SPECIFICATION
POLYMERIZABLE COMPOSITION FOR PHOTOCHROMIC OPTICAL MATERIALS
5 TECHNICAL FIELD
[0001]
The present invention relates to a polymerizable composition
for photochromic optical materials and optical materials obtained
using the same.
10 BACKGROUND ART
[0002]
Since plastic lenses are light, not easily cracked, and can be
stained in comparison to inorganic lenses, plastic lenses have been
rapidly distributed as optical elements such as spectacle lenses and
15 camera lenses, and hitherto, a variety of resins for spectacle lenses
have been developed and used. Among these, representative examples
include an allyl resin obtained from diethylene glycol bisallyl
carbonate and diallyl isophthalate, a (meth)acrylic resin obtained
from (meth)acrylate, and a polythiourethane resin obtained from
20 isocyanate and thiol.
[0003]
In recent years, plastic photochromic lenses using organic
photochromic dyes are commercially available as glasses. Examples
of techniques in the related art for the photochromic lenses include
25 the following.
[0004]
Patent Document 1 describes that by combining a specific
2
aromatic (meth)acrylic acid ester and an aromatic vinyl, favorable
light adjusting performance is obtained.
Patent Document 2 describes a lens formed of a composition
including a predetermined photochromic compound and a
5 di (meth) acrylate compound. In paragraph [ 0009], it is described that
in a case where a urethane resin or a thiourethane resin having a
high refractive index is used, isocyanate which is a resin raw material
in a monomer state reacts with the photochromic compound, and due
to this, photochromic performance is completely eliminated.
10 [0005]
Patent Document 3 discloses a lens obtained by providing a
coating layer formed of a composition including a photochromic
compound having a chromene skeleton and a phenol compound on a surface
of a thiourethane-based plastic lens.
15 Patent Document 4 discloses a photochromic lens having a lens
substrate formed of a thiourethane resin and a photochromic film
formed by applying a solution including a photochromic compound and
a radically polymerizable monomer on the substrate.
Patent Document 5 discloses a compound having photochromic
20 characteristics.
[ 0006]
Patent Document 6 describes a process for producing a
photochromic optical material by curing a monomer composition
including a photochromic compound, a polythiol, and a polyisocyanate.
25 Patent Document 7 discloses an optical resin composition
containing a thiol-ene prepolymer.
[0007]
5
RELATED DOCUMENT
PATENT DOCUMENT
3
[Patent Document 1] PCT Japanese Translation Patent
Publication No. 11-511765
[Patent Document 2] Japanese Unexamined Patent Publication No.
8-272036
[Patent Document 3] Japanese Unexamined Patent Publication No.
2005-23238
[Patent Document 4] Japanese Unexamined Patent Publication No.
10 2008-30439
15
20
25
[Patent Document 5] Japanese Unexamined Patent Publication No.
2011-144181
[Patent Document 6] Japanese Unexamined Patent Publication No.
2004-78052
[Patent Document 7] PCT Japanese Translation Patent
Publication No. 2004-511578
SUMMARY OF THE INVENTION
[0008]
The techniques described in the above-described Patent
Documents have points to be improved in the follm-1ing respects.
The lens obtained by combining specified monomers described in
Patent Documents 1 and 2 has a refractive index of about 1. 55 to 1. 57;
however, the lens needs to be improved in the refractive index.
The lens described in Patent Document 6 needs to be improved
in light adjusting characteristics.
In addition, the molded product by the method of Patent Document
4
7 needs to be improved in refractive index and light adjusting
characteristics.
[0009]
Therefore, a photochromic optical material which has a high
5 refractive index, and is excellent in balance between light adjusting
characteristics and optical properties has been required. The
present inventors have performed thorough studies in order to solve
the above problems.
10
[0010]
As a result of thorough studies in order to solve the above
problems, the present inventors found that, in a polymerizable
composition for photochromic optical materials including a
polymerizable monomer (A) having two or more ethylene-based
unsaturated groups, an ethylene-based unsaturated polymerizable
15 monomer (B) having one (meth)acrylic group and an aromatic ring, a
pol ythiol (C) having three or more mercapto groups, and a photochromic
compound (D), the above problems can be solve in an optical material
obtained from a polymerizable composition for photochromic optical
materials in which the molar number of the mercapto groups included
20 in the polythiol (C) having three or more mercapto groups is not more
than 0. 3 times with respect to the total molar number of the entirety
of ethylene-based unsaturated groups included in the polymerizable
monomer (A) having t1vo or more ethylene-based unsaturated groups and
the ethylene-based unsaturated polymerizable monomer (B) having one
25 (meth) acrylic group and an aromatic ring, and completed the present
invention. The present inventors also found that, by including the
ethylene-based unsaturated polymerizable monomer (B) having one
5
5
(meth)acrylic group and an aromatic ring as a constituent, it is
possible to provide a photochromic optical material which is
excellent in light adjusting performance and a refractive index.
[ 00 11]
That is, the invention is as follows.
[1] A polymerizable composition for photochromic optical materials
including a polymerizable monomer (A) having two or more
ethylene-based unsaturated groups, an ethylene-based unsaturated
polymerizable monomer (B) having one (meth)acrylic group and an
10 aromatic ring, a polythiol (C) having three or more mercapto groups
and a photochromic compound (D), in which the molar number of the
mercapto groups included in the polythiol (C) having three or more
mercapto groups is not more than 0. 3 times with respect to the total
molar number of the ethylene-based unsaturated groups included in
15 the polymerizable monomer (A) having t1-10 or more ethylene-based
unsaturated groups and the ethylene-based unsaturated polymerizable
monomer (B) having one (meth)acrylic group and an aromatic ring.
[2] The polymerizable composition for photochromic optical materials
according to [ 1], in which the polythiol (C) is at least one selected
20 from the group consisting of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), and
25 1,1,3,3-tetrakis(mercaptomethylthio)propane.
[3] The polymerizable composition for photochromic optical materials
according to [1] or [2], in which the polymerizable monomer (A)
6
includes an ethylene-based unsaturated·polymerizable monomer (a1)
having two or more vinyl groups or isopropenyl groups and an
ethylene-based unsaturated polymerizable monomer (a2) having two or
more (meth)acrylic groups.
5 [ 4) The polymerizable composition for photochromic optical materials
according to [3), in v1hich the polymerizable monomer (a1) is at least
one selected from divinylbenzene, diisopropenylbenzene,
trivinylbenzene, and divinylnaphthalene.
[5] The polymerizable composition for photochromic optical materials
10 according to [3] or [4), in \vhich the polymerizable monomer (a2) is
at least one selected from polymerizable monomers represented by the
follov1ing General Formula ( 4) ;
wherein, in Formula ( 4) , each of m and n is 0 or greater number, and
15 m and n satisfy m + n = 0 to 50; X1 is a hydrogen atom or a methyl
group, and a plurality of X1 may be the same as or different from
each other; X2 is a hydrogen atom or an alkyl group having 1 or 2
carbon atoms; and a plurality of X2 may be the same as or different
from each other.
20 [6] The polymerizable composition for photochromic optical materials
according to any one of [1] to [5], in which the polymerizable monomer
(B) is at least one selected from aromatic (meth) acrylic acid esters
represented by the following General Formula (5);
7
O X'
CH -0-C-t=CH 2 II 2
0 (5)
wherein, in Formula (5), X3 is a hydrogen atom or a methyl group)
[7] A process for producing photochromic optical materials including
a step of obtaining the polymerizable composition according to any
of [l] to [6], a step of casting the polymerizable composition into
5 a mold, and a step of polymerizing the composition.
[8] A molded product obtained by polymerization of the polymerizable
composition for optical materials according to any one of [l] to [6].
[9] A photochromic optical material comprised of the molded product
according to [8].
10 [10] A plastic lens comprised of the photochromic optical material
according to .[.9]_ .
[0012]
According to the polymerizable composition for optical
materials of the present invention, it is possible to obtain a
15 photochromic optical material which has a high refractive index and
is excellent in light adjusting characteristics. Such a photochromic
optical material is suitably used in a spectacle lens which requires
high optical properties.
20 DESCRIPTION OF EMBODIMENTS
[0013]
Hereinafter, embodiments of the polymerizable composition for
photochromic optical material of the present invention will be
described 11i th reference to specific examples.
8
[0014]
[Po1ymerizable Composition for Photochromic Optical Material]
A polymerizable composition for optical materials of the
embodiment includes a polymerizable monomer (A) having two or more
5 ethylene-based unsaturated groups (hereinafter, simply referred to
as "polymerizable monomer (A)"), an ethylene-based unsaturated
polymerizable monomer (B) having one (meth)acrylic group and an
aromatic ring (hereinafter, simply referred to as "polymerizable
monomer (B)"), a polythiol (C) having three or more mercapto groups
10 (hereinafter, simply referred to as "polythiol (C)"), and a
photochromic compound (D), and the molar number of the mercapto groups
included in the polythiol (C) is not more than 0. 3 times with respect
to the total molar number of the entirety of ethylene-based
unsaturated groups included in the polymerizable monomer (A) and the
15 polymerizable monomer (B) .
Hereinafter, the components used in the embodiment will be
described.
[0015]
(Polymerizable Monomer (A) having T1vo or More Ethylene-Based
20 Unsaturated Groups)
The polymerizable monomer (A) has two or more ethylene-based
unsaturated groups (two or more radical polymerizable ethylene-base
unsaturated groups), and for example, at least one ethylene-based
unsaturated polymerizable monomer (a1) (hereinafter, simply referred
25 to as "polymerizable monomer (a1) ") having two or more vinyl groups
or isopropenyl groups and/or at least one ethylene-based unsaturated
polymerizable monomer (a2) having two or more (meth)acrylic group
9
(hereinafter, simply referred to as "polymerizable monomer (a2) ") .
In the embodiment, the ethylene-based unsaturated polymerizable
monomer having two or more (meth)acrylic group is not included in
the ethylene-based unsaturated polymerizable monomer having two or
5 more vinyl groups or isopropenyl groups.
[0016]
Examples of the polymerizable monomer (al) include
divinylbenzene, diisopropenylbenzene, trivinylbenzene,
divinylnaphthalene, trivinylnaphthalene, divinylbiphenyl,
10 trivinylbiphenyl, divinyldimethylbenzene, and
trivinyldiethylnaphthalene. These can be used alone or in
combination of two or more types thereof.
In the embodiment, the polymerizable monomer (al) is preferably
at least one selected from divinylbenzene, diisopropenylbenzene,
15 trivinylbenzene, and divinylnaphthalene.
Here, divinylbenzene is selected m-divinylbenzene or
p-divinylbenzene, and may be a mixture of m-divinylbenzene and
p-divinylbenzene. In addition, divinylbenzene may include
ethyl vinylbenzene.
20 [0017]
Examples of the polymerizable monomer (a2) include
polyfunctional (meth)acrylic acid esters such as glycerin
di(meth)acrylate and trimethylolpropane tri(meth)acrylate,
pentaerythritol tri(meth)acrylate, and the compound represented by
25 the follmving General Formula (1).
[0018]
10
[0019]
In Formula (1), each of m and n is 0 or greater number, and m
and n satisfy m + n = 0 to 50, preferably satisfy m + n = 2 to 30,
5 and more preferably satisfy m + n = 2 to 4.
X1 is a hydrogen atom or a methyl group, and a plurality of X1
may be the same as or different from each other. X2 is a hydrogen
atom or an alkyl group having 1 or 2 carbon atoms, and a plurality
of X2 may be the same as or different from each other.
10 A is selected from a linear or branched alkylene group having
1 to 10 carbon atoms, a cyclic alkylene group having 1 to 10 carbon
atoms, a phenylene group, an alkyl-substituted phenylene group having
1 to 9 carbon atoms, or the group represented by the follm.zing General
Formula (2) or (3) .
15 [0020]
*--< y >----*
(2)
[0021]
In Formula (2), each of Q1 and Q2 is an alkyl group having a 1 to 4
carbon atoms, chlorine, or bromine. A plurality of Q1 may be the same
20 as or different from each other, and a plurality of Q2 may be the
same as or different from each other. Each of p and q is an integer
5
11
of 0 to 4. Y is an oxygen atom, a sulfur atom, -CH2-, or -C(CH3 ) 2-.
"*" represents a valence bond.
[0022]
*--<2J z
(3)
[0023]
In Formula (3), each of Q3 and Q4 is an alkyl group having a l
to 4 carbon atoms, chlorine, or bromine. A plurality of Q3 may be
the same as or different from each other, and a plurality of Q4 may
10 be the same as or different from each other. Each of p and q is an
integer of 0 to 4. z is an oxygen atom, a sulfur atom, -S (02 ) -, -c (0) -,
-CHr, -CH=CH-, -C {CH3 ) r, or -C (CH3 ) (C6H5 )-. "*"represents a valence
bond.
15
20
[0024]
Examples of the compound represented by General Formula (1)
include polyethylene glycol di (meth) acrylate, ethoxylated bisphenol
A di(meth)acrylate, 1,10-decanediol diacrylate, 1,6-hexanediol
di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate.
[0025]
As the polymerizable monomer (a2), at least one selected from
compounds represented by the follmving General Formula (4) can be
preferably used.
[0026]
12
X1 X' CH X' 1
H,c=Ic -c-E-oHIc -cH,-Jo O\ 1 'D? \ -/. ofcH;-CIH o}--wc~= cH,
~ m \\ II CH, \\ II n o (4)
[0027]
Each of X1
, X2
, m, and n in Formula ( 4) has the same meaning as
that in Formula (1) . Examples of the polymerizable monomer
5 represented by General Formula (4) include
2,2'-bis(4-(methacryloyloxyethoxy)phenyl)propane.
As the polymerizable monomer (A), the polymerizable monomer (all
and the polymerizable monomer (a2) are preferably used in combination
with each other from the viewpoint of operability and a refractive
10 index, and in this case, the weight ratio between the polymerizable
monomer (al) and the polymerizable monomer (a2) is 1:1, preferably
0.9:1, and particularly preferably 0.7:1.
[0028]
(Ethylene-Based Unsaturated Polymerizable Monomer (B) having One
15 (Meth)acrylic Group and Aromatic Ring)
Examples of the ethylene-based unsaturated polymerizable
monomer (B) having one (meth)acrylic group and an aromatic ring
include aromatic (meth)acrylic acid esters such as naphthyl
(meth)acrylates such as a-naphthyl (meth)acrylate and 0-naphthyl
20 (meth)acrylate; phenoxyethyl (meth)acrylate, and the compound
represented by the follm~ing General Formula (5) .
[ 002 9]
13
O X'
cH -o-c-b=cH 2 II 2
0 (5)
[0030]
In General Formula (5), X3 is a hydrogen atom or a methyl group.
In the embodiment, as the polymerizable monomer (B), at least
one selected from compounds represented by the following General
5 Formula (5) can be preferably used, and specific examples thereof
include benzyl methacrylate and benzyl acrylate.
[ 0031]
The polymerizable monomer (B) is equal to or greater than 1%
by weight, and preferably equal to or greater than 3% by \veight, and
10 the upper limit is equal to or less than 20% by weight, and preferably
equal to or less than 15% by weight, with respect to the total weight
of the polymerizable monomer (A), the polymerizable monomer (B) , and
the pol ythiol (C) . The upper limit and the lower limit can be suitably
combined.
15 When the amount of the polymerizable monomer (B) is within the
above range, it is possible to obtain a molded product which is
excellent in optical properties or strength, and light adjusting
performance.
[0032]
20 (Polythiol (C) having Three or More Mercapto Groups)
The polythiol (C) is not particularly limited as long as it is
a compound having three or more mercapto groups. Examples of the
polythiol (C) include a polythiol compound and a thiol compound having
a hydroxy group. These can be used in suitable combination.
14
[0033]
Examples of the polythiol (C) include aliphatic polythiol
compounds such as 1,2,3-propanetrithiol,
tetrakis(mercaptomethyl)methane, trimethylolpropane
5 tris(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolethane
tris(2-mercaptoacetate), trimethylolethane
tris(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
10 tetrakis(3-mercaptopropionate), pentaerythritol
tris(3-mercaptopropionate), pentaerythritol tris(thioglycolate),
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
15 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
tetrakis(mercaptomethylthiomethyl)methane,
20 tetrakis(2-mercaptoethylthiomethyl)methane,
tetrakis(3-mercaptopropylthiomethyl)methane,
bis (2, 3-dimercaptopropyl) sulfide, esters of these thioglycolic acid
and mercaptopropionic acid, 2-mercaptoethylether
bis(3-mercaptopropionate),
25 1,1,3,3-tetrakis(mercaptomethylthio)propane,
1,1,2,2-tetrakis(mercaptomethylthio)ethane,
tris(mercaptomethylthio)methane, and
15
tris{mercaptoethylthio)methane;
aromatic polythiol compounds such as 1,3,5-trimercaptobenzene,
1,3,5-tris{mercaptomethyl)benzene,
1,3,5-tris{mercaptomethyleneoxy)benzene, and
5 1, 3, 5-tris {mercaptoethyleneoxy) benzene; and heterocyclic polythiol
compounds such as 2-methylamino-4,6-dithiol-sym-triazine.
[0034]
Furthermore, oligomers of these active hydrogen compounds or
halogen substitutes such as a chlorine substitute and a bromine
10 substitute may be used. These active hydrogen compounds can be used
alone or in combination of t1vo or more types thereof.
[0035]
As the polythiol {C), pentaerythritol
tetrakis{2-mercaptoacetate), pentaerythritol
15 tetrakis{3-mercaptopropionate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
20 1,1,3,3-tetrakis{mercaptomethylthio)propane are preferably used,
and pentaerythritol tetrakis{3-mercaptopropionate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
25 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane are
particularly preferably used.
[0036]
il
'I
16
The molar number of the mercapto groups included in the polythiol
(C) is not more than 0.3 times, preferably not more than 0.25 times,
and more preferably not more than 0. 2 times with respect to the total
molar number of the entirety of ethylene-based unsaturated groups
5 included in the polymerizable monomer (A) and the polymerizable
monomer (B). The lmver limit is preferably not less than 0.05 times,
from the viewpoint of the operability and the refractive index of
the molded product obtained.
When the molar number is within the above-described range, a
10 molded product suitably used as an optical material, in particular,
a spectacle lens, can be obtained, and desired photochromic
performance can be exhibited.
[0037]
(Photochromic Compound (D))
15 In the embodiment, the photochromic compound (D) is not
particularly limited, and an arbitrary one can be suitably selected
from compounds knmm in the related art which can be used for
photochromic lenses and used. For example, one or tlvo or more types
of a spiropyran-based compound, a spirooxazine-based compound, a
20 fulgide-based compound, a naphthopyran-based compound, and a
bisimidazole compound can be used depending on the desired color.
[0038]
Examples of the spiropyran-based compound include each
substitute obtained by substituting the indole ring or the benzene
25 ring of indolinospirobenzopyran 1vith 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
17
the naphthalene ring of indolinospironaphthopyran 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 of indolinospiroquinolinopyran with a halogen atom, a
5 methyl group, an ethyl group, a methylene group, an ethylene group,
or a hydroxyl group, and each substitute obtained by substituting
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.
10 [0039]
Examples of the spirooxazine-based compound include each
substitute obtained by substituting the indole ring or the benzene
ring of indolinospirobenzoxazine with a halogen atom, a methyl group,
an ethyl group, a methylene group, an ethylene group, or a hydroxyl
15 group, each substitute obtained by substituting the indole ring or
the naphthalene ring of indolinospironaphthoxazine 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 of indolinospirophenanthroxazine with a halogen atom,
20 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 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
25 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
18
group.
[0040)
Examples of the fulgide-based compound include
N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzo[b)thi
5 ophenedicarboximide-7, 2' -tricyclo [3. 3 .1.13' 7] decane],
N-cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl)-4-methylspiro(5,6-
benzo[b)thiophene-dicarboximide-7,2'-tricyclo[3.3.1.13'7]decane),
6,7-dihydro-N-methoxycarbonylmethyl-4-methyl-2-phenylspiro(5,6-b
enzo[b)thiophene-dicarboximide-7,2'-tricyclo[3.3.1.13' 7)decane),
10 6,7-dihydro-4-methyl-2-(p-methylphenyl)-N-nitromethylspiro(5,6-b
enzo[b)thiophenedicarboximide-7,2'-tricyclo[3.3.1.13' 7]decane),
N-cyanomethyl-6,7-dihydro-4-cyclopropyl-3-methylspiro(5,6-benzo[
b)thiophenedicarboximide-7,2'-tricyclo[3.3.1.13' 7]decane),
N-cyanomethyl-6,7-dihydro-4-cyclopropylspiro(5,6-benzo[b)thiophe
15 nedicarboximide-7,2'-tricyclo[3.3.1.13' 7)decane), and
N-cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl)-4-cyclopropylspiro
(5,6-benzo[b]thiophenedicarboximide-7,2'-tricyclo[3.3.1.13' 7]deca
ne) .
20
[0041)
Examples of the naphthopyran-based compound include
spiro[norbornane-2,2'-[2H)benzo[h)chromene],
spiro[bicyclo[3.3.1)nonane-9,2'-[2H)benzo[h]chromene),
7'-methoxyspiro[bicyclo[3.3.1)nonane-9,2'-[2H)benzo[h)chromene),
7'-methoxyspiro[norbornane-2,2'-[2H)benzo[f)chromene],
25 2,2-dimethyl-7-octoxy[2H]benzo[h]chromene,
spiro[2-bicyclo[3.3.1]nonene-9,2'-[2H]benzo[h]chromene],
spiro[2-bicyclo[3.3.1]nonene-9,2'-[2H]benzo[f]chromene],
19
6-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 ( 6), and the
compound represented by the following General Formula (7) .
5 [0042]
(6)
(R3) I
[0043]
(R3)m (7)
10
[0044]
In General Formulas (6) and (7), R1 and R2 may be the same as
or different from each other, and each of R1 and R2 independently
represents a hydrogen atom; a linear or branched alkyl group having
15 1 to 12 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms;
a substituted or unsubstituted aryl group having 6 to 24 carbon atoms
20
or a substituted or unsubstituted heteroaryl group having 4 to 24
carbon atoms; or an aralkyl or heteroaralkyl group (a linear or
branched alkyl group having 1 to 4 carbon atoms is substituted with
an aryl group or a heteroaryl group) .
5 [0045]
The substituent of a substituted aryl group having 6 to 24 carbon
atoms or a substituted heteroaryl group having 4 to 24 carbon atoms
is at least one selected from a halogen atom, a hydroxy group, a linear
or branched alkyl group having 1 to 12 carbon atoms, a linear or
10 branched alkoxy group having 1 to 12 carbon atoms, a linear or branched
haloalkyl group having 1 to 12 carbon atoms which is substituted with
at least one halogen atom, a linear or branched haloalkoxy group having
1 to 12 carbon atoms \vhich is substituted with at least one halogen
atom, a phenoxy group or a naphthoxy group which is substituted with
15 at least one linear or branched alkyl group or alkoxy group having
1 to 12 carbon atoms, a linear or branched alkenyl group having 2
to 12 carbon atoms, and an -NH2 group, an -NHR group, or a -N (R) 2 group
(R is a linear or branched alkyl group having 1 to 6 carbon atoms.
In a case \vhere two Rs are present, the t\vo Rs may be the same as
20 or different from each other), and a methacryloyl group or an acryloyl
group.
[0046]
R3s may be the same as or different from each other, and each
R3s independently represents a halogen atom; a linear or branched
25 alkyl group having 1 to 12 carbon atoms; a cycloalkyl group having
3 to 12 carbon atoms; a linear or branched alkoxy group having 1 to
12 carbon atoms; a linear or branched haloalkyl group having 1 to
;::;1
'=l
21
12 carbon atoms which is substituted with at least one halogen atom,
a halocycloalkyl group having 3 to 12 carbon atoms Hhich is substituted
Hi th at least one halogen atom, a linear or branched haloalkoxy group
having 1 to 12 carbon atoms which is substituted with at least one
5 halogen atom; an aryl group having 6 to 24 carbon atoms or a heteroaryl
group having 4 to 24 carbon atoms which is substituted or unsubstituted
(which has at least one substituent selected from a halogen atom,
a hydroxy group, a linear or branched alkyl group having 1 to 12 carbon
atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms,
10 a linear or branched haloalkyl group having 1 to 12 carbon atoms which
is substituted Hith at least one halogen atom, a linear or branched
haloalkoxy group having 1 to 12 carbon atoms 1vhich is substituted
1vith at least one halogen atom, a phenoxy group or a naphthoxy group
1vhich is substituted with at least one linear or branched alkyl group
15 or alkoxy group having 1 to 12 carbon atoms, a linear or branched
alkenyl group having 2 to 12 carbon atoms, and an amino group as a
substituent); an aralkyl or heteroaralkyl group (a linear or branched
alkyl group having 1 to 4 carbon atoms is substituted with the aryl
group or the heteroaryl group); a substituted or unsubstituted
20 phenoxy or naphthoxy group (which has at least one substituent
selected from a linear or branched alkyl group or alkoxy group having
1 to 6 carbon atoms as a substituent); -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
25 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms,
or in R1 and R2 , a phenyl group which is substituted with at least
one substituent of a substituted aryl group or a substituted
22
heteroaryl group or an unsubstituted phenyl group) .
[0047]
It is possible to form one or more aromatic ring groups or
non-aromatic ring groups by bonding of at least two adjacent R3s to
5 each other and by including the carbon atom to which R3 is bonded.
10
The aromatic ring group or non-aromatic ring group includes one ring
or tv10 annelated rings which may include a heteroatom selected from
the group consisting of oxygen, sulfur, and nitrogen.
[0048]
1 is an integer of 0 to 2. m is an integer of 0 to 4.
In addition, examples of the naphthopyran-based compound
include compounds described in W02013/78086, W02012/149599,
W02010/020770, and W02009/146509, and a compound having two or more
naphthopyran rings in one molecule by bonding of structures
15 represented by General Formula (6) or (7) by a linking group.
[0049]
Preferable examples of the naphthopyran-based compound
represented by General Formula (6) include the compound represented
by the following General Formula (8) (hereinafter, also referred to
20 as· the compound (8)).
[0050]
23
(8)
[0051]
Each of R1 , R2, R3 , and m has the same meaning as that described
above, and A represents annelated rings represented by the follm1ing
5 Formulas (A1 ) to (As) o
10
[0052]
(~)
[0053]
/~
u(R4)n
(As)
co:)q
(R?)q
(A5)
In these annelated rings (A1 ) to (As), a dotted line represents
a carbon Cs-carbon C6 bond of the naphthopyran ring in General Formula
(8) o The Ci bond of the annelated ring (A4 ) or (As) is bonded to the
carbon Cs or C6 of the naphthopyran ring in General Formula (8) 0
24
[0054]
R4 's may be the same as or different from each other, and each
R4 ' s independently represents OH or an linear or branched alkyl group
or alkoxy group having 1 to 6 carbon atoms, or two R4 ' s form a carbonyl
5 group (CO) •
[0055]
Each of R5 , R6 , and R7 independently represents a halogen atom
(preferably, a fluorine atom, a chlorine atom, or a bromine atom);
a linear or branched alkyl group having 1 to 12 carbon atoms
10 (preferably, a linear or branched alkyl group having 1 to 6 carbon
atoms);
15
a linear or branched haloalkyl group having 1 to 6 carbon atoms
which is substituted with at least one halogen atom (preferably, a
fluoroalkyl group);
a cycloalkyl group having 3 to 12 carbon atoms;
a linear or branched alkoxy group having 1 to 6 carbon atoms;
a substituted or unsubstituted phenyl or benzyl group (which
has at least one of substituents described above in the definition
of R1 and R2 groups as a substituent in a case where each of R1 and
20 R2 groups in General Formula (7) independently corresponds to an aryl
or heteroaryl group);
-NH2 or -NHR
(here, R is a linear or branched alkyl group having 1 to 6 carbon
atoms); a substituted or unsubstituted phenoxy or naphthoxy group
25 (lvhich has at least a linear or branched alkyl group or alkoxy group
having 1 to 6 carbon atoms as a substituent); or
a -COR9 , -COOR9 , or -CONHR9 group (here, R9 represents a linear
25
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 (which has at least one of substituents described
above in the definition of R1 and R2 groups as a substituent in a case
5 where each of R1 and R2 groups in General Formula (7) independently
corresponds to an aryl or heteroaryl group)).
[0056]
n is an integer of 0 to 6, o is an integer of 0 to 2, p is an
integer of 0 to 4, and q is an integer of 0 to 3.
10 In a case 1vhere A represents (A4 ), n is an integer of 0 to 2,
and p is an integer of 0 to 4, and in a case where A represents (A2 ),
n is an integer of 0 to 2.
[0057]
The photochromic compound (D) of General Formula (8) has high
15 coloring adaptability even at 40°C by being combined with the
discoloration reaction rate that is applied to the use being required.
The colors capable of being easily achieved are colors from orange
to blue.
[0058]
20 In the embodiment, a mixture of the compound (8) belonging to
at least one different type selected from the group consisting of
the compound ( 8) in which A is (All, the compound ( 8) in 1vhich A is
(A2 ), the compound (8) in which A is (A3), the compound (8) in which
A is (A4), and the compound (8) in which A is (A5 ) also is included.
25 [0059]
In the embodiment, as the compound (8), the compound represented
by the following General Formula (9) can be preferably used.
26
[0060]
Ar, Ar2
0
(9)
[0061]
5 Ar1 and Ar2 are aromatic groups, and these may be the same as
or different from each other, and each of Ar1 and Ar2 represents a
benzene ring or a thiophene ring which may be substituted. As the
substituent of the benzene ring or the thiophene ring, a linear or
branched alkyl group having 1 to 10 carbon atoms, a linear or branched
10 alkoxy group having 1 to 10 carbon atoms, or a linear or branched
alkyl mono (or di) substituted amino group having 1 to 6 carbon atoms
can be exemplified. Each of R3 , R4 , R5 , m, n, and p has the same meaning
as that described above.
[0062]
15 As the compound (8), the compound represented by the following
General Formula (10) can be further preferably used.
[0063]
27
[0064]
In Formula (10), R10 and R11 may be the same as or different from
each other, and each of R10 and R11 represents a linear or branched
5 alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy
group having 1 to 10 carbon atoms, or a linear or branched alkyl mono
(or di) substituted amino group having 1 to 6 carbon atoms. When
m is 2, it is possible to form a ring structure by bonding of adjacent
R3s to each other and by including the carbon atom to which R3 is bonded.
10 Each of rands is an integer of 0 to 4. The above ring structure
is a structure of a substituted or unsubstituted aryl group having
6 to 24 carbon atoms or a substituted or unsubstituted heteroaryl
group having 3 to 24 carbon atoms.
Each of R3 , R4 , R5 , m, n, and p has the same meaning as that
15 described above.
[0065]
As specific examples of the compound represented by General
Formula (10), the compound represented by the follmving Formula (11)
or (12) can be exemplified.
28
[0066]
0 < 0
(11)
[0067]
5
o i-Pr
MeO
(12)
[0068]
The compound represented by General Formula (8) Hhich is the
photochromic compound (D) can be synthesized by a knmm method. For
10 example, the compound can also be synthesized by the method described
in Japanese Unexamined Patent Publication No. 2004-500319.
[0069]
29
As specific examples of the compound represented by General
Formula (6), the compound represented by the foll01ving Formula (13)
can be preferably exemplified.
[0070)
5
(13)
[0071]
In the embodiment, preferable specific examples of the
naphthopyran-based compound include the compounds represented by
10 Formula (11), (12), or (13), and the compound manufactured by Vivimed
Labs Ltd. (trade name: Reversacol Humber Blue).
As the naphthopyran-based compound, one or more compounds
selected from the above-described compounds may be used.
[ 0072)
15 In the embodiment, the photochromic compound (D) can be used
in 0.01% by weight to 3% by Height, preferably 0.01% by Height to
1% by Height, and more preferably 0. 01% by \•Ieight to 0. 2% by weight,
Hith respect to the total of 100% by weight of the component (A),
the component (B), and the component (C), from the vie1vpoint of the
30
effects of the present invention.
[0073]
(Polymerization Catalyst)
Examples of a polymerization catalyst include a radical
5 polymerization initiator, amines, a quaternary ammonium salt,
complexes of amines with borane and 1-1ith boron trifluoride, and a
phosphine-based compound, and two or more types thereof may be used
in combination.
10
[0074]
The radical polymerization initiator may be any one which
generates radicals by heat, ultraviolet rays, or an electron beam,
and examples thereof include peroxides such as
acetylcyclohexylsulfonyl peroxide, isobutyl peroxide, cumyl peroxy
neodecanoate, diisopropyl peroxy dicarbonate, diallyl peroxy
15 dicarbonate, di-n-propyl peroxy dicarbonate, dimyristyl peroxy
dicarbonate, cumyl peroxy neohexanoate, di(2-ethoxyethyl)peroxy
dicarbonate, di(methoxyisopropyl)peroxy dicarbonate,
di(2-ethylhexyl)peroxy dicarbonate, tert-hexyl peroxy neodecanoate,
di(3-methyl-3-methoxybutyl)peroxy dicarbonate, tert-butyl peroxy
20 neodecanoate, tert-hexyl peroxy neohexanoate, tert-butyl peroxy
neohexanoate, 2,4-dichlorobenzoyl peroxide, tert-hexyl peroxy
pivalate, tert-butyl peroxy pivalate, 3,5,5-trimethyl hexanoyl
peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide,
25 tert-butyl peroxy(2-ethylhexanoate), m-toluoyl peroxide, benzoyl
peroxide, tert-butyl peroxy isobutyrate,
1,1-bis(tert-butylperoxy)-3,3,5-trimethyl cyc1ohexane,
31
1,1-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxy maleic
acid, tert-butyl peroxyllaurate, tert-butyl peroxy-3, 5, 5-trimethyl
hexanoate, cyclohexanone peroxide, tert-butyl peroxy allyl carbonate,
tert-butyl peroxy isopropyl carbonate,
5 2,5-dimethyl-2,5-di(benzoylperoxy)hexane,
2,2-bis(tert-butylperoxy)octane, tert-butyl peroxy acetate,
2,2-bis(tert-butylperoxy)butane, tert-butyl peroxy benzoate,
n-butyl-4,4-bis(tert-butylperoxy)valerate, di-tert-butyl peroxy
isophthalate, methyl ethyl ketone peroxide, dicumyl peroxide,
10 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,
a,a'-bis(tert-butylperoxy-m-isopropyl)benzene, tert-butyl cumyl
peroxide, di-tert-butyl peroxide, and
2,5-dimethyl-2,5-di(tert-butylperoxy)3-hexyne; hydroperoxides
such as diisopropylbenzene hydroperoxide, p-menthane hydroperoxide,
15 1,1,3,3-tetramethylbutyl hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, and
tert-butyl hydroperoxide; known thermal polymerization catalysts
including azo-based compounds such as
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
20 2, 2 '-azobis (2-cyclopropylpropionitrile) ,
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile),
1,1'-azobis(cyclohexane-1-carbonitrile),
1-[(1-cyano-1-methylethyl)azo]formamide, and
25 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, carbonyl
compounds such as benzoin, benzoin monomethyl ether, benzoin
isopropyl ether, acetoin, benzil, benzophenone,
32
p-methoxybenzophenone, diethoxyacetophenone, 2-hydroxy-4-methoxy
benzophenone, benzil dimethyl ketal, 2,2-diethoxy acetophenone,
1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate,
ethylphenyl glyoxylate, and
5 2-hydroxy-2-methyl-1-phenylpropan-1-one, and sulfur compounds such
as tetramethyl thiuram monosulfide and tetramethyl thiuram
disulfide; and known photopolymerization catalysts including
acylphosphine oxides such as 2,4,6-trimethylbenzoyl diphenyl
phosphine oxide.
10 [0075]
Among these, peroxides, hydroperoxides, or azo-based compounds
are preferable, peroxides or azo-based compounds are more preferable,
and azo-based compounds such as
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
15 2,2'-azobis(2-cyclopropylpropionitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile),
1,1'-azobis(cyclohexane-1-carbonitrile),
1-[(1-cyano-1-methylethyl)azo]formamide, and
20 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile are most
preferable.
As the azo-based compound,
2,2'-azobis(2,4-dimethylvaleronitrile) is preferably used. These
can be used in combination.
25 [0076]
Examples of the amines include amine compounds represented by
primary amines such as ethylamine, n-propylamine, sec-propylamine,
33
n-butylamine, sec-butylamine, i-butylamine, t-butylamine,
pentylamine, hexylamine, heptylamine, octylamine, decylamine,
laurylamine, myristyl amine, 1,2-dimethylhexylamine, 3-pentylamine,
2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol,
5 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol,
3-ethoxypropylamine, 3-propoxypropylamine,
3-isopropoxypropylamine, 3-butoxypropylamine,
3-isobutoxypropylamine, 3-(2-ethylhexyloxy)propylamine,
aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethyl
10 cyclohexane, aminobenzene, benzylamine, phenethylamine,
a-phenylethylamine, naphthylamine, and furfurylamine; primary
polyamines such as ethylenediamine, 1,2-diaminopropane,
1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane,
1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
15 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine,
diethylaminopropylamine, bis-(3-aminopropyl)ether,
1,2-bis-(3-aminopropoxy)ethane,
1,3-bis-(3-aminopropoxy)-2,2'-dimethylpropane, aminoethyl
ethanolamine, 1,2-, 1,3-, or 1,4-bisaminocyclohexane, 1,3- or
20 1,4-bisaminomethyl cyclohexane, 1,3- or 1,4-bisaminoethyl
cyclohexane, 1,3- or 1,4-bisaminopropyl cyclohexane, hydrogenated
4,4'-diaminodiphenyl methane, 2- or 4-aminopiperidine, 2- or
4-aminomethyl piperidine, 2- or 4-aminoethyl piperidine,
N-aminoethyl piperidine, N-aminopropyl piperidine, N-aminoethyl
25 morpholine, N-aminopropyl morpholine, isophoronediamine,
menthanediamine, 1,4-bisaminopropyl piperazine, o-, m-, or
p-phenylenediamine, 2,4- or 2,6-tolylenediamine,
34
2,4-toluenediamine, m-aminobenzylamine,
4-chloro-9-phenylenediamine, tetrachloro-p-xylylenediamine,
4-methoxy-6-methyl-m-phenylenediamine, m- or p-xylylenediamine,
1,5- or 2,6-naphtha1enediamine, benzidine, 4,4'-bis(o-to1uidine),
5 dianisidine, 4,4'-diaminodiphenyl methane,
2,2-(4,4'-diaminodiphenyl)propane, 4,4'-diaminodiphenyl ether,
4,4'-thiodianiline, 4,4'-diaminodiphenyl sulfone,
4,4'-diaminotolylsulfone, methylene bis(o-chloroaniline),
3,9-bis(3-aminopropyl) 2,4,8,10-tetraoxaspiro[5,5)undecane,
10 diethylenetriamine, iminobispropylamine,
methyliminobispropy1amine, bis(hexamethylene)triamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, N-aminoethyl piperazine, N-aminopropyl
piperazine, 1,4-bis(aminoethylpiperazine),
15 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, and
bis(3,4-diaminophenyl)sulfone; secondary amines such as
diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine,
diisobuty1amine, di-n-pentylamine, di-3-pentylamine, dihexylamine,
octylamine, di(2-ethylhexyl)amine, methylhexylamine, diallylamine,
20 pyrro1idine, piperidine, 2-, 3-, 4-picoline, 2,4-, 2,6-,
3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline,
dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole,
indoline, indole, and morpholine; secondary polyamines such as
N,N'-dimethylethylenediamine, N,N'-dimethyl-1,2-diaminopropane,
25 N,N'-dimethyl-1,3-diaminopropane, N,N'-dimethyl-1,2-diaminobutane,
N,N'-dimethyl-1,3-diaminobutane, N,N'-dimethyl-1,4-diaminobutane,
N,N'-dimethyl-1,5-diaminopentane, N,N'-dimethyl-1,6-diaminohexane,
35
N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine,
N,N'-diethy1-1,2-diaminopropane, N,N'-diethyl-1,3-diaminopropane,
N,N'-diethyl-1,2-diaminobutane, N,N'-diethyl-1,3-diaminobutane,
N,N'-diethyl-1,4-diaminobutane, N,N'-diethyl-1,6-diaminohexane,
5 piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethy1piperazine,
homopiperazine, 1,1-di-(4-piperidyl)methane,
1,2-di-(4-piperidyl)ethane, 1,3-di-(4-piperidyl)propane,
1,4-di-(4-piperidyl)butane, and tetramethylguanidine; tertiary
amines such as trimethylamine, triethylamine, tri-n-propylamine,
10 tri-iso-propylamine, tri-1,2-dimethy1propylamine,
tri-3-methoxypropy1amine, tri-n-buty1amine, tri-iso-butylamine,
tri-sec-butylamine, tri-pentylamine, tri-3-pentylamine,
tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine,
tri-dodecylamine, tri-laurylamine, tri-cyclohexylamine,
15 N,N-dimethylhexylamine, N-methyldihexylamine,
N,N-dimethylcyclohexylamine, N-methyldicyclohexylamine,
triethanolamine, tribenzylamine, N,N-dimethylbenzylamine,
diethylbenzylamine, triphenylamine, N,N-dimethylamino-p-cresol,
N,N-dimethylaminomethyl phenol, 2-(N,N-dimethylaminomethyl)phenol,
20 N,N-dimethylaniline, N,N-diethylaniline, pyridine, quinoline,
N-methylmorpholine, N-methylpiperidine, and
2-(2-dimethylaminoethoxy)-4-methyl-1,3,2-dioxabornane; tertiary
polyamines such as tetramethylethylenediamine, pyrazine,
N,N'-dimethylpiperazine, N,N'-bis((2-hydroxy)propyl) piperazine,
25 hexamethylenetetramine, N,N,N',N'-tetramethyl-1,3-butanamine,
2-dimethylamino-2-hydroxypropane, diethylaminoethanol,
N,N,N-tris(3-dimethylaminopropyl)amine,
36
2,4,6-tris(N,N-dimethylaminomethyl)phenol, and heptamethyl
isobiguanide; various imidazoles such as; imidazole,
N-methylimidazole, 2-methylimidazole, 4-methylimidazole,
N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole,
5 N-butylimidazole, 2-butylimidazole, N-undecylimidazole,
2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole,
N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-methylimidazole,
N-(2'-cyanoethyl)-2-methylimidazole,
N-(2'-cyanoethyl)-2-undecylimidazole,
10 N-(2'-cyanoethyl)-2-phenylimidazole,
3,3-bis-(2-ethyl-4-methylimidazolyl)methane, an adduct of
alkylimidazole and isocyanuric acid, and a condensate of
alkylimidazole and formaldehyde; and amidines such as
1,8-diazabicyclo(5,4,0)undecene-7 and
15 1,5-diazabicyclo(4,3,0)nonene-5,6-dibutylamino-1,8-diazabicyclo(
5,4,0)undecene-7. These may be used alone or in combination of t1vo
or more types thereof.
[0077]
Examples of the quaternary ammonium salt include quaternary
20 ammonium salts formed between the above-described amines and a
halogen, a mineral acid, a Lewis acid, an organic acid, silicic acid,
or tetrafluoroboric acid. These may be used alone or in combination
of two or more types thereof.
25
[0078]
Examples of the complexes of amines 1·1ith borane and with boron
trifluoride include the above-described complexes of amines with
borane and 1vi th boron trifluoride.
37
[0079]
Examples of the phosphine-based compound can include
trimethylphosphine, triethylphosphine, triisopropylphosphine,
tri-n-propylphosphine, tri-tert-butylphosphine,
5 triisobutylphosphine, tri-n-butylphosphine,
tricyclohexylphosphine, triphenylphosphine,
methyldiphenylphosphine, dimethylphenylphosphine,
tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine,
diethylphenylphosphine, dichloro(ethyl)phosphine,
10 dichloro(phenyl)phosphine, and chlorodiphenylphosphine. These may
be used alone or in combination of two or more types thereof.
As the phosphine-based compound, dimethylphenylphosphine or
tributylphosphine is preferably used.
[0080]
15 (Other Components)
Other components can be added as long as the components do not
affect optical properties or photochromic performance.
Examples of the other components include ethylvinylbenzene;
styrene, methylstyrene, dimethylstyrene, ethylstyrene,
20 a-methylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, and
p-chloromethylstyrene; a-methylstyrene dimer; vinyl naphthalenes
such as 1-vinylnaphthalene and 2-vinylnaphthalene; aromatic
polymerizable monomers such as 4-vinylbiphenyl and
vinylphenylsulfide; acrylonitrile, methacrylonitrile, maleic
25 anhydride, and N-substitutedmaleimide; and allyl compounds such as
diethylene glycol bisallyl carbonate and diallyl phthalate.
The above other components can be used alone or in combination
38
of two or more types thereof.
[0081]
The polymerizable composition for optical materials of the
embodiment can includes a light stabilizer, an ultraviolet absorbent,
5 an antioxidant, a coloration inhibitor, a dye, or a resin modifier,
depending on the purpose. Regarding a mixing method of a light
stabilizer, an ultraviolet absorbent, an antioxidant, a coloration
inhibitor, a dye, or a resin modifier, since preparation orders vary
depending on the type and the amount used of the component used (the
10 polymerizable monomer (A), the polymerizable monomer (B), the
polythiol (C), or the photochromic compound (D)), the method cannot
be generally limited, and is suitably selected in consideration of
the solubility, operability, safety, convenience, and the like of
the additive.
15 [0082]
According to the polymerizable composition for optical
materials of the embodiment, it is possible to obtain an optical
material which is excellent in optical properties and also in light
adjusting characteristics. That is, according to the embodiment,
20 it is possible to obtain a photochromic optical material which is
excellent in balance therebetween.
[0083]
[Uses]
A molded product formed of the photochromic polymerizable
25 composition of the embodiment can be obtained in various shapes by
changing molds during cast polymerization. Since the molded product
has photochromic performance, a high refractive index, and high
39
transparency, the molded product can be used in various optical
materials such as a plastic lens. In particular, the molded product
is suitable as optical materials such as a plastic spectacle lens,
and optical elements.
5 [0084]
[Process for Producing Photochromic Optical Material]
The process for producing photochromic optical materials will
be described with reference to a first embodiment and a second
embodiment.
10 [0085]
(First Embodiment)
In the embodiment, the process for producing photochromic
optical materials has the following Steps (l) to (3).
Step (1): a step of obtaining a polymerizable composition for
15 photochromic optical materials by mixing the above components (A) to
(D)
Step (2): a step of casting the polymerizable composition into a mold
Step (3) : a step of polymerizing the composition by initiating
polymerization of the polymerizable composition
20 [0086]
Step (1)
In Step (1), it is possible to obtain a polymerizable composition
for photochromic optical materials by mixing the above components (A)
to (D) by a predetermined method. Examples of the catalyst include
25 a knmm radical polymerization initiator, amines, a quaternary
ammonium salt, complexes of amines \•lith borane and 1-1ith boron
trifluoride, and a phosphine-based compound, and these may be used.
40
As the catalyst, at least two types of the above catalysts may be
used in combination. In addition, the mixing order or the mixing
method of respective components in the composition is not
particularly limited as long as the respective components can be
5 homogeneously mixed by the mixing order or the mixing method, and
the mixing can be performed by a known method. Examples of the known
method include a method in which a master batch including a
predetermined amount of additives is prepared, and the master batch
is dispersed and dissolved in a solvent.
10
15
In addition, in Step (1), a light stabilizer, an ultraviolet
absorbent, an antioxidant, a coloration inhibitor, a dye, or a resin
modifier can be included depending on the purpose.
[0087]
Step (2)
First, the polymerizable composition is injected into a mold
held using a gasket, tape, or the like. At this time, there are many
cases in which a defoaming treatment, a filtration treatment such
as pressurization or depressurization, and the like under reduced
pressure are preferably carried out as necessary depending on
20 properties that obtained plastic lenses require.
[0088]
Step (3)
Since polymerization conditions significantly vary depending
on the composition ratio of the polymerizable composition, the types
25 and the amount used of the catalyst, the shape of the mold, and the
like, the polymerization conditions are not limited; however, the
polymerization is performed at a temperature of about -50°C to 150°C
41
over a period of 1 hour to 50 hours. Depending on cases, the
polymerizable composition is preferably held in a temperature range
of 10 °C to 150 °C or slowly heated, and cured for 1 hour to 25 hours.
The molded product obtained in the present invention may be
5 subjected to a treatment such as annealing, as necessary. The
treatment is performed typically at a temperature 1-1ithin a range of
50°C to 150°C, and preferably performed at a temperature within a
range of 90°C to 140°C, and more preferably performed at a temperature
within a range of 100°C to 130°C.
10 [0089]
(Second Embodiment)
A second embodiment has the following Steps (i) to (iii) .
Step (i): a prepolymer is obtained by reacting at least one
polymerizable monomer (A), at least one polymerizable monomer (B),
15 and at least one polythiol (C) .
Step (ii): a polymerizable composition is obtained by mixing the
prepolymer obtained in Step (i) and the photochromic compound (D) .
Step (iii): the polymerizable composition obtained in Step (ii) is
polymerized.
20 [0090]
25
Step (i)
In Step (i), a prepolymer is obtained by reacting the
polymerizable monomer (A), the polymerizable monomer (B), and the
polythiol (C) .
Moreover, in Step (i), the reaction between the polymerizable
monomer (A) and the polythiol (B) is preferably prioritized over the
reaction between the polymerizable monomers (A) .
5
10
15
42
Examples of the catalyst include a known· radical polymerization
initiator, amines, a quaternary ammonium salt, complexes of amines
with borane and 1vith boron trifluoride, and a phosphine-based
compound, and at least two types thereof may be used in combination.
In Step (i), since the reaction between "the polymerizable
monomer (A) and the polymerizable monomer (B)" and "the polythiol
(C)" is prioritized over the reaction between the polymerizable
monomers (A), as a preferably catalyst, a phosphine-based compound
is exemplified.
In Step (i), other components may be added as long as the
components do not affect handling of the prepolymer. Although the
reaction temperature is not particularly limited, the reaction is
preferably performed at room temperature (equal to or lower than
30°C) .
The prepolymer obtained in Step (i) can have a viscosity of equal
to or less than 1000 mPa ·s at 20°C. When the viscosity is 1vithin
the above range, handling of the prepolymer is easy, and there is
no difficulty in working at room temperature, and thus, it is
preferable.
20 [0091]
25
Step (ii)
In Step (ii), a polymerizable composition is obtained by mixing
the prepolymer obtained in Step (i) and the photochromic compound
(D) .
Specifically, it is possible to mix the prepolymer obtained in
Step (i), the photochromic compound (D), and a polymerization
catalyst.
43
As the polymerization catalyst used in Step (ii), the
above-described catalyst can be used. A catalyst which is less likely
to affect the photochromic compound used and can promote the reaction
between the polymerizable monomers (A) is preferable. Examples of
5 such a polymerization catalyst include an azo-based compound.
10
Although the mixing temperature in Step (ii) is not particularly
limited, the reaction is preferably performed at room temperature
(equal to or lower than 30"C) .
[0092]
In the embodiment, an additive such as a light stabilizer, an
ultraviolet absorbent, an antioxidant, a coloration inhibitor, a dye,
or a resin modifier can be included depending on the purpose.
Regarding an adding method of an additive, since preparation orders
vary depending on the component used (the polymerizable monomer (A),
15 the polymerizable monomer (B), the polythiol (C), or the photochromic
compound (D)), and the type and the amount used of the additive, the
method cannot be generally limited, and is suitably selected in
consideration of the solubility, operability, safety, convenience,
and the like of the additive. These additives can be added in Step
20 (i) or Step (ii), and can be added in any of Step (i) and Step (ii).
[0093]
Step (iii)
In Step (iii), the polymerizable composition obtained in Step
(ii) is polymerized. Specifically, the polymerizable composition
25 can be polymerized in the presence of a polymerization catalyst,
preferably, in the presence of an azo-based compound. Thereby, it
is possible to obtain a photochromic optical material.
44
Examples of the photochromic optical material can include a
photochromic lens, and specifically, the photochromic lens can be
obtained in the foll01ving manner.
[0094]
5 The polymerizable composition obtained in the embodiment is
injected into a mold held using a gasket, tape, or the like. At this
time, a defoaming treatment, a filtration treatment such as
pressurization or depressurization, and the like under reduced
pressure are preferably performed, as necessary, depending on
10 properties that the obtained molded product requires.
[0095]
Since the polymerization conditions of the polymerizable
composition significantly vary depending on the types and the amount
of the component used, the shape of the mold, and the like, the
15 polymerization conditions are not limited; however, polymerization
is performed at a temperature of about 0°C to 140°C over a period
of 1 hour to 48 hours.
[0096]
The molded product obtained in the above manner may be subjected
20 to a treatment such as annealing, as necessary. The treatment is
performed typically at a temperature within a range of 50°C to 150°C,
and preferably performed at a temperature lvithin a range of 90°C to
140°C, and more preferably performed at a temperature within a range
25 [0097]
Plastic lenses using the molded product of the embodiment may
be provided with a coating layer on a single surface or both surfaces
45
thereof as necessary, and then used. Examples of the coating layer
include a primer layer, a hard coating layer, an antireflection film
layer, an antifog coated film layer, an antifouling layer, and a
water-repellent layer. These coating layers may respectively be used
5 alone, or may be used after multilayering the plurality of coating
layers. In a case 1vhere the coating layers are provided on both
surfaces, similar coating layers may be provided on the respective
surfaces, or different coating layers may be provided.
10
[0098]
In the coating layers, an ultraviolet absorbent for the purpose
of protecting lenses or eyes from ultraviolet rays, infrared
absorbent for the purpose of protecting eyes from infrared rays, a
light stabilizer or an antioxidant for the purpose of improving
weather resistance of lenses, a stain or pigment, furthermore, a
15 photochromic stain or photochromic pigment for the purpose of
improving fashionability of lenses, an antistatic agent and other
lvell-known additives for enhancing performances of lenses may
respectively be jointly used. For layers coated by coating, a variety
of leveling agents may be used for the purpose of improving
20 coatability.
[0099]
The primer layer is generally formed bet1veen the hard coating
layer described below and an optical lens. The primer layer is a
coating layer having an object of improving adhesion between the hard
25 coating layer formed on the primer layer and the lens, and, depending
on cases, it is also possible to improve impact resistance. Any
material can be used for the primer layer as long as it has high
46
adhesion to an obtained optical lens. In general, a primer
composition mainly including a urethane-based resin, an epoxy-based
resin, a polyester-based resin, a melanin-based resin, polyvinyl
acetal, or the like is used. For the primer composition, a suitable
5 solvent having no influence on lenses may be used for the purpose
of adjusting a viscosity of the composition. It is needless to say
that the primer composition may be used without a solvent.
[0100]
The primer composition can be formed using any one of a coating
10 method and a dry method. In a case in which the coating method is
used, the primer layer is formed by applying the composition on a
lens using a well-known coating method, such as spin coating or dip
coating, and then solidifying the composition. In a case ~1here the
dry method is performed, the primer layer is formed by a 1-1ell-kn01m
15 dry method such as a CVD method or a vacuum deposition method. When
the primer layer is formed, a pretreatment such as an alkali treatment,
a plasma treatment, or an ultraviolet treatment may be performed on
surfaces of a lens as necessary for the purpose of improving adhesion.
The hard coating layer is a coating layer for the purpose of
20 supplying functions of abrasion resistance, wear resistance,
moisture resistance, Harm water. resistance, thermal resistance,
weather resistance, and the like to the surfaces of a lens.
[0101]
As the hard coating layer, a hard coating composition including
25 one or more types of fine particles formed of a curable organic silicon
compound and fine particles of one or more oxides of elements selected
from an element group of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr,
47
In, and Ti and/or a composite oxide of two or more elements selected
from the above element groups is generally used.
[0102]
The hard coating composition preferably includes at least any
5 one of amines, amino acids, metal acetylacetonate complexes, organic
acid metallic salts, perchloric acids, salts of perchloric acids,
acids, metallic chlorides, and polyfunctional epoxy compounds, in
addition to the above-described components. For the hard coating
composition, a suitable solvent having no influence on lenses may
10 be used. It is needless to say that the primer composition may be
used without a solvent.
[0103]
The hard coating layer is generally formed by coating 1vith the
hard coating composition by a ~Yell-known coating method such as a
15 spin coating or a dip coating, and then curing the composition.

CLAIMS
1. A polymerizable composition for photochromic optical materials,
comprising:
a polymerizable monomer (A) having two or more ethylene-based
unsaturated groups;
an ethylene-based unsaturated polymerizable monomer (B) having
one (meth)acrylic group and an aromatic ring;
a polythiol (C) having three or more mercapto groups; and
a photochromic compound (D),
wherein the molar number of the mercapto groups included in the
polythiol (C) having three or more mercapto groups is not more than
0. 3 times with respect to the total molar number of the ethylene-based
unsaturated groups included in the polymerizable monomer (A) having
15 two or more ethylene-based unsaturated groups and the ethylene-based
unsaturated polymerizanle monomer (B) having one (meth) acrylic group
and an aromatic ring.
2. The polymerizable composition for photochromic optical materials
20 according to Claim 1 1
wherein the polythiol (C) is at least one selected from the group
consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4, 8-, 4, 7-, or
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
25 pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), and
1,1,3,3-tetrakis(mercaptomethylthio)propane.
69
3. The polymerizable composition for photochromic optical materials
according to Claim 1 or 2,
wherein the polymerizab1e monomer (A) includes an
5 ethylene-based unsaturated polymerizable monomer (a1) having two or
more vinyl groups or isopropenyl groups and an ethylene-based
unsaturated polymerizable monomer (a2) having two or more
(meth)acrylic groups.
10 4. The polymerizable composition for photochromic optical materials
according to Claim 3,
\vherein the polymerizable monomer (a1) is at least one selected
from divinylbenzene, diisopropenylbenzene, trivinylbenzene, and
divinylnaphthalene.
15
5. The polymerizable composition for photochromic optical materials
according to Claim 3 or 4,
wherein the polymerizable monomer (a2) is at least one selected
from polymerizable monomers represented by the following General
20 Formula (4);
wherein, in Formula ( 4), each of m and n is 0 or greater number,
and m and n satisfy m + n = 0 to 50; X1 is a hydrogen atom or a methyl
25. group, and a plurality of X1 may be the same as or different from
,!;,!
70
each other; X2 is a hydrogen atom or an alkyl group having 1 or 2
carbon atoms, and a plurality of X2 may be the same as or different
from each other.
5 6. The polymerizable composition for photochromic optical materials
according to any one of Claims 1 to 5,
wherein the polymerizable monomer {B) is at least one selected
from aromatic {meth) acrylic acid esters represented by the follmving
General Formula {5);
10
O X'
CH -0-C-t=CH
2 II 2
0 (5)
wherein, in Formula {5), X3 is a hydrogen atom or a methyl group.
7. A process for producing photochromic optical materials,
15 comprising:
a step of obtaining the polymerizable composition according to
any of Claims 1 to 6;
a step of casting the polymerizable composition into a mold;
and
20 a step of polymerizing the composition.
8. A molded product obtained by polymerization of the polymerizable
composition for optical materials according to any one of Claims 1
to 6.
71
9. A photochromic optical material comprised of the molded product
according to Claim 8.
5 10. A plastic lens comprised of the photochromic optical material
according to Claim 9.