for forming thin film, a product of ULVAC,
Inc.). Furthermore, ITO directly formed into a film on the
borosilicate glass was also prepared.
[0130] This application is based on Japanese patent application No.
2009-260449 filed on Nov. 13, 2009 and Japanese patent application
No. 2010-067563 filed on Mar. 24, 2010, the contents of which are
incorporated hereinto by reference.
[0131] The present invention includes the following
embodiments:
[0132] (1) A film comprising a resin having a thiourethane bond,
wherein the molar ratio (S/N) of sulfur to nitrogen contained in
said resin is equal to or more than 0.8 and less than 3.
[0133] (2) The film according to (1), wherein the refractive index
in a sodium D line is equal to or more than 1.6, the in-plane
retardation Re of a film having a film thickness of 1 to 200 .mu.m
at a wavelength 590 nm is equal to or less than 10 nm, and the mean
value of the light transmittance to the light having a wavelength
400 to 800 nm is equal to or more than 80%.
[0134] (3) The film according to (1) or (2), wherein the resin
having a thiourethane bond has an aromatic group, a heterocyclic
group or an alicyclic group in the structure.
[0135] (4) The film according to any one of (1) to (3), obtained by
a casting method.
[0136] (5) An optical film composed of the film according to any
one of (1) to (4).
[0137] (6) An optical member equipped with the optical film
according to (5).
[0138] (7) A display equipped with the optical film according to
(5).
[0139] (8) A light emitting device equipped with the optical film
according to (5).
[0140] (9) A lighting device using the light emitting device
according to (8).
[0141] (10) An image display device using the light emitting device
according to (8).
[0142] Incidentally, the film of the present invention also
includes a sheet-like one.
* * * * *