SPECIFICATION
POLYMERIZABLE COMPOSITION FOR OPTICAL MATERIALS, OPTICAL MATERIAL
AND PLASTIC LENS OBTAINED FROM COMPOSITION
TECHNICAL FIELD
The present invention r e l a t e s t o a polyrnerizable composition
f o r optical materials including a photochromic compound, and an
10 o p t i c a l material and a p l a s t i c lens obtained from the composition.
BACKGROUND ART
Since p l a s t i c lenses are l i g h t and not e a s i l y cracked in
comparison to inorganic l e n s e s , p l a s t i c lenses have been rapidly
15 d i s t r i b u t e d a s o p t i c a l elements such as spectacle lenses, camera
lenses. In recent years, development of p l a s t i c lenses having
photochromic property has been progressing.
In addition, among these, a lens obtained from
poly(thio)urethane has a t t r a c t e d attention from the viewpoint t h a t
20 the lens has+ h5gh r e f r a c t i v e index and physical properties thereof
such as strength is excellent.
[0003]
Patent Document 1 describes a lens formed of a composition
including a predetermined photochromic compound and a
25 d i (meth) acrylate compound. In paragraph "0009", it is described t h a t
i n a case where a urethane r e s i n o r a thiourethane r e s i n having a
highrefractiveindex is used, isocyanatewhichisa resinrawmaterial
i n a monomer s t a t e reacts with a photochromic compound, and due t o
t h i s , photochromic property is completely eliminated.
[00041
Patent Document 2 discloses a lens obtained by providing a
5 coating l a y e r formed of a composition including a photochromic
compoundhavingachromene skeletonandaphenolcompoundona surface
of a thiourethane-based p l a s t i c lens.
[00051
Patent Document 3 discloses a photochromic lens having a lens
10 s u b s t r a t e formed of a thiourethane resin and a photochromic film
formed by applying a solution including a photochromic compound and
a radicallypolymerizablemonomertothe substrate. Patent Document
4 discloses a compound having photochromic properties.
[00061
15 Patent Document 5 discloses a polymerizable composition f o r
o p t i c a l m a t e r i a l s including a t l e a s t one kindof isocyanate compounds
selected from a l i p h a t i c isocyanate compounds and a l i c y c l i c
isocyanate compounds, a di- or higher functional active hydrogen
compound, and a photochromic compound.
20 RELATED DOCUMENT L.
PATENT DOCUMENT
[00071
[Patent Document 11 Japanese Unexamined Patent Publication No.
8-272036
25 [Patent Document 21 Japanese Unexamined Patent PublicationNo.
2005-23238
[Patent Document31 Japanese Unexamined Patent Publication No.
[PatentDocument4] JapaneseUnexaminedPatent PublicationNo.
2011-144181
[Patent Document 51 Pamphlet of International Publication No.
5 W02014/002844
[Patent Document 61 United States Patent No. 6506538
[PatentDocument7] Japanese Unexamined Patent PublicationNo. '
2005-305306
[Patent Document 81 W02005/087829
10 [Patent Document 91 W02006/109765
[Patent Document 101 W02007/020817
[Patent Document 111 W02007/020818
[Patent Document 121 W02014/002844
15 SUMMARY OF THE INVENTION
[OOOS]
Even in a case where an o p t i c a l material having photochromic
propertyformedofpoly(thio)urethaneis obtained, thereisaproblem
t h a t the photochromic compound reacts with isocyanate which is a
20 monomer, - and%dcceto .th.is,--photochromic property is not exhibited a t
a l l , as described in paragraph "0009" of Patent Document 1.
In addition, Patent Document 5 describes t h a t , according to a
poly(thio)urethane-basedcomposition foropticalmaterialsobtained
by using a s p e c i f i c polyisocyanate compound, photochromic property
25 is impartedtotheobtainedopticalmaterial. However, there is room
for f u r t h e r i m p r o v e m e n t i n a p p l i c a t i o n s ~ ~ i t h t h e m a i n p u r p o s e o f l i g h t
shielding, such as sunglasses, from the viewpoint of the amount of
changes in light transmittance.
[0009]
The present invention can be described as follows.
[I] A polymerizable composition for optical materials,
5 comprising:
a polyisocyanate compound (A),
a polyol compound (B) represented by the following General
Formula (1) having a number average molecular weight of 100 or more,
a di- or higher functional active hydrogen compound (C) in which
10 the compound (B) is excluded and
a photochromic compound ( D ) ,
wherein, in Formula ( I ) , m represents a numerical value of 1
15 to 20, k represents 0 to Zm, n represents a numerical value of 1 to
20, 1 represents 0 to 2n, a represents a numerical value of 0 or more,
b represents a numerical value of 0 or more, d represents a numerical
value of 0 or ,mow, a;nd.e=representsa numerical value of 1 or more;
Q' represents a hydrogen atom or an alkyl group having 1 to 6 carbon
20 atoms, and a plurality of ~l'sma y be the same as or different from
each other; Q~ represents a hydrogen atom or an alkyl group having
1 to 6 carbon atoms, and a plurality of ~ ~may' bes the same as or
different from each other; and Z represents a divalent organic group
having1to30carbonatomswhichoptionallyincludeanaromaticgroup,
25 andapluralityof Z'smaybethe same as ordifferentfromeachother.
[21 The polymerizable composition for optical materials
according to [ll,
wherein the polyisocyanate compound (A) is at least one kind
selected from the group consisting of hexamethylene diisocyanate,
5 pentamethylene diisocyanate, xylylene diisocyanate, isophorone
diisocyanate, bis(isocyanatomethy1) cyclohexane,
dicyclohexylmethane diisocyanate,
2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene
10 diisocyanate, phenylene diisocyanate, and diphenylmethane
diisocyanate.
[ 3 ] The polymerizable composition for optical materials
according to [I] or [21,
wherein the polyol compound (B) is at least one kind selected
15 from compounds which have a number average molecular weight of 100
or more and which are represented by the following General Formulas
(1) to ( I V ) ,
wherein, in Formula (I), p represents a numerical value of 4
20 ta100, Xrepresents ahydrogenatomoramethylgroup, andaplurality
of X's may be the same as or different from each other,
wherein, in Formula (11) , q and r may be the same as or different
from each other, each of q and r represents a numerical value of 1
or more, and the sum of q and r represents a numerical value of 2
to 100; R' and R2 may be the same as or different from each other,
each of R1 and RZ represents a hydrogen atom or a methyl group, and
5 a plurality of R1's or R2's may be the same as or different from each
other; and Z represents a substituted or unsubstituted divalent
aromaticgroup ora divalent aliphatic groupr~hichoptionallyinclude
a substituted or unsubstituted aromatic group having 1 to 20 carbon
atoms,
.wherein, inFormula (III), qandrmaybethe sameasordifferent
from each other, each of q and r represents a numerical value of 1
or more, and the sum of q and r represents a numerical value of 2
to 100; and R1 and R2 may be the same as or different from each other,
15 each of R' and R2 represents a hydrogen atom or a methyl group, and
a plurality of R1's or R2's may be the same as or different from each
other,
wherein, in Formula (IV), m represents a numerical value of 1
20 to 20, k represents 0 to 2m, n represents a numerical value of 1 to
20, 1 represents 0 to 2n, f represents a numerical value of 0 or more,
g represents a numerical value of 1 or more, h represents a numerical
value of 1 or more, and j represents a numerical value of 1 or more;
Q1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, and a plurality of Q1's may be the same as or different from
each other; Q2 represents a hydrogen atom or an alkyl group having
1 to 6 carbon atoms, and a plurality of Q2's may be the same as or
5 different from each other; and R~ represents a linear or branched
alkylene group having 1 to 20 carbon atoms or a phenylene group which
optionallyhave alinearorbranchedalkyl grouphavingltolo carbon
atoms as a substituent, and the plurality of R~'S may be the same
as or different from each other.
10 [4] The polymerizable composition for optical materials
according to [3],
wherein the polyol compound (B) is the compound represented by
General Formula (I), (111) , or (IV) .
[S] The polymerizable composition for optical materials
15 according to [31 or [ 4 ] ,
wherein the compound represented by General Formula (I) is
polyethylene glycol or polypropylene glycol.
[ 6 ] The polymerizable composition for optical materials
according to any one of [3] to [S],
20 whereGn the~~nxmbearv erage molecular weight of the compound
represented by General Formula (~I) is 200 to 4000.
.,~ [ 7 ] Thepolymerizable composition for optical materials ..~
according to any one of [3] to [5],
wherein the number average molecular weight of the compound
25 represented by General Formula (I) is 300 to 3000.
[ 8 ] The polymerizable composition for optical materials
according to [3] or [ 4 1 ,
wherein the number average molecular weight of the compound
represented by General Formula (11) is 400 to 2000.
[9] The polymerizable composition for optical materials
according to [3] or [4],
5 wherein the number average molecular weight of the compound
represented by General Formula (111) is 400 to 2000.
[lo] The polymerizable composition for optical materials
according to [3] or [4],
wherein the number average molecular weight of the compound
10 represented by General Formula (IV) is 600 to 3000.
[ll] The polymerizable composition for optical materials
according to any one of [I] to [lo],
wherein the active hydrogen compound (C) is at least one kind
selected from the group consisting of polyol compounds, polythiol
15 compounds, and thiol compounds having a hydroxy group.
1121 The polymerizable composition for optical materials
according to any one of [I] to [Ill,
wherein the active hydrogen compound (C) is a tri- or higher
functional active hydrogen compound.
2 0 [I31 I?he pal3merizable composition for optical materials
according to any one of [I] to [12],
wherein the active hydrogen compound (C) is at least one kind
selected from the group consisting of glycerin, pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
25 tetrakis (3-mercaptopropionate) ,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
1,1,3,3-tetrakis (mercaptomethylthio) propane, and
trimethylolpropane tris(3-mercaptopropionate) .
5 [I41 The polymerizable composition for optical materials
according to any one of [I] to 1131,
wherein the photochromic compound (D) is represented by the
following General Formula (5),
10 wherein in the formula, RI and RZ may be identical or different,
and independently represent
a hydrogen atom;
a linear or branched alkyl group having 1 to 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
15 a subs.titutedor.ilnsubstituted aryl group having 6 to 24 carbon
atoms or a substituted or unsubstituted heteroaryl group having 4
to24 carbonatomsinwhichthesesubstitutedgroups, as asubstituent,
include at least one substituent selected from a halogen atom, a
hydroxylgroup, alinearorbranchedalkylgrouphaving 1 to12 carbon
20 atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms,
a linear or branched haloalkyl group having 1 to 12 carbon atoms that
is substituted by at least one halogen atom, a linear or branched
haloalkoxy group having 1 t o 12 carbon atoms t h a t is substituted by
a t l e a s t one halogen atom, a phenoxy group or naphthoxy group
substituted by a t l e a s t one l i n e a r or branched alkyl group or alkoxy
group having 1 t o 12 carbon atoms, a l i n e a r or branched alkenyl group
5 having 2 to 12 carbon atoms, a -NH2 group, a -NHR group, a -N (R) group
i n which R represents a l i n e a r or branched alkyl group having 1 to
6 carbon atoms, i n which in a case that two Rs a r e p r e s e n t , the two
Rs maybe i d e n t i c a l or d i f f e r e n t , amethacryloylgroupandanacryloyl
group; or
10 an aralkyl or heteroaralkyl group t h a t a l i n e a r or branched alkyl
group having 1 t o 4 carbon atoms is substituted by t h e a r y l group
or the heteroaryl group,
R3 may be identical or d i f f e r e n t , and independently represent
a halogen atom;
15 a l i n e a r or branched alkyl group having 1 t o 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
a l i n e a r or branched alkoxy group having 1 t o 12 carbon atoms;
a l i n e a r or branchedhaloalkyl group having 1 t o 12 carbon atoms
t h a t is substituted by a t l e a s t one halogen atom, a halocycloalkyl
20 group having.3 &o .12.-aa-rbon atoms t h a t is substituted by a t l e a s t
one halogen atom, a l i n e a r or branched haloalkoxy group having 1 to
12 carbon atoms that--is substituted by a t l e a s t one halogen.atom;
a substituted or unsubstituted aryl group having 6 t o 24 carbon
atoms or a substituted or unsubstituted heteroaryl group having 4
25 to24 carbonatomsinwhichthesesubstitutedgroups, as a s u b s t i t u e n t ,
include a t l e a s t one substituent selected from a halogen atom, a
hydroxylgroup, alinearorbranchedalkylgroup having I t 0 1 2 carbon
atoms, a l i n e a r or branched alkoxy group having 1 t o 12 carbon atoms,
a l i n e a r or branched haloalkyl group having 1 to 12 carbon atoms t h a t
is substituted by at l e a s t one halogen atom, a l i n e a r or branched
haloalkoxy group having 1 to 12 carbon atoms t h a t is substituted by
5 a t l e a s t one halogen atom, a phenoxy group or naphthoxy group
substituted by a t l e a s t one l i n e a r or branched alkyl group or alkoxy
group having 1 to 12 carbon atoms, a l i n e a r or branched alkenyl group
having 2 to 12 carbon atoms, and an amino group;
anaralkylorheteroaralkylgroupthatalinearorbranchedalkyl
10 group having 1 t o 4 carbon atoms is substituted by the aryl group
or heteroaryl group;
asubstitutedorunsubstitutedphenoxygroupornaphthoxygroup,
inwhichthese substitutedgroups, as a substituent, include a t l e a s t
one substituent selected from a l i n e a r or branched alkyl group or
15 alkoxy group having 1 to 6 carbon atoms;
-NH2, -NHR, -CONH2, or -CONHR in which R represents a l i n e a r or
branched alkyl group having 1 to 6 carbon atoms; or
-OCOR8 or -COORg i n rnrhich Rg represents a l i n e a r or branched alkyl
group having 1 t o 6 carbon atoms, a cycloalkyl group having 3 t o 6
20 carbon atoms,>or.a phenyl group substituted by a t l e a s t one
substituents of the substituted aryl and the substituted heteroaryl
group of R1 or RzC or an unsubstituted phenyl group;
m is an integer of 0 to 4;
A represents an annelated ring represented by the following
25 Formula (A2) or ( A d ) , and
wherein, in these annelated rings,
the dotted lines represent a chemical bond between a carbon Cs
and a carbon C6 in a naphthopyran ring of a formula (5);
5 an a bond in the annelated ring (A4) can be bonded with the carbon
C5 or the carbon C6 in the naphthopyran ring of Formula (5);
Rq is identical or different, and independently represents OH,
a linear or branched alkyl group or alkoxy group having 1 to 6 carbon
atoms; two Rqs form carbonyl (CO) ;
10 R5 represents halogen atom;
a linear or branched alkyl group having 1 to 12 carbon atoms;
a linear or branched haloalkyl group having 1 to 6 carbon atoms
that is substituted by at least one halogen atom;
a cycloalkyl group having 3 to 12 carbon atoms;
15 a linear or branched alkoxy group having 1 to 6 carbon atoms;
a s u b s t i * , z t e d ~ o ~ - u n s u b s t i t u t epdhe nyl or benzyl group in which
these substitutedgroups include at least one substituents described
in the defin2tion of the R1 and R2 groups as a substituent in a case
that R1 and R2 in Formula (5) independently correspond to an aryl or
20 heteroaryl group;
-NH2 or -NHR in which R represents a linear or branched alkyl
group having 1 to 6 carbon atoms;
a substitutedorunsubstitutedphenoxy group or naphthoxygroup
in which these substitutedgroups, as a suhstituent, include at least
one substituent selected from a linear or branched alkyl group or
alkoxy group having 1 to 6 carbon atoms; or
a -CORg, -COORg, or -CONHR9 group in which Rg represents a linear
5 or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group
having 3 to 6 carbon atoms, or a substituted or unsubstituted phenyl
or benzyl group in which these substituted groups include at least
one substituents described in the definition of the R1 and R2 groups
as a substituent in a case that R1 and RZ in Formula ( 5 ) independently
10 correspond to an aryl or heteroaryl group,
in a case in which A represents (A4), n is an integer of 0 to
2, p is an integer of 0 to 4, and in a case in which A represents
(A2), n is an integer of 0 to 2.
[15] The polymerizable composition for optical materials
15 according to any one of [I] to [14],
wherein the functional group equivalent ratio (B/A) of the
polyol compound (B) to the polyisocyanate compound (A) is 0.02 to
0.6, and the functional group equivalent ratio (C/A) of the active
hydrogen compound (C) to the polyisocyanate compound (A) is 0.4 to
20 0.98. ..-
[16] A molded product comprised of a cured product of the
polymerizable composition for opticalmaterials according to any one
of [I] to [15].
1171 An optical material comprised of the molded product
25 according to [161.
1181 A plastic lens comprised of the molded product according
to [16].
[I91 A process for producing a plastic lens, comprising:
a step of preparing a polymerizable composition for optical
materials by mixing a polyisocyanate compound (A), a polyol compound
(B) represented by the following General Formula (1) having a number
5 average molecular weight of 100 or more, a di- or higher functional
active hydrogen compound (C) in which the compound (B) is excluded,
and a photochromic compound (D) and
a step of forming a lens substrate by cast-polymerizing the
polymerizable composition for optical materials in a mold,
wherein, in Formula (I), m represents a numerical value of 1
to 20, k represents 0 to 2m, n represents a numerical value of 1 to
20, 1 represents 0 to 2n, a represents a numerical value of 0 or more,
b represents a numerical value of 0 or more, d represents a numerical
15 value of 0 or more, and e represents a numerical value of 1 or more;
Q1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, and a plurality of Q1's may be the same as or different from
each other; Q2 represents a hydrogen atom or.an alkyl group having
1 to 6 carbon atoms, and a plurality of QT!S may be the same as or
20 different from each other; and Z represents a divalent organic group
having1to30carbonatomsr~hichoptionallyincludeanaromaticgroup,
a n d a p l u r a l i t y o f Z 1 s m a y b e t h e same as ordifferentfromeach other.
[00101
According to the polymerizable composition for optical
materials of the present invention, it is possible to obtain a
polyurethane-based optical material or a polythiourethane-based
5 optical material including a photochromic compound, which exhibits
excellent photochromic property without causing deterioration in
property of the photochromic compound, and is also excellent in
physical properties such as mechanical strength.
10 DESCRIPTION OF EMBODIMENTS
[00111
The polymerizable composition for optical materials of the
present invention will be described based on the following
embodiment.
15 The polymerizable composition for optical materials of the
present embodiment includes
a polyisocyanate compound (A),
a polyol compound (B) represented by the following General
Formula (1) having a number average molecular weight of 100 or more,
20 a di- or ,higher functional active hydrogen compound (C) (here,
the compound (B) is excluded), and
-. a photochromic compound (D). -
In Formula (I), m represents a numerical value of 1 to 20, k
r e p r e s e n t s 0 t o 2m, n represents a numerical value of 1 to 20, 1
represents 0 to 2n, a represents a numerical value of 0 or more, b
represents a numerical value of 0 or more, d represents a numerical
value of 0 or more, and e represents a numerical value of 1 or more;
5 Q1 represents a hydrogen atom or an alkyl group having 1 t o 6 carbon
atoms, and a p l u r a l i t y of Q1's may be the same as or d i f f e r e n t from
each other; Q2 represents a hydrogen atom or an alkyl group having
1 to 6 carbon atoms, and a p l u r a l i t y of Q''S may be the same as or
d i f f e r e n t from each other; and Z represents a divalent organic group
10 having1to30carbonatomswhichoptionallyincludeanaromaticgroup,
a n d a p l u r a l i t y o f Z'smaybethe sameas ordifferentfromeachother.
[a0121
It is consideredthat the polyrnerizable composition f o r o p t i c a l
materials of the present embodiment e f f e c t i v e l y suppresses the
15 f a i l u r e of an isomerization reaction o f the photochromic compound
(D) inthepolymermatrixofthecompositionbyincludingthecompounds
(A) t o (C) i n the configuration thereof. That is, it is thought t h a t ,
by adding the compound (B) which is an e s s e n t i a l component of the
present invention t o a resin in t h e r e l a t e d a r t , used in lenses for
20 spectacles -mrthe l i k e formed of the compounds (A) and (C), an
. appropriatespacewhereanisomerizationreactionofthephotochromic
compound is l i k e l y to occur is formed i n the matrix molecular chain, ...
a n d a s a r e s u l t , goodphotochromicpropertyisachieved. Inaddition,
w i t h t h i s configuration, highphotochromicpropertycanbeexhibited,
25 and excellent mechanical properties which a r e t h e features of a
poly(thio)urethane-based resin can be exhibited. That is, the
present invention can provide an o p t i c a l material which is excellent
in terms of balance of these properties.
Hereinafter, each component will be described.
[0013]
[Polyisocyanate Compound (A11
5 Examples of the polyisocyanate compound (A) include aliphatic
polyisocyanate compounds such as hexamethylene diisocyanate,
pentamethylene diisocyanate, 2,2,4-trimethyl hexanediisocyanate,
2,4,4-trimethyl hexamethylene diisocyanate, lysine
diisocyanatomethyl ester, lysine triisocyanate, m-xylylene
10 diisocyanate, o-xylylene diisocyanate, p-xylylene diisocyanate,
xylylenediisocyanate, a,a,ar,a'-tetramethylxylylenediisocyanate,
bis(isocyanatomethy1) naphthalene, mesitylylene triisocyanate,
bis(isocyanatomethy1) sulfide, bis(isocyanatoethy1) sulfide,
bis(isocyanatomethy1) disulfide, bis(isocyanatoethy1) disulfide,
15 bis(isocyanatomethylthio) methane, bis(isocyanatoethy1thio)
methane, bis(isocyanatoethy1thio) ethane, and
bis(isocyanatomethy1thio) ethane; alicyclic polyisocyanate
compounds such as isophorone diisocyanate, bis(isocyanatornethy1)
cyclohexane, 1,2-bis(isocyanatomethy1) cyclohexane,
20 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl)
cyclohexane, dicyclohexyl methane diisocyanate, dicyclohexyl
methane-4,4'-diisocyanate, dicyclohexyl
methane-2,4'-diisocyanate, cyclohexane diisocyanate,
methylcyclohexane diisocyanate, dicyclohexyldirnethylmethane
25 isocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane,
3,8-bis(isocyanatomethy1) tricyclodecane,
3,9-bis(isocyanatomethy1) tricyclodecane,
4,8-bis (isocyanatornethyl) tricyclodecane, and
4,9-bis(isocyanatomethy1) tricyclodecane; aromatic polyisocyanate
compounds such as diphenylsulfide-4,4-diisocyanate, tolylene
5 diisocyanate, phenylene diisocyanate, 1,3-phenylene diisocyanate,
1,4-phenylene diisocyanate, and diphenylmethane diisocyanate; and
heterocyclic polyisocyanate compounds such as
2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethy1) thiophene,
2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethy1)
10 tetrahydrothiophene, 3,4-bis(isocyanatomethy1)
tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane,
2,5-bis(isocyanatomethy1)-1,4-dithiane,
4,5-diisocyanato-1,3-dithiolane, and
4,5-bis(isocyanatomethy1)-1,3-dithiolane. As the polyisocyanate
15 compound (A), at least one kind selected from these can be used.
[0014]
As the polyisocyanate compound (A), the case of a modified
product and/or a mixture with a modified product is also included,
inadditiontomonomers, andexamples ofthemodifiedproductinclude
20 multimers, biu~tmodifiedproducts, allophanatemodifiedproducts,
oxadiazinetrione modified products, and polyol modified products.
Examples of the multimers include dimers such as uretdione,
uretoimine, and carbodiimide, and multimers of tri- or higher mers
such as isocyanurate and iminooxadiazine dione.
25 [0015]
Asthepolyisocyanatecompound (A), hexamethylenediisocyanate,
pentamethylene diisocyanate, m-xylylene diisocyanate, isophorone
diisocyanate, bis(isocyanatomethy1) cyclohexane,
dicyclohexylmethane diisocyanate,
2,s-bis (isocyanatornethyl)b icyclo- [2.2,1]- heptane,
2,6-bis (isocyanatomethyl)b icyclo- [2.2.1]- hptane tolylene
5 diisocyanate, phenylene diisocyanate, or diphenylrnethane
diisocyanate is preferable, and m-xylylene diisocyanate,
bis(isocyanatomethy1) cyclohexane, dicyclohexylmethane
diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
or 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-ha is more
10 preferable. Thesepolyisocyanate compoundsmaybeusedaloneorused
as a mixture of two or more kinds thereof.
[0016]
[Polyol Compound (B)]
In the present embodiment, as the polyol compound (B), at least
15 one kind of compounds selected from the compounds represented by the
following General Formula (1) having a number average molecular
weight of 100 or more can be used.
[0017]
20 [0018]
The lower limit of the number average molecular weight of the
polyol compound (B) is 100 or more, preferably 200 or more, more
preferably 300 or more, and still more preferably 400 or more, and
the upper limit thereof is 4000 or less, preferably 3000 or less,
andmore preferably2000 or less. The upper limit and the lower limit
can be suitably combined.
[0019]
In Formula (I), m represents a numerical value of 1 to 20,
5 preferably a numerical value of 1 to 10, and more preferably a
numerical value of 2 to 5.
nrepresents a numericalvalue of 1to20, preferablyanumerical
value of 1 to 10, and more preferably a numerical value of 2 to 5.
a represents a numerical value of 0 or more, preferably a
10 numerical value of 0 to 100, and more preferably a numerical value
of 0 to 25.
b represents a numerical value of 0 or more, preferably a
numerical value of 0 to 200, and more preferably a numerical value
of 0 to 100.
15 d represents a numerical value of 0 or more, preferably a
numerical value of 1 to 200, and more preferably a numerical value
of 1 to 100.
e represents a numerical value of 1 or more, preferably a
numerical value of 1 to 200, and more preferably a numerical value
20 of 1 to 10'2-
k represents 0 to 2m, and 1 represents 0 to 2n.
[0020]
Q1 represents a hydrogen atom or an alkyl group having 1 to 6
carbon atoms, andpreferably a hydrogen atomor an alkylgrouphaving
25 1 to 3 carbon atoms. Aplurality of Q1's may be the same as or different
from each other.
Q2 represents a hydrogen atom or an alkyl group having 1 to 6
carbon atoms, andpreferablya hydrogen atomor an alkylgrouphaving
1 to 3 carbon atoms. Aplurality of Q''S may be the same as or different
from each other.
[00211
5 Z is a divalent organic group having 1 to 30 carbon atoms which
optionally include an aromatic group, and preferably a divalent
organic group having 1 to 20 carbon atoms which optionally include
anaromaticgroup. Apluralityof Z'smaybethe sameas ordifferent
from each other.
10 Examples of the "divalent organic group having 1 to 30 carbon
atomswhichoptionallyinc1udeanaromaticgroup"include substituted
or unsubstituted linear or cyclic aliphatic groups having 1 to 30
carbon atoms such as a methylene group, an ethylene group, a
trimethylene group, a tetramethylene group, a pentamethylene group,
15 acyclopentylenegroup, ahexamethylenegroup, acyclohexylene group,
a heptamethylene group, an octamethylene group, a nonamethylene
group, a decamethylene group, an undecamethylene group, a
dodecamethylene group, a tridecamethylene group, a
tetradecamethylene group, and a pentadecamethylene group;
20 substituted or unsubstituted aromatic groups having 6 to 30 carbon
atoms such as a phenylene group, a naphthylene group, an anthracene
group, a diphenylmethane group, a 1,l-diphenylethane group, a
l,l,l-methyldiphenylethane group, a diphenylpropane group, a
diphenylether group, a diphenylsulfide group, a diphenylsulfoxide
25 group, a diphenylsulfone group, a diphenylketone group, a
phenylbenzoate group, a biphenyl group, a stilbene group, a
diazobenzene group, and an aniline benzylidene group; substituted
or unsubstituted aromatic-aliphatic groups having 6 t o 30 carbon
atoms such as a -CsHd-CHz- group, a -CHz-C6H4-CH2- group, a
-CHz-CsH3 (C1) -CHz- group, a -CIOH~-CH~- group, a -CHz-CloH6-CHz- group,
and a -CH~CH~-C~H~-CH~CHgZr-o up; and carbonyl group-containing
5 compounds having 1 t o 30 carbon atoms such as -C (0)-R ~-c (0)- (R'
representsa substitutedorunsubstitutedlinearorbranchedalkylene
group having 1 to 20 carbon atoms or a substituted or unsubstituted
aromatic group having 6 to 20 carbon atoms) and -c(o) -R8- (Re
representsasubstitutedorunsubstitutedlinearorbranchedalkylene
10 group having 1 t o 20 carbon atoms).
Theseorganicgroupsmaybe substitutedwitha l i n e a r orbranched
alkyl grouphaving 1 t o 10 carbonatoms o r a Linearorbranchedalkoxy
group having 1 to.10 carbon atoms.
[00221
15 To impartgoodcolor-developingpropertytothepolymer (molded
product) obtained fromthe polymerizable composition of the present
embodiment, it is necessary t o set the molecular weight of the polyol
compound (B) to be added t o a s u i t a b l e range.
[0023]
2 0 In the present embodiment, as the polyol compound (B) , a t l e a s t
one kindof compounds selected fromthe compounds representedbyeach
of General Formulas (I) t o ( I V ) can be used.
[0024]
(Compound Represented by General Formula ( I ) )
[00251
In Formula (I), p r e p r e s e n t s a numerical value of 4 t o 100, and
p r e f e r a b l y a numerical value of 15 t o 50. X r e p r e s e n t s a hydrogen
atom or a methyl group, and a p l u r a l i t y of X ' s may be the same a s
5 o r d i f f e r e n t from each o t h e r . X is p r e f e r a b l y a methyl group.
[00261
Examples of t h e compound represented by General Formula (I)
i n c l u d e polyethylene glycol and polypropylene g l y c o l . These may
i n c l u d e a lowmolecular oligomer such as e t h y l e n e g l y c o l , d i e t h y l e n e
10 glycol, o r t r i e t h y l e n e glycol, and may be used alone o r used as a
mixture of two o r more kinds t h e r e o f .
[00271
The lower l i m i t of t h e number average molecular weight of t h e
compoundrepresentedbyGenera1 Formula (I) i s 1 0 0 ormore, p r e f e r a b l y
15 200 o r more, more p r e f e r a b l y 300 o r more, and still more p r e f e r a b l y
400 o r more, and t h e upper l i m i t thereof is 4000 o r less, p r e f e r a b l y
3000 o r less, and more p r e f e r a b l y 2000 o r less. The upper l i m i t and
t h e lower l i m i t can be s u i t a b l y combined.
[00281
2 0 In a csse-where *he number average molecular weight of t h e
compoundrepresentedbyGeneralFormula (I) i s w i t h i n t h e a b o v e range,
it is p o s s i b l e t o e f f e c t i v e l y e x h i b i t photochromic property without
impairing c h a r a c t e r i s t i c s such a s high mechanical s t r e n g t h of a
p o l y ( t h i o ) u r e t h a n e r e s i n .
25 For example, i n a casewhere the compound representedbyGenera1
Formula (I) is polyethylene glycol, when t h e number average
molecular weight is less than 400, improvement of t h e
color-developingpropertyisnotsufficientlyobtainedinsome cases,
and when the number average molecular weight is greater than 2000,
the polymer becomes clouded, in some cases.
In a case where the compound represented by General Formula (I)
5 is polypropylene glycol, when the number average molecular vreight
is less than 400, improvement of the color-developing property is
notsufficientlyobtainedinsomecases, and tihen thenumberaverage
molecular weight is greater than 1000, the polymer becomes clouded,
in some cases.
10 In addition, the obtained polymer in the case of polypropylene
glycol exhibits higher heat resistance and rigidity than that in the
case of polyethylene glycol. Accordingly, in applications used in
various environments or conditions, such as lenses for spectacles,
polypropylene glycol is more preferable than polyethylene glycol in
15 some cases.
[00291
(Compound Represented by General Formula (11))
[00301
20 _ In Formula (11), q and r may be the:same as or different from
each other, each of q and r represents a numerical value of 1 or more,
and preferably a numerical value of 6 to 25. q and r take numerical
values such that the sum of q and r satisfies a numerical value of
2 to 100, and preferably a numerical value of 12 to 50.
2 5 R1 and R2 may be the same as or different from each other, each
of R' and R2 represents a hydrogen atom or a methyl group, and a
plurality of R"S or R2's may be the same as or different from each
other.
[0031]
5 Z represents a substituted or unsubstituted divalent aromatic
group or a divalent aliphatic group which optionally include a
substituted or unsubstituted aromatic group having 1 to 20 carbon
atoms. Moreover, Z does not include -Ph-C (CH3) 2-Ph- (Ph: phenylene
group) .
10 [0032]
Examples of the substituted or unsubstituted divalent aromatic
group include a phenylene group, a naphthylene group, an anthracene
group, a diphenylmethane group, a 1,l-diphenylethane group, a
l,l,l-methyldiphenylethane group, a 1,3-diphenylpropane group, a
15 1,2-diphenylpropane group, a diphenylethergroup, a diphenylsulfide
group, a diphenylsulfoxide group, a diphenylsulfone group, a
diphenylketone group, a phenylbenzoate group, a biphenyl group, a
stilbene group, a diazobenzene group, an aniline benzylidene group,
and derivatives thereof.
20 Examples of the divalent aliphatic group which optionally
include a substituted or unsubstituted aromatic group having 1 to
20 carbon atoms include divalent groups derived from a substituted
or unsubstituted alkylene group having 1 to 20 carbon atoms and a
bisalkoxy aromatic compound having 1 to 20 carbon atoms.
25 Examples of the substituted or unsubstituted alkylene group
having 1 to 20 carbon atoms include a butylene group, a pentylene
group, and a nonylene group.
Examples ofthebisalkoxyaromaticcompoundhaving1to 20 carbon
atoms include 1,4-bis (hydroxyethoxy) benzene, (1,3-bis
(m-hydroxyethoxy) benzene, and
2,2-[ (1,l-biphenyl)-4,4-diylbis(oxy) l bisethanol.
5 Examples of the substituent of a divalent aromatic group or a
divalent aliphatic group include an alkyl group having 1 to 10 carbon
atoms and an alkoxy group having 1 to 10 carbon atoms.
In the present embodiment, Z is preferably a phenylene group,
a naphthylene group, or a biphenylene group.
10 [0033l
Examples of the compound represented by General Formula (11)
include polyethylene glycol adducts or polypropylene glycol adducts
such as 1,4-butanediol, 3-methyl-l,5-pentanediol, 1,9-nonanediol,
1,4-bis(hydroxyethoxy) benzene, 1,3-bis(m-hydroxyethoxy) benzene,
15 and 2,2 [ (1,l-biphenyl) -4,4-diylbis (oxy) I bisethanol, and these may
be used alone or used as a mixture of two or more kinds thereof.
Moreover, the compoundrepresentedby General Formula (11) does
not include the compound represented by General Formula (111).
[00341
20 The lower limit of the number average molecular weight of the
compound represented by General Formula (11) is 200 or more,
preferably 300 or more, more preferably 400 or more, and still more
preferably 500 or more, and the upper limit thereof is 4000 or less,
preferably 3000 or less, more preferably 2000 or less, and still more
25 preferably 1000 or less. The upper limit and the lower limit can
be suitably combined.
In a case where the number average molecular weight of the
compound represented by General Formula (11) is within the above
range, it is possible to effectively exhibit photochromic property
without impairing characteristics such as high mechanical strength
of a poly(thio)urethane resin.
5 [00351
(Compound Represented by General Formula (111))
LO0361
In Formula (III), q and r may be the same as or different from
10 each other, each of q and r represents a numerical value of 1 or more,
and preferably a numerical value of 6 to 25. q and r take numerical
values such that the sum of q and r satisfies a numerical value of
2 to 100, and preferably a numerical value of 12 to 50.
R1 and R2 may be the same as or different from each other, each
15 of R1 and R2 represents a hydrogen atom or a methyl group, and a
plurality of R"S or R2's may be the same as or different from each
other.
[0037]
Examples of the compound represented by General Formula (111)
20 include polyethylene glycol adducts ofbisphenol Aandpolypropylene
glycol adducts of bisphenol A, and these may be used alone or used
as a mixture of two or more kinds thereof.
[00381
The lower limit of the number average molecular weight of the
25 compound represented by General Formula (111) is 200 or more,
preferably 300 or more, more preferably 400 or more, and still more
preferably 500 or more, and the upper l i m i t thereof i s 4000 or less,
preferably 3000 or l e s s , more preferably 2000 or less, and s t i l l more
preferably 1500 or l e s s . The upper l i m i t and the lower l i m i t can
5 be suitably combined.
In a case where the number average molecular weight of the
compound represented by General Formula (111) is within the above
range, it is possible to e f f e c t i v e l y e x h i b i t photochromic property
without impairing c h a r a c t e r i s t i c s such as high mechanical strength
10 of a poly(thio)urethane resin.
For example, i n a case where the compound representedbyGenera1
Formula (111) is a polyethylene glycol adduct of bisphenol A or a
polypropylene glycol adduct of bisphenol A, when the number average
molecular weight is less than 400, improvement of the
15 color-developingpropertyisnotsufficientlyobtainedinsomecases,
and when the number average molecular weight is greater than 1000,
the polymer becomes clouded, in some cases.
[0039]
(Compound Represented by General Formula ( I V ) )
[0040]
In Formula (IV), m represents a numerical value of 1 to 20,
preferably a numerical value of 1 t o 10, and more preferably a
numerical value of 2 to 5.
25 nrepresents anumericalvalue o f 1 to 20, plieferablyanumerical
value of 1 t o 10, and more preferably a numerical value of 2 to 5.
f represents a numerical value of 0 or more, preferably a
numerical value of 0 to 100, and more preferably a numerical value
of 0 to 25.
5 g represents a numerical value of 1 or more, preferably a
numerical value of 1 to 200, and more preferably a numerical value
of 1 t o 100.
h represents a numerical value of 1 or more, preferably a
numerical value of 1 to 200, and more preferably a numerical value
10 of 1 t o 100.
j represents a numerical value of 1 or more, preferably a
numerical value of 1 t o 200, and more preferably a numerical value
of 1 t o 100.
k represents 0 t o 2m, and 1 represents 0 t o 2n.
15 [0041]
Q1 represents a hydrogen atom or an alkyl group having 1 t o 6
carbon atoms, andpreferablya hydrogenatomor an alkylgroup having
1 t o 3 carbon atoms. A p l u r a l i t y of Q" s may be the same as or d i f f e r e n t
from each other.
20 Q2 represents a hydrogen atom or an alkyl group having 1 t o 6
carbon atoms, andpreferablya hydrogen atomor an alkylgroup having
1to3carbonatoms. A p l u r a l i t y o f ~ 2 t ~ m a y b e t h e s a m e a s o r d i f f e r e n t
from each other.
R3 represents a l i n e a r or branched alkylene group having 1 t o
25 20 carbon atoms or a phenylene group which optionally have a l i n e a r
or branched alkyl group having 1 t o 10 carbon atoms as a s u b s t i t u e n t .
A p l u r a l i t y of R 3 ' s may be the same as or d i f f e r e n t from each other.
Examples of the compound represented by General Formula (IV)
include a polyether compound formed of a diol compound and a
dicarboxylic acid.
5 Although the diol compound configuring the polyester compound
is not particularly limited, an aliphatic diol having 2 to 12 carbon
atomsin themainchainis suitablyused, andexamplesthereof include
ethylene glycol, propylene glycol, 1,4-butanediol,
3-methyl-1,5-pentanediol, and 1,9-nonanediol.
10 In addition, although dicarboxylic acid configuring the
polyester compound is not particularly limited, an aliphatic
dicarboxylic acid or an aromatic dicarboxylic acid having 2 to 12
carbonatoms in themain chain is suitably used, andexamplesthereof
include succinic acid, adipic acid, sebacic acid, isophthalic acid,
15 and terephthalic acid.
The polyester compound can be formed by using one kind or two
or more kinds of diol compounds and one kind or two or more kinds
of dicarboxylic acids in suitable combination.
In addition, a polyester compound obtained by ring-opening
20 polymerizat-ion of lactone can also be used in the present invention.
Examples of the lactone compound include a-acetolactone,
6-propiolactone, y-butyrolactone, and 6-valero1actone.-.
roo431
The lower limit of the number average molecular weight of the
25 compound represented by General Formula (IV) is 600 or more,
preferably 800 or more, more preferably 1000 or more, and the upper
limit thereof is 4000 or less, preferably 3000 or less, and more
p r e f e r a b l y 2000 or less. The upper l i m i t and the lower l i m i t can
be s u i t a b l y combined.
[00441
In a case where the number average molecular weight of t h e
5 compound represented by General Formula ( I V ) is within t h e above
range, it is possible t o e f f e c t i v e l y e x h i b i t photochromic property
without impairing c h a r a c t e r i s t i c s such as high mechanical s t r e n g t h
of a poly ( t h i o ) urethane r e s i n .
For example, i n a casewherethecompoundrepresentedbyGenera1
10 Formula (IV) isapolyestercompoundobtainedbyreactinganequimolar
mixture of a d i p i c acid and i s o p h t h a l i c a c i d with
3-methyl-l,5-pentanediolin e q u i m o l a r r a t i o , whenthenumber average
molecular weight is less than 1000, improvement of t h e
color-developingpropertyisnotsufficientlyobtainedin somecases,
15 and when t h e number average molecular weight is g r e a t e r than 2000,
t h e polymer becomes clouded, i n some cases.
[00451
By using t h e polyol compound (B) formed of t h e compound as
described above, it is p o s s i b l e t o e f f e c t i v e l y e x h i b i t photochromic
20 property.
[00461
In t h e present embodiment, as t h e polyol compound (B) , a t l e a s t
one kind of compounds s e l e c t e d from t h e compounds represented by
General Formulas (I) t o ( I V ) can be used, and from t h e viewpoint of
25 t h e above-described e f f e c t , t h e compound represented by General
Formula (I), ( I I I ) , o r ( I V ) can be p r e f e r a b l y used.
[00471
In the present embodiment, the polyol compound (B) can be used
~ i i t h i n ara nge of 0.3times byweight t o 6timesbyweightwith respect
totheweight o f t h e di- orhigher functional activehydrogen compound
( C ) . In the present embodiment, the polyol compound (B) is used
5 within the above range such that resin property required depending
on the application is obtained while maintaining high photochromic
property. The preferable range is 0.7 times by weight t o 5 times
by weight.
[0048]
10 In a case where the t i m e s by weight of the polyol compound (B)
t o the active hydrogen compound (C) is within the above range, high
photochromic property, t h a t is, high color forming density and f a s t
changes i n density can be s u i t a b l y exhibited. Furthermore, since
the crosslinking density is within an optimal range, an optical
15 m a t e r i a l e x c e l l e n t i n r i g i d i t y , surface hardness, heat resistance,
and the l i k e can be obtained.
[00491
[Di- or Higher Functional Active Hydrogen Compound (C)]
The di- or higher functional active hydrogen compound (C)
20 ( h e r e i n a f t e r , simply referred t o as "active hydrogen compound (C) ")
is not p a r t i c u l a r l y limited, and examples thereof include polyol
compounds, polythiol compounds, a n d t h i o l compounds having a hydroxy
group. These can be used in s u i t a b l e combination. Moreover, the
a c t i v e hydrogen compound (C) does not include the polyol compound
25 ( B ) .
[0050]
Examples of the polyol compound include a l i p h a t i c polyols such
as ethyleneglycol, diethyleneglycol, propylene glycol, dipropylene
glycol, tripropylene glycol, butylene glycol, neopentyl glycol,
glycerin, trimethylol ethane, trimethylol propane, ditrimethylol
propane, butanetriol, 1,2-methyl glucoside, pentaerythritol,
5 dipentaerythritol, tripentaerythritol, sorbitol, erythritol,
threitol, ribitol, arabinitol, xylitol, allitol,mannitol, dorsitol,
iditol, glycol, inositol, hexanetriol, triglycerose, diglyperol,
triethylene glycol, polyethylene glycol, tris(2-hydroxyethyl)
isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexane diol,
10 cycloheptane diol, cyclooctane diol, cyclohexane dimethanol,
hydroxypropyl cyclohexanol, tricyclo r5.2.1. o~'d~e]c ane-dimethanol,
bicyclo [4,3,0] -nonanediol, dicyclohexanediol,
tricyclo [5,3,1,l] dodecanediol, bicyclo [4,3,O] nonanedimethanol,
tricyclo[5,3,l,l]dodecane-diethanol, hydroxypropyl
15 tricyclo [5,3,1,l] dodecanol, spiro [3,4] octanediol, butyl
cyclohexanediol, 1,l'-bicyclohexylidenediol, cyclohexanetriol,
maltitol, and lactose; aromatic polyols such as
dihydroxynaphthalene, trihydroxynaphthalene,
tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyl
20 tetraol, pyr~gsl.lol, (hydroxynaphthyl) pyrogallol,
trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol,
di(2rhydroxyethoxy) benzene, bisphenol ?.-.
A-bis-(2-hydroxyethylether), tetrabromobisphenol A, and
tetrabromobisphenol A-bis-(2-hydroxyethylether); halogenated
25 polyols such as dibromoneopentylglycol; and polymeric polyols such
as an epoxy resin. In the present embodiment, at least one kind
selected from these can be used in combination.
[0051]
Additionally, examples of the polyol compound include
condensationreactionproductsofanorganicacidsuchasoxalicacid,
glutamic acid, adipic acid, acetic acid, propionic acid,
5 cyclohexanecarboxylic acid, P-oxocyclohexanepropionic acid, dimer
acid, phthalic acid, isophthalic acid, salicylic acid,
3-bromopropionic acid, 2-bromoglycol, dicarboxycyclohexane,
pyromelliticacid, butanetetracarboxylicacid, orbromophthalicacid
with the above-described polyols; addition reaction products of the
10 above-describedpolyolswithanalkylene oxide suchasethyleneoxide
orpropyleneoxide; additionreactionproductofanalkylenepolyamine
with an alkylene oxide such as ethylene oxide or propylene oxide;
bis- [4- (hydroxyethoxy)p henyl] sulfide,
bis-[4-(2-hydroxypropoxy)phenyll sulfide,
15 bis- [4- (2,3-dihydroxypropoxy)phenyl] sulfide,
bis-[4-(4-hydroxycyclohexyloxy)phehyl] sulfide,
bis-[2-methyl-4-(hydroxyethoxy)-6-butylphenyl] sulfide, and
compounds obtained by adding three molecules or less on average of
ethylene oxide and/or propylene oxide per hydroxyl group to these
20 compounds; snd palyols containing a sulfur atom such as
di- (2-hydroxyethyl) sulfide, 1,2-bis- (2-hydroxyethylmercapto)
'ethane, bis(2-hydroxyethyl) disulfide,'- 1,4-dithiane-2,5-diol, bis
(2,3-dihydroxypropyl) sulfide, tetrakis(4-hydroxy-2-thiabutyl)
methane, bis(4-hydroxyphenyl) sulfone (trade name: bisphenol S),
25 tetrabromobisphenol S, tetramethyl bisphenol S,
4,4'-thiobis(6-tert- butyl-3-methylphenol), and
'1,3-bis(2-hydroxyethylthioethy1)-cyclohexane. In the present
embodiment, at least one kind selected from these can be used in
combination.
100521
Examples ofthe polythiol compound include aliphatic polythiol
5 compounds such as methanedithiol, 1,2-ethanedithiol,
1,2,3-propanetrithiol, 1,2-cyclohexanedithiol,
bis(2-mercaptoethyl) ether, tetrakis(mercaptomethy1) methane,
diethylene glycol bis(2-mercaptoacetate), diethylene glycol
bis(3-mercaptopropionate), ethylene glycolbis(2-mercaptoacetate),
10 ethylene glycol bis(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolethane
tris(2-mercaptoacetate), trimethylolethane
tris(3-mercaptopropionate), pentaerythritol
15 tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), bis(mercaptomethy1) sulfide,
bis(mercaptomethy1) disulfide, bis(mercaptoethy1) sulfide,
bis(mercaptoethy1) disulfide, bis(mercaptopropy1) sulfide,
bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane,
20 bis(3-mercaptopropylthio) methane, 1,2-bis(mercaptomethy1thio)
ethane, 1,2-bis(2-mercaptoethylthio) ethane,
1,2-bis(3-mercaptopropylthio) ethane,
1,2,3-tris(mercaptomethylthio) propane,
1,2,3-tris (2-mercaptoethylthio) propane,
25 1,2,3-tris (3-mercaptopropylthio) propane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
tetrakis(mercaptomethylthiomethyl) methane,
tetrakis(2-mercaptoethylthiomethyl) methane,
5 tetrakis(3-mercaptopropylthiomethyl) methane,
bis (2,3-dimercaptopropyl) sulfide,
2,5-dimercaptomethyl-l,4-dithiane, 2,5-dimercapto-l,4-dithiane,
2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and esters of
these thioglycolic acid and mercaptopropionic acid, hydroxymethyl
10 sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide
bis(3-mercaptopropionate), hydroxyethyl sulfide
bis(2-mercaptoacetate), hydroxyethyl sulfide
bis(3-mercaptopropionate), hydroxymethyl disulfide
bis(2-mercaptoacetate), hydroxymethyl disulfide
15 bis(3-mercaptopropionate), hydroxyethyl disulfide
bis(2-mercaptoacetate), hydroxyethyl disulfide
bis(3-mercaptopropionate), 2-mercaptoethyl ether
bis(2-mercaptoacetate), 2-mercaptoethyl ether
bis(3-mercaptopropionate), thiodiglycolic acid
20 bis(2-mercaptoethylester), thiodipropionic acid
bis(2-mercaptoethylester), dithiodiglycolic acid
bis(2-mercaptoethyl ester), . dithiodipropionic acid
bis (2-mercaptoethylester) , 1,1,3,3-tetrakis (mercaptomethylthio)
propane, 1,1,2,2-tetrakis(mercaptomethy1thio) ethane,
25 4,6-bis(mercaptomethy1thio)-1,3-dithiane,
tris(mercaptomethy1thio) methane, and tris(mercaptoethy1thio)
methane; aromaticpolythiolcompounds suchas 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene,
1,2-bis(mercaptomethy1) benzene, 1,3-bis(mercaptomethy1) benzene,
1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene,
1,3-bis(mercaptoethy1) benzene, 1,4-bis(mercaptoethy1) benzene,
5 1,3,5-trimercaptobenzene, 1,3,5-tris (mercaptomethyl) benzene,
1,3,5-tris(mercaptomethy1eneoxy) benzene,
1,3,5-tris(mercaptoethy1eneoxy) benzene, 2,5-toluenedithiol,
3,4-toluenedithiol, 1,5-naphthalenedithiol, and
2,6-naphthalenedithiol; heterocyclic polythiol compounds such as
10 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophene dithiol,
bismuthiol, 4,6-bis(mercaptomethy1thio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane; and a
compound represented by the following General Formula ( 2 ) , but the
present invention is not limited to these exemplary compounds. In
15 the present embodiment, at least one kind selected from these can
be used in combination.
[0053]
[0054]
20 (in the formula, each of a and b independently represents an
integer of 1 to 4, and c represents an integer of 1 to 3; and Z is
a hydrogen atom or a methyl group, and in a case where a plurality
of Z's are present, Z's may be the same as or different from each
other)
[00551
Examples of the thiol compound having a hydroxy group include
2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerine
bis(mercaptoacetate), 4-mercaptophenol,
5 2,3-dimercapto-1-propanol, pentaerythritol
tris(3-mercaptopropionate), and pentaerythritol
tris(thioglycolate), but the present invention is not limited to
these exemplary compounds.
[0056]
10 Furthermore, oligomers of these active hydrogen compounds or
and halogen substitutes such as a chlorine substitute and a bromine
substitute may be used. These active hydrogen compounds can be used
alone or in combination of two or more kinds thereof.
[60571
15 In the present embodiment, as the active hydrogen compound (C) ,
a tri- or higher functional active hydrogen compound is preferably
used, fromthevier~pointofthephysicalpropertiessu chasmechanical
strength of the obtained molded product.
Specifically, at least one kind selected from glycerin,
20 pentaerythritml tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis (3-mercaptopropionate) ,
4-mercaptomethyl-li8-dimercapto-3,6-dithiaoctafie,
5,7-dimercaptomethyl-l,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
25 4,8-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
1,1,3,3-tetrakis (mercaptomethylthio) propane, and
trimethylolpropane tris(3-mercaptopropionate) is preferably used.
LO0581
In addition, examples of the preferable combination of the
polyol compound (B) and the active hydrogen compound ( C ) include a
combination of polyethylene glycol and at least one kind selected
5 from glycerin, pentaerythritol tetrakis(2-mercaptoacetate), and
4-mercaptomethyl-l,8-dimercapto-3,6-dithiaoctane, a combination of
polypropylene glycol and at least one kind selected from
pentaerythritol tetrakis(2-mercaptoacetate) and
4-mercaptomethyl-l,8-dimercapto-3,6-dithiaoctane, a combination of
10 a polypropylene glycol adduct of bisphenol A and
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and a
combination of at least one kind selected from polyester compounds
formedof 3-methyl-l,5-pentanediol, adipicacid, orisophthalicacid
and 4-mercaptomethyl-l,8-dimercapto-3,6-dithiaoctane, but the
15 present invention is not limited to these combinations.
[0059]
[Photochromic Compound (D)]
In the present embodiment, the photochromic compound (D) is not
particularly limited, and an arbitrary one can be suitably selected
20 from compounds .known in the related art which can be used for
photochromic lenses and used. For example, at least one kind of a
spiropyran-based cpmpound, a spirooxazine-based compound,. a
fulgide-based compound, a naphthopyran-based compound, and a
bisimidazole compound can be used depending on the desired color.
25 [0060]
Examples of the spiropyran-based compound include each
substitute obtained by substituting the indole ring or the benzene
ring of indolinospirobenzopyran with a halogen atom, a methyl group,
an ethyl group, a methylene group, an ethylene group, or a hydroxyl
group, each substitute obtained by substituting the indole ring or
the naphthalene ring of indolinospironaphthopyran with a halogen
5 atom, a methyl group, an ethyl group, a methylene group, an ethylene
group, or a hydroxyl group, each substitute obtained by substituting
the indole ring of indolinospiroquinolinopyran with a halogen atom,
a methyl group, an ethyl group, a methylene group, an ethylene group,
or a hydroxyl group, and each substitute obtained by substituting
10 the indole ring of indolinospiropyridopyran with a halogen atom, a
methyl group, an ethyl group, a methylene group, an ethylene group,
or a hydroxyl group.
[00611
Examples of the spirooxazine-based compound include each
15 substitute obtained by substituting the indole ring or the benzene
ringof indolinospirobenzoxazinewithahalogenatom, amethyl group,
an ethyl group, a methylene group, an ethylene group, or a hydroxyl
group, each substitute obtained by substituting the indole ring or
the naphthalene ring of indolinospironaphthoxazine with a halogen
20 atom, a methyl group, an ethyl group, a methylene group, an ethylene
group, or a hydroxylgroup, each substitute obtainedby substituting
theindolering,ofindolinospirophenanthroxazinewithahalogenatom,
a methyl group, an ethyl group, a methylene group, an ethylene group,
or a hydroxyl group, each substitute obtained by substituting the
25 indole ring of indolinospiroquinolinoxazine with a halogen atom, a
methyl group, an ethyl group, a methylene group, an ethylene group,
or a hydroxyl group, and each substitute obtained by substituting
the piperidine ring and the naphthalene ring of
piperidinospironaphthoxazine with a halogen atom, a methyl group,
an ethyl group, a methylene group, an ethylene group, or a hydroxyl
group.
5 [0062]
Examples of the fulgide-based compound include
N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzo[b]thi
ophenedicarboximide-7,2'-tricyclo[3.3.1.13'7]decane],
N-cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl)-4-methylspiro(5,6-
10 benzo [b] thiophene-dicarboximide-7,2 ' -tricycle [3.3.1. 13,'] decane) ,
6,7-dihydro-N-methoxycarbonylmethyl-4-methyl-2-phenylspiro(5,6-b
enzo [b] thiophene-dicarboximide-7,2 ' -tricycle [3.3.1.1~,d~e]c ane) ,
6,7-dihydro-4-methyl
-2- (p-methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophenedica
15 rboximide-7,2 ' -tricycle l3.3.1. 13'7] decane) ,
N-cyanomethyl-6,7-dihydro-4-cyclopropyl-3-methylspiro(5,6-benzo[
b] thiophenedicarboximide-7,2 ' -tricycle [3.3.1.1 3r7d]e cane),
N-cyanomethyl-6,7-dihydro-4-cyclopropylspiro(5,6-benzo[b]thiophe
nedicarboximide-7,2'-tricyclo[3.3.1.13'7]decane), and
20 N-cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl)-4-cyclopropylspiro
(5,6-benzo [b] thiophenedicarboximide-7,2 ' -tricycle [3.3.1. 13"] deca
ne) . .-
[0063]
Examples of the naphthopyran-based compound include
25 spiro [norbornane-2,2'- [2Hl benzo [hl chromene] ,
spiro [bicyclo [3.3.1] nonane-9,2 ' - [2Hl benzo [h] chromene] ,
7 ' -methoxyspiro [bicyclo [3.3.l] nonane-9,2 ' - [2H] benzo [h] chromene] ,
7 ' -methoxyspiro [norbornane-2,2 ' - [2H] benzo [f] chromene] ,
2,2-dimethyl-7-octoxy [2H] benzo [h] chromene,
spiro [2-bicyclo [3.3. l] nonene-9,2 ' - [2H] benzo [h] chromene] ,
spiro [2-bicyclo [3.3.l]nonene-9,2'- [2H]henzo [f ]chromene] ,
5 G-morpholino-3,3-bis(3-fluoro-4-methoxyphenyl)-3H-benzo
(f)chromene, 5-isopropyl-2,2-diphenyl-2H-benzo (h)chromene, the
compound represented by the following General Formula ( 3 ) , and the
compound represented by the following General Formula (4).
100641
[00661
In General Formulas (3) and (4), R1 and RZ may be the same as
15 or different from each other, and each of R1 and RZ independently
represents a hydrogen atom;
a linear or branched alkyl group having 1 to 12 carbon atoms;
a cycloalkyl group having 3 t o 12 carbon atoms;
an aryl group having 6 t o 24 carbon atoms or a heteroaryl group
having 4 to 24 carbon atoms which is s u b s t i t u t e d o r unsubstituted;
or
5 an aralkyl or heteroaralkyl group ( a l i n e a r or branched alkyl
group having 1 to 4 carbon atoms is substituted with an aryl group
or a heteroaryl group).
[0067]
The s u b s t i t u e n t o f a substitutedarylgrouphaving 6 t o 24 carbon
10 atoms or a substituted heteroaryl group having 4 to 24 carbon atoms
i s a t l e a s t one selected fromahalogenatom, ahydroxygroup, a l i n e a r
or branched alkyl group having 1 to 12 carbon atoms, a l i n e a r or
branchedalkoxygrouphaving1to12 carbonatoms, a l i n e a r o r b r a n c h e d
haloalkylgroup having 1 t o 12 carbonatoms which is substitutedwith
15 a t leastonehalogenatom, alinearorbranchedhaloalkoxygrouphaving
.1 t o 12 carbon atoms which is substituted with a t l e a s t one halogen
atom, a phenoxy group or a naphthoxy group which is substituted with
a t l e a s t one l i n e a r or branched alkyl group or alkoxy group having
1 to 12 carbon atoms, a l i n e a r or branched alkenyl group having 2
20 t o 12 carbon atoms, and an -NH2 group, an -NHR group, or a -N (R) 2 group
(R is a l i n e a r or branched alkyl group having 1 t o 6 carbon atoms,
and in a case where two Rs are present, the two Rs may be the same
as or d i f f e r e n t from each o t h e r ) , and a methacryloyl group or an
acryloyl group.
25 [0068]
R 3 ' s may be the same as or d i f f e r e n t from each other, and each
R ~ ' S independently represents a halogen atom;
a l i n e a r or branched alkyl group having 1 t o 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
a l i n e a r or branched alkoxy group having 1 t o 12 carbon atoms;
a l i n e a r orbranchedhaloalkylgrouphaving 1 t o 12 carbon atoms
5 which is substitutedwith a t l e a s t one halogen atom, a halocycloalkyl
group having 3 to 12 carbon atoms which i s substituted with a t l e a s t
one halogen atom, a l i n e a r or branched haloalkoxy group having 1 t o
12 carbon atoms which is substituted with a t l e a s t one halogen atom;
an aryl group having 6 to 24 carbon atoms or a heteroaryl group
10 having 4 t o 24 carbon atoms which is substituted or unsubstituted
(which has a t l e a s t one s u b s t i t u e n t s e l e c t e d from a halogen atom,
ahydroxygroup, a linearorbranchedalkylgrouphaving I t 0 1 2 carbon
atoms, a l i n e a r or branched alkoxy group having 1 t o 12 carbon atoms,
a l i n e a r o r b r a n c h e d h a l o a l k y l g r o u p h a v i n g 1 t o 12 carbonatoms which
15 is substituted with a t l e a s t one halogen atom, a l i n e a r or branched
haloalkoxy group having 1 t o 12 carbon atoms which is substituted
with a t l e a s t one halogen atom, a phenoxy group or a naphthoxy group
which is substituted with a t l e a s t one l i n e a r or branched alkyl group
or alkoxy group having 1 to 12 carbon atoms, a l i n e a r or branched
20 alkenyl growp-having 2 t o 12 carbon atoms, and an amino group as a
s u b s t i t u e n t ) ;
.- an aralkyl or heteroaralkyl group (a l i n e a r or branched alkyl
group having 1 to 4 carbon atoms is substituted with the aryl group
or the heteroaryl group);
2 5 a substitutedorunsubstitutedphenoxyornaphthoxygroup (which
has a t l e a s t one s u b s t i t u e n t s e l e c t e d fromalinearorbranchedalkyl
group or alkoxy group having 1 t o 6 carbon atoms as a s u b s t i t u e n t ) ;
-NH2, -NHR, -CONH2, or -CONHR (R is a linear or branched alkyl
group having 1 to 6 carbon atoms); or
-OCOR8 or -COoR8 (here, R8 is a linear or branched alkyl group
having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon
5 atoms, or a phenyl group which is substituted with at least one
substituent of a substituted arylgroup or a substituted heteroaryl
group of R1 and R2 or an unsubstituted phenyl group).
[0069]
It is possible to form at least one aromatic ring groups or
10 non-aromatic ring groups by bonding of at least two adjacent R3's
to each other and by including the carbon atom to which R3 is bonded.
The aromatic ring group or non-aromatic ring group includes one ring
or two annelated ringsr.rhichoptionallyinclude aheteroatomselected
from the group consisting of oxygen, sulfur, and nitrogen.
15 [0070]
1 is an integer of 0 to 2. m is an integer of 0 to 4.
Additionally, examples of the naphthopyran-based compound
include compounds obtainedby adding a light adjusting dye molecule
to at least one terminal of each of a polysiloxane oligomer, a
20 polyalkylene~a%ide; andapolyalkylester, describedinW02013/78086,
W02012/149599, W02010/020770, and W02009/146509, and a compound
having two or more naphthopyran rings in one molecule by bonding of
structures represented by General Formula (3) or (4) by a linking
group.
25 [0071]
Preferable examples of the naphthopyran-based compound
represented by General Formula (3) include the compound represented

a carbon Cs-carbon C,j bond of the naphthopyran ring in General Formula
( 5 ) . The oc bond of the annelated ring (A4) or (A5) is bonded t o the
carbon C5 or the carbon C6 of the naphthopyran ring in General Formula
( 5 ) .
5 [00761
R 4 ' s may be the same as o r d i f f e r e n t from each other, and each
R a g s independently represents OH or a l i n e a r or branched alkyl group
or alkoxy group having 1 t o 6 carbon atoms, or two R q ' s form a carbonyl
group (CO) .
10 LO0771
Each of R5, R6, and R7 independently represents a halogen atom
(preferably, a fluorine atom, a chlorine atom, or a bromine atom) ;
a l i n e a r or branched alkyl group having 1 t o 12 carbon atoms
(preferably, a l i n e a r or branched alkyl group having 1 t o 6 carbon
15 atoms);
a l i n e a r or branched haloalkyl group having 1 t o 6 carbon atoms
which is substituted with a t l e a s t one halogen atom (preferably, a
fluoroalkyl group);
a cycloalkyl group having 3 to 12 carbon atoms;
20 a l i n e a r or branched alkoxy group having 1 to 6 carbon atoms;
a substituted or unsubstituted phenyl or benzyl group (which
has a t l e a s t one of substituents described above i n t h e d e f i n i t i o n
of R1 and R2 groups as a substituent in a case where each of R1 and
R2 groups i n General Formula (5) independently corresponds to an aryl
25 or heteroaryl group);
-NH2 or -NHR (here, R is a l i n e a r or branched alkyl group having
1 t o 6 carbon atoms);
4 8
asubstitutedorunsubstitutedphenoxyornaphthoxygroup (which
has a t l e a s t a l i n e a r or branched alkyl group or alkoxy group having
1 t o 6 carbon atoms as a s u b s t i t u e n t ) ; or
a -CORg, -COOR9, or -CONHR9 group (here, Rg represents a l i n e a r
5 orbranched a l k y l g r o u p h a v i n g l t o 6 carbonatoms, a cycloalkylgroup
having 3 to 6 carbon atoms, or a substituted or unsubstituted phenyl
or benzyl group (which has a t l e a s t one of substituents described
above in t h e d e f i n i t i o n of R1 and RZ groups as a substituent in a case
where each of R1 and Rz groups in General Formula (5) independently
10 corresponds t o an aryl or heteroaryl group)).
[0078]
n is an integer of 0 t o 6, o is an integkr of 0 t o 2, p is an
integer of 0 t o 4, and q is an integer of 0 to 3.
In a case where A represents (A*), n is an integer of 0 t o 2,
15 and p is an integer of 0 to 4, and in a case where A represents (Az) ,
n is an integer of 0 to 2.
[0079]
The photochromic compound (D) of General Formula (5) has high
coloring adaptability even a t 40°C by being combined with the
20 discolorationreactionratethatisappliedtotheusebeingrequired.
The colors capable of being e a s i l y achieved are colors from orange
to blue.

CLAIMS
1. A polymerizable composition for optical materials, comprising:
a polyisocyanate compound (A),
5 a polyol compound (B) represented by the following General
Formula (1) having a number average molecular weight of 100 or more,
a di- or higher functional active hydrogen compound (C) in which
the compound (B) is excluded and
a photochromic compound (D),
wherein, in Formula (I), m represents a numerical value of 1
to 20, k represents 0 to 2m, n represents a numerical value of 1 to
20, 1 represents 0 to 2n, a represents a numerical value of 0 or more,
15 b represents a numerical value of 0 or more, d represents a numerical
value of 0 or more, and e represents a numerical value of 1 or more;
Q' represents a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, and a plurality of Q1's may be the same as or different from
each other; Q2 represents a hydrogen atom or an alkyl group having
20 1 to 6 carbon atoms, and a plurality of Q2's may be the same as or
different from each other; and Z represents a divalent organic group
having1t030carb0nat0mswhi~h0pti0nallyincludeanaromaticgroup,
andapluralityof Z'smaybethe sameas ordifferentfromeachother.
25 2. The polymerizable composition for optical materials according
to Claim 1,
wherein the polyisocyanate compound (A) is at least one kind
selected from the group consisting of hexamethylene diisocyanate,
pentamethylene diisocyanate, xylylene diisocyanate, isophorone
5 diisocyanate, bis (isocyanatomethyl) cyclohexane,
dicyclohexylmethane diisocyanate,
2,5-his (isocyanatomethyl) bicyclo- [2.2.1] -heptane,
2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene
diisocyanate, phenylene diisocyanate, and diphenylmethane
10 diisocyanate.
3. The polymerizable composition for optical materials according
to Claim 1 or 2,
wherein the polyol compound (B) is at least one kind selected
15 from compounds which have a number average molecular weight of 100
or more and 18ihich are represented by the following General Formulas
(1) to (IV),
wherein, in Formula (I), p represents a numerical value of 4
. 20 to100, Xrepresentsahydrogenatomoramethylgroup, andaplurality
of X's may be the same as or different from each other,
wherein, in Formula (II), q and r may be the same as or different
from each other, each of q and r represents a numerical value of 1
or more, and the sum of q and r represents a numerical value of 2
to 100; R1 and R2 may be the same as or different from each other,
each of R1 and R2 represents a hydrogen atom or a methyl group, and
5 a plurality of R1's or R2' s may be the same as or different from each
other; and Z represents a substituted or unsubstituted divalent
aromaticgrouporadivalentaliphaticgroupwhichoptionallyinclude
a substituted or unsubstituted aromatic group having 1 to 20 carbon
atoms,
wherein, in Formula (III), qandrmaybethe sameasordifferent
from each other, each of q and r represents a numerical value of 1
or more, and the sum of q and r represents a numerical value of 2
to 100; and R1 and R2 may be the same as or different from each other,
15 each of R' and R2 represents a hydrogen atom or a methyl group, and
a plurality of R 1 ' s or R2' s may be the same as or different from each
other,
wherein, in Formula (IV), m represents a numerical value of 1
20 to 20, k represents 0 to 2m, n represents a numerical value of 1 to
20, 1 represents 0 to 2n, f represents a numerical value of 0 or more,
g represents a numerical value of 1 or more, h represents a numerical
value of 1 or more, and j represents a numerical value of 1 or more;
Q' represents a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, and a plurality of Q1's may be the same as or different from
each other; Q' represents a hydrogen atom or an alkyl group having
1 to 6 carbon atoms, and a plurality of Q2's may be the same as or
5 different from each other; and R~ represents a linear or branched
alkylene group having 1 to 20 carbon atoms or a phenylene group which
optionally have alinear orbranched alkyl group having 1to 10 carbon
atoms as a substituent, and the plurality of R~'Sm ay be the same
as or different from each other.
10
4. The polymerizable composition for optical materials according
to Claim 3,
wherein the polyol compound (B) is the compound represented by
General Formula (I), (111) , or (IV) .
15
5. The polymerizable composition for optical materials according
to Claim 3 or 4,
wherein the compound represented by General Formula (I) is
polyethylene glycol or polypropylene glycol.
20
6. The polymerizable composition for optical materials according
to any one of Claims 3 to 5,
wherein the number average molecular weight of the compound
represented by General Formula (I) is 200 to 4000.
2 5
7. The polymerizable composition for optical materials according
to any one of Claims 3 to 5,
wherein the number average molecular weight of the compound
represented by General Formula (I) is 300 to 3000.
8. The polymerizable composition for optical materials according
5 to Claim 3 or 4,
wherein the number average molecular weight of the compound
represented by General Formula (11) is 400 to 2000.
9. The polymerizable composition for optical materials according
10 to Claim 3 or 4,
wherein the number average molecular weight of the compound
represented by General Formula (111) is 400 to 2000.
10. The polymerizable composition for optical materials according
15 to Claim 3 or 4,
wherein the number average molecular weight of the compound
represented by General Formula (IV) is 600 to 3000.
11. The polymerizable composition for optical materials according
20 to any one of Claims 1 to 10,
wherein the active hydrogen compound (C) is at least one kind
selected from the group consisting of polyol compounds, polythiol
compounds, and thiol compounds having a hydroxy group.
25 12. The polymerizable composition for optical materials according
to any one of Claims 1 to 11,
wherein the active hydrogen compound (C) is a tri- or higher
functional active hydrogen compound.
13. The polymerizable composition for optical materials according
to any one of Claims 1 to 12,
5 wherein the active hydrogen compound (C) is at least one kind
selected from the group consisting of glycerin, pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis (3-mercaptopropionate) ,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
10 5,7-dimercaptomethyl-l,ll-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-l,1l-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-l,1l-dimercapto-3,6,9-trithiaundecane,
1,1,3,3-tetrakis(mercaptomethy1thio) propane, and
trimethylolpropane tris(3-mercaptopropionate).
15
14. The polymerizable composition for optical materials according
to any one of Claims 1 to 13,
wherein the photochromic compound (D) is represented by the
following General Formula ( 5 ) ,
wherein in the formula, R1 and Rz may be identical or different,
and independently represent
a hydrogen atom;
a l i n e a r or branched alkyl group having 1 to 12 carbon atoms;
a cycloalkyl group having 3 t o 12 carbon atoms;
a substituted or unsubstituted aryl group having 6 t o 24 carbon
5 atoms or a substituted or unsubstituted heteroaryl group having 4
to24 c a r b o n a t o m s i n r i h i c h t h e s e s u b s t i t u t e d g r o u p s , a s a s u b s t i t u e n t ,
include a t l e a s t one substituenf selected from a halogen atom, a
hydroxylgroup, alinearorbranchedalkylgroup having I t 0 1 2 carbon
atoms, a l i n e a r or branched alkoxy group having 1 to 12 carbon atoms,
10 a l i n e a r or branched haloalkyl group having 1 t o 12 carbon atoms t h a t
is substituted by a t l e a s t one halogen atom, a l i n e a r or branched
haloalkoxy group having 1 to 12 carbon atoms t h a t is substituted by
a t l e a s t one halogen atom, a phenoxy group or naphthoxy group
s u b s t i t u t e d by a t l e a s t one l i n e a r or branched alkyl group or alkoxy
15 group having 1 t o 12 carbon atoms, a l i n e a r or branched alkenyl group
having 2 t o 12 carbon atoms, a -NH2 group, a -NHR group, a -N (R) group
i n which R represents a l i n e a r or branched alkyl group having 1 t o
6 carbon atoms, in which i n a case t h a t two Rs are present, the two
R s m a y b e i d e n t i c a l o r d i f f e r e n t , amethacryloylgroupandanacryloyl
20 group; or
an aralkyl or heteroaralkyl group t h a t a l i n e a r or branched alkyl
group having 1 t o 4 carbon atoms is substituted by the aryl group
or the heteroaryl group,
R3 may be i d e n t i c a l or d i f f e r e n t , and independently represent
25 a halogen atom;
a l i n e a r o r branched alkyl group having 1 to 12 carbon atoms;
a cycloalkyl group having 3 t o 12 carbon atoms;
a l i n e a r or branched alkoxy group having 1 t o 12 carbon atoms;
a l i n e a r or branched haloalkyl group having 1 t o 12 carbon atoms
t h a t is substituted by a t l e a s t one halogen atom, a halocycloalkyl
group having 3 to 12 carbon atoms t h a t i s substituted by a t l e a s t
5 one halogen atom, a l i n e a r or branched haloalkoxy group having 1 to
12 carbon atoms t h a t is substituted by a t l e a s t one halogen atom;
a substituted or unsubstituted aryl group having 6 t o 24 carbon
atoms or a substituted or unsubstituted heteroaryl group having 4
to24 carbonatomsinwhichthesesubstitutedgroups, a s a substituent,
10 include a t l e a s t one substituent selected from a halogen atom, a
hydroxylgroup, a l i n e a r o r b r a n c h e d a l k y l g r o u p h a v i n g l t o 1 2 carbon
atoms, a l i n e a r or branched alkoxy group having 1 t o 12 carbon atoms,
a l i n e a r o r branched haloalkyl group having 1 t o 12 carbon atoms t h a t
is substituted by a t l e a s t one halogen atom, a l i n e a r or branched
15 haloalkoxy group having 1 to 12 carbon atoms t h a t is substituted by
a t Zeast one halogen atom, a phenoxy group or naphthoxy group
substituted by a t l e a s t one l i n e a r or branched alkyl group or alkoxy
group having 1 to 12 carbon atoms, a l i n e a r or branched alkenyl group
having 2 t o 12 carbon atoms, and an amino group;
2 0 a n a r a l . k ~ f ~ o r h e t e r o a r a l k y l g r o u p t h a t a l i n e a r o r b r a n c h e d a l k y l
group having 1 t o 4 carbon atoms is substituted by the a r y l group
or het.eroary1 group;
asubstitutedorunsubstitutedphenoxygroupornaphthoxygroup,
i n which t h e s e s u b s t i t u t e d groups, as a substituent, include a t l e a s t
25 one s u b s t i t u e n t s e l e c t e d from a l i n e a r or branched alkyl group or
alkoxy group having 1 to 6 carbon atoms;
-NH2, -NHR, -CONHz, or -CONHR in which R represents a l i n e a r or
101
branched alkyl group having 1 to 6 carbon atoms; or
-OCOR8 or -COOR8inwhichR8 represents a l i n e a r o r b r a n c h e d a l k y l
group having 1 t o 6 carbon atoms, a cycloalkyl group having 3 t o 6
carbon atoms, or a phenyl group substituted by a t l e a s t one
5 substituents of the substituted aryl and the substituted heteroaryl
group of R1 or Rz, or an unsubstituted phenyl group;
m is an integer of 0 to 4;
A represents an annelated ring represented by the following
Formula (A2) or (Aq), and
10
wherein, in these annelated rings,
t h e dotted l i n e s represent a chemical bond between a carbon Cs
and a carbon C6 in a naphthopyran ring of a formula ( 5 ) ;
an a bond in the anne \ ated ring (A4) can be bonded with the carbon
15 C5 or the carbon C6 in the naphthopyran ring of Formula (5);
Rq is i d e n t i c a l or d i f f e r e n t , and independently represents OH,
a l i n e a r or branched alkyl group or alkoxy group having 1 t o 6 carbon
atoms; two Rqs form carbonyl (CO) ;
Rg represents halogen atom;
20 a l i n e a r o r branched alkyl group having 1 t o 12 carbon atoms;
a l i n e a r o r branched haloalkyl group having 1 t o 6 carbon atoms
t h a t is substituted by a t l e a s t one halogen atom;
a cycloalkyl group having 3 to 12 carbon atoms;
a l i n e a r or branched alkoxy group having 1 t o 6 carbon atoms;
a substituted or unsubstituted phenyl or benzyl group in which
these substitutedgroups include a t l e a s t one substituents described
i n the d e f i n i t i o n of the R1 and R2 groups as a substituent in a case
5 t h a t R1 and Rz in Formula (5) independently correspond t o an a r y l or
heteroaryl group;
-NH2 or -NHR in which R represents a l i n e a r or branched alkyl
group having 1 to 6 carbon atoms;
a substitutedorunsubstitutedphenoxygroup or naphthoxygroup
10 inwhich these substitutedgroups, as a substituent, includeat l e a s t
one substituent selected from a l i n e a r or branched alkyl group or
alkoxy group having 1 t o 6 carbon atoms; or
a -CORg, -COORg, or -CONHRg group i n which Rg represents a l i n e a r
or branched alkyl group having 1 t o 6 carbon atoms, a cycloalkyl group
15 having 3 t o 6 carbon atoms, or a substituted or unsubstituted phenyl
or benzyl group in which these substituted groups include a t l e a s t
one substituents described i n t h e d e f i n i t i o n of the R1 and R2 groups
as a substituent in a case that R1 and RZ i n Formula (5) independently
correspond t o an aryl or heteroaryl group,
20 in a case in which A represents (A4), n is an integer of 0 t o
2, p is an integer of 0 t o 4, and in a case i n which A represents
. (A2), n is an integer of 0 to 2. ..
15. The polymerizable composition for o p t i c a l materials according
25 t o any one of Claims 1 t o 14,
wherein the functional group equivalent r a t i o (B/A) of the
polyol compound (B) to the polyisocyanate compound (A) is 0.02 t o
0.6, and the functional group equivalent ratio (C/A) of the active
hydrogen compound (C) to the poly~socyanate compound (A) is 0.4 to
0.98.
5 16. A molded product comprised of a cured product of the
polymerizable composition for opticalmaterials according toanyone
of Claims 1 to 15.
17. An optical material comprised of the molded product according
10 to Claim 16.
18. Aplasticlens comprisedofthemoldedproductaccordingtoClaim
16.
15 19. A process for producing a plastic lens, comprising:
a step of preparing a polymerizable composition for optical
materials by mixing a polyisocyanate compound (A), a polyol compound
(B) represented by the folloriing General Formula (1) having a number
average molecular weight of 100 or more, a di- or higher functional
20 active hydrogen compound (C) in which the compound (B) is excluded,
and a photochromic compound (D) and
a step of forming a lens substrate by cast-polymerizing the
polymerizable composition for optical materials in a mold,
wherein, in Formula (I), m represents a numerical value of 1
to 20, k represents 0 to 2m, n represents a numerical value of - 1 to
20, 1 represents o to 2n, a represents a numerical valuk of o or more,
b represents a numerical value of 0 or more, d represents a numerical
5 value of 0 or more, and e represents a numerical value of 1 or more;
Q1 .re presents a hydrogen atom or an alkyl group having 1 to 6 carbon
atoms, and a plurality of ~l'sma y be the same as or different from
each other; Q2 represents a hydrogen atom or an alkyl group having
1 to 6 carbon atoms, and a plurality of Q2's may be the same as or
10 different from each other;, and Z represents a divalent organic group
having 1 to 30 carbon atoms which optionally includk an aromatic
and,apluralityofZ'smaybethe same as ordifferent fromeachother.