POLYMERIZABLE COMPOSITION, OPTICAL MATERIAL, AND MANUFACTURING
METHOD OF THE SAME
5
TECHNICAL FIELD
[OOOl]
The present invention r e l a t e s to a polymerizable composition,
an o p t i c a l m a t e r i a l , and a manufacturing method of t h e same.
10 BACKGROUND ART
[0002]
P l a s t i c lenses arelighterthaninorganiclenses, a r e n o t e a s i l y
broken, and a r e dyeable. Therefore, they have been r a p i d l y become
w i d e s p r e a d a n d a r e u s e d f o r o p t i c a l elements s u c h a s s p e c t a c l e l e n s e s
15 and camera l e n s e s . Up t o now, various r e s i n s f o r lenses have been
developed and used, and t y p i c a l examples thereof include a
thiourethane r e s i n obtained from a polymerizable composition which
contains an isocyanate compound and a t h i o l compound.
For example, t h e following Patent Documents 1 to 5 r e l a t e t o
20 p l a s t i c lenses comprised of t h e thiourethane r e s i n .
[0003]
Patent Documents 1 and 2 d i s c l o s e a polymerizable composition
obtainedbymixingaprepolymer, r i h i c h i s o b t a i n e d b y r e a c t i n g s u l f u r
withanepithiogroup-containingcompoundbyusinganimidazole-based
25 c a t a l y s t a s a vulcanization a c c e l e r a t o r , with a polyisocyanate
compound and a p o l y t h i o l compound, and a p l a s t i c lens obtained from
t h e composition.
[00041
Patent Document 3 discloses a photosensitive resin composition
containing a thiourethane compound, which is obtained from a thiol
compound and an isocyanate compound, and a photopolymerization
5 initiator such as an imidazole compound.
[00051
Patent Document 4 discloses a process for producing a
polythiourethane resin in which a polythiol oligomer is reacted with
a poly(thio)isocyanate group-containing compound. According tothe
10 document, the polythiol oligomer is obtained by reacting a polythiol
compound having two or more functional groups with sulfur by usiny
an imidazole-based catalyst.
[00061
Patent Document 5 discloses a polymerizable composition
15 containing (A) a compound having one or more mercapto groups, (B1)
a polyurethane prepolymer and/or a polythiourethane prepolymer
havingterminals totally or partially composed of a mercapto group,
and (C) a polyisocyanate compound and/or a polyisothiocyanate
compound. According tothe document, when the composition is heated
20 andpolymerizedinthepresenceofacuringcatalystsuchasimidazoles,
a resincanbeproduced. However, thedocument does not specifically
disclose a case of using imidazoles.
RELA'l'ED DOCUMENT
PATENT DOCUMENT
25 [0007]
[Patent Document11 Japanese Unexamined Patent PublicationNo.
2005-121679
[Patent Document21 JapaneseUnexamined Patent PublicationNo.
2005-281527
[Patent Document 31 W02008/023603
[Patent Document 41 W02008/026727
5 [Patent Document51 Japanese Unexamined Patent Publication No.
2006-265408
DISCLOSURE OF THE INVENTION
[0008]
In optical materials such as plastic lenses obtained from the
10 polymerizable compositions described in the above documents, striae
or cloudiness is caused in some cases. This exerts a negative
influence on the performance ofthe optical materials and decreases
yield of products in some cases.
As a result of performing intensive research to solve the above
15 problem, the present inventors foundthat theuse ofa specificcuring
catalyst in a predetermined amount can inhibit cloudiness or striae
of polythiourethane-based resin lenses.
[0009]
The present invention includes the following.
20 [I] A polymerizable composition containing: (A) an alicyclic
isocyanate compound (al) having two or more functional groups and/or
an aliphatic isocyanate compound (a2) having two or more functional
groups; (B) a thiol compound having one or more sulfide bonds and/or
one or more ester bonds and having two or more functional groups;
25 and (C) an imidazole-based curing catalyst, in which the amount of
the imidazole-based curing catalyst (C) is 5 ppm to 3,000 ppm with
respect to the total amount of the isocyanate compound (A) and the
thiol compound (B) .
[2] The polymerizable composition described in [I], in which
the alicyclic isocyanate compound (al) is at least one kind selected
from the group consisting of 1,3-his (isocyanatomethyl)c yclohexane,
5 1,4-bis (isocyanatomethyl) cyclohexane,
bis(4-isocyanatocyclohexyl)methane,
bis(isocyanatomethy1)-bicyclo[2.2.llheptane, and isophorone
diisocyanate, and the aliphatic isocyanate compound (a2) is at least
one kindselectedfromthegroup consistingofm-xylylenediisocyanate,
10 hexamethylene diisocyanate, and pentamethylene diisocyanate.
[3] The polymerizable composition described in [I] or [2], in
which in the thiol compound (B), the thiol compound having one or
more sulfide bonds and two or more functional groups is at least one
kind selected from the group consisting of
15 4-mercaptomethyl-l,8-dimercapto-3,6-dithiaocatane, 4,8-, 4,7-, or
5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
bis(mercaptoethyl)suIfide, 2,5-bis(mercaptomethy1)-1,4-dithiane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-his (mercaptomethylthio)- 1,3-dithiane, and
20 2- (2,2-his( mercaptomethylthio)e thyl) -l,3-dithietane.
[4] The polymerizable composition described in any one of [I]
to [3], in which in the thiol compound (B) , the thiol compound having
one or more ester bonds and two or more functional groups is at least
one kind selected from the group consisting of pentaerythritol
25 tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), andathiol compound represented by
the following Formula (1).
[OOll]
In the formula, each of 1, m, and r independently represents
5 an integer of 1 to 4; n represents an integer of 1 to 3; R represents
hydrogen or a methyl group; and when there is a plurality of Rs, Rs
may be the same as or different from each other.
[5] The polymerizable composition described in any one of [I]
to [4], in which the irnidazole-based curing catalyst (C) includes
10 at least one kind of compounds represented by the following Formula
(2).
[0012]
[0013]
15 In the formula, each of R1, R2, R3, and R4 independently
represents hydrogen, a mercapto group, a cyano group, an alkyl group
which may be substituted, or a phenyl group which may be substituted;
and R1, R2, R3, and R4 may be the same as or different from each other.
[6] The polymerizable composition described in any one of [I]
20 to [5], in which the imidazole-based curing catalyst (C) is at least
one kind selected fromthe group consistingof dimethylimidazole and
benzylmethylimidazole.
[7] The polymerizable composition described in any one of [4]
to [6], in rihich in the thiol compound represented by Formula (I),
5 each of 1 and m independently represents an integer of 1 to 2, r
represents an integer of 1 to 3, and n represents 1 or 2.
181 An optical material comprised of the polymerizable
composition described in any one of [I] to [7].
[9] A manufacturing method of an optical material, including
10 a step of casting the polymerizable composition describedin anyone
of [I] to [7] intoamold; anda stepofpolymerizingthepolymerizable
composition by heating the composition.
[lo] A plastic spectacle lens in rihich a primer layer, a hard
coat layer, and an antireflection layer are laminated in this order
15 overasubstratecomprisedofthepolymerizablecompositiondescribed
in any one of [I] to [7].
[11] A manufacturing method of a plastic spectacle lens,
including a step of casting the polymerizable composition described
in any one of [I] to [7] into amold; a step of obtaining a lens substrate
20 by polymerizing the polymerizable composition by heating the
composition; and a step of forming a primer layer, a hard coat layer,
and an antireflection layer in this order over at least one surface
of the lens substrate.
[0014]
25 According to the polymerizable composition of the present
i n v e n t i o n , i t i s p o s s i b l e t o p r o v i d e a p l a s t i c l e n s w h i c h h a s e x c e l l e n t
optical characteristics such as refractive index and in which
cloudiness or striae are inhibited.
DESCRIPTION OF EMBODIMENTS
[0015]
Thepolymerizable compositionofthepresent invention contains
5 (A) an alicyclic isocyanate compound (al) having trio or more
functionalgroupsand/oranaliphaticisocyanatecompound (a2) having
two or more functional groups, (B) a thiol compound having one or
more sulfide bonds and/or one or more ester bonds and having two or
more functional groups, and (C) an imidazole-based curing catalyst.
10 The amount of the imidazole-based curing catalyst (C) is 5 ppm to
3,000 ppm with respect to the total amount of the isocyanate compound
(A) and the thiol compound (B) .
Hereinafter, each of the components will be described.
[0016]
15 [Isocyanate compound (A)]
Theisocyanatecompound (A) isthealicyclicisocyanatecompound
(al) having two or more functional groups and/or the aliphatic
isocyanate compound (a2) having two or more functional groups.
Examples oftheisocyanatecompound (A) includeoneormore kinds
20 of compound selected from compounds included in the alicyclic
isocyanate compound (al), one ormore kinds of compound selected from
compounds included in the aliphatic isocyanate compound (a2), and
a combinationof oneormore kinds ofcompoundselectedfromcompounds
included in the alicyclic isocyanate compound (dl) and one or more
25 kinds of compound selected from compounds included in the aliphatic
isocyanate compound (a2).
Furthermore, the isocyanate compound (A) may be in the form of
a monomer, a modified product, and/or a mixture of a monomer and a
modified product. Examples of the modified product of isocyanate
include a multimer, a biuret-modified product, an
allophanate-modifiedproduct, an oxadiazinetrione-modifiedproduct,
5 a polyol-modified product, and the like. Examples of the multimer
include a dimer such as uretdione, uretonimine, or carbodimide and
amultimerconsisting ofthreeormoremonomers, suchas isocyanurate
or i-mino oxadiazine dione. Examples of the modified product of
aliphatic polyisocyanate preferably include a multimer of aliphatic
10 polyisocyanate and more preferably include an isocyanurate product
oL aliphatic polyisocyanate.
In the present invention, as the isocyanate compound (A), one
or more kinds selected from the alicyclic isocyanate compound (al)
and the aliphatic isocyanate compound (a2) are preferably used.
15 [00171
The alicyclic isocyanate compound (al) having trio or more
functional groups is a compound rihich has a ring-like skeleton other
thananaromaticringandhastwoormoreisocyanatogroups. Specific
examples of the alicyclic isocyanate compound (al) include
20 1,3-bis (isocyanatomethyl)c yclohexane,
1,4-bis(isocyanatomethyl)cyclohexane,
bis(4-isocyanatocyclohexyl)methane,
bis (isocyanatomethyl)- bicycle [2.2.l ] heptane, isophorone
diisocyanate, and the like, and at least one kind of these can be
25 used.
[00181
Bis(isocyanatomethy1)-bicyclo[2.2.l]heptane is a mixture of
isomers of 2,5-bis(isocyanatomethy1)-bicyclo[2.2.1lheptane and
2,6-bis(isocyanatomethy1)-bicyclo[2.2.l]heptane. In the present
invention, the compound comprised of the mixture of isomers is used
as one kind of compound'.
5 In the present invention, as the alicyclic isocyanate compound
(al), one kind of bis(4-isocyanatocyclohexy1)methane or
bis (isocyanatomethyl) -bicycle [2.2.1] heptane is preferably used, or
alternatively, two kindsthereof are preferablyusedin combination.
[0019]
10 The aliphatic isocyanate compound (a2) having two or more
functional groups is a compound which has an alkylene chain having
1 to 15 carbon atoms and has two or more isocyanato groups.
Examples of the aliphatic isocyanate compound (a2) include
pentamethylene diisocyante, hexamethylene diisocyanate,
15 heptamethylene diisocyanate, octamethylene diisocyanate,
2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane
diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate,
1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate,
1,8-diisocyanato-4-isocyanatomethyl octane,
20 bis (isocyanatoethyl)c arbonate, bis (isocyanatoethyl)e ther,
o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene
diisocyanate, and the like, and at least one kind of these can be
used.
[0020]
25 In the present invention, as the aliphatic isocyanate compound
(a2), pentamethylene diisocyanate, hexamethylene diisocyanate, or
m-xylylene diisocyanate is preferably used. From the viewpoint of
r e f r a c t i v e index of the obtained resin, m-xylylene diisocyanate is
more preferably used.
[00211
[Thiol compound (B) 1
5 The t h i o l compound (B) is a t h i o l compound having one or more
s u l f i d e bonds and/or one or more e s t e r bonds and having two or more
functional groups.
Specific examples of the t h i o l compound (B) include a t h i o l
compound ( b l ) having one or more s u l f i d e bonds and two or more
10 functional groups (hereinafter, the compound w i l l be abbreviated t o
"thiol compound ( b l ) " in some cases), a t h i o l compound (b2) having
oneormoreesterbondsandtwoormore functionalgroups (hereinafter,
the compound w i l l be abbreviated to " t h i o l compound (b2)" i n some
cases), and a t h i o l compound (b3) having one or more e s t e r bonds and
15 one or more s u l f i d e bonds and having two or more functional groups
( h e r e i n a f t e r , t h e compound w i l l be abbreviated to "thiol compound
(b3) " i n some cases) .
[00221
Examples of the t h i o l compound (B) include one or more kinds
20 of compound selected from compounds included i n any one of the t h i o l
compounds ( b l ) to (b3), one or more kinds of compound selected from
compounds included i n any two out of the t h i o l compounds ( b l ) t o (b3),
and one or more kinds of compound selected from compounds included
in the t h i o l compounds ( b l ) to (b3).
25 In the present invention, a s t h e t h i o l compound (B) , one or more
kinds selected from the t h i o l compound ( b l ) and the t h i o l compound
(b2) arepreferablyused. Furthermore, acompoundselectedonlyfrom
the thiol compound (bl) or one or more kinds of compound selected
from compounds included in the thiol compound (bl) can be more
preferably used in combination with one or more kinds of compound
selected from compounds included in the thiol compound (b2).
5 [0023]
The thiol compound (bl) is a compound which has one or more
sulfide bonds and has two or more SH groups.
Specific examples of the thiol compound (bl) include
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7- or
10 5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
tetrakis(mercaptomethyl)methane, bis(mercaptomethyl)sulfide,
2,5-bis (mercaptomethyl) -1,4-dithiane,
bis(mercaptomethyl)disulfide, bis(rnercaptoethyl)sulfide,
bis(mercaptoethyl)disulfide, bis(mercaptomethylthio)methane,
15 bis (2-mercaptoethylthio)methane,
1,2-bis (mercaptomethylthio)e thane,
1,2-bis (2-mercaptoethylthio) ethane,
1,3-bis (mercaptomethylthio)propane,
1,3-bis(2-mercaptoethylthio)propane,
20 1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris (2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethy1thio)-1,3-dithiane,
25 2- (2,2-bis( mercaptomethylthio)e thyl) -l,3-dithietane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
bis(2,3-dimercaptopropyl)sulfide, andthelike, andat least one kind
of these can be used.
[0024]
In the present invention, as the thiol compound (bl), at least
5 one kind selected from the group consisting of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or
5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
bis(mercaptoethyl)sulfide, 2,5-bis(mercaptomethy1)-1,4-dithiane,
1,1,3,3-tetrakis (mercaptomethylthio)propane,
10 4,6-bis (mercaptomethylthio)- 1,3-dithiane, and
2- (2,2-bis( mercaptomethylthio)e thyl)- 1,3-dithietane is preferably
used.
[0025]
Thethiolcompound (b2) is a compoundwhichhas one ormore ester
15 bonds and has two or more SH groups.
Specific examples of the thiol compound (b2) include
2,3-dimercapto-1-propanol(3-mercaptopropionate),
3-mercapto-1,2-propanediol bis(2-mercaptoacetate),
3-mercapto-1,2-propanediol di(3-mercaptopropionate),
20 trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolethane
tris(2-mercaptoacetate), trimethylolethane
tris(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
25 tetrakis(3-mercaptopropionate), pentaerythritol
bis(3-mercaptopropionate), pentaerythritol
tris(3-mercaptopropionate), glycerin tris(2-mercaptoacetate),
glycerin tris(3-mercaptopropionate), 1,4-cyclohexanediol
bis(2-mercaptoacetate), 1,4-cyclohexanediol
bis(3-mercaptopropionate), hydroxymethylsulfide
bis(2-mercaptoacetate), hydroxymethylsulfide
5 bis(3-mercaptopropionate), thioglycolic acid
bis(2-mercaptoethylester), thiodipropionic acid
biS(2-mercaptoethylester), hydroxyethylsulfide
(2-mercaptoacetate), hydroxyethylsulfide (3-mercaptopropionate), a
thiolcompoundrepresentedbythe following Formula (I), and thelike.
10 [0026]
[0027]
In the formula, each of 1, m, and r independently represents
an integer of 1 to 4, and n represents an integer of 1 to 3. R
15 represents hydrogen or a methyl group, and tihen there is a plurality
of Rs, Rs may be the same as or different from each other. Each of
1 and m preferably independently represents an integer of 1 to 2,
r preferably represents an integer of 1 to 3, and n preferably
represents 1 or 2.
20 [0028]
The thiol compound represented by Formula (1) is a condensate
of ethylene glycol, diethylene glycol, triethyleneglycol, propylene
glycol, and mercaptoalkyl carboxylic acid. Specific examples
thereof include ethylene glycol bis(mercaptoacetate), ethylene
glycol bis(mercaptopropionate), ethylene glycol
bis(mercaptobutyrate), diethylene glycol bis(mercaptoacetate),
diethylen glycol bis(rnercaptopropionate), diethylene glycol
bis(mercaptobutyrate), triethylene glycol bis(rnercaptoacetate),
5 triethylene glycol bis(mercaptopropionate), triethylene glycol
bis(mercaptobutyrate), bis(3-mercaptopropionic acid)
1,4-butanediol, and the like. Among these, one kind can be used,
or alternatively, two or more kinds can be used in combination.
[0029]
10 As the thiol compound represented by Formula (I), diethylene
glycol bis(mercaptopropionate) or bis(3-mercaptoprop2onic acid)
1,4-butanediol can be preferably used.
[0030]
Thethiolcompound (b2) ispreferablyatleastone kind selected
15 from the group consisting of pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis (3-mercaptopropionate) , and the thiol compound represented
by Formula (1).
[0031]
20 In the present invention, as the thiol compound (b2),
pentaerythritol tetrakis(3-mercaptopropionate), diethylene glycol
bis(mercaptopropionate), or bis(3-mercaptopropionic acid)
1,4-butanediol can be more preferably used.
[0032]
25 The thiol compound (b3) is a compound which has one or more ester
bonds, one or more sulfide bonds, and two or more SH groups.
Specific examples of the thiol compound (b3) include
2,2'-thiodiethanol bis(2-mercaptoacetate), 2,2'-thiodiethanol
bis(3-mercaptopropionate), thiodimethanol bis(2-mercaptoacetate),
thiodimethanol bis(3-mercaptopropionate), and the like. Among
these, one kind can be used, or alternatively, two or more kinds can
5 be used in combination.
[0033]
[Imidazole-based curing catalyst (C)]
The imidazole-based curing catalyst (C) is not particularly
limited. As the catalyst, a compound represented by the following
10 Formula (2) can be used, and the catalyst can contain at least one
kind of the compound.
[0034]
[0035]
15 In the formula, each of R1, R2, R3, and R4 independently
represents hydrogen, a mercapto group, a cyano group, an alkyl group
which may be substituted, or a phenyl group which may be substituted.
R1, R2, R3, and R4 may be the same as or different from each other.
The alkyl group which may be substituted is a substituted or
20 unsubstituted alkyl group having 1 to 12 carbon atoms.
Examples of the substituent of the substituted alkyl group
having 1 to 12 carbon atoms include a hydroxyl group, a cyano group,
a mercapto group, and the like. Examples of the substituent of the
substituted phenyl group include a hydroxyl group, a cyano group,
a mercapto group, and the like.
[0036]
Specific examples of the imidazole-based curing catalyst
5 include 2-methylimidazole, 2-ethylimidazole,
2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole,
1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole,
2-mercapto-1-methylimidazole, dimethylimidazole,
N-benzylimidazole, 1-phenylimidazole,
10 1-(2-cyanoethy1)-2-ethyl-4-methylimidazole, 2-isopropylimidazole,
4-methylimidazole, benzylmethylimidazole, imidazole, and the Like.
Preferable examples thereof include dimethylimidazole and
benzylmethylimidazole. Preferable examples of position isomers of
dimethylimidazole and benzylmethylimidazole include
15 1,2-dimethylimidazole and 1-benzyl-2-methylimidazole.
[0037]
In the present invention, from the viewpoint of manufacturing
a plastic lens, in which cloudiness or striae are inhibited, with
excellent efficiency, the imidazole-based curing catalyst (C) can
20 be used in an amount of equal to or greater than 5 ppm, preferably
in an amount of equal to or greater than 10 ppm, more preferably in
an amount of equal to or greater than 50 ppm, and particularly
preferably in an amount of equal to or greater than 100 ppm, with
respect to the total amount of the isocyanate compound (A) and the
25 thiol compound ( B ) . Meanwhile, from the viewpoint of inhibiting
cloudiness or striae of the plastic lens, and from the vieb~point of
workability such as pot life, the upper limit thereof can be used
i n an amount of equal t o or l e s s than 3,000 ppm, p r e f e r a b l y equal
t o o r less than 2,000 ppm, and more p r e f e r a b l y equal t o or less than
1,000 ppm.
The amount of t h e imidazole-based curing c a t a l y s t (C) used can
5 be set by a p p r o p r i a t e l y combiningthe upper l i m i t and the lower l i m i t
described above. The amount can be set t o be 5 ppm t o 3,000 ppm,
p r e f e r a b l y 5 ppm t o 2,000 ppm, more preferably 5 pprn t o 1,000 ppm,
evenmore p r e f e r a b l y 50 ppmto1,OOO ppm, andparticularlypreferably
100 pprn t o 1,000 ppm. When the imidazole-based curing c a t a l y s t (C)
10 is used i n t h e amount described above, it is p o s s i b l e t o obtain a
p l a s t i c l e n s , inwhichcloudiness o r s t r i a e areeffectivelyinhibited,
with e x c e l l e n t workability.
[0038]
[Other components]
15 The polymerizable composition of t h e present invention may
f u r t h e r contain o t h e r a d d i t i v e s such a s an a c t i v e hydrogen compound,
an i n t e r n a l r e l e a s e agent, a r e s i n modifier, a l i g h t s t a b i l i z e r , a
bluing agent, an u l t r a v i o l e t absorber, an a n t i o x i d a n t , a c o l o r i n g
i n h i b i t o r , and a dye.
20 [0039]
(Active hydrogen compound)
In t h e p r e s e n t invention, t h e polymerizable composition can
f u r t h e r contain an a c t i v e hydrogen compound other than the compound
(A) and t h e compound (B) .
25 Examples of the t h i o l compound a s the a c t i v e hydrogen compound
i n t h e present i n v e n t i o n i n c l u d e an a l i p h a t i c t h i o l compound, an
aromatic t h i o l compound, and t h e l i k e .
[0040]
The aliphatic thiol compound is a compound not containing a
sulfide bond and an ester bond. Examples thereof include
methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol,
5 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol,
1,6-hexanedithiol, 1,2-cyclohexanedithiol,
3,4-dimethoxydibutane-1,2-dithiol,
2-methylcyclohexane-2,3-dithiol, 1,2-dimercaptopropylmethylether,
2,3-dimercaptopropyl methyl ether, bis(2-mercaptoethyl)ether,
10 tetrakis(mercaptomethyl)methane, and the like.
[0041]
Examples of the aromatic thiol compound include
1,2-dimercaptobenzene, 1,3-dimercaptobenzene,
1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl)b enzene,
15 1,4-bis (mercaptomethyl)b enzene, 1,2-bis (mercaptoethyl)b enzene,
1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,
1,2,3-tris (mercaptomethyl)b enzene,
1,2,4-tris (mercaptomethyl)b enzene,
20 1,3,5-tris (mercaptomethyl)b enzene,
1,2,3-tris (mercaptoethyl)b enzene,
1,3,5-tris (mercaptoethyl)b enzene,
1,2,4-tris(mercaptoethyl)benzene, 2,5-toluenedithiol,
3,4-toluenedithiol, 1,4-naphthalenedithiol,
25 1,5-naphthalenedithiol, 2,6-naphthalenedithiol,
2,7-naphthaleneditihol, 1,2,3,4-tetramercaptobenzene,
1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis( mercaptomethyl)b enzene,
1,2,3,5-tetrakis( mercaptomethyl)b enzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene,
1,2,3,4-tetrakis (mercaptoethyl)b enzene,
5 1,2,3,5-tetrakis (mercaptoethyl) benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene, 2,2'-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl, and the like.
[0042]
(Internal release agent)
10 The polymerizable composition of the present invention can
contain an internal release agent, for the propose that a molded
product obtained fromthe composition is releasedbetter fromamold.
As the internal release agent, an acidic phosphoric acid ester
can be used. Examples of the acidic phosphoric acid ester include
15 a phosphoric acid monoester and a phosphoric acid diester. One kind
of these can be used singly, or tb~o or more kinds thereof can be used
in the form of a mixture.
Forexample,itispossibletouseZelecUNmanufacturedbyStepan
Company, interal release agents for MR manufactured by Mitsui
20 Chemicals, Inc., a JP series manufactured by Johoku Chemical Co.,
Ltd., a PhosphanolseriesmanufacturedbyTohoChemicalIndustryCo.,
Ltd., an AP or DP series manufactured by Daihachi Chemical Industry
Co., Ltd., and the like.
[0043]
2 5 (Resin modifier)
Moreover, in order to regulate various physical properties such
as optical properties, impact resistance, and specific gravity of
the obtained resin and to adjust viscosity or pot life of the
composition, a resin modifier can be added to the polymerizable
composition of the present invention, within a range that does not
diminish the effects of the present invention.
5 Examples of the resin modifier include an episulfide compound,
analcohol compound, anamine compound, an epoxy compound, an organic
acid and an anhydride thereof, an olefin compound including a
(meth)acrylate compound, and the like.
[0044]
10 (Light stabilizer)
As the light stabilizer, a hindered amine-based compound can
be used. Examples of the hindered amine-based compound include
commercially available products such as Loriilite 76 and Lowilite 92
manufactured by Chemtura Corporation, Tinuvin 144, Tinuvin 292, and
15 Tinuvin 765 manufactured by BASE Corporation, Adeka Stab LA-52 and
LA-72 manufactured by Adeka Corporation, and JE-95 manufactured by
Johoku Chemical Co., Ltd.
[0045]
(Bluing agent)
2 0 Examples of the bluing agent include substances that have an
absorption band in a wavelength region from orange to yellow within
a visible light region and function to adjust the color of an optical
material comprised of a resin. More specifically, the bluing agent
includes substances that are blue to violet in color.
25 [0046]
(Ultraviolet absorber)
Examples oftheultravioletabsorherincludehenzophenone-based
ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone,
2-hydroxy-4-acryloyloxybenzophenone,
2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, and
2-hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone,
5 triazine-based ultraviolet absorbers such as
2- [4- [ (2-hydroxy-3-dodecyloxypropyl)o xy]- 21 -hydroxyphenyl]
4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine,
2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bi
s (2,4-dimethylphenyl) -1,3,5-triazine,
10 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-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-l
,3,5-triazine, and
2- (2-hydroxy-4- [l-octyloxycarbonylethoxy]phenyl) -4,6-bis (4-pheny
15 1phenyl)-l,3,5-triazine, benzotriazole-basedultravioletabsorbers
such as 2-(2H-benzotriazol-2-y1)-4-methylphenol,
2-(2H-benzotriazol-2-y1)-4-tert-octylphenol,
2-(2H-benzotriazol-2-yl)-4,6-bis(l-methyl-l-phenylethyl)phenol,
2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol,
20 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' -methylene
bis 16- (2H-benzotriazol-2-yl)- 4- (1,1,3,3-tetramethylbutyl)ph enol],
and the like. Among these, benzotriazole-based ultraviolet
25 absorbers such as 2-(2H-benzotriazol-2-y1)-4-tert-octylpnehol and
2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol are
preferable. One kind of these ultraviolet absorbers can be used
singly, or two or more kinds thereof can be used concurrently.
[00471

In the present invention, a molar r a t i o of the mercapto group
5 in the t h i o l compound to the isocyanate group i n the isocyanate
compound is within a range of 0.8 to 1.2, preferably within a range
of 0.85 t o 1.15, and even more preferably within a range of 0 . 9 t o
1.1. When the molar r a t i o is within the above range, it is possible
t o obtaina r e s i n s u i t a b l y u s e d a s an o p t i c a l m a t e r i a l , p a r t i c u l a r l y ,
10 a p l a s t i c lens material for spectacles.
[0048]
Whenapolymerizable compositionispreparedbymixingamonomer
t o b e used, a c a t a l y s t , an i n t e r n a l releaseagent, andother additives
together, the mixing temperature is generally equal to or l e s s than
15 25'C. Fromtheviervpointofpotlifeofthepolymerizablecomposition,
it is preferable t o further reduce the temperature i n some cases.
However, when t h e s o l u b i l i t y of the c a t a l y s t , t h e i n t e r n a l release
agent, and the additives i n the monomer is poor, they can be heated
i n advance and then dissolved i n the monomer and a resin modifier
20 in some case.
[0049]

By varying the type of mold a t the time of cast polymerization,
itispossibletodiversifytheformofthethiourethaneresinobtained
25 fromthe polymerizable composition o f t h e present invention. Having
ahigh refractiveindexandahighdegreeoftransparency, t h e o p t i c a l
material of the present invention can be used as an o p t i c a l r e s i n
for various purposes such as a plastic lens, a camera lens, a Light
Emitting Diode (LED), a prism, optical fiber, an information
recording substrate, and a filter. Particularly, the optical
material ofthe present invention is suitable as an opticalmaterial
5 such as a plastic lens, a camera lens, or a light emitting diode and
as an optical element. That is, the polymerizable composition of
the present invention can be suitably used as a polymerizable
composition for optical use.
Examples of the plastic lens include a plastic spectacle lens
10 comprised of a polythiourethane resin and a plastic polarizing lens
in which a layer comprised of a polythiourethane resin is laminated
over at least one surface of a polarizing film.
[0050]

15 In the present invention, the optical material comprised of the
thiourethaneresinisnotparticularlylimited. However, the optical
material is preferably obtained by a manufacturing method which is
cast polymerization including the following steps.
Step a: casting the polymerizable composition of the present
20 invention into a mold
Step b: polymerizing the polymerizable composition by heating
the composition
[005l]
(Step a)
2 5 First, the polymerizable composition is casted into a mold
(casting mold) held by a gasket, a tape, or the like. At this time,
in many cases, depending on the properties required for the plastic
lens to be obtained, if necessary, it is preferable to perform
degassingprocessingunder reducedpressure or filtration processing
such as pressurization or pressure reduction.
[0052]
5 (Step b)
The polymerization conditions are not limited since the
conditions greatly vary with the makeup of the polymerizable
composition, the typeandamount ofthe catalyst used, themold shape,
and the like. However, the polymerization is performed for about
10 1 hour to 50 hours at a temperature of about -50°C to 150°C. In some
cases, the polymerizable composition is preferably cured for 1 hour
to 25 hours by being kept at a temperature within a range of 10°C
to 150°C or by being gradually heated within the temperature range.
[0053]
15 Ifnecessary, the opticalmaterialcomprisedofthethiourethane
resin of the present invention may be subjected to processing such
as annealing. The processing is generally performed within a
temperature range of 50°C to 150°C, preferably within a temperature
range of 9 0 ° C t o 140°C, andmore preferablyiiithinatemperature range
20 of 100°C to 130°C.
[0054]
In the present invention, when the optical material comprised
ofthethiourethane resinismolded, accordingtothepurpose, various
additives such as a chain extender, a crosslinking agent, an
25 oil-soluble dye, a filler, and an adhesion improver may be added to
the composition, in addition to the 'other components" described
above.
[0055]
[ P l a s t i c spectacle lens]
If necessary, the p l a s t i c spectacle lens comprised of the
t h i o u r e t h a n e r e s i n o f t h e p r e s e n t i n v e n t i o n m a y b e u s e d a f t e r a c o a t i n g
5 layer is provided over one surface or both surfaces thereof.
The p l a s t i c spectacle lens of the present invention contains
a lens substrate, which is comprisedof the o p t i c a l m a t e r i a l obtained
from the polymerizable composition, and a coating layer.
[0056]
10 Specific examples of the coating layer include a primer layer,
a h a r d c o a t l a y e r , a n a n t i r e f l e c t i o n l a y e r , anantifoggingcoatlayer,
an antifouling layer, a water repellent layer, and the l i k e . Each
of these coating layers can be used singly, o r a p l u r a l i t y of the
coating layers can be used in the form of a multi-layer. When the
15 coating layers are provided over both surfaces of the p l a s t i c
spectacle lens, the same coating layer or d i f f e r e n t coating layers
may be provided over the surfaces.
The p l a s t i c spectacle lens of the present invention can be
obtainedbyamanufacturingmethodincludingastepofformingaprimer
20 layer, a hard coat layer, and an a n t i r e f l e c t i o n l a y e r in t h i s order
over a t l e a s t one surface of the l e n s s u b s t r a t e comprised of the
o p t i c a l m a t e r i a l . Furthermore, o t h e r l a y e r s can a l s o b e formedover
the l e n s s u b s t r a t e .
[0057]
25 For each of the coating layers, an u l t r a v i o l e t absorber for
protecting the lens or the eye from u l t r a v i o l e t rays, an infrared
absorber f o r p r o t e c t i n g t h e e y e frominfraredrays, a l i g h t s t a b i l i z e r
o r an a n t i o x i d a n t f o r improving weather r e s i s t a n c e of the l e n s , a
dye or a pigment formakingthe lensmore fashionable, a photochromic
dye, a photochromic pigment, an a n t i s t a t i c agent, and other known
a d d i t i v e s f o r improving t h e performance of t h e l e n s can be
5 c o n c u r r e n t l y u s e d . F o r t h e l a y e r t o b e s u b j e c t e d t o coating, various
l e v e l i n g agents f o r improving coating p r o p e r t i e s may be used.
[0058]
Theprimerlayerisgenerallyformedbetweenthehardcoatlayer,
which w i l l be described l a t e r , and t h e l e n s . The primer l a y e r is
10 a coating l a y e r f o r improving the adhesiveness between t h e hard coat
l a y e r t o be formed over the primer l a y e r and t h e l e n s . I n some case,
t h e primer l a y e r can a l s o improve impact r e s i s t a n c e . For the primer
l a y e r , any m a t e r i a l can be used as long a s it e x h i b i t s a high degree
of adhesiveness with r e s p e c t t o t h e obtained l e n s . However,
15 g e n e r a l l y , a primer composition o r t h e l i k e t h a t contains a
u r e t h a n e - b a s e d r e s i n , anepoxy-basedresin, a p o l y e s t e r - b a s e d r e s i n ,
amelanin-basedresin, o r p o l y v i n y l a c e t a l a s amaincomponentisused.
In order t o a d j u s t t h e v i s c o s i t y of t h e primer composition, an
a p p r o p r i a t e s o l v e n t t h a t does not e x e r t an influence on t h e l e n s may
20 be used f o r t h e composition. Needless t o say, a solvent may not be
used f o r t h e composition.
[0059]
The primer l a y e r can be formed by any of a coating method and
a dry method. When t h e coating method is used, t h e l e n s is coated
25 with t h e primer compositi.on by a known coating method such a s spin
coating o r dip coating, andthen t h e r e s u l t a n t is s o l i d i f i e d , whereby
t h e primer l a y e r is formed. When the dry method is used, t h e primer
layer is formed by a known dry method such as a CVD method or a vacuum
deposition method. In forming the primer layer, if necessary, in
order to improve the adhesiveness, the lens surface may be subjected
to preprocessing such as alkali processing, plasma processing, or
5 ultraviolet processing.
[0060]
The hard coat layer is a coating layer for imparting functions
such as scratch resistance, abrasion resistance, moistureresistance,
hot water resistance, heat resistance, and weather resistance to the
10 lens surface
For the hard coat layer, generally, a hard coat composition is
used which contains an organic silicon compound having curability,
one or more kinds of oxide particles of an element selected from the
group of elements including Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
15 Zr, In, and Ti and/or one or more kinds of particles composed of a
composite oxide of two or more kinds of elements selected from the
group of elements.
[0061]
The hard coat composition preferably contains at least any of
20 amines, amino acids, metal acetylacetonate complexes, organic acid
metal salts, perchloric acids, salts of perchloric acids, acids,
metal chlorides, and polyfunctional epoxy compounds, in addition to
the aforementioned components. For the hard coat composition, an
appropriate solvent that does not exert an influence on the lens may
25 be used. Furthermore, a solvent may not be used for the composition.
[0062]
Generally, the lens is coated with the hard coat composition
by a known coating method such as spin coating or dip coating, and
then the composition is cured, whereby the hard coat layer is formed.
Examples of curing methods include thermal curing, curing methods
performed by i r r a d i a t i o n of energy rays such as u l t r a v i o l e t rays or
5 v i s i b l e rays, and the l i k e . In order t o i n h i b i t formation of
i n t e r f e r e n c e f r i n g e s , a difference between t h e r e f r a c t i v e index of
thehardcoat layer andthe r e f r a c t i v e index o f t h e lens is preferably
within a range of f O . l .
100631
10 Generally, the a n t i r e f l e c t i o n l a y e r is formedoverthehardcoat
layer i f necessary. The a n t i r e f l e c t i o n layer is c l a s s i f i e d i n t o an
inorganic a n t i r e f l e c t i o n layer and an organic a n t i r e f l e c t i o n layer.
The i n o r g a n i c a n t i r e f l e c t i o n layer is comprisedofaninorganicoxide
suchas Si02 o r T i 0 2 b y a d r y m e t h o d s u c h a s a vacuumdepositionmethod,
15 a sputtering method, an ion plating method, an ion beam-assisted
method, and a CVD method. The organic a n t i r e f l e c t i o n layer is
comprised of a composition, which contains an organic s i l i c o n
compound and silica-based p a r t i c l e s having i n t e r n a l c a v i t i e s , by a
wet method.
20 LO0641
The a n t i r e f l e c t i o n layer is composed of a single layer or
multiple layers. When it i s used in the form of a s i n g l e l a y e r , a
value obtained by subtracting t h e r e f r a c t i v e index of the
a n t i r e f l e c t i o n l a y e r fromtherefractiveindexofthehardcoatlayer
25 preferably become lower a t l e a s t equal to or greater than 0.1. In
order to cause the a n t i r e f l e c t i o n layer t o effectively perform an
a n t i r e f l e c t i o n function, it is preferable t o constitute the
a n t i r e f l e c t i o n f i l m with m u l t i p l e films, and i n t h i s case, a film
with a low r e f r a c t i v e index and a f i l m with a high r e f r a c t i v e index
a r e a l t e r n a t e l y laminated on each o t h e r . Even i n t h i s case, a
d i f f e r e n c e i n r e f r a c t i v e indexbetween the f i l m w i t h a low r e f r a c t i v e
5 index and t h e film with a high r e f r a c t i v e index is p r e f e r a b l y equal
t o o r g r e a t e r than 0.1. Examples of t h e f i l m with a high r e f r a c t i v e
index include films of ZnO, Ti02, CeOz, Sb205, SnO2, Z r 0 2 , Ta205, and
t h e l i k e , and examples of t h e f i l m with a low r e f r a c t i v e index include
films of Si02 and t h e l i k e .
10 [0065]
I f necessary, an antifogging l a y e r , an a n t i f o u l i n g l a y e r , o r
a water r e p e l l e n t l a y e r may be formed over t h e a n t i r e f l e c t i o n f i l m
l a y e r . Regarding t h e method f o r forming t h e antifogging l a y e r , t h e
a n t i f o u l i n g l a y e r , and t h e water r e p e l l e n t l a y e r , t h e method,
15 m a t e r i a l , and t h e l i k e used f o r t r e a t i n g t h e s e l a y e r s a r e not
particularlylimitedaslong astheydonotexertanegativeinfluence
on t h e a n t i r e f l e c t i o n function. It is p o s s i b l e t o use known methods
used f o r an a n t i f o g g i n g t r e a t m e n t , an a n t i f o u l i n g treatment, and a
water repellency treatment and m a t e r i a l s . Examples of the methods
20 used f o r the a n t i f o g g i n g t r e a t m e n t and t h e a n t i f o u l i n g treatment
include a method of covering t h e s u r f a c e with a s u r f a c t a n t ; a method
of giving water absorbing p r o p e r t i e s t o t h e l a y e r by adding a
hydrophilic film t o t h e s u r f a c e of t h e l a y e r ; a method of improving
t h e water absorbing p r o p e r t i e s by forming f i n e c o n c a v i t i e s and
25 convexities on t h e surface of t h e l a y e r ; a method of giving water
absorbing p r o p e r t i e s t o t h e l a y e r by u t i l i z i n g p h o t o c a t a l y t i c
a c t i v i t y ; a method performing a super water repellency treatment on
the layer to prevent water drops from adhering to the layer; and the
like. Examplesofthemethodsusedforther~~aterrepellencytreatment
include amethod of forming a water repellency treatment layer by
vapor deposition or sputtering of a fluorine-containing silane
5 compoundor the like; amethodof forming awater repellencytreatment
layer by dissolving a fluorine-containing silane compound in a
solvent and then coating; and the like.
[0066]
The 'plastic spectacle lens using the thiourethane resin of the
10 present invention may be used after being dyed with a dye for such
purpose, sothat the lensbecomes fashionableor exhibits chromogenic
properties. The lens can be dyed by a known dyeing method, but
generally, the following method is used.
[0067]
15 Generally, the lens is dyed by a method in which an original
plastic lens, which has undergone finishing to have a predetermined
optical surface, is dipped in a dyeing liquid in which a dye to be
used is dissolved or uniformly dispersed (dyeing step), and then the
lens is heated if necessary to fix the dye (annealing step after
20 dyeing) . The dye used in the dyeing step is not particularly limited
as long as it is a known dye, but generally, an oil-soluble dye or
a disperse dye is used. The solvent used in the dyeinq step is not
particularly limited as long as the dye to be used can be dissolved
or uniformly dispersed in the solvent. In the dyeing step, if
25 necessary, a surfactant for dispersing the dye in the dyeing liquid
or a carrier for accelerating dyeingmaybe added. Duringthe dyeing
step, a dye and a surfactant, which is added if necessary, are
dispersed in water or a mixture consisting of water and an organic
solvent so as to prepare a dyebath, t h e o p t i c a l lens is dipped i n
the dyebath, and the lens is dyed for a predetermined time a t a
predetermined temperature. The dyeing temperature and time can be
5 varied according t o the intended color concentration. Generally,
the lensmaybedyed f o r a fer.iminutestotens ofhours a t atemperature
equal t o orlowerthan12O0C, and the dye concentrationofthe dyebath
is s e t t o be 0.01% by weight t o 10% by weight. Moreover, when the
lens is not e a s i l y dyed, dyeing may be performed under applying
10 pressure. The annealing step a f t e r dyeing t h a t is performed i f
necessary is a step of performing heating processing on the dyed
o r i g i n a l lens. In the heating processing, water remaining on the
surface of the original lens, which has been dyed in the dyeing step,
is removed by using a solvent or the l i k e , or a l t e r n a t i v e l y , the
15 solvent i s air-dried, and t h e n t h e lens is c a u s e d t o s t a y i n a furnace
such a s a n i n f r a r e d h e a t i n g furnace in theatmosphereor a resistance
heating furnace. In the annealing step a f t e r dyeing, color l o s s of
the dyed o r i g i n a l l e n s is prevented (color loss-preventing
processing), and water having penetrated inside of t h e o r i g i n a l lens
20 a t the time of dyeing is removed.
[0068]
[ P l a s t i c polarizing lens]
In the present invention, the p l a s t i c polarizing lens can be
obtained by a manufacturing method including the following steps.
2 5 Step i: fixing a polarizing lens in a mold for molding a lens,
i n a s t a t e in which a t l e a s t one surface of the polarizing film is
separated from the mold
Stepii: injectingthepolymerizable composition ofthe present
invention into a space between the polarizing film and the mold
Stepiii: polymerizingandcuringthepolymerizable composition
by heating the composition, and laminating a layer comprised of a
5 polyurethane resin over at least one surface of the polarizing film
Hereinafter, each of the steps will be described in order.
[0069]
(Step i)
A polarizing film comprised of thermoplastic polyester or the
10 like is disposed in the internal space of the mold for molding a lens,
such that at least one of the film surfaces becomes parallel to the
inner surface of the mold facing the film surface. Between the
polarizing filmandthemold, a space is formed. The polarizing film
may be shaped beforehand.
15 [0070]
(Step ii)
Thereafter, within the internal space of the mold for molding
a lens, by a predetermined injection unit, the polymerizable
composition for an optical material of the present invention is
20 injected into the space between the mold and the polarizing film.
[0071]
(Step iii)
Then the mold for molding a lens, into which the polymerizable
composition for an optical material has been injected and in which
25 the polarizing film has been fixed, is heated for several hours to
tens of hours according to a predetermined temperature program in
a heating device such as an oven or water, thereby performing curing
and molding.
[0072]
The temperature of t h e polymerization and curing cannot be
s p e c i f i e d s i n c e t h e conditions vary with t h e makeup of the
5 polymerizable composition, t h e type o f t h e c a t a l y s t , themold shape,
and t h e l i k e . However, the polymerization and curing is performed
f o r 1 hour t o 48 hours at a temperature of O°C t o 140°C.
[0073]
After t h e curing and molding ends, the molded a r t i c l e is taken
10 out of t h e mold f o r molding a l e n s . In t h i s way, it is p o s s i b l e t o
obtaintheplasticpolarizinglens o f t h e p r e s e n t e m b o d i m e n t i n ~ ~ h i c h
t h e l a y e r comprisedo f a p o l y u r e t h a n e r e s i n i s laminatedove r a t l e a s t
one s u r f a c e of t h e p o l a r i z i n g film.
The r e l e a s e d p l a s t i c p o l a r i z i n g l e n s of t h e present invention
15 is d e s i r a b l y s u b j e c t e d t o annealingprocessingperformedbyheating,
such t h a t s t r a i n r e s u l t i n g from polymerization is r e l i e v e d .
[0074]
If necessary, the p l a s t i c p o l a r i z i n g lens of t h e present
invention is used a f t e r a coating l a y e r is provided over one s u r f a c e
20 o r both s u r f a c e s t h e r e o f . Examples of t h e coating l a y e r include a
primer l a y e r , a hard coat l a y e r , an a n t i r e f l e c t i o n l a y e r , a n
a n t i f o g g i n g c o a t l a y e r , a n a n t i f o u l i n g l a y e r , a w a t e r r e p e l l e n t l a y e r ,
and t h e l i k e , s i m i l a r l y t o the p l a s t i c s p e c t a c l e l e n s .
[Examples]
25 [0075]
H e r e i n a f t e r , the present invention w i l l be more s p e c i f i c a l l y
d e s c r i b e d b a s e d o n examples, b u t t h e p r e s e n t invention is not l i m i t e d
thereto.
[0076]
The lens obtained by polymerization was evaluated by being
subjected to performance tests. By the performance tests, a
5 refractive index, an Abbe number, heat resistance, specific gravity,
cloudiness, and striae were tested, and the lens was evaluated by
the following test methods.
.Refractive index (ne), Abbe number (ve): a refractive index
and an Abbe number were measured at 20°C by using a Pulfrich
10 refractometer KPR-30 manufactured by Shimadzu Corporation.
.Heat resistance: a glass transition temperature (Tg) measured
by a TMA penetration method (load: 50 g, pin tip: 0.5 mm0) by using
TMA-60 manufactured by Shimadzu Corporation was taken.as heat
resistance.
15 *Specific gravity: a specific gravity was measured at 20°C by
an Archimedes method.
[0077]
Cloudiness of resin: the prepared lens was visually observed
byusinga slideprojector (CS-15manufacturedbyCABIN(r)) as alight
20 source. The lens in which cloudiness was not observed was evaluated
tobe 'O", andthe lens inwhich cloudinesswas observed~qase valuated
to be "X".
[0078]
.Striae: the prepared lens was visually observed by using a
25 high-pressure mercury lamp (manufactured by USHIO, INC. ) as a light
source. The lens in which striae were not observed was evaluated
to b "Or', and the lens in which striae were observed was evaluated
to be 'Xu.
[0079]
[Example 11
2.00 g of 1,2-dimethylimidazole as a catalyst was added to 8.00
5 g of Zelec UN (acidic phosphoric acid ester: registered trademark,
manufactured by Stepan Company) as an internal release agent, and
the components weremixed and dissolvedtogether at room temperature
until a uniform solution was formed, thereby preparing a
catalyst/release agent master liquid. Furthermore, 49.50 g of
10 bis(4-isocyanatocyc1ohexyl)methane was mixed with 8.74 g of
2,s (6)- bis (isocyanatomethyl)- bicycle [2.21 heptane, and to this
mixture, 1.50 g of Biosorb 583 as an ultraviolet absorber and 0.18
g of the catalyst/release agent master liquid prepared as above were
added. These components were mixed and dissolvedtogether at 20°C,
15 thereby preparing a uniform solution. After the dissolution, 37.59
gof 4-mercaptomethyl-l,8-dimercapto-3,6-dithiaoctane and 4.17 g of
diethylene glycol dimercaptopropionate were added thereto, and the
components were mixed and dissolved together at 20°C, thereby
preparing a uniform solution. After being degassed for 30 minutes
20 at 150 Pa, the uniform solution was filtered through a 1 pm Teflon
(registered trademark) filter and then injected into a mold
consisting of a glass mold and a tape. The mold was put into an oven
andgradua11yheatedto20"Cto120"Cforover35hours soas toperform
polymerization. After the polymerization ended, the mold was taken
25 out of the oven, and the molded article was released from the mold,
thereby obtaining a lens. Furthermore, the obtained resin was
annealed for 4 hours at 120°C. The results of the performance
evaluation of the obtained lens are summarized in Table 1.
[0080]
[Example 21
3.33 g of 1-benzyl-2-methyiimidazole as a catalyst was added
5 to 6.67 g of Zelec UN as an internal release agent, and the components
weremixedanddissolvedtogetherat roomtemperatureuntilauniform
solution was formed, thereby preparing a catalyst/release agent
master liquid. A lens was obtained by performing polymerization in
the same manner as in Example 1, except that 49.50 g of
10 bis(4-isocyanatocyclohexy1)methane was mixed with 8.74 g of
2,5 (6)- bis (isocyanatomethyl)- bicycle [2.21 heptane; 1.50 g of
Biosorb 583 as an ultraviolet absorber and 0.15 g of the
catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
15 at 20°C. The results of the performance eval.uation of the obtained
lens are summarized in Table 1.
[0081]
[Example 31
1.00 g of 1,2-dimethylimidazole and 1.66 g of
20 1-benzyi-2-methylimidazole as catalyst were addedto 7.34 g of Zelec
UN as an internal release agent, and the components were mixed and
dissolved together at room temperature until a uniform solution was
formed, thereby preparing a cataiyst/release agent master liquid.
A lens was obtained by performing polymerization in the same manner
25 as in Example 1, except that 49.50 g of
bis(4-isocyanatocyclohexy1)methane was mixed with 8.74 g of
2,5 (6) -bis (isocyanatomethyl) -bicycle [2.2 1 heptane; 1.50 g of
Biosorb 583 as an ultraviolet absorber and 0.25 g of the
catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
at 20°C. The results of the performance evaluation of the obtained
5 lens are summarized in Table 1.
[0082]
[Example 41
2.50 g of l,2-dimethylimidazole as a catalyst tias added to 7.50
gofJP-506H (manufacturedbyJohokuChemicalCo., Ltd.) asaninternal
10 release agent, and the components were mixed and dissolved together
at room temperature until a uniform solution was formed, thereby
preparing a catalyst/release agent master liquid. A lens was
obtainedbyperformingpolymerizationinthe samemannerasinExample
1, except that 49.50 g of bis(4-isocyanatocyclohexyl)methane was
15 mixed with 8.74 g of
2,5 (6)- bis (isocyanatomethyl)- bicycle L2.2 1 hepane; 1.50 g of
Biosorb 583 as an ultraviolet absorber and 0.20 g of the
catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
20 at 20°C. The results of the performance evaluation of the obtained
lens are summarized in Table 1.
[0083]
[Example 51
4.00 g of 1-benzyl-2-methylimidazole as a catalyst was added
25 to 6.00 g of JP-506H as an internal release agent, and the components
igeremixedanddissolvedtogether at roomtemperature untila uniform
solution was formed, thereby preparing a catalyst/release agent
master liquid. A lens was obtained by performing polymerization in
the same manner as in Example 1, except that 49.50 g of
bis(4-isocyanatocyclohexy1)methane was mixed with 8.74 g of
2,s (6) -bis (isocyanatomethyl) -bicycle 12.211 heptane; 1.50 g of
5 Biosorb 583 as an ultraviolet absorber and 0.20 g of the
catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
at 20°C. The results of the performance evaluation of the obtained
lens are summarized in Table 1.
10 [0084]
[Example 61
0.44 g of 1,2-dimethylimidazole and 2.60 g of
1-benzyl-2-methylimidazole as catalyst were added to 6.96 g of
JP-506H as an internal release agent, and the components were mixed
15 and dissolved together at room temperature until a uniform solution
was formed,therebypreparingacatalyst/releaseagentmasterliquid.
A lens was obtained by performing polymerization in the same manner
as in Example 1, except that 49.50 g of
bis(4-isocyanatocyclohexy1)methane was mixed with 8.74 g of
20 2,s (6)- bis (isocyanatomethyl)- bicycle [2.2.1]h eptane; 1.50 g of
Biosorb 583 as an ultraviolet absorber and 0.32 g of the
catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
at 20°C. The results of the performance evaluation of the obtained
25 lens are summarized in Table I
[0085]
[Example 71
2.00 g of 1,2-dimethylimidazole as a catalyst was added to 8.00
g of Zelec UN (acidic phosphoric acid ester: registered trademark,
manufactured by Stepan Company) as an internal release agent, and
the components were mixed and dissolvedtogether at roomtemperature
5 until a uniform solution was formed, thereby preparing a
catalyst/release agent master liquid. Furthermore, 45.70 g of
bis(4-isocyanatocyc1ohexyl)methane was mixed with 11.40 g of
2,5(6)-bis(isocyanatomethyl)-bicyclo[2.2.1lheptane, and to this
mixture, 1.50 g of Biosorb 583 as an ultraviolet absorber and 0.18
10 g of the catalyst/release agent master liquid prepared as above were
added. These components were mixed and dissolvedtogether at 20°C.
After dissolution, 35.80 g of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 7.10 g of
bis(3-mercaptopropionic acid) 1,4-butanediol were added to the
15 resultant, and the components were mixed and dissolved together at
20°C, thereby preparing a uniform solution. After being degassed
for 30 minutes at 150 Pa, the uniform solution was filtered through
a 1 pm Teflon (registered trademark) filter and then injected into
a mold consisting of a glass mold and a tape. The mold was put into
20 an oven and gradually heated to 20°C to 120°C for over 35 hours so
as to perform polymerization. After the polymerization ended, the
mold was taken out of the oven, and the molded article was released
from the mold, thereby obtaining a lens. Furthermore, the obtained
resin was annealed for 4 hours at 120°C. The results of the
25 performance evaluation of the obtained lens are summarized in Table
1.
[0086]
[Example 81
1.66 g of 1,2-dimethylimidazole as a catalyst was added to 8.43
g of JP-506H as an internal release agent, and the components were
mixed and dissolved together at room temperature until a uniform
5 solution was formed, thereby preparing a 1,2-dimethylimidazole
catalyst/release agent master liquid. Moreover, 2.00 g of
1-benzyl-2-methylimidazole as a catalyst was added to 8.00 g of
JP-506H as an internal release agent, and the components were mixed
and dissolved together at room temperature until a uniform solution
10 was formed, thereby preparing a 1-benzyl-2-methylimidazole
catalyst/release agent master liquid. A lens was obtained by
performing polymerization in the same manner as in Example 1, except
that 50.60 g of 2,5 (6)- his (isocyanatomethyl)- bicycle [2.2.1]h eptane,
1.50 g of Biosorb 583 as an ultraviolet absorber, and 0.05 g of the
15 1,2-dimethylimidazole catalyst/release agent master liquidand 0.20
g of the 1-benzyl-2-methylimidazole catalyst/release agent master
liquid prepared as above were mixed and dissolved together at 20°C;
then 23.90 g of pentaerythritoltetrakis(3-mercaptopropionate) and
25.50 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were
20 added to the mixture; and the components were mixed and dissolved
together at 20°C. The results of the performance evaluation of the
obtained lens are summarized in Table 1.
[0087]
[Example 91
25 1.33 g of 1-benzyl-2-methylimidazole as a catalyst was added
to 8.67 g of Zelec UN (acidic phosphoric acid ester: registered
trademark, manufactured by Stepan Company) as an internal release
agent, and the components were mixed and dissolved together at room
temperature until a uniform solution was formed, thereby preparing
a catalyst/release agent master liquid. A lens was obtained by
performing polymerization in the same manner as in Example 1, except
5 that 52.00 g of m-xylylene diisocyanate, 1.50 g 'of Biosorb 583 as
an ultraviolet absorber, and 0.10 g of the catalyst/release agent
master liquid prepared as above were mixed and dissolved together;
then 48.00 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
was added to the mixture; and the components were mixed and dissolved
10 together at 20°C. The results of the performance evaluation of the
obtained lens are summarized in Table 1.
[00881
[Example 101
1.33 g of 1-benzyl-2-methylimidazole as a catalyst was added
15 to 8.67 g of Zelec UN (acidic phosphoric acid ester: registered
trademark, manufactured by Stepan Company) as an internal release
agent, and the components were mixed and dissolved together at room
temperature until a uniform solution was formed, thereby preparing
a catalyst/release agent master liquid. A lens was obtained by
20 performing polymerization in the same manner as in Example 1, except
that 50.6 g of m-xylylene diisocyanate, 1.50 g of Biosorb 583 as an
ultraviolet absorber, andO.10 q ofthe catalyst/release agent master
liquidprepared as aboveweremixedanddissolved together; then 49.4
g of polythiol, which contained
25 4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane, and
5,7-dimercaptomethy1-1,11-dimercapto-3,6,9-trithiaundecane as
main components, was added to the mixture; and the components were
mixedanddissolvedtogetherat2O0C. The results ofthe performance
evaluation of the obtained lens are summarized in Table 1.
[00891
5 [Comparative example 11
1.82 g of triethylamine as a catalyst was added to 8.18 g of
Zelec UN as an internal release agent, and the components were mixed
and dissolved together at room temperature until a uniform solution
was formed, therebypreparingacatalyst/releaseagentmasterliquid.
10 A lens was obtained by performing polymerization in the same manner
as in Example 1, except that 49.50 g of
bis(4-isocyanatocyclohexy1)methane was mixed with 8.74 g of
2,5 (6) -his (isocyanatomethyl) -bicycle l2.2 1 e t a ; 1.50 g of
Biosorb 583 as an ultraviolet absorber and 0.088 g of the
15 catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
at 20°C. The results of the performance evaluation of the obtained
lens are summarized in Table 1.
[0090]
20 [Comparative example 21
1.82 g of triethylamine as a catalyst was added to 8.18 g of
Zelec UN as an internal release aqent, and the components were mixed
and dissolved together at room temperature until a uniform solution
was formed, t h e r e b y p r e p a r i n g a c a t a l y s t / r e l e a s e a g e n t m a s t e r l i q u i d .
25 A lens was obtained by performing polymerization in the same manner
as in Example 1, except that 49.50 g of
bis(4-isocyanatocyclohexy1)methane was mixed with 8.74 g of
2,5 (6)- bis (isocyanatomethyl)- bicycle [ 2 . 2he ptane; 1. SO g of
Biosorb 583 as an ultraviolet absorber and 0.50 g of the
catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
5 at 20°C. The results of the performance evaluation of the obtained
lens are summarized in Table 1.
[0091]
[Comparative example 31
2.00 g of triethylamine as a catalyst was added to 8.00 g of
10 JP-506H as an internal release agent, and the components tiere mixed
and dissolved together at room temperature untila uniform solution
was formed,therebypreparingacatalyst/releaseagentmas~erliquid.
A lens was obtained by performing polymerization in the same manner
as in Example 1, except that 49.50 g of
15 bis(4-isocyanatocyclohexyl)methane was mixed with 8.74 g of
2,5 (6)- bis (isocyanatomethyl)- bicycle [2.21 heptane; 1. SO g of
Biosorb 583 as an ultraviolet absorber and 0.30 g of the
catalyst/release agent master liquid prepared as above were added
to the mixture; and the components were mixed and dissolved together
20 at 20°C. The results of the performance evaluation of the obtained
lens are summarized in Table 1.
100921
[Comparative example 41
1.00 g of triethylamine as a catalyst was added to 9.00 g of
25 Zelec UN (acidic phosphoric acid ester: registered trademark,
manufactured by Stepan Company) as an internal release agent, and
the components weremixed and dissolvedtogether at room temperature
until a uniform solution was formed, thereby preparing a
catalyst/release agent master liquid. A lens was obtained by
performing polymerization in the same manner as in Example 1, except
that 50.60 g of 2,5 (6)- bis (isocyanatomethyl)- bicycle [2.2.1] heptane,
5 1.50 g of Biosorb 583 as an ultraviolet absorber, and 0.10 g of the
catalyst/release agent master liquid prepared as above were mixed
and dissolved together at 20°C; then 23.90 g of pentaerythritol
tetrakis(3-mercaptopropionate) and 25.50 g of
4-mercaptomethyl-l,8-dimercapto-3,6-dithiaoctane were added to the
10 mixture; andthecomponentsweremixedanddissolvedtogetherat20oC.
The results of the performance evaluation of the lens are summarized
in Table 1.
[0093]
[Comparative example 51
15 1.5 goftriethylarnine as a catalyst was addedto 8.50 gof Zelec
UN (acidicphosphoricacidester: registeredtrademark, manufactured
by Stepan Company) as an internal release agent, and the components
\ieremixedanddissolvedtogether at roomtemperature untila uniform
solution was formed, thereby preparing a catalyst/release agent
20 master liquid. A lens was obtained by performing polymerization in
the same manner as in Example 1, except that 50.60 g of
2,5 (6) -bis (isocyanatomethyl) -bicycle [2.2 1 heptane, 1.50 g of
Biosorb 583 as an ultraviolet absorber, and 0.10 g of the
catalyst/release agent master liquid prepared as above were mixed
25 and dissolved together at 20°C; then 23.90 g of pentaerythritol
tetrakis(3-mercaptopropionate) and 25.50 g of
4-mercaptomethyl-l,8-dimercapto-3,6-dithiaoctane were addedto the
mixture; andthecomponents~ieremixedanddisso1vedtogetherat20"C.
The results ofthe performance evaluation ofthe lens are summarized
in Table 1.
[0094]

4 7
Table 1 (continued)
(C) Curing Amount Refractive Abbe Heat Specific Presence of Presence of
Exp. No. Thiol imidazole-based Amount catalyst of index number resistance gravity cloudiness striae
compound curing catalyst of catalyst [nel be1 TCl I20"CJ (visuai [visual
(b2) catalyst ( ,""-, P P ~ ) observation) observation) , , " y , , , , , I 1
Comparative
I I I
Compound Compound . 1
TEA * 107 1.22 X
example
X
Compound
(4) (6)
x r n m n n 1 8 l l n i
7r h " " " I 4 cno ,A " " C A A,
I I
Compound
P r-o- mnnln.i i m ,v-- - -.mpound Compound - TEA 100 ppm 1.594 39 90 129 X 0 I (1) 1 (4) (8)
5
(1) 14)
Compound Compound
(8)
. Compound - TEA 150 ppm 1.595 39 96 1.29 0 X
Thiolcompound (bl): athiolcompoundhaving one ormore sulfide
bonds and two or more functional groups
Thiol compound (b2) : a thiol compound having one or more ester
bonds and two or more functional groups
5 Catalyst amount (ppm): the amount of a curing catalyst with
respect to the total amount of the isocyanate compound (A) and the
thiol compound (B)
Compound (1) :
2,5 (6)- bis (isocyanatomethyl)- bicycle [2.2.1]h eptane
10 Compound (2): bis(4-isocyanatocyclohexy1)methane
Compound (3): m-xylylene diisocyanate
Compound (4) :
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
Compound (5): polyol containing
15 4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane, and
5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane as
main components
Compound (6): diethylene glycol dimercaptopropionate
20 Compound (7): bis(3-mercaptopropionic acid) 1,4-butanediol
Compound (8): pentaerythritol tetrakis(3-mercaptopropionate)
DMIM: 1,2-dimethylimidazole
BMIM: 1-benzyl-methylimidazole
TEA: triethylamine
25 [0095]
From the results of Examples 1 to 10, it is understood that the
polymerizable composition of the present invention containing an
imidazole-based curing catalyst in a predetermined amount satisfies
optical properties such as heat resistance and a refractive index
required for lens products, and makes it possible to obtain a lens
in which cloudiness or striae are further inhibited, compared to the
5 polymerizable compositions containing the triethylamine catalyst
shown in Comparative examples 1 to 5. Moreover, because the
polymerizable composition of the present invention uses the
imidazole-based curing catalyst in a predetermined amount and does
not use a metal-containing compound as a catalyst, a lens extremely
10 safe for the human body or the environment can be obtained.
[00961
ThepresentapplicationclaimsprioritybasedonJapanesePatent
Application No. 2012-251913 filed on November 16, 2012, the entire
disclosure of which is incorporated herein.
15 [0097]
Thepresent inventioncanalso employthe Eollowingembodiments.
[I] A polymerizable composition containing: (A) an alicyclic
isocyanate compound (al) having two or more functional groups and/or
an aliphatic isocyanate compound (a21 having two or more functional
20 groups; (B) a thiol compound having one or more sulfide bonds and/or
one or more ester bonds and having two or more functional groups;
and (C) an imidazole-based curinq catalyst, in which the amount of
the imidazole-based curing catalyst (C) is 5 ppm to 3,000 ppm with
respect to the total amount of the isocyanate compound (A) and the
25 thiol compound (B) .
[2] The polymerizable composition described in [I], in which
the alicyclic isocyanate compound (al) is at least one kind selected
from the group consisting of 1,3-bis (isocyanatomethyl)c yclohexane,
1,4-his (isocyanatomethyl) cyclohexane,
bis(4-isocyanatocyclohexyl)methane,
bis(isocyanatomethy1)-bicyclo[2.2.1]heptane, and isophorone
5 diisocyanate, andthe aliphatic isocyanate compound (a2) is at least
one kind selected from the group consisting of m-xylylene
diisocyanate, hexamethylene diisocyanate, and pentamethylene
diisocyanate.
[3] The polymerizable composition described in [I] or [2], in
10 which in the thiol compound (B), the thiol compound having one or
more sulfide bonds and trio or more functional groups is at least one
kind selected from the group' consisting of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaocatane, 4,8-, 4,7-, or
5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
15 bis (mercaptoethyl) sulfide, 2,5-bis (mercaptomethyl) -l,4-dithiane,
1,1,3,3-tetrakis( mercaptomethylthio)p ropane,
4,6-bis(mercaptomethy1thio)-1,3-dithiane, and
2- (2,2-his( mercaptomethylthio)e thyl)- 1,3-dithietane,
[4] The polymerizable composition described in any one of [I]
20 to [3], in which in the thiol compound (B) , the thiol compound having
one or more ester bonds and two or more functional groups is at least
one kind selected from the group consisting of pentaerythritol
tetrakismercaptoacetate, pentaerythritol
tetrakismercaptopropionate, and a thiolcompound represented by the
25 folloiiing Formula (I),
wherein, in the formula, each of 1, m, and r independently
represents an integer of 1 to 4; n represents an integer of 1 to 3,
Rrepresents hydrogen or amethyl group; andwhen there is aplurality
5 of Rs, Rs may be the same as or different from each other.
[5] The polymerizable composition described in any one of [I]
to [4], in which the imidazole-based curing catalyst (C) includes
at least one kind of compound represented by the following Formula
(21,
wherein, in the formula, each of R1, R2, R3, and R4 independently
represents hydrogen, a mercapto group, a cyano group, an alkyl group
whichmaybe substituted, or a phenylgroup whichmaybe substituted;
andR1, R2, R3, andR4maybethe same as ordifferentfromeachother).
15 [6] The polymerizable composition described in any one of [I]
to [5], in which the imidazole-based curing catalyst (C) is at least
one kind selected fromthe group consisting of dimethylimidazole and
benzylmethylimidazole.
[7] The polymerizable composition described in any one of [4]
20 to [6], in which in the thiol compound represented by Formula (I),
each of 1 and m independently represents an integer of 1 to 2, and
r and n represent 1.
[8] An optical material comprised of the polymerizable
composition described in any one of 111 to 171.
5 [9] A manufacturing method of an optical material, including
a step of molding the polymerizable composition described in any one
of [I] to [7] by cast polymerization.
[lo] A plastic spectacle lens in which a primer layer, a hard
coat layer, and an antireflection layer are laminated in this order
10 overasubstratecomprisedofthepolymerizablecompositiondescribed
any one of [I] to [7].
[ll] A manufacturing method of a plastic spectacle lens,
including a step of molding a substrate by performing cast
polymerization ofthe polymerizable composition describedin any one
15 of [I] to [7], and a step of forming a primer layer, a hard coat layer, and an antireflection layer in this order over the substrate.

CLAIMS
1. A polymerizable composition comprising:
(A) an alicyclic isocyanate compound (al) having two or more
5 functionalgroupsand/oranaliphaticisocyanatecompound (a2) having
two or more functional groups;
(B) a thiol compound having one or more sulfide bonds and/or
one or more ester bonds and having two or more functional groups;
and
10 (C) an imidazole-based curing catalyst,
wherein the amount of the imidazole-based curing catalyst (C)
is 5 ppm to 3,000 ppm with respect to the total amount of (A) an
isocyanate compound and (B) a thiol compound.
15 2. The polymerizable composition according to claim 1,
wherein the alicyclic isocyanate compound (al) is at least one
kind selected from the group consisting of
1,3-bis(isocyanatomethyl)cyclohexane,
1,4-bis(isocyanatomethyl)cyclohexane,
20 bis (4-isocyanatocyclohexyl)methane,
bis(isocyanatomethy1)-bicyclo[2.2.l1heptaner and isophorone
diisocyanate, andthe aliphatic isocyanate compound (a2) is at least
one kindseiectedfromthegroupconsistingofm-xylylenediisocyanate,
hexamethylene diisocyanate, and pentamethylene diisocyanate.
25
3. The polymerizable composition according to claim 1 or 2,
wherein in the thiol compound (B), the thiol compound having
one or more sulfide bonds and two or more functional groups is at
least one kind selected from the group consisting of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaocatane, 4,8-, 4,7-, or
5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
5 bis(mercaptoethyl)sulfide, 2,5-bis(mercaptomethy1)-1,4-dithiane,
1,1,3,3-tetrakis (mercaptomethylthio)p ropane,
4,6-bis (mercaptomethylthio)- 1,3-dithiane, and
2-[2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.
10 4. The polymerizable composition according to any one of claims 1
to 3,
wherein in the thiol compound ( B ) , the thiol compound having
one or more ester bonds and two or more functional groups is at least
one kind selected from the group consisting of pentaerythritol
15 tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), and athiolcompound representedby
the following Formula (I),
wherein, in the formula, each of 1, m, and r independently
20 represents an integer of 1 to 4; n represents an integer of 1 to 3;
Rrepresents hydrogen or amethyl group; andwhen there is a plurality
of Rs, Rs may be the same as or different from each other.
5. The polymerizable composition according to any one of claims 1
55
to 4,
wherein the imidazole-based curing catalyst (C) includes at
least one kind of compound represented by the following Formula (2),
5 wherein, in the formula, each of R1, R2, R3, and R4 independently
represents hydrogen, a mercapto group, a cyano group, an a1 kyl group
whichmaybe substituted, or a phenylgroup whichmaybe substituted;
and R1, R2, R3, and R4 may be the same as or different from each other.
10 6. The polymerizable composition according to any one of claims 1
to 5,
wherein the imidazole-based curing catalyst (C) is at least one
kind selected from the group consisting of dimethylimidazoie and
benzylmethylimidazole.
15
7. The polymerizable composition according to any one of claims 4
to 6,
wherein in the thiol compound represented by Formula (I), each
of 1 and m indeper~deritlyr epresents an integer of 1 to 2, r represents
20 an integer of 1 to 3, and n represents 1 or 2.
8. An optical material comprised of the polymerizable composition
according to any one of claims 1 to 7.
9. A manufacturing method of an optical material, con~prising:
a step of casting the polymerizable composition according to
any one of claims 1 to 7 into a mold; and
5 a stepofpolymerizingthepolymerizablecompositionbyheating.
10. A plastic spectacle lens in which a primer layer, a hard coat
layer, and an antireflection layer are laminated in this order over
a substrate comprised of the polymerizabla composition according to
10 any one of claims 1 to 7.
11. Amanufacturingmethod of a plastic spectacle lens, comprising:
a step of casting the polymerizable composition according to
any one of claims 1 to 7 into a mold;
15 a step of obtaining a lens substrate by polymerizing the
polymerizable composition by heating the composition; and
a step of forming a primer layer; a hard coat layer, and an
antireflection layer in this order over at least one surface of the
lens substrate.