SPECIFICATION
POLYMERIZABLE COMPOSITION FOR OPTICAL MATERIAL, OPTICAL MATERIAL,
AND METHOD OF MANUFACTURING OPTICAL MATERIAL
TECHNICAL FIELD
[ 000 1]
The present invention relates to a polymerizable composition
for an optical material, an optical material, and a method of
10 manufacturing an optical material.
BACKGROUND ART
[0002]
Plastic lenses are light 1-1eight, less broken, and dyeable, as
15 compared with inorganic lenses. Therefore, in recent years, the
application of the plastic lenses to optical materials for a spectacle
lens, a camera lens, or the like has increased rapidly. Particularly,
from the viewpoint of reducing the thickness of a lens, a plastic
material having a high refractive index is desired, and, from the
20 viewpoint of reducing chromatic aberration, a plastic material having
a high Abbe number is desired. Among them, a plastic lens, which
is comprised of a polythiourethane resin obtained by reacting a
polythiol and a polyiso (thio) cyanate compound, has a high refractive
index, and is.excellent in impact resistance, dye-affinity,
25 workability, and the like.
Further, in recent years, from the viewpoint of fashionability,
lens having a two point frame, in which a frame for holding a spectacle
-------------------------------
2
lens is not provided at the periphery of a spectacle lens, has been
used. When using the two point frame, in order to perform a drilling
processing (two point processing) at both ends of the spectacle lens,
the spectacle lens was required to have excellent workability and
5 high strength.
[0003]
Patent Document 1 discloses a polymerizable composition for an
optical material containing a phenylene diisocyanate and a
predetermined polythiol compound, and an ultrahigh refractive
10 polythiourethane plastic lens having a refractive index of 1.7 or
more, the lens being obtained from the composition.
Further, Patent Document 2 discloses a polymerizable
composition for an optical material containing episulfide
(thioepoxide). Additionally, it is described that an
15 episulfide-based plastic lens having a refractive index of about 1. 7
was obtained using the composition.
Further, Patent Document 3 discloses a composition for plastic
lenses containing a compound having at least one radical
polymerizable unsaturated double bond in a molecule, a predetermined
20 alicyclic or aromatic polyisocyanate compound, and a predetermined
polythiol compound, and discloses a plastic lens obtained from the
composition.
RELATED DOCUMENT
PATENT DOCUMENT
25 [0004]
[Patent Document 1] Pamphlet of International Publication No.
W02010-032365
5
3
[Patent Document 2] Japanese Unexamined Patent Publication No.
11-322930
[Patent Document 3] Japanese Unexamined Patent Publication No.
05-25240
DISCLOSURE OF THE INVENTION
[0005]
However, the plastic lens obtained from the polymerizable
composition for an optical material, described in Patent Document
10 1, has a high refractive index, but has 101-1 Abbe number and relatively
large chromatic aberration. That is, there is room for improvement
in the Abbe number.
Further, the plastic lens obtained from the polymerizable
composition for an optical material containing an episulfide compound,
15 described in Patent Document 2, has a high refractive index, but there
Here cases in which mechanical strength 1-1as lowered.
The plastic lens obtained from the composition described in
Patent Document 3 has a low refractive index, and has room for
improvement in optical properties. Here, the composition contains
20 three polymerization components, and thus manufacturing processes
or manufacturing conditions become complicated; thereby reducing the
yield of the plastic lens. Therefore, it is hard to say that this
plastic lens has a configuration excellent in· manufacturing
stability.
25 [ 0006]
The present invention has been made in vi el-l of such circumstances,
and an object of the present invention is to provide a thiourethane
4
optical material having excellent mechanical strength as well as
having excellent optical properties such as refractive index and Abbe
number, that is, a thiourethane optical material which is excellent
in the balance between these properties.
5 [0007]
The present invention may be described as follows.
[1] A polymerizable composition for an optical material,
including: (A) a compound having a carbon-carbon triple bond and at
least one group selected from an isocyanate group and an
10 isothiocyanate group in a molecule; and (B) a polythiol compound.
[2] The polymerizable composition for an optical material
according to [ 1] , in which the compound (A) is represented by following
general formula (1);
R=--_
2 ----===:=--+( A~ R
1
n (1)
15 wherein, in formula (1), A1 represents an alkylene group of 1
to 4 carbon atoms which may be substituted or a pheny1ene group which
may be substituted, n is an integer of 0 or 1, R1 represents an
isocyanate group or an isothiocyanate group, and R2 represents a
hydrogen atom, an alkyl group of 1 to 4 carbon atoms or a group
20 represented by the following formula;
wherein, A2 and R3 have the same meaning as A1 and R1
, respectively,
and may be the same as or different from these groups, * represents
a coupling hand.
5
[3] The polymerizable composition for an optical material
according to [2], in which the compound (A) is represented by following
general formula (2);
5 wherein, in formula (2), A3 is an alkylene group of 1 to 4 carbon
atoms which- may be s-ubstituted or a phenylene group which may be
substituted, R4 represents an isocyanate group or an isothiocyanate
group, and n is an integer of 0 or 1)
[4] The polymerizable composition for an optical material
10 according to any one of [1] to [3], in which the polythiol compound
(B) is at least one selected from the group consisting of
pentaerythritol tetrakis(3-mercaptopropionate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
15 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
20 -1,1,2,2-tetrakis(mercaptomethylthio)ethane, and
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane.
[5] The polymerizable composition for an optical material
according to any one of [ 1] to [ 4] , in which a functional group molar
ratio represented by the follmving formula is 0. 5 to 3. 0.
25._ Formula: [(number of moles of isocyanate group included in
polymerizable composition + number of moles of isothiocyanate group
6
included in polymerizable composition + (number of triple bonds) x
2 I number of moles of thiol group included in polymerizable
composition)]
[6] A method of manufacturing an optical material, including:
5 mixing the compound (A) and the polythiol compound (B) to prepare
the polymerizable composition for an optical material according to
any one of [1] to [5] ; injecting the polymerizable composition into
a casting mold; and polymerizing and curing the polymerizable
composition in the casting mold.
10 [7] An optical material, which is obtained by the manufacturing
method according to [6].
[ 8] The optical material according to [ 7] , in Nhich a refractive
index of e-line is in a range of 1.60 to 1.80.
[9] A plastic spectacle lens, \vhich is comprised of the optical
15 material according to [7] or [8].
[0008]
According to the polymerizable composition for an optical
material of the present invention, it is possible to obtain an optical
material Nhich has a high refractive index and a high Abbe number
2 0 and Nhich is also excellent in mechanical strength, that is, an optical
material 1vhich is excellent in the halance between these properties.
25
DESCRIPTION OF EMBODIMENTS
[0009]
The polymerizable composition for an optical material of the
present invention includes: (A) a. compound having a carbon-carbon
triple bond and at least one group selected from an isocyanate group
7
and an isothiocyanate group in a molecule; and (B) a polythiol polymer.
The present inventor found that, in such a configuration,
particularly, when a compound (A) having a relatively small molecular
1-1eight and having an isocyanate group and a carbon-carbon triple bond
5 in a molecule is used, an optical material having a high refractive
index is obtained. Further, they found that, when a combination of
a compound (A) -and a polythiol compound (B) is used, an optical
material having a high refractive index and a high Abbe number and
having excellent mechanical strength is obtained. The present
10 invention has been completed based on these findings.
[0010]
Hereinafter, the polymerizable composition for an optical
material according to the present invention will be described with
reference to embodiments.
15 First, each component will be described.
[DOll]
[Compound (A)]
A compound (A) used in the present embodiment has a carbon-carbon
triple bond and at least one group selected from an isocyanate group
20 and an isothiocyanate group.
- The compound (A) may be represented by following general formula
( 1) .
[ 0012]
(1)
25 [0013]
In formula (1), A1 represents an alkylene group of 1 to 4 carbon
8
atoms which may be substituted or a phenylene group which may be
substituted.
As the substituent group of the alkylene group of l to 4 carbon
atoms which may be substituted, a monomethyl group, a dimethyl group,
5 or the like can be exemplified. As the substituent group of the
phenylene group which may be substituted, a methyl group or the like
can be exemplified.
Preferably, A1 is a methylene group, an ethylene group, a
propylene group, a butylene group, an o-phenylene group, a
10 p-phenylene group, or a m-phenylene group.
In formula (1), n is an integer of 0 or 1.
In formula (1), R1 represents an isocyanate group or an
isothiocyanate group, and is preferably an isocyanate group.
In formula (1), R2 is a hydrogen atom, an alkyl group of 1 to
15 4 carbon atoms or a group represented by the following formula.
[0014]
[0015]
··, In the formula, A2 and R3 have the same ·meaning as A1 and R1
,
20 respectively, and may be the same as or different from these groups.
* represents a coupling hand.
R2 in general formula .(1) is preferably a hydrogen atom, a methyl
group, or an isocyanatomethylene group.
[0016]
25 As the compound (A), preferably, a compound represented by
9
following general formula (2) can be used.
[0017)
[0018)
5 In formula (2), A3 represents an alylene group of 1 to 4 carbon
atoms 1vhich may be substituted or a phenylene group 1vhich may be
substituted.
As the substituent group of the alkylene group of 1 to 4 carbon
atoms which may be substituted, a monomethyl group, a dimethyl group,
10 or the like can be exemplified. As the substituent group of the
phenylene group which may be substituted, a methyl group or the like
can be exemplified. Preferably, A3 is a methylene group, an ethylene
group, or a phenylene group.
R4 represents an isocyanate group or an isothiocyanate group,
15 and is preferably an isocyanate group.
n is an integer of 0 or 1.
[0019)
Examples of the compound represented by general formula (2)
include propargyl isocyanate, ethynyl isocyanate, 3-butyl isocyanate,
20 · .. · ethynyl phenylene isocyanate, propargyl isothiocyanate, ethynyl
isothiocyanate, 3-butynyl isothiocyanate, and ethynyl phenylene
isothiocyanate. In the present embodiment, propargyl isocyanate,
propargyl isothiocyanate, ethynyl phenylene isocyanate, and ethynyl
phenylene isothiocyanate can be preferably used.
25 [0020)
The compound represented by general formula (1) can be obtained
I
5
10
by reacting an amine compound or a hydrochloride salt thereof with
phosgene or a phosgene equivalent such as triphosgene in a solvent.
[0021]
[Polythiol compound (B)]
Examples of the polythiol compound (B) may include: aliphatic
polyol compounds, such as methane dithiol, 1,2-ethane dithiol,
1,2,3-propane trithiol, 1,2-cyclohexane dithiol,
bis(2-mercaptoethyl) thioether, tetrakis(mercaptomethyl)methane,
diethylene glycol bis(2-mercaptoacetate), diethylene glycol
10 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
15 tris(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), bis(mercaptomethyl) sulfide,
bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide,
bis(mercaptoethyl) disulfide, bis(mercaptopropyl) sulfide,
20 bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane,
bis ( 3-mercaptopropyl thio) methane, ·
1,2-bis(mercaptomethylthio)ethane,
1,2~bis(2-mercaptoethylthio)ethane,
1, 2-bis ( 3-mercap.t.opropyl thio) ethane,
25 1, 2,3-tris (mercaptomethylthio) propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
11
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,
5 tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
tetrakis(3-mercaptopropylthiomethyl)methane,
bis(2,3-dimercaptopropyl) sulfide,
2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane,
10 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and esters of
thioglycolic acid and mercaptopropionic acid thereof, hydroxymethyl
sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide
bis(3-mercaptopropionate), hydroxyethyl sulfide
bis(2-mercaptoacetate), hydroxyethyl sulfide
15 bis(3-mercaptopropionate), hydroxymethyl disulfide
bis(2-mercaptoacetate), hydroxymethyl disulfide
bis(3-mercaptopropionate), hydroxyethyl disulfide
bis(2-mercaptoacetate), hydroxyethyl disulfide
bis(3-mercaptopropionate), 2-mercaptoethyl ether
20 bis(2-mercaptoacetate), 2-mercaptoethyl ether
bis (3-mercaptopropionate), thiodiglycolic acid bis (2~mercaptoethyl
ester), thiodipropionic acid bis(2-mercapto ethyl ester),
dithiodiglycolic acid bis(2-mercapto ethyl ester),
dithiodiprop~onic acid bis(2-mercapto ethyl ester.),.
25 1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
12
tris(mercaptomethy1thio)methane, tris(mercaptoethy1thio)methane;
aromatic po1ythio1 compounds, such as 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene,
1,2-bis(mercaptomethy1)benzene, 1,3-bis(mercaptomethyl)benzene,
5 1,4 bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene,
1,3-bis(mercaptoethy1)benzene, 1,4-bis(mercaptoethyl)benzene,
1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethy1eneoxy)benzene,
1,3,5-tris(mercaptoethy1eneoxy)benzene, 2,5-to1uene dithio1,
10 3,4-to1uene dithio1, 1,5-naphthalene dithiol, and 2,6-naphthalene
dithiol; and heterocyclic polythiol compounds, such as
2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophene dithiol,
bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane. At least
15 one of these polythiol compounds can be used as the polythiol compound
(B) •
Further, oligomers or halogen substitution products such as
chlorine substitution products and bromine substitution products of
these polythiol compounds can also be used as the polythiol compound
20 (B) .
[0022]
As the polyt,hiol compound (B), at least one selected from the
group consisting of pentaerythritol tetrakis (3-mercaptopropionate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
25 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,
13
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane, and
5 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane can be used.
[0023]
[Other components]
The polymerizable composition for an optical material according
to the present embodiment can contain a reaction catalyst, a radical
10 polymerization initiator, a polyisocyanate compound, an isocyanate
compound having an isothiocyanate group or a polyisothiocyanate
compound, and a thiol compound having a hydroxy group, in addition
to the above-mentioned compound (A) and polythiol compound (B) .
[0024]
15 Examples of the reaction catalyst may include: tin compounds,
such as dibutyltin dilaurate, dibutyltin dichloride, and,
dimethyl tin dichloride; and amine compounds such as tertiary amines.
These compounds can be used alone or in a combination of two or more
thereof. A knmm urethane-forming catalyst or thiourethane-forming
20 catalyst can also be used as the reaction catalyst.
25
The amount of the reaction catalyst used is not particularly
limited, but is generally in a range of 0 parts by Height to 10 parts
by weight based on 100 parts by weight of a polymerizable component.
[ 0025]
The radical polymerization initiator is not particularly
limited as long as it is responsive to an active energy ray such as
heat or ultraviolet. In thermal polymerization, organic peroxides
14
or azo compounds known in the related art can be used. Here, generally,
compounds having a 10-hour half-life temperature of 120°C or lower
are preferably used depending on heating conditions. Examples of
these compounds can include cumyl peroxyneodecanoate, di-n-propyl
5 peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, t-butyl
peroxyneodecanoate, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide,
acetyl peroxide, t- butyl peroxy-2-ethylhexanoate, benzoyl peroxide,
t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl
peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropylcarbonate,
10 t-butyl peroxyacetate, t-butyl peroxybenzoate, methyl ethyl ketone
peroxide, dicumyl peroxide, t-butyl cumyl peroxide, and the like.
As the azo compounds, azobisisobutyronitrile,
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and
azobis (methylbutylnitrile) can be exemplified. These catalysts may
15 be used alone or in a combination of two or more thereof.
The reaction catalyst and the radical polymerization initiator
may be used alone or in a combination thereof.
[0026]
Examples of the polyisocyanate compound may include: aliphatic
20 polyisocyanate compounds, such as hexamethylene diisocyanate,
2, 2, 4-trimethylhexane di·isocyanate, 2, 4, 4-trimethylhexamethyiene
diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate,
m-xylylene diisocyanate, a,a,a',a'-tetramethylxylylene
~ piisocyanate, bis(isocyanatomethyl)naphthalene, mesitylene
25 triisocyanate, bis(isocyanatomethyl) sulfide, bis(isocyanatoethyl)
sulfide, bis(isocyanatomethyl) disulfide, bis(isocyanatoethyl)
disulfide, bis(isocyanatomethylthio)methane,
15
bis(isocyanatoethylthio)methane, bis(isocyanatoethy1thio)ethane,
and bis(isocyanatomethy1thio)ethane; alicyclic polyisocyanate
compounds, such as isophorone diisocyanate,
bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane
5 diisocyanate, cyclohexane diisocyanate, methylcyclohexane
diisocyanate, dicyclohexyldimethylmethane isocyanate,
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
3,8-bis(isocyanatomethyl)tricyclodecane,
10 3,9-bis(isocyanatomethyl)tricyclodecane,
4,8-bis(isocyanatomethyl)tricyclodecane, and
4,9-bis(isocyanatomethyl)tricyclodecane; aromatic polyisocyanate
compounds, such as diphenyl sulfide-4,4-diisocyanate; and
heterocyclic polyisocyanate compounds, such as
15 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,
20 4,5-diisocyanato-1,3-dithiolane, and
4,5-bis(isocyanatomethyl)-1,3-dithiolane.
[0027]
As the isocyanate compound having an isothiocyanate group, there
can be exemplified an isocyanate compound in which some of isocyanate
25 groups of the above-exemplified polyisocyanate compound are changed
to isothiocyanate groups.
[0028]
16
Examples of the polyisothiocyanate compound may include:
aliphatic polyisothiocyanate compounds, such as hexamethylene
diisothiocyanate, lysine diisothiocyanatomethyl ester, lysine
triisothiocyanate, m-xylylene diisothiocyanate,
5 bis(isothiocyanatomethyl) sulfide, bis(isothiocyanatoethyl)
sulfide, and bis(isothiocyanatoethyl) disulfide; alicyclic
polyisothiocyanate compounds, such as isophorone diisothiocyanate,
bis(isothiocyanatomethyl)cyclohexane, dicyclohexylmethane
diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane
10 diisothiocyanate,
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,
15 4,8-bis(isothiocyanatomethyl)tricyclodecane, and
4,9-bis(isothiocyanatomethyl)tricyclodecane; aromatic
polyisothiocyanate compounds, such as
diphenyldisulfide-4,4-diisothiocyanate; and sulfur-containing
heterocyclic polyisothiocyanate compounds, such as
20 2,5-diisothiocyanatothiophene,
2, 5-bis (isothi·ocyanatomethyl) thiophene,
2,5-diisothiocyanatotetrahydrothiophene,
2,5-bis(isothiocyanatomethyl)tetrahydrothiophene,
3, 4-bis (isothiocyanatomethyl) t,etrahydrothiophene,
25 2,5-diisothiocyanato-1,4-dithiane,
2,5-bis(isothiocyanatomethyl)-1,4-dithiane,
4,5-diisothiocyanato-1,3-dithiolane, and
17
4,5-bis(isothiocyanatomethyl)-1,3-dithiolane.
[0029]
Further, halogen substitution products such as chlorine
substitution products and bromine substitution products, alkyl
5 substitution products, alkoxy substitution products, and nitro
substitution products of these polyisocyanate compounds, isocyanate
compounds having an isothiocyanate group, and polythioisocyanate
compounds; prepolymer modified products, carbodiimide modified
products, urea modified products, and biuret modified products
10 thereof with polyhydric alcohols; or dimerization or trimerization
reaction products thereof can also be used.
Examples of the thiol compound having a hydroxy group may include
2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin
bis(mercaptoacetate), 4-mercaptophenol, 2,3-dimercapto-1-propanol,
15 pentaerythritol tris(3-mercaptopropionate), and pentaerythritol
tris(thioglycolate).
[0030]
Meanwhile, the polymerizable composition for an optical
material according to the present embodiment, if necessary, in the
20 same manner as that in the known molding method, may further include
an ultraviolet absorber such as benzotriazole, ·an internal release
agent such as an acidic phosphoric acid ester, a resin modifier, a
light stabilizer, an antioxidant, a chain extender, a crosslinker,
an anticolorant, an oil-soluble dye, or a filler.
25 [0031]
(Ultraviolet absorber)
Examples of the ultraviolet absorber include:
18
benzophenone-based u1traviolet.absorbers, such as
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2-hydroxy-4-acryloyloxybenzophenone,
2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone,
5 2-hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone, and
2-hydroxy-4-methoxybenzophenone; triazine-based ultraviolet
absorbers, such as
2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bi
s(2,4-dimethy1phenyl)-1,3,5-triazine,
10 2-[4-(2-hydroxy-3-tridecy1oxypropyl)oxy]-2-hydroxypheny1]-4,6-bi
s(2,4-dimethylphenyl)-1,3,5-triazine,
2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis
(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-butyloxypheny1)-6-(2,4-bis-butyloxyphenyl)-1
15 ,3,5-triazine, and
2-(2-hydroxy-4-[1-octyl-oxycarbony1ethoxy]phenyl)-4,6-bis(4-phen
ylphenyl)-1,3,5-triazine; and benzotriazole-based ultraviolet
absorbers, such as 2-(2H-benzotriazol-2-yl)-4-methylpheno1,
2-(2H-benzotriazol-2-y1)-4-tert-octylphenol,
20 2-(2H-benzotriazol-2-y1)-4,6-bis(1-methyl-1-phenylethy1)phenol,
'2~(2H-benzotriazol-2-yl)~4,6-di-tert-pentylphenol,
2-(5-:chloro-2H-benzotriazol-2-yl)-4-methyl--,6-tert-butylphenol,
2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol, and
2, 2' -methylenebis [ 6-.. (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethy
25 1butyl)phenol], but preferably include: benzotriazo1e-based
ultraviolet absorbers, such as
2-(2H-benzotriazol-2-yl)-4-tert-octylphenol and
19
2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert- butylphenol;
and benzophenone-based ultraviolet absorbers, such as
2-hydroxy-4-methoxybenzophenone. These ultraviolet absorbers can
be used alone or in a combination of two or more thereof.
5 [0032]
(Internal release agent)
As the internal release agent, an acidic phosphoric acid ester
can be used. Examples of the acidic phosphoric acid ester may include
phosphoric acid monoesters and phosphoric acid diesters, and can be
10 used alone or in a mixture of two or more thereof.
For example, ZELEC UN manufactured by STEPAN Corporation,
internal release agent for MR manufactured by Mitsui Chemicals, Inc. ,
JP series manufactured by JOHOKU Chemical Co., Ltd., PHOSPHANOL
series manufactured by TOHO Chemical Industry Co., Ltd., AP series
15 and DP series manufactured by DAIHACHI Chemical Industry Co., Ltd.,
and the like can be used.
[0033]
(Resin modifier)
Further, in the polymerizable composition of the present
20 embodiment, for the purpose of adjusting the physical properties,
25
·such as optical properties, impact··-resistance, specific gravity of
a resin to be obtained and adjusting the viscosity and pot life of
the composition, a resin modifier can be added within the range in
which the effects of the present invention are not deteriorated.
Examples of the resin modifier include episulfide compounds,
alcohol compounds,.amine compounds, epoxy compounds, organic acids
and anhydrides thereof, and olefin compounds containing
20
(meth)acrylate compounds and the like.
[0034]
(Light stabilizer)
As the light stabilizer, a hindered amine compound can be used.
5 Commercially available products of the hindered amine compound may
include: Lowilite 76 and Lowilite 92 manufactured by Chemtura
Corporation; Tinuvin 144, Tinuvin 292 and Tinuvin 765 manufactured
by BASF Corporation; ADK STAB LA-52 and ADK STAB LA-72 manufactured
by ADEKA Corporation; and JF-95 manufactured by JOHOKU Chemical Co.,
10 Ltd.
[0035]
(Bluing agent)
As the bluing agent, there is exemplified a bluing agent having
an absorption band in a 1vavelength range of orange to yellow in a
15 visible light region and having a function of adjusting the color
of an optical material comprised of a resin. Specifically, the bluing
agent contains a material indicating a blue color to a violet color.
[0036]
The polymerizable composition for an optical material can be
20 obtained by mixing the above-mentioned components in a predetermined
·manner.
The mixing order and mixing method of respective components in
the composition are not particularly limited as long as respective
compone.nts can .be uniformly mixed, and can be performed by a knmvn
25 method. As a known method, there is exemplified a method of preparing
a master batch containing a predetermined amount of additives and
dispersing or dissolving this master batch in a solvent.
21
[0037]

The optical material of the present embodiment can be
manufactured by the following processes. Hereinafter, a method of
5 manufacturing an optical material 1-1hich is a plastic spectacle lens
will be described. Here, the method of manufacturing an optical
material according to the present embodiment includes a method of
preparing a polymerizable composition for an optical material as
process (a) .
10 Process (a) : a compound (A) and a polythiol compound (B) are
mixed to prepare a polymerizable composition for an optical material.
Process (b) : the polymerizable composition is injected into a
mold for lens casting.
Process (c) : the polymerizable composition is polymerized and
15 cured in the mold.
[0038]
[Process (a)]
In process (a), a compound (A) and a polythiol compound (B) are
mixed, and, if necessary, are mixed 1-1ith a polyisocyanate compound,
20 an isocyanate compound having an isothiocyanate group or a
polyisothiocyanate compound, and a thiol compound having a hydroxy
group to obtain a mixture. Moreover, a catalyst, and, if necessary,
various additives are added to this mixture, and then mixed and
dis sol ve.d ..
25 [0039]
From.the viewpoint of effects of the present invention, the
polymerizable composition containing a compound (A) and a polythiol
22
compound (B) and, if necessary, a polyisocyanate compound, an
isocyanate compound having an isothiocyanate group or a
polyisothiocyanate compound, and a thiol compound having a hydroxy
group can be used such that the formula [(number of moles of isocyanate
5 group included in polymerizable composition + number of moles of
isothiocyanate group included in polymerizable composition+ (number
of triple bonds) x 2) I number of moles of thiol group included in
polymerizable composition] is 0. 5 to 3. 0, and preferably 0. 5 to 1. 5.
If it is within the above range, it is possible to prevent the
10 polymerizable composition from becoming rubbery or to prevent the
color of the polymerizable composition from becoming poor during
curing, and thus it is possible to obtain a molded product suitable
for applications of optical materials.
15
[0040]
A polyisocyanate compound, an isocyanate compound having an
isothiocyanate group, or a polyisothiocyanate compound, which is
added as needed, can be selected from the viewpoint of satisfying
optical properties such as a refractive index and physical properties
required for the obtained molded product. Specific examples thereof
20 may include 2,5-bis(isocyanatomethyl)-bicyclo-[2.2.1)-heptane and
2,6-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane.
[0041]
The mixing process is generally performed at a temperature of
30 °C. or lower. From the vieHpoint of pot life of the polymerizable
25 composition, there is a case in which the mixing process is preferred
to be .performed at even l01ver temperature. When additives such as
a catalyst and a release agent do not exhibit good solubility with
23
respect to a compound (A) and a polythiol compound (B), a
polyisocyanate compound, an isocyanate compound having an
isothiocyanate group, a polyisothiocyanate compound, and a thiol
compound having a hydroxy group which are added as needed,, there
5 is a case in which these additives are previously warmed, and then
dissolved in a compound (A) and a polythiol compound (B) or a mixture
thereof.
10
[0042]
[Process (b) l
In process (b), the polymerizable composition for an optical
material, obtained in process (a), is injected into a mold for lens
casting, held by a gasket or tape.
Depending on the properties required for the plastic spectacle
lens which will be obtained, it is preferable that, if necessary,
15 degassing treatment under reduced pressure or filtration treatment
under pressure or reduced pressure is previously performed.
[0043]
[Process (c)]
In process (c), after the composition is injected, a mold for
20 lens casting is heated in heatable equipment_ such as an oven or in
water over a period· of several hours to several tens of hours using
a predetermined temperature program to cure and mold the composition.
[0044]
The temperature of polymerization and curing is not limited
25 because conditions change according to the combination ratio of the
polymerizable composition, the kind of catalyst or the shape of a
mold, but the polymerization and curing of the polymerizable
----------------------- ----- ----------
24
composition is performed over 1 hour to 100 hours at about -50°C to
200°C. Generally, the polymerization and curing thereof starts at
a temperature ranging from 5°C to 40°C, and then the temperature is
gradually raised to a range of 80°C to 130°C to cure the polymerizable
5 composition.
[0045]
After the curing and molding, the plastic spectacle lens
according to the present embodiment can be obtained by taking out
the resulting cured and molded product from the mold for lens casting.
10 In order to alleviate the distortion due to polymerization, the
plastic spectacle lens according to the present embodiment is desired
to be annealed by heating the released lens. Annealing temperature
is generally 80°C to 150°C, preferably 100°C to 130°C, and more
preferably 110°C to 130°C. Annealing time is generally 0.5 hours
15 to 5 hours, and preferably 1 hour to 4 hours.
[0046]
The plastic spectacle lens according to the present embodiment,
if necessary, may be provided on one side or both sides thereof with
a coating layer, and then used. Examples of the coating layer include
20 a primer layer, a hard coat layer, an anti-reflective layer, an
anti-fogging >Coating layer, an anti~contamination 1-veather resistance of a lens, a dye
or pigment, particularly, a photochromic dye or photochromic pigment
for enhancing the fashionability of a lens, an antistatic agent, and
other known additives for improving the performance of a lens may
be used in a combination thereof. Various leveling agents may also
10 be used for the purpose of improvement of coatability.
15
Further, the plastic spectacle lens according to the present
embodiment, if necessary, may be subjected to back side polishing,
antistatic treatment, dyeing treatment, photochromic treatment, or
the like.
The plastic spectacle lens according to the present embodiment,
obtained in this way, has a high refractive index, and the e-line
refractive index thereof is in a range of 1.60 to 1.80.
[0048]
Heretofore, an example in which the optical material of the
20 present embodiment is used as a plastic spectacle lens has been
described; "'but,- for example, this optical matericd can· be used as:
various plastic.lenses, such as a spectacle lens for vision correction,
a polarizing lens, a photochromic lens, a lens for imaging equipment,
a Fresnel lens for liquid crystal projectors, a lenticular lens, and
25 a contact lens; sealing materials for light-emitting diodes (LEOs);
optical waveguides; optical adhesives used in bonding optical lenses
or optical 1vaveguides; anti-reflective films used for optical lenses;
26
and transparent coatings or transparent substrates used in liquid
crystal display members (substrate, light guide plate, film, sheet,
and the like) .
5 Examples
10
15
[0049]
Hereinafter, the present invention will be described in more
detail with reference to Preparation Examples and Examples, but the
present invention is not limited to these Examples.
The lens obtained by polymerization was evaluated by performance
tests. In the performance tests, refractive index and Abbe number,
specific gravity, bending strength, and tensile strength were
evaluated by the following test method.
[0050]
- Refractive index (ne) and Abbe number ( v e) were measured using
Pulfrich refractometer KPR-30, manufactured by Shimadzu Corporation,
at 20°C.
-Specific gravity was measured by an Archimedes method at 20°C.
- Bending test: bending strength was measured by AUTOGRAPH AGS-J
20 manufactured by Shimadzu Corporation. The maximum point stress
(N/mm2 ) was measured when a load 1vas applied t-o the center of a resin
test piece. having a thickness of 3. 0 mm, a length of 7.5 mm and a width
of 25.0 mm at a descending speed of 1.2 mm/min.
- Tensile strength test: a resin flat plate prepared to have
25 a lens diameter of 45 mm and a thickness of 2.5 mm was drilled by
assuming a two-point frame processing to form holes having a diameter ..
of 1.6 mm at two places of both ends of the resin flat plate.
27
Subsequently, a metal shaft having a diameter of 1. 6 mm passed through
the holes to attach both ends of a sample to a fixing jig, and then
the sample was stretched at a speed of 5, and the test force of the
maximum point was mea~ured using AUTOGRAPH AGS-J manufactured by
5 Shimadzu Corporation. The value (kgf/mm) of the obtained maximum
point test force divided by the thickness of the resin flat plate
was calculated.
10
[0051]
[Reference Preparation Example 1]
11.2 g of propargylamine, 300 ml of an aqueous saturated sodium
bicarbonate solution, and 300 ml of dichloromethane were charged into
a reactor equipped with a stirrer and a thermometer, and stirred to
obtain a solution, and the solution was cooled to 5°C using an ice
water bath. 19.6 g of triphosgene was added to this solution.
15 Stirring was conducted between 5 °C and 10 °C for 1 hour to perform
a reaction, and then filtration under reduced pressure was conducted
to remove insoluble solids. The remaining mixed solution was
statically left, and then liquid separation operation 1vas performed
to take out an organic layer (lower layer) . The same reaction was
20 performed five times to obtain a reaction solution, and the obtained
reaction solution was distilled at normal·pressure to remove a sol vent,
and was then distilled under reduced pressure .. Fractions having a
boiling point of 50°C at a pressure of 160 Pa were collected to obtain·
31.3 g of propargyl isocyanate (compound No. 1-1), which is a colorless
25 transparent liquid target material, at a purity of 97.7% in a yield
of 37.1%.
[0052]
28
[Reference Preparation Example 2]
Polythiol A containing
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
5 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane as main
components was synthesized in accordance with the method described
in Preparation Example 2 of Japanese Unexamined Patent Publication
No. 2004-2820.
164.2g (1mol) o£1,1,3,3-tetra-methoxypropane, 488.8g (4mol)
10 of acetylthiomethyl thiol, and 7.6 g (0.04 mol) of
para-toluenesulfonic acid were put into a 2L bottom cock-equipped
flask provided with a stirring blade, a thermometer, a distillation
column and a capillary for nitrogen introduction, and heated to 40°C
while maintaining a degree of vacuum of 1 kPa or less with stirring.
15 Heating was continued for about 18 hours until distillation of
methanol stopped. After cooling, the vacuum was released, a
condenser was fitted instead of the distillation column, and then
400 ml of methanol, 400 ml of chloroform and 200 ml of 36% hydrochloric
acid were added thereto and heated to 60°C to perform alcoholysis,
20 thereby synthesizing polythiol A (target compound) containing
1, 1, 3, 3-tetrakis (me:rcaptomethy1thio)·propane as a main component .
. Appropriate amounts of water and chloroform were added to
perform liquid separation, and a chloroform layer was washed with
water several time.s. Chloroform and low~boiling fractions >vere
25 removed by desolvation, and then filtration was performed with a 3
pm Teflon (registered trade mark) filter to obtain 340.0 g of polythiol
A. By LC analysis of polythiol A, t>vo other polythiol compound
29
components were detected ( 9. 8% and 9. 8% at a chromatogram area ratio,
respectively) . When these components were purified and analyzed by
LC, they were 4,6-bis(mercaptomethylthio)-1,3-dithiane and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
5 respectively. The analysis results thereof are shown below.
Further, the thiol equivalent of polythiol A was measured by
the following method. 0.05 mol/L of an iodine solution was slowly
dropped into a mixed solvent solution of 95.1 mg of polythiol A, 30
ml of chloroform and 30 ml of methanol. When the brown color of the
10 dropped iodine no longer disappeared at the time of dropping 9. 7 ml
of the iodine solution, the amount of SH groups contained in polythiol
A was calculated by setting this point as an equivalent point, and,
as a result, the amount thereof was 9.64 meq/g.
15
[ 0053]
i) 1,1,3,3-tetrakis(mercaptomethylthio)propane
1H-NMR i5 (CDC13) : 2.18 (t, 4H), 2. 49 (t, 2H), 3. 78-3.90 (m, 8H),
4. 64 (t, 2H)
13C-NMR i5 (CDCl3) : 26.7, 41.3, 48.7
FT-IR: 538 cm-1
20 MS: m/z ~ 356 (M+)
25
[0054]
ii) 4,6-bis(mercaptomethy1thio)-1,3-dithiane
1H-NMR i5 (CDC13) : 2. 02 (t, 2H), 2. 56 (t, 2H), 3. 77-3.91 (m, 8H),
3.97 (S, 2H), .. 4.66 (t, 2H)
13C-NMR i5 (CDCl3): 27.1, 28.8, 38.1, 44.6
FT-IR: 2538 cm-1
MS: m/z ~ 276 (M+)
5
10
30
[0055]
iii) 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane
1H-NMR i5 (CDC13 ): 2. 03 (t, 2H), 2.13-2.21 (m, lH), 2. 75-2.80 (m,
lH), 3.79-3.84 (m, lH), 3.90-3.96 (m, 3H), 4.32-4.35 (m, 2H)
13C-NMR i5 (CDC13): 27.2, 32.3, 38.9, 46.2
FT-IR: 2538 cm-1
MS: m/z = 276 (M+)
[0056]
[Example 1]
21 parts by weight of the compound represented by the compound
No. 1-1 prepared in Reference Preparation Example 1, 7 9 parts by weight
of the polythiol compound A (prepared in Reference Preparation
Example 2) containing 1, 1, 3, 3-tetrakis (mercaptomethylthio) propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
15 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane as main
components, 100 ppm of dimethyl tin dichloride, 2500 ppm of "PERBUTYL
(R) 0" manufactured by NOF Corporation, and 1500 ppm of a mixture of
monobutyl phosphate and dibutyl phosphate (mixing ratio of 1: 9) \vere
mixed and dissolved at room temperature, filtered using a PTFE-made
20 filter under reduced pressure, and then sufficiently degassed until
foaming cou1d ·not be recogn·ized under a reduced pressure of 150 kPa
to 200 kPa. Subsequently, the polymerizable composition was injected
into a mold composed of a glass mold and a tape, and then put into
a heating oven and gradually heated to 25°C to .. l20°C to perform
25 polymerization for 22 hours. The value of [(number of moles of
isocyanate.group included in polymerizable composition + number of
moles of isothiocyanate group included in polymerizable composition
31
+ (number of triple bonds) x 2) I number of moles of thiol group
included in polymerizable composition] of this polymerizable
composition was 1.0.
The molded piece of the obtained resin had good transparency,
5 and had a good appearance without distortion. The evaluation results
thereof are shown in Table 1 below.
[0057]
[Examples 2 and 3]
Operations were performed in the same manner as in Example 1,
10 except for changing the composition as shown in Table 1. The
compositions and evaluation results are shown in Table 1 below.
[0058]
[Comparative Example 1]
In a glass beaker, 100 ppm of dimethyl tin dichloride as a
15 catalyst, 1500 ppm of ZELEC-UN (trade name, manufactured by STEPAN
Corporation: acidic phosphoric acid ester), 44 parts by weight of
m-xylene diisocyanate (compound (a)), and 56 parts by weight of
polythiol A containing 1, 1, 3, 3-tetrakis (mercaptomethylthio) propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
20 2-(2,2-bis(mercaptomethylthio)ethy1)-1,3-dithiethane as main
components were charged," and then stirred and mixed at room ··· .,
temperature. The mixed compounds 1vere subjected to degassing under.
reduced pressure. Subsequently, the polymerizable composition was
injected into a mold composed of a glass mold.and a tape, and then
25 put into a heating oven and gradually heated to 25°C to 120°C to perform
polymerization for 20 hours.
The molded piece of the obtained resin had good transparency,
32
and had good appearance l·li thout distortion, but the Abbe number
thereof was 30. The evaluation results thereof are shown in Table
1 below.
33
[0059]
Table 1
Composition (parts by weight Evaluation items
in parenthesis)
Isocyanate Thiol compound Molar ratio* of Optical properties
compound 1 functional group Refractive Abbe number Specific
index gravity d
Comp. Ex. 1 Compound(a) A (56) 0.9 1. 695 30 1. 43
( 44)
Ex. 1 No. 1-1 (21) A (79) 1.0 1. 730 34 1. 47
Ex. 2 No. 1-1 (28) A (72) 1.5 1.721 35 1. 46
Ex. 3 No. 1-1 (18) A (82) 0.8 1. 733 33 1. 44
No. 1-1: compound of Reference Preparation Example 1
A: polythiol 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 as main components
Compound(a): m-xylene diisocyanate
*: (number of moles of isocyanate group included in polymerizable composition+ number of moles of isothiocyanate group
included in polymerizable composition+ (number of triple bonds) x 2) I number of moles of thiol group included in polymerizable
composition
34
[0060]
From the results of Table 1 above, it was found that each of
the molded products of Examples 1 to 3, which was obtained using the
compound No. 1-1 having a carbon-carbon triple bond and an isocyanate
5 group in a molecule as an isocyanate compound, 1·1as excellent in even
any of Abbe number and refractive index, compared to the molded product
of Comparative Example 1, 1vhich was obtained using m-xylene
diisocyanate.
10
[ 00 61]
[Example 4]
23 parts by weight of the compound represented by the compound
No. 1-1 prepared in Reference Preparation Example 1, 77 parts by weight
of polythiol B containing
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
15 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as
main components, 100 ppm of dimethyl tin dichloride, 2500 ppm of
"PERBUTYL (R)O" manufactured by NOF Corporation, and 1500 ppm of a
mixture of monobutyl phosphate and dibutyl phosphate (mixing ratio
20 of 1: 9) were mixed and dissolved at room temperature, filtered using
a-PTFE-made filte:cunder reduced pressure, and then sufficiently
degassed until foaming could not be recognized under a reduced,
pressure of 150 kPa to 200 kPa. Subsequently, the polymerizable
_composition was injected into a mold composed of a glass mold and
25 a tape, and then put into a heating oven and gradually heated to 25°C
to 120°C to perform polymerization for 22 hours.
The molded piece of the obtained resin had good transparency,
------------------------------
5
10
35
and had a good appearance without distortion. The evaluation results
thereof are shown in Table 2 below.
[0062]
[Examples 5 to 7]
Operations were performed in the same manner as in Example 4,
except for adding pentaerythritol tetrakismercaptopropionate
(polythiol C) and changing the composition as shown in Table 2. The
compositions and evaluation results are shown in Table 2 below.
[0063]
[Comparative Example 2]
In a glass beaker, 100 ppm of dimethyl tin dichloride as a
catalyst, 1500 ppm of Zelec-UN (trade name, manufactured by Stepan
Corporation: acidic phosphoric acid ester), 51 parts by weight of
m-xylene diisocyanate (compound (a)), and 49 parts by weight of
15 polythiol B containing
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 as
main components were charged, and then stirred and mixed at room
20 temperature. The mixed compounds were subjected to degassing under
·reduced pressure: Subsequently, the polymerizable composition was
injected into a mold, composed of a glass mold and a tape,. and then
put into a heating oven and gradually heated to 25 °C to 120 °C to perform
polymerization for 20 hours.
25 The molded piece of the obtained resin had good transparency,
and had a good appearance •vi thout distortion, but the Abbe number
thereof was 31. The evaluation results thereof are shown in Table
36
2 below.
37
[0064]
Table 2
-
Composition (parts by weight in Evaluation items
parenthesis)
Isocyanate Thiol Thiol Molar ratio* Optical properties
compound compound 1 compound 2 of functional Refractive
group index
Comp. Ex. 2 Compound(a) B ( 4 9) - 1.0 1. 668
(51)
Ex. 4 No. 1-1 ( 23) B ( 7 7) - 1.0 1. 697
Ex. 5 No. 1-1 (2 5) B (59) c ( 16) 1.2 1. 665
Ex. 6 No. 1-1 (22) B (62) c (16) 1.0 1. 670
Ex. 7 No. 1-1 (19) B ( 64) c (17) 0.8 1. 673
No. 1-1: compound of Reference Preparation Example 1
B: polythiol containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptornethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
5,7-dimercaptornethyl-1,11-dimercapto-3,6,9-trithiaundecane as main components
C: pentaerythritol tetrakis mercaptopropionate
Compound(a): rn-xylene diisocyanate
Abbe number
31
35
36
37
35
.
Specific
gravity d
1. 37
1. 40
1. 39
1. 36
1.38 -
*: (number of moles of isocyanate group included in polymerizable composition+ number of moles of isothiocyanate group
included in polymerizable composition+ (number of triple bonds) x 2) I number of moles of thiol group included in polymerizable
composition
_,,
-----~-------------------------------------------
38
[ 00 65]
From the results of Table 2 above, it was found that each of
the molded products of Examples 4 to 7, which was obtained using the
compound No. l-1 having a carbon-carbon triple bond and an isocyanate
5 group in a molecule as an isocyanate compound, is excellent in Abbe
number, compared to the molded product of Comparative Example 2, which
was obtained using m-xylylene diisocyanate.
10
[0066]
[Example 8]
14 parts .by weight of the compound represented by the compound
No. 1-1 prepared in Reference Preparation Example 1, 21 parts by weight
of a mixture (compound(b)) of
2,5-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane and
2,6-bis(isocyanatomethyl)-bicyclo-[2.2.1]- heptane as an
15 isocyanate compound, 65 parts by weight of polythiol B containing
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 as
main components, 100 ppm of dimethyl tin dichloride, 2500 ppm of
20 "PERBUTYL (R) 0" manufactured by NOF Corporation, and 1500 ppm of a
mixture ·of monobutyl phosphate and dibutyl phosphate (mixing ratio
of 1:9) were mixed and dissolved at room temperature, filtered by
a PTFE-made filter under reduced pressure, and then sufficiently
degassed until foaming cannot be recognized under a reduced pressure
25 of 150 kPa to 200 kPa. Subsequently, the polymerizable composition
was injected into a mold composed of a glass mold and a tape, and
then put into a heating oven and gradually heated to 25°C to 120°C
---------------------- -----------------------------
39
to perform polymerization for 22 hours.
The molded piece of the obtained resin has good transparency,
and has good appearance without distortion. The evaluation results
thereof are shown in Table 3 below.
5 [0067)
[Examples 9 to 14)
Operation \·las performed in the same manner as in Example 8, except
for changing the composition as shown in Table 3. The compositions
and evaluation results are shown in Table 3 below.
10 [0068)
[Comparative Example 3)
In a glass beaker, 100 ppm of dimethyl tin dichloride as a
catalyst, 1500 ppm of Zelec-UN (trade name, manufactured by Stepan
Corporation: acidic phosphoric acid ester), 53 parts by weight of
15 a mixture (compound(b)) of
2,5-bis(isocyanatomethyl)-bicyclo-[2.2.1)-heptane and
2, 6-bis (isocyanatomethyl) -bicyclo- [2. 2. 1)- heptane, and 47 parts by
weight of polythiol B containing
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
20 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
5, 7~dimercaptomethyl-1, 11-dimercapto-3, 6, 9·-trithiaundecane as
main components were charged, and then stirred and mixed at room
temperature. The mixed compounds >vere subjected to degassing under
reduced pressure. Subsequently, the po1ymerizable composition was.
25 injected into a mold composed of a glass mold and a tape, and then
put into a heating oven and gradually heated to 25"C to 120"C to perform
polymerization for 20 hours. The evaluation results thereof are
40
shown in Table 3 below.
41
[0069]
Table 3
Composition (parts by weight in Evaluation items
parenthesis)
Isocyanate compound Thiol Molar ratio* Optical properties
compound of functional Refractive
' group index
Comp. Ex. 3 - Compound(b) (53) B (47) 1.0 1. 629
Ex. 8 No. 1-1 (14) Compound(b) (21) B (65) 1.0 1. 668
Ex. 9 No. 1-1 ( 16) Compound(b) ( 16) B ( 68) 1.0 1. 665
Ex. 10 No. 1-1 (11) Compound(b) (27) B (62) 1.0 1. 657
Ex. 11 No. 1-1 ( 9) Compound(b) (24) B (67) 1.1 1. 665
Ex. 12 No. 1-1 (13) Compound(b) (20) B (67) 0.9 1. 663
Ex. 13 No. 1-1 (13) Compound(b) ( 21) B ( 66) 1.0 1. 662
Ex. 14 No. 1-1 (11) Compound(b) (25) B (64) 0.9 1. 658
No. 1-1: compound of Ref~rence Preparation Example l
B: polythiol containing 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 as main components
Compound(b): a mixture of 2,5-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane and
2,6-bis(isocyanatomethyl)-bicyclo-[2.2.1]- heptane
Abbe number
37
38
37
37
38
37
37
37
Specific
gravity d
1. 31
1. 33
1. 36
1. 34
1. 33
1. 34
1. 33
1. 35
*: (number of moles of isocyanate group included in polymerizable composition+ number of moles of isothiocyanate group included
in polymerizable compositio:J. + (number of triple bonds) x 2) I number of moles of thiol group included in polymerizable composition
42
[0070]
From the results of Table 3 above, it was found that, comparing
each of the molded products of Examples 8 to 14, which were obtained
using the compound No. 1-1 having a carbon-carbon triple bond and
5 an isocyanate group in a molecule as an isocyanate compound, is
excellent in Abbe number with the molded product of Comparative
Example 3, which was obtained using only the compound(b), a molded
product having higher refractive index 1vhile exhibiting the same Abbe
number was obtained by the addition of the compound No. 1-1.
10 [ 0071]
[Example 15]
24 parts by weight of propargyl isothiocyanate (manufactured
by Fluorochem Ltd.) represented by the compound No. 1-2 as an
isothiocyanate compound, 76 parts by weight of polythiol A containing
15 1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane as main
components, 100 ppm of dimethyl tin dichloride, 2500 ppm of "PERBUTYL
(R) O" manufactured by NOF Corporation, and 1500 ppm of a mixture of
20 monobutyl phosphate and dibutyl phosphate (mixing ratio of 1: 9) were
mixed and dissolved at room temperature, filtered using a PTFE-made
filter under reduced pressure, and then sufficiently degassed until
foaming could not be recognized under a reduced pressure of 150 kPa
to 200 kPa. Subsequently, the polymerizable composition was injected
25 into a mold composed of a glass mold and a tape, and then put into
a heating oven and gradually heated to 25°C to 120°C to perform
polymerization for 22 hours.
!
5
----------------------
43
The molded piece of the obtained resin had good transparency,
and had a good appearance 1vi thout distortion. The evaluation results
thereof are shown in Table 4 below.
[0072]
Table 4
Composition (parts by Evaluation items
weight in parenthesis)
Isothiocyanate Thiol Molar Optical properties
compound compound ratio* of Refractive Abbe
l functional index number
group
Ex. 15 No. l-2 ( 24) A ( 7 6) 1.0 1. 759 28
No. 1-2: propargyl isothiocyanate
A: polythiol 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 as main components
*: (number of moles of isocyanate group included in polymerizable composition+
number of moles of isothiocyanate group included in polymerizable composition +
(number of triple bonds) x 20 I number of moles of thiol group included in
polymerizable composition
[0073]
[Comparative Example 4]
90. 9 parts by \veight of bis ( 2, 3-epi thiopropyl) disulfide
10 (compound (E-1)) and 1 part by weight of an ultraviolet absorber (trade
name: Tinuvin PS) were mixed and dissolved at 20°C to obtain a
homogenous solution. Then, 9.1 parts by weight of polythiol B
containing
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
15 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundec;,ne as
main components was added to this solution, mixed and dissolved, and
then filtered using a 3 ~m PTFE-made filter. Subsequently, 910 ppm
I
44
of dicyclohexylmethylamine and 190 ppm of dimethylcyclohexylamine
1>1ere added to this solution, mixed in and dissolved, and then injected
into a mold composed of a glass mold and a tape, and gradually heated
from 30°C to 80°C over 21 hours to be polymerized. After the
5 completion of the polymerization, the mold was released to obtain
a resin molded product. The obtained resin molded product was
annealed at 120°C for 3 hours. Data of drilling tension test are
shown in Table 5 belmv.
45
[0074]
Table 5
Composition (par~s by weight in Evaluation items
parenthesis)
Monomer Thiol Molar Optical properties Three-point Drilling
compound ratio* of bending test tension test
functional Refractive Abbe Maximum Test force I
group index number point stress thickness
(N/mm2
) (kgf/mm)
Comp. E-1 ( 90. 9) B ( 9. 1) - 1. 737 32 121 16.6
Ex. 4
Ex. 1 No. 1-1 (21) A ( 7 9) 1.0 1. 730 34 163 25.3
Ex. 9 No. 1-1 (16) I Compound(b) B ( 68) 1.0 1. 665 37 160 24.3
( 16) -- -----··-
E-1: bis(2,3-epithiopropyl) disulfide
No. 1-1: compound of Reference Preparation Example 1
A: polythiol containing 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptornethylthio)-1,3-dithiane and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane as main components
B: polythiol containing 4,8-dirnercaptomethyl-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 as main components
Compound(b): a mixture of 2,5-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane and
2,6-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane
*: (number of moles of isocyanate group included in polymerizable composition+ number of moles of isothiocyanate group
included in polymerizable composition+ (number of triple bonds) x 2) I number of moles of thiol group included in polymerizable
composition
46
[ 007 5]
From the results of Table 5 above, it was found that each of
the molded products of Examples 1 and 9, v1hich was obtained using
the compound No. 1-1 having a carbon-carbon triple bond and an
5 isocyanate group in a molecule as an isocyanate compound, is excellent
in physical properties, such as refractive index, Abbe number,
bending strength and tensile strength, compared to the molded product
of Comparative Example 4, which was obtained using
bis (2, 3-epithiopropyl) disulfide, and thus it was possible to obtain
10 a thiourethane optical material having a good balance between these
physical properties.
[0076]
This application claims the benefit of Japanese Patent
Application No. 2013-071284, filed March 29, 2013, 1-1hich is hereby
15 incorporated by reference in its entirety into this application.

CLAIMS
1. A polymerizable composition for an optical material, comprising:
(A) a compound having a carbon-carbon triple bond and at least
5 one group selected from an iso·cyanate group and an isothiocyanate
group in a molecule; and
(B) a polythi.ol compound.
2. The polymerizable composition for an optical material according
10 to claim 1,
1vherein the compound (A) is represented by following general
formula ( 1) ;
R2 (A~R1
n (1)
1-lherein, in formula ( 1) ' Al represents an alkylene group of 1
15 to 4 carbon atoms which may be substituted or a phenylene group which
may be substituted, n is an integer of 0 or 1, R1 represents an
isocyanate group or an isothiocyanate group, and R2 represents a·
hydrogen atom, an alkyl group of 1 to 4 carbon atoms or a group
represented by the following formula;
20
wherein, A2 and R3 have the same meaning as A1 and R1
, respectively,
and may be the same as or different from these groups, * represents
a coupling hand.
48
3. The polymerizable composition for an optical material according
to claim 2,
wherein the compound (A) is represented by following general
formula ( 2) ;
( Aq-R4
n (2)
5
wherein, in formula ( 2) , A3 is an alkylene group of 1 to 4 carbon
atoms which may be substituted or a phenylene group which may be
substituted, R4 represents an isocyanate group or an isothiocyanate
group, and n is an integer of 0 or 1.
10
4. The polymerizable composition for an optical material according
to any one of claims 1 to 3,
wherein the polythiol compound (B) is at least one selected from
the group consisting of pentaerythritol
15 tetrakis(3-mercaptopropionate),
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,
20 1, 1, 3, 3-tetrakis (mercaptomethylthio) propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane, and
3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane.
25
5. The polymerizable composition for an optical material according
49
to any one of claims 1 to 4,
wherein a functional group molar ratio represented by the
following formula is 0.5 to 3.0,
Formula: [(number of moles of isocyanate group included in
I ·.
5 polymerizable composition + number of moles of isothiocyanate group
included in polymerizable composition + (number of triple bonds) x
2) I number of moles of thiol group included in polymerizable
composition] .
10 6. A method of manufacturing an optical material, comprising:
mixing the compound (A) and the polythiol compound (B) to prepare
the polymerizable composition for an optical material according to
any one of claims 1 to 5;
injecting the polymerizable composition tnto a casting mold;
I
15 and
po~ymerizing and curing the polymerizable composition in the
casting mold.
7. An optical material, which is obtained by the manufacturing method
20 according to claim 6.
25
8. The optical material according to claim 7,
Hherein a refractive index of e-rine is in a range of 1.60 to
1.80.
9. A plastic spectacle lens, which is compris~d o'f the optical
material according to claim 7 or 8.