SPECIFICATION .
PROCESS FOR PRODUCING PHOTOCHROMIC OPTICAL MATERIAL
5
TECHNICAL FIELD
[0001)
The present invention relates to a process for producing a
photochromic optical material and an optical material obtained using
10 the same.
BACKGROUND ART
[0002)
Since plastic lenses are light, not easily cracked, and can be
stained in comparison to inorganic lenses, plastic lenses have been
15 rapidly distributed as optical elements such as spectacle lenses and
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
20 from (meth)acrylate, and a polythiourethane resin obtained from
isocyanate and thiol.
[0003)
In recent years, plastic photochromic lenses through
application of organic photochromic dyes are commercially available
25 as glasses. As the process for producing photochromic lenses, a
method in which a photochromic compound is dissolved in a monomer
mixed liquid for lens in advance, the resultant product is injected
2
into a mold, and polymerized, as a result, a photochromic lens is
obtained is exemplified.
[0004]
Patent Document 1 describes that by combining a specific
5 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
Eli-(-metch-)-ae-r-yl-crtce-eemJ30Hn<:h--:JCn-]3ara~FaJ3h-[-G{)G-9-h-:ict-iB-Elese-r-'iceeEl-tch-a-E'-----
10 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.
15
[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.
Patent Document 4 discloses a photochromic lens having a lens
20 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
characteristics.
25 [0006]
Patent Document 6 describes a method of producing a photochromic
optical material by curing a monomer composition including a
3
photochromic compound, a polythiol, and a polyisocyanate.
Patent Document 7 discloses an"optical resin composition
containing a thiol-ene prepolymer.
RELATED DOCUMENT
5 PATENT DOCUMENT
[0007]
[Patent Document 1] PCT Japanese Translation Patent
Publication No. 11-511765
--------[-f'atoent-Eleeumen~-----Jaj'>anese--&fte*am-i-ned-P-aeene-Puhl-i-eat--:icen--No'-c.----
10 8-272036
15
[Patent Document 3] Japanese Unexamined Patent Publication No.
2005-23238
[Patent Document 4] Japanese Unexamined Patent Publication No.
2008-30439
[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
20 Publication No. 2004-511578
SUMMARY OF THE INVENTION
[0008]
The techniques described in the above-described Patent
25 Documents have points to be improved in the following respects.
As the methods disclosed in Patent Documents 1, 2, and 6, a method
of dissolving a photochromic compound in a composition liquid in
4
advance is preferable as a process in which the number of step in
the production is small since light adjusting performance is imparted
with molding at the same time, and is extremely useful as a method
of mass-producing a molded product with stable quality since the
5 photochromic compound can be easily homogeneously dispersed into a
substrate. However, the lens obtained in Patent Document 1 or 2 has
a refractive index of about 1.55 to 1.57, and thus, the lens needs
to be improved in the refractive index. In addition, the lens
described in Patent Document 6 needs to be improved in light adjusting
10 characteristics.
15
The process described in Patent Document 7 is a method in which
prepolymerization is performed when a lens substrate is produced.
The lens needs to be improved in the refractive index, and the balance
between light adjusting characteristics and optical properties.
In addition, in the photochromic optical material obtained in
the techniques described above, the desired photochromic performance
could not be exhibited in some cases, and the inventors have performed
thorough studies on an industrial process in order to provide a
photochromic optical material which has a high refractive index and
20 is excellent in light adjusting characteristics.
[0009]
As a result of thorough studies in order to solve the above
problems, the present inventors found that a process in which a
prepolymer is obtained using a polymerizable monomer (A) having two
25 or more ethylene-based unsaturated groups and a polythiol (B) having
t1vo or more mercapto groups, and then, using a polymerizable
composition obtained by mixing the prepolymer and a photochromic
5
5
compound can obtain an optical material which has stable photochromic
performance and is excellent in optical properties is produced, and
completed the present invention.
[0010]
That is, the invention is as follows.
[1] The process for producing photochromic optical materials,
including a step (i) of reacting at least one polymerizable monomer
(A) having two or more ethylene-based unsaturated groups with at least
- -- - ---OnB -poJ.-ytch±oJ.--(-B-)-ha-v-i-n<:~-t-we-er-me-re-me£ea]3t0-EJ-l"0U]3S--ico-ohic-a±n-a------
10 prepolymer;
a step (ii) of mixing the prepolymer and a photochromic compound
(C) to obtain a polymerizable composition; and
a step (iii) of polymerizing the polymerizable composition,
wherein, before the reaction of the step (i), the molar number of
15 the mercapto groups included in the polythiol (B) is smaller than
the molar number of the ethylene-based unsaturated groups included
in the polymerizable monomer (A) .
[2] The process for producing photochromic optical materials
according to [ 1] , in which, before the reaction of the step ( i) , the
20 molar number of the mercapto groups included in the polythiol (B)
is equal to or less than 0.3 times with respect to the molar number
of the entirety of ethylene-based unsaturated groups included in the
polymerizable monomer (A).
[3] The process for producing photochromic optical materials
25 according to [1] or [2], in which the polymerizable monomer (A)
includes at least one ethylene-based unsaturated polymerizable
monomer (al) having two or more vinyl groups or isopropenyl groups
6
and/or at least one ethylene-based unsaturated polymerizable monomer
(a2) having two or more (meth)acrylic groups.
[4) The process for producing photochromic optical materials
according to any one of [1) to [3), in which, in the step (i) or (ii),
5 an ethylene-based unsaturated polymerizable monomer having one
(meth)acrylic group is included.
[5] The process for producing photochromic optical materials
according to any one of [1) to [4), in which, in the step (i), the
-pelymer-i-zable- merwmer--(-A-)-reaetcs witch -the po±yth±ol--(-B)-in the- - ---- -
10 presence of a phosphine-based compound.
[6) The process for producing photochromic optical materials
according to any one of [1) to [5), in which the step (ii) is a step
of mixing the prepolymer, the photochromic compound (C), and an
azo-based compound.
15 [7) The process for producing photochromic optical materials
according to [6], in which the step (iii) is a step of polymerizing
the polymerizable composition in the presence of an azo-based
compound.
[8) The process for producing photochromic optical materials
20 according to [ 3), in which the polymerizable monomer (a1) is at least
one selected from divinylbenzene, diisopropenylbenzene,
trivinylbenzene, and divinylnaphthalene.
[9) The process for producing photochromic optical materials
according to [3), in which the polymerizable monomer (a2) is at least
25 one selected from polymerizable monomers represented by the following
general formula (4);
7
X1 X2
· CH X' ,
H,c=Ic -c-foHcI -cH,J:oO \ 1 'Dy , -;. ofcH;-CIH oj-R-c~= cH,
~ m \\ II CH, \\ II n o (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
group, and a plurality of X1 may be the same as or different from
5 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 eacn-6fi1er: - - ----- - -- - --- - - ----- -- - ------
[10] The process for producing photochromic optical materials
according to [4], in which the ethylene-based unsaturated
10 polymerizable monomer (D) is at least one selected f.rom aromatic
(meth)acrylic acid esters represented by the following general
formula (5);
O X'
CH -0-C-t=CH .
' II ' 0 (5)
15 wherein, in formula ( 5) , X3 is a hydrogen atom or a methyl group.
[11] The process for producing photochromic optical materials
according to any one of [1] to [10], in which the polythiol (B) is
at least one selected from the group consisting of
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7-, or
20 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate),
8
2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl)sulfide,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.
5 [12] The process for producing photochromic optical materials
according to any one of [1] to [11], in which the photochromic compound
(C) is represented by the following general formula (7) or (8);
- -- - ----- ------ .R.j -- _R2---- ---------
10
15
(7)
(8)
wherein, in formulas (7) and (8),
R1 and Rz 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 1 to 12 carbon atoms;
5
9
a cycloalkyl group having 3 to 12 carbon atoms;
a substituted or unsubstituted aryl group having 6 to 24 carbon
atoms or a substituted or unsubstituted heteroaryl group having 4
to 24 carbon atoms,
wherein the substituted aryl group or the substituted
heteroaryl group, as a substituent, 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
-- ---- --g-reu]"l -hav±ncy-1----Ee-1-2 --ea-rben-aicems,----a-l±ne-a-r- =-b-r-anehed-htd:eCI-1-ky±-----
10 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 which is substituted with at least one halogen atom,
a phenoxy group or a naphthoxy group which is substituted with at
least one linear or branched alkyl group or alkoxy group having 1
15 to 12 carbon atoms, a linear or branched alkenyl group having 2 to
12 carbon atoms, an -NH2 group, an -NHR group, a-N (R) 2 group, wherein
R is a linear or branched alkyl group having 1 to 6 carbon atoms,
and in a case where two Rs are present, the two Rs may be the same
as or different from each other,
20 a methacryloyl group, and an acryloyl group; or
an aralkyl or heteroaralkyl group which is formed by
substituting a linear or branched alkyl group having 1 to 4 carbon
atoms with an aryl group or a heteroaryl group,
R3s may be the same as or different from each other, and each R3s
25 independently represents
a halogen atom;
a linear or branched alkyl group having 1 to 12 carbon atoms;
10
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 12 carbon atoms
which is substituted with at least one halogen atom, a linear or
5 branched halocycloalkyl group having 3 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 which is substituted
with at least one halogen atom;
- - -- - -- - -ana-ryl-group-ha-v-ing-6--t'o-2-4-e-a-rloon-a-tcoms--or- a-hetcero-ar-y-1--gEoup - - - ---
10 having 4 to 24 carbon atoms which is substituted or unsubstituted,
wherein the substituted aryl group or the substituted
heteroaryl group 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
15 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
which is substituted with at least one halogen atom, a phenoxy group
or a naphthoxy group which is substituted with at least one linear
20 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 amino group as a substituent;
an aralkyl or heteroaralkyl group which is formed by
substituting a linear or branched alkyl group having 1 to 4 carbon
25 atoms with the aryl group or the heteroaryl group;
a substituted or unsubstituted phenoxy or naphthoxy group,
wherein the substituted phenoxy or the substituted naphthoxy group
11
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, wherein R is a linear or branched
alkyl group having 1 to 6 carbon atoms; or
5 -OCOR8 or -COOR8 , wherein R8 is a linear or branched alkyl group
having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon
atoms, or a phenyl group which is substituted with at least one
substituent of a substituted aryl group or a substituted heteroaryl
--- - -g-FOI±J3 -in-R-r anEl-R-2 -er-an-unsubst-it-uted-phenyl-g-roup,-- and------- ---
10 one or more aromatic ring groups or non-aromatic ring groups
are formed by bonding of at least two adjacent R3s to each other and
by including the carbon atom to which R3 is bonded, wherein the aromatic
ring group or non-aromatic ring group includes one ring or two
annelated rings which may include a heteroatom selected from the group
15 consisting of oxygen, sulfur, and nitrogen;
1 is an integer 0 to 2; and
m is an integer 0 to 4.
[13] The process for producing photochromic optical materials
according to [12], in which the photochromic compound (C) is
20 represented by the following general formula (9)
(9)
12
wherein, in formula (9), each of R1 , R2 , and R3 has the same meaning
as that in formula (7);
A represents an annelated ring represented by the above formula (A2 )
5
wherein, in these annelated rings, a dotted line represents a
C5-C6 bond of the naphthopyran ring in general formula (9);
an a bond of an annelated ring (A4 ) can be normally bonded to the
10 C5 or C6 of the naphthopyran ring in general formula (9);
R4's are 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
group (CO);
15 R5 represents a 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 which
is substituted with at least one halogen atom;
a cycloalkyl group having 3 to 12 carbon atoms;
20 a linear or branched alkoxy group having 1 to 6 carbon atoms;
a substituted or unsubstituted phenyl or benzyl group, wherein the
substituted phenyl or the substituted benzyl group has at least one
of substituents described above in the definition of R1 and R2 groups
13
as a substituent in a case where each of R1 and R2 groups in general
formula (9) independently corresponds to an aryl or heteroaryl group;
-NH2 or -NHR, wherein R is a linear or branched alkyl group having
1 to 6 carbon atoms;
5 a substituted or unsubstituted phenoxy or naphthoxy group, wherein
the substituted phenoxy or the substituted naphthoxy group has at
least a linear or branched alkyl group or alkoxy group having 1 to
6 carbon atoms as a substituent; or
- - --- -a--GE1R.,,----G00R9,-- e-r--G0NHR,--greu!",-- whecre±n-R,-re}'Tresen~tcs-a-l+nea~r-e-r -~---~
10 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 , wherein the substituted phenyl or the substituted
benzyl group has at least one of substituents described above in the
definition of R1 and R2 groups as a substituent in a case where each
15 of R1 and R2 groups in general formula (9) independently corresponds
to an aryl or heteroaryl group; and
in a case where A represents (A4), n is an integer of 0 to 2, pis
an integer of 0 to 4, and in a case where A represents (A2), n is
an integer of 0 to 20
20 [14] A photochromic optical material obtained by the process
according to any one of [1] to [13] 0
[ 15] A plastic lens formed of the optical material according to [ 14] 0
[0011]
According to the process for producing photochromic optical
25 materials of the present invention, it is possible to industrially
stably obtain a photochromic optical material which has a high
refractive index and is excellent in light adjusting characteristics,
14
from a polymerizable composition including at least one polymerizable
monomer (A) having two or more ethylene-based unsaturated groups,
at least one polythiol (B) having two or more mercapto groups, and
a photochromic compound (C). AS the result, the process of the
5 present invention can improve production stability of photochromic
optical materials. In particular, in the production step, by
obtaining a polymerizable composition by performing a
prepolymerization step under specific conditions and by mixing the
- -------prepe-1-ymer---anct-a-plwt-eeh-r-em±e--eempcn:uld, it 'ics-po:5s-:i:b-l-e-te----------
10 industrially produce a photochromic optical material which has a high
refractive index and is excellent in light adjusting characteristics.
15
DESCRIPTION OF EMBODIMENTS
[0012)
Hereinafter, the present invention will be described with
reference to embodiments.
The process for producing photochromic optical materials of the
embodiment has the following Steps (i) to (iii).
Step (i): a prepolymer is obtained by reacting at least one
20 polymerizable monomer (A) having two or more ethylene-based
unsaturated groups (hereinafter, simply referred to as
"polymerizable monomer (A)") with at least one polythiol (B) having
two or more mercapto groups (hereinafter, simply referred to as
"polythiol (B)").
25 Step (ii) : a polymerizable composition is obtained by mixing the
prepolymer obtained in Step (i) and the photochromic compound (C).
Step (iii) : the polymerizable composition obtained in Step (ii) is
polymerized.
[0013)

15
In Step (i), a prepolymer is obtained by reacting the
5 polymerizable monomer (A) with the polythiol (B).
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) from the viewpoint
- - --~~-~-e£-e-xhJcbi-t-:icnEJ-{7hetceeh-rem-i-e-f7erl-e>Lmo.nce--o~f- the-obtai-rTed--mo-1--de-cr-----
10 product.
15
Each component used in the present invention will be described
below.
[0014)
[Polymerizable Monomer (A))
The polymerizable monomer (A) may have 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 (al) having two or
more vinyl groups or isopropenyl groups (hereinafter, simply referred
20 to as "polymerizable monomer (al)") and/or at least one
ethylene-based unsaturated polymerizable monomer (a2) having two or
more (meth)acrylic group (hereinafter, simply referred to as
"polymerizable monomer (a2)").
In the embodiment, the ethylene-based unsaturated polymerizable
25 monomer having two or more (meth)acrylic group is not included in
the ethylene-based unsaturated polymerizable monomer having two or
more vinyl groups or isopropenyl groups.
16
[0015]
Examples of the polymerizable monomer (a1) include divinylbenzene,
diisopropenylbenzene, trivinylbenzene,divinylnaphthalene,
trivinylnaphthalene, divinylbiphenyl,trivinylbiphenyl,
5 divinyldimethylbenzene, and trivinyldiethylnaphthalene, and the
like. These can be used alone or in combination of two or more kinds
thereof.
In the embodiment, the polymerizable monomer (a1) is preferably
- -a-t- Jcga-S-\;-Gn@-Se-lect;eEI-f-:cem- Eliv-inylcbenzene-,-di-iso]:7r0]:7eny-ll3en-zene-,--- -
10 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 ethylvinylbenzene.
[0016]
15 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
the following general formula (1).
20 [0017]
[0018]
In formula (1), each of m and n is 0 or greater number, and m
25 and n satisfy m + n = 0 to 50. m and n preferably satisfy m + n =
17
2 to 30, 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
5 of X2 may be the same as or different from each other.
A is selected from a linear or branched alkylene group having
1 to 10 carbon atoms, a cyclic alkylene group, a phenylene group,
an alkyl-substituted phenylene group having 1 to 9 carbon atoms, or
-- -----t-he-EJ-I'0H!3-Eer:>Ee-sent-eEi-0y-t-he-:l'el-l-Bw-i-ng-EJener-a-l-:l'e-rmu±-a-(-2-)-C>-r-(-3-)--:.----
10 [0019]
*---< y >--*
(2)
[0020]
In formula (2), each of Q1 and Q2 is an alkyl group having a 1 to 4
15 carbon atoms, chlorine, or bromine. A plurality of Q1 may be the same
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
of 0 to 4. Y is an oxygen atom, a sulfur atom, -CH2-, or -C(CH3 ) 2-.
"*" represents a bonding hand.
20 [ 0021]
18
*--{ z >----*
(3)
[0022)
In formula (3), each of Q3 and Q4 is an alkyl group having a 1
to 4 carbon atoms, chlorine, or bromine. A plurality of Q3 may be
5 the same as or different from each other, and a plurality of Q4 may
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 )-. "*" representsabonding
hand.
10 [0023)
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, and the like.
15 [0024)
As the polymerizable monomer (a2), at least one selected from
compounds represented by the following general formula (4) can be
preferably used.
[0025)
20
19
[0026] .
Each of X1
, X2
, m, and n in formula ( 4) has the same meaning as
that in general formula (1). Examples of the polymerizable monomer
represented by general formula (4) include
5 2,2'-bis(4-(methacryloyloxyethoxy)phenyl)propane, and the like.
As the polymerizable monomer (A), the polymerizable monomer (a1)
and the polymerizable monomer (a2) are preferably used in combination
with each other from the viewpoint of operability and a refractive
------i-nEle~-,--aREl--icn-t-R-i-s-ea-sBy---ERe-wci(j'fl-t-FaE-iB-ee'Eweefl-t'-fie--pecl-ymer-iL-ab-lce----
10 monomer (a1) and the polymerizable monomer (a2) is 1:1, preferably
0.9:1, and particularly preferably 0.7:1.
[0027]
In the embodiment, it is possible to use an ethylene-based
unsaturated polymerizable monomer (D) having one (meth) acrylic group
15 (hereinafter, referred to as "polymerizable monomer (D)") together
with the polymerizable monomer (A) .
Examples of the polymerizable monomer (D) can include
monofunctional (meth)acrylic acid esters such as methyl
(meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate,
20 ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, isobornyl
(meth)acrylate, and adamantyl (meth)acrylate; naphthyl
(meth)acrylates such as a-naphthyl (meth)acrylate and ~-naphthyl
(meth)acrylate; aromatic (meth)acrylic acid esters such as
25 phenoxyethyl (meth)acrylate; and the compound represented by the
following general formula (5).
[0028]
20
O X'
CH -0-C-t=CH 2 II ,
0 (5)
[0029]
In general formula (5), X3 is a hydrogen atom or a methyl group.
5 In the embodiment, as the polymerizable monomer (D), at least
one selected from compounds represented by the following general
formula (5) can be preferably used, and specific examples thereof
include benzyl methacrylate and benzyl acrylate.
[0030]
10 In the case of including the polymerizable monomer (D), the
polymerizable monomer (D) is equal to or greater than 1% by weight,
and preferably equal to or greater than 3% by weight, and 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
15 the polymerizable monomer (A), the polymerizable monomer (D), and
the polythiol (B) described below. The upper limit and the lower
limit can be suitably combined.
When the amount of the polymerizable monomer (D) is within the
above range, it is possible to obtain a molded product which is
20 excellent in optical properties or strength of the molded product,
and light adjusting performance.
The polymerizable monomer (D) can be added in any step of Step
(i) and Step (ii).
[0031]
21
[Polythiol (B)]
The polythiol (B) is not particularly limited as long as it is
a compound having two or more mercapto groups. Examples of the
polythiol compound include a polythiol compound having a hydroxy
5 group. These can be used in suitable combination.
[0032]
Examples of the polythiol compound include aliphatic polythiol
compounds such as methanedithiol, 1,2-ethanedithiol,
----1,2-,-;:l-j3-F0panet-r-:bt-hiol-,---1,~-eye-l-BfiE*afieEl#h±e±c-.,-----
10 bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl) methane,
diethylene glycol bis(2-mercaptoacetate), diethylene glycol
bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate),
ethylene glycol bis(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), trimethylolpropane
15 tris(3-mercaptopropionate), trimethylolethane
tris(2-mercaptoacetate), trimethylolethane
tris(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), pentaerythritol
20 tris(3-mercaptopropionate), pentaerythritol tris(thioglycolate),
bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide,
bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide,
bis(mercaptopropyl) sulfide, bis(mercaptomethylthio) methane,
bis(2-mercaptoethylthio) methane, bis(3-mercaptopropylthio)
25 methane, 1,2-bis(mercaptomethylthio) ethane,
1,2-bis(2-mercaptoethylthio) ethane,
1,2-bis(3-mercaptopropylthio) ethane,
22
1,2,3-tris(mercaptomethylthio) propane,
1,2,3-tris(2-mercaptoethylthio) propane,
1,2,3-tris(3-mercaptopropylthio)
propane,4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5 5,7-mercaptomethyl-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(mercaptomethy1thiomethyl) methane,
-----'t-st--:~;e-k-i-S--(-2 -m&r-Gapt-ee-t-ll-y-1-t-h-iemeffiy-l-)-met-h-ane-, -------------------
10 tetrakis(3-mercaptopropylthiomethy1) methane,
bis(2,3-dimercaptopropyl) sulfide,
2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane,
2,5-dimercaptomethyl-2,5-dimethy1-1,4-dithiane, and esters of
these thioglycolic acid and mercaptopropionic acid, hydroxymethyl
15 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
20 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
25 bis(2-mercaptoethylester), thiodipropionic acid
bis(2-mercaptoethylester), dithiodiglycolic acid
bis(2-mercaptoethyl ester), dithiodipropionic acid
23
bis(2-mercaptoethylester), 1,1,3,3-tetrakis(mercaptomethylthio)
propane, 1,1,2,2-tetrakis(mercaptomethy1thio) ethane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
tris(mercaptomethylthio) methane, and tris(mercaptoethylthio)
5 methane; aromatic polythiol compounds such as 1, 2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene,
1,2-bis(mercaptomethyl) benzene, 1,3-bis(mercaptomethyl) benzene,
1,4-bis(mercaptomethyl) benzene, 1,2-bis(mercaptoethyl) benzene,
- - -----1-,-3~f>i-s-(me-reaptoeeEhy-l-}- l:lencene-, -11 4-bi-s-(-mer-eaptcoethyl-)- -benzene-,------
10 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl) benzene,
1,3,5-tris(mercaptomethyleneoxy) benzene,
1,3,5-tris(mercaptoethyleneoxy) benzene, 2,5-toluenedithiol,
3,4-toluenedithiol, 1,5-naphthalenedithiol, and
2,6-naphthalenedithiol; heterocyclic polythiol compounds such as
15 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophene dithiol,
bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-{2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane; and the
compounds represented by the following general formula (6), and the
present invention is not limited to the exemplified compounds.
20 [0033]
(6)
[0034]
In the formula, each of a and b independently represents an
24
integer of 1 to 4, and c represents an integer of 1 to 3. W is a
hydrogen atom or a methyl group, and in a case where a plurality of
Ware present, W's may be the same as or different from each other.
[0035]
5 Examples of the polythiol compound having a hydroxy group can
include glycerine bis(mercaptoacetate) and
2, 3-dimercapto-1-propanol, and the present invention is not limited
to the exemplified compounds.
[0036]
10 Furthermore, oligomers of these active hydrogen compounds or
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 types thereof.
[0037]
15 As the polythiol (B), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), bis(mercaptoethyl)sulfide,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
20 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
2,5-bis(mercaptomethyl)-1,4-dithiane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
25 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane are
preferably used, and pentaerythritol
tetrakis(3-mercaptopropionate),
25
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
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane are
5 particularly preferably used.
10
(0038]
(Catalyst]
In Step (i), a reaction is preferably performed in the presence
of a catalyst.
Examples of such a catalyst include a radical polymerization
initiator, amines, a quaternary ammonium salt, complexes of amines
with borane and with boron trifluoride, and a phosphine-based
compound, and at least two types thereof can also be used in
combination.
15 [0039]
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
20 neodecanoate, diisopropyl peroxy dicarbonate, diallyl peroxy
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,
25 di(3-methyl-3-methoxybutol)peroxy dicarbonate, tert-butyl peroxy
neodecanoate, tert-hexyl peroxy neohexanoate, tert-butyl peroxy
neohexanoate, 2,4-dichlorobenzoyl peroxide, tert-hexyl peroxy
26
pivalate, tert-butyl peroxypivalate, 3,5,5-trimethyl hexanoyl
peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide,
tert-butyl peroxy(2-ethylhexanoate), m-toluoyl peroxide, benzoyl
5 peroxide, tert-butyl peroxy isobutyrate,
1,1-bis(tetr-butylperoxy)-3,3,5-trimethyl cyclohexane,
1,1-bis(tetr-butylperoxy)cyclohexane, tert-butyl peroxy maleic
acid, tert-butyl peroxyl laurate, tert-butyl peroxy-3, 5, 5-trimethyl
----hcie-xaBBa~e-,--eye-l-Bfle~-aR0Re--J3e-r-ex4Ele,--t-e-Fto-l3H~E-yl-j'le-r-eK~-aC!.-±y-l-ea~rl>on-a-E-e-.,----
10 tert-butyl peroxy isopropyl carbonate,
2,5-dimethyl-2,5-di(benzoylperoxy)hexane,
2,2-bis(tetr-butylperoxy)octane, tert-butyl peroxy acetate,
2,2-bis(tetr-butylperoxy)butane, tert-butyl peroxy benzoate,
n-butyl-4,4-bis(tetr-butylperoxy)valerate, di-tetr-butyl peroxy
15 isophthalate, methyl ethyl ketone peroxide, dicumyl peroxide,
2,5-dimethyl-2,5-di(tetr-butylperoxy)hexane, a,a'-bis(tetr-butyl
peroxy-m-isopropyl)benzene, tert-butyl cumyl peroxide,
di-tetr-butyl peroxide, and
2,5-dimethyl-2,5-di(tert-butylperoxy)3-hexyne; hydroperoxides
20 such as diisopropylbenzene hydroperoxide, p-menthane hydroperoxide,
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
25 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis(2-cyclopropylpropionitrile),
2,2'-azobis(2,4-dimethylvaleronitrile ),
27
2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile),
1,1'-azobis(cyclohexane-1-carbonitrile), azobiscyclohexane
carbonitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, and
2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, and dimethyl
5 azobisisobutyrate, carbonyl compounds such as benzoin, benzoin
monomethyl ether, benzoin isopropyl ether, acetoin, benzil,
benzophenone, p-methoxybenzophenone, diethoxyacetophenone,
2-hydroxy-4-methoxy benzophenone, benzil dimethyl ketal,
- - --~~--El±e4cllB-X'}'--aeeice]3hefi0ne-,-- -1--hyclrexyeye-le-hexy-l-phen-y-l-k-eeene-,--------
10 methylphenyl glyoxylate, ethylphenyl glyoxylate, and
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
15 phosphine oxide.
[0040]
Examples of the amines include amine compounds represented by
primary amines such as ethylamine, n-propylamine, sec-propylamine,
n-butylamine, sec-butylamine, i-butylamine, t-butylamine,
20 pentylamine, hexylamine, heptylamine, octylamine, decylamine,
laurylamine, myristyl amine, 1, 2-dimethylhexylamine, 3-pentylamine,
2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol,
2-aminopropanol, aminobutanol, aminopentanol, aminohexanol,
3-ethoxypropylamine, 3-propoxypropylamine,
25 3-isopropoxypropylamine, 3-butoxypropylamine,
3-isobutoxypropylamine, 3-(2-ethylhexyloxy)propylamine,
aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethyl
28
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,
5 1,4-diaminobutane, 1,5-aminopentane, 1,6-diaminohexane,
1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine,
diethy1aminopropylamine, bis-(3-aminopropyl)ether,
1,2-bis-(3-aminopropoxy)ethane,
---------1-,-3=bi..s~(-3=am-i-=p.ropox.y-f-=2-,2.-'=cJim@.l;h.y-1.p=pan€>-,-ami-nG€>-t-h.y-1~--
10. ethanolamine, 1,2-, 1,3-, or 1,4-bis aminocyclohexane, 1,3- or
1,4-bisaminomethyl cyclohexane, 1,3- or 1,4-bis aminoethyl
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,
15 N-aminoethyl piperidine, N-aminopropyl piperidine, N-aminoethyl
morpholine, N-aminopropyl morpholine, isophoronediamine,
menthanediamine, 1,4-bisaminopropyl piperazine, o-, m-, or
p-phenylenediamine, 2,4- or 2,6-tolylenediamine,
2,4-toluenediamine, m-aminobenzylamine,
20 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine,
4-methoxy-6-methyl-m-phenylenediamine, m- or p-xylylenediamine,
1,5- or 2,6-naphthalenediamine, benzidine, 4,4'-bis(o-toluidine),
dianisidine, 4,4'-diaminodiphenyl methane,
2,2-(4,4'-diaminodiphenyl)propane, 4,4'-diaminodiphenyl ether,
25 4,4'-thiodianiline, 4,4'-diaminodiphenyl sulfone,
4,4'-diaminoditolylsulfone, methylene bis(o-chloroaniline),
3,9-bis(3-aminopropyl) 2,4,8,10-tetraoxaspiro[5,5]undecane,
29
diethylenetriamine, iminobispropylamine,
methyliminobispropylamine, bis(hexamethylene)triamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, N-aminoethyl piperazine, N-aminopropyl
5 piperazine, 1,4-bis(aminoethylpiperazine),
1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, and
ii3\3~Iaffilnophenyl)sulfone; secondary amines such as
diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine,
diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine,
10 octylamine, di(2-ethylhexyl)amine, methylhexylamine, diallylamine,
pyrrolidine, 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
15 N,N'-dimethylethylenediamine, N,N'-dimethyl-1,2-diaminopropane,
N,N'-dimethyl-1,3-diaminopropane, N,N'-dimethyl-1,2-diaminobutane,
N,N'-dimethyl-1,3-diaminobutane, N,N'-dimethyl-1,4-diaminobutane,
N,N'-dimethyl-1,5-diaminopentane, N,N'-dimethyl-1,6-diaminohexane,
N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine,
20 N,N'-diethyl-1,2-diaminopropane, N,N'-diethyl-1,3-diaminopropane,
N,N'-diethyl-1,2-diaminobutane, N,N'-diethyl-1,3-diaminobutane,
N,N'-diethyl-1,4-diaminobutane, N,N'-diethyl-1,6-diaminohexane,
piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine,
homopiperazine, 1,1-di-(4-piperidyl)methane,
25 1,2-di-(4-piperidyl)ethane, 1,3-di-(4-piperidyl)propane,
1,4-di-(4-piperidyl)butane, and tetramethylguanidine; tertiary
amine such as trimethylamine, triethylamine, tri-n-propylamine,
30
tri-iso-propylamine, tri-1,2-dimethylpropylamine,
tri-3-methoxypropylamine, tri-n-butylamine, tri-iso-butylamine,
tri-sec-butylamine, tri-pentylamine, tri-3-pentylamine,
tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine,
5 tri-dodecylamine, tri-laurylamine, tri-cyclohexylamine,
N,N-dimethylhexylamine, N-methyldihexylamine,
N,N-dimethylcyclohexylamine, N-methyldicyclohexylamine,
triethanolamine, tribenzylamine, N,N-dimethylbenzylamine,
diethylbenzylamine, triphenylamine, N,N-dimethylamino-p-cresol,
10 N,N-dimethylaminomethyl phenol, 2-(N,N-dimethylaminomethyl)phenol,
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,
15 N,N'-dimethylpiperazine, N,N'-bis((2-hydroxy)propyl) piperazine,
hexamethylenetetramine, N,N,N',N'-tetramethyl-1,3-butanamine,
2-dimethylamino-2-hydroxypropane, diethylaminoethanol,
N,N,N-tris(3-dimethylaminopropyl)amine,
2,4,6-tris(N,N-dimethylaminomethyl)phenol, and heptamethyl
20 isobiguanide; various imidazoles such as; imidazole,
N-methylimidazole, 2-methylimidazole, 4-methylimidazole,
N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole,
N-butylimidazole, 2-butylimidazole, N-undecylimidazole,
2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole,
25 N-benzylimidazole, 2-benzylimidazole, 1-benzyl-2-methylimidazole,
N-(2'-cyanoethyl)-2-methylimidazole,
N-(2'-cyanoethyl)-2-undecylimidazole, N-(2'-cyanoethyl)-2-phenyl
31
imidazole, 3,3-bis-(2-ethyl-4-methylimidazolyl)methane, an adduct
of alkylimidazole and isocyanuric acid, and a condensate of
alkylimidazole and formaldehyde; amidines such as
1,8-diazabicyclo{5,4,0)undecene-7 and
5 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 two or more types
thereof.
--------~G4~]1----------------------------------------------------------
10 Examples of the quaternary ammonium salt include quaternary
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.
15 [0042]
Examples of the complex of amines with borane and with boron
trifluoride include the above-described complexes of amines with
borane and with boron trifluoride.
Examples of the phosphine-based compound can include
20 trimethylphosphine, triethylphosphine, triisopropylphosphine,
tri-n-propylphosphine, tri-tert-butylphosphine,
triisobutylphosphine, tri-n-butylphosphine,
tricyclohexylphosphine, triphenylphosphine,
methyldiphenylphosphine, dimethylphenylphosphine,
25 tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine,
dimethylphenylphosphine, diethylphenylphosphine,
dichloro(ethyl)phosphine, dichloro(phenyl)phosphine, and
32
chlorodipheny lphosphine. These may be used alone or in combination
of two or more types thereof.
[0043]
In Step (i), since the reaction between the polymerizable
5 monomer (A) and the polythiol (B) is prioritized over the reaction
between the polymerizable monomers (A) from the viewpoint of
exhibiting photochromic performance of the obtained molded product,
as a preferably catalyst, a phosphine-based compound is exemplified.
In the embodiment, dimethylphenylphosphine or tributylphosphine is
10 preferably used.
[0044]
The amount used of the phosphine-based compound is within a range
of 50 ppm to 1000 ppm, and preferably within a range of 100 ppm to
800 ppm, with respect to the total weight of the polymerizable monomer
15 (A) and the polythiol (B).
20
[0045]
[Other Components]
In Step (i), other components can be added as long as the
components do not affect handling of the prepolymer.
Examples of the other components include ethylvinylbenzene;
styrene, methylstyrene, dimethylstyrene, ethylstyrene,
~-methylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, and
p-chloromethylstyrene; ~-methylstyrene dimer; vinyl naphthalenes
such as 1-vinylnaphthalene and 2-vinylnaphthalene; aromatic
25 polymerizable monomers such as 4-vinylbiphenyl and
vinylphenylsulfide; acrylonitrile, methacrylonitrile, maleic
anhydride, and N-substituted maleimide; and allyl compounds such as
5
33
diethylene glycol bisallyl carbonate and diallyl phthalate.
The above other components can be used alone or in combination
of two or more types thereof.
[0046)
Step (i) is a step of obtaining a prepolymer by reacting the
polymerizable monomer (A) with the polythiol (B), the molar number
before the reaction, that is, of the mercapto groups included in the
polythiol (B) to be added is less than the molar number of the
ethylene-based unsaturated groups included in the polymerizable
10 monomer (A) to be added.
[0047)
The molar number of the mercapto groups included in the polythiol
(B) to be added is preferably equal to or less than 0.3 times, and
more preferably equal to or less than 0.27 times with respect to the
15 molar number of the entirety of the ethylene-based unsaturated groups
included in the polymerizable monomer (A) to be added. The lower
limit is equal to or greater than 0.05 times, and preferably equal
to or greater than 0.08, from the viewpoint of the operability and
the refractive index of the molded product obtained.
20 When the molar number is within the above range, it is possible
to suppress the viscosity increase during the prepolymerization, and,
since the dispersibilities of the photochromic compound (C) and the
polymerization catalyst in Step (ii) are excellent, it is possible
to obtain an optical material exhibiting desired photochromic
25 performance. Furthermore, when the molar number is within the above
range, it is possible to perform polymerization of the polymerizable
composition in Step (iii) with favorable controllability, and it is
34
possible to obtain an optical material with a high yield.
[ 0048]
Although the reaction temperature in Step (i) is not
particularly limited, the reaction is preferably performed at room
5 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 within
the above range, handling of the prepolymer is easy, and there is
no difficulty in working at room temperature, and thus, it is
10 preferable.
As the end point of the prepolymer reaction, the amount of
residual mercapto groups after the reaction may be measured and
managed. The amount of residual mercapto groups can be measured by
a general method, and examples thereof can include a titration by
15 an iodine oxidation method and an analytical method using IR.
[0049]

In Step (ii), a polymerizable composition is obtained by mixing
the prepolymer obtained in Step (i) and the photochromic compound
20 (C) .
Specifically, it is possible to mix the prepolymer obtained in
Step (i), the photochromic compound (C), and a polymerization
catalyst.
[0050]
25 [Photochromic Compound (C)]
In the embodiment, the photochromic compound (C) is not
particularly limited, and an arbitrary one can be suitably selected
35
from compounds known in the related art which can be used for
photochromic lenses and used. For example, one or two or more types
of a spiropyran-based compound, a spirooxazine-based compound, a
fulgide-based compound, a naphthopyran-based compound, and a
5 bisimidazole compound can be used depending on the desired color.
[0051]
Examples of the spiropyran-based compound include compounds
such as each substitute obtained by substituting the indole ring or
the benzene ring of indolinospirobenzopyran with a halogen atom, a
10 methyl group, an ethyl group, a methylene group, an ethylene group,
or a hydroxyl group and the like; each substitute obtained by
substituting the indole ring or 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
15 and the like; 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 the like; and each substitute obtained by
substituting the indole ring of indolinospiropyridopyran with a
20 halogen atom, a methyl group, an ethyl group, a methylene group, an
ethylene group, or a hydroxyl group and the like; .
[0052]
Examples of the spirooxazine-based compound include compounds
such as each substitute obtained by substituting the indole ring or
25 the benzene ring of indolinospirobenzoxazine with a halogen atom,
a methyl group, an ethyl group, a methylene group, an ethylene group,
or a hydroxyl group and the like; each substitute obtained by
36
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
and the like; each substitute obtained by substituting the indole
5 ring of indolinospirophenanthroxazine with a halogen atom, a methyl
group, an ethyl group, a methylene group, an ethylene group, or a
hydroxyl group and the like; 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,
10 or a hydroxyl group and the like; and each substitute obtained by
substituting the piperidine ring and 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
and the like.
15 [0053]
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-
20 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),
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),
25 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
37
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) and the like.
5 [0054]
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],
10 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[3.3.1]nonene-9,2'-[2H]benzo[f]chromene],
6-morpholino-3,3-bis(3-fluoro-4-methoxyphenyl)-3H-benzo
15 (f)chromene, 5-isopropyl-2,2-diphenyl-2H-benzo (h)chromene, the
compound represented by the following general formula {7), and the
compound represented by the following general formula (8) and the
like.
[0055]
20
(7)
[0056]
38
(8)
[0057)
In general formulas {7) and {8), R1 and R2 may be the same as
5 or different from each other, and each of R1 and R2 independently
represents a hydrogen atom;
a linear or branched alkyl group having 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
10 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) .

CLAIMS
1. A process for producing photochromic optical materials,
comprising:
a step (i) of reacting at least one polymerizable monomer (A)
having two or more ethylene-based unsaturated groups with at least
one polythiol (B) having two or more mercapto groups to obtain a
prepolymer;
a step ( ii) _of mixing the prepolymer and a photochromic compound
10 (C) to obtain a polymerizable composition; and
a step (iii) of polymerizing the polymerizable composition,
wherein, before the reaction of the step (i), the molar number
of the mercapto groups included in the polythiol (B) is smaller than
the molar number of the ethylene-based unsaturated groups included
15 in the polymerizable monomer (A) .
2. The process for producing photochromic optical materials
according to Claim 1,
wherein, before the reaction of the step (i), the molar number
20 of the mercapto groups included in the polythiol (B) is equal to or
less than 0. 3 times with respect to the molar number of the entirety
of ethylene-based unsaturated groups included in the polymerizable
monomer (A) .
25 3. The process for producing photochromic optical materials
according to Claim 1 or 2,
wherein the polymerizable monomer (A) includes at least one
5
10
15
20
25
76
ethylene-based unsaturated polymerizable monomer (al) 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 groups.
4. The process for producing photochromic optical materials
according to any one of Claims 1 to 3,
wherein, in the step (i) or (ii), an ethylene-based unsaturated
polymerizable monomer (D) having one (meth) acrylic group is included.
5. The process for producing photochromic optical materials
according to any one of Claims 1 to 4,
wherein, in the step (i), the polymerizable monomer (A) reacts
with the polythiol (B) in the presence of a phosphine-based compound.
6. The process for producing photochromic optical materials
according to any one of Claims 1 to 5,
wherein the step (ii) is a step of mixing the prepolymer, the
photochromic compound (C), and an azo-based compound.
7. The process for producing photochromic optical materials
according to Claim 6,
wherein the step (iii) is a step of polymerizing the
polymerizable composition in the presence of an azo-based compound.
8. The process for producing photochromic optical materials
according to Claim 3,
77
wherein the polymerizable monomer (al) is at least one selected
from divinylbenzene, diisopropenylbenzene, trivinylbenzene, and
divinylnaphthalene.
5 9. The process for producing photochromic optical materials
according to Claim 3,
wherein the polymerizable monomer (a2) is at least one selected
from polymerizable monomers represented by the following general
formula (4);
10
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
group, and a plurality of X1 may be the same as or different from
15 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. The process for producing photochromic optical materials
20 according to Claim 4,
wherein the ethylene-based unsaturated polymerizable monomer
(D) is at least one selected from aromatic (meth) acrylic acid esters
represented by the following general formula (5);
78
0 )0
CH -0-C-t=CH
2 II 2
0 (5)
wherein, in formula ( 5) , X3 is a hydrogen atom or a methyl group.
11. The process for producing photochromic optical materials
5 according to any one of Claims 1 to 10,
wherein the polythiol (B) 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,
10 pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate),
2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl)sulfide,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
15 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.
12. The process for producing photochromic optical materials
according to any one of Claims 1 to 11,
wherein the photochromic compound (C) is represented by the
20 following general formula (7) or (8);
79
(7)
(8)
wherein, in formulas (7) and (8),
R1 and R2 may be the same as or different from each other, and each
5 of R1 and R2 independently represents
a hydrogen atom;
a linear or branched alkyl group having 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
10 atoms or a substituted or unsubstituted heteroaryl group having 4
to 24 carbon atoms,
wherein the substituted aryl group or the substituted
heteroaryl group, as a substituent, has at least one substituent
selected from a halogen atom, a hydroxy group, a linear or branched
15 alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy
group having 1 to 12 carbon atoms, a linear or branched haloalkyl
80
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 which is substituted with at least one halogen atom,
a phenoxy group or a naphthoxy group which is substituted with at
5 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, an -NH2 group, an -NHR group, a -N (R) 2 group, wherein
R is a linear or branched alkyl group having 1 to 6 carbon atoms,
and in a case where two Rs are present, the two Rs may be the same
10 as or different from each other,
a methacryloyl group, and an acryloyl group; or
an aralkyl or heteroaralkyl group which is formed by
substituting a linear or branched alkyl group having 1 to 4 carbon
atoms with an aryl group or a heteroaryl group,
15 R3s may be the same as or different from each other, and each R3s
20
independently represents
a halogen atom;
a linear or branched 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 12 carbon atoms
which is substituted with at least one halogen atom, a linear or
branched halocycloalkyl group having 3 to 12 carbon atoms which is
substituted with at least one halogen atom, a linear or branched
25 haloalkoxy group having 1 to 12 carbon atoms which is substituted
with at least one halogen atom;
an aryl group having 6 to 24 carbon atoms or a heteroaryl group
81
having 4 to 24 carbon atoms which is substituted or unsubstituted,
wherein the substituted aryl group or the substituted
heteroaryl group has at least one substituent selected from a halogen
atom, a hydroxy group, a linear or branched alkyl group having 1 to
5 12 carbon 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 which is substituted with at least one halogen atom,
a linear or branched haloalkoxy group having 1 to 12 carbon atoms
which is substituted with at least one halogen atom, a phenoxy group
10 or a naphthoxy group which is substituted with 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 amino group as a substituent;
an aralkyl or heteroaralkyl group which is formed by
15 substituting a linear or branched alkyl group having 1 to 4 carbon
atoms with the aryl group or the heteroaryl group;
a substituted or unsubstituted phenoxy or naphthoxy group,
wherein the substituted phenoxy or the substituted naphthoxy group
has at least one substituent selected from a linear or branched alkyl
20 group or alkoxy group having 1 to 6 carbon atoms as a substituent;
-NH2 , -NHR, -CONH2 , or -CONHR, wherein R is a linear or branched
alkyl group having 1 to 6 carbon atoms; or
-OCOR8 or -COOR8 , wherein Rs is a linear or branched alkyl group
having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon
25 atoms, or a phenyl group which is substituted with at least one
substituent of a substituted aryl group or a substituted heteroaryl
group in R1 and R2 or an unsubstituted phenyl group, and
82
one or more aromatic ring groups or non-aromatic ring groups
are formed by bonding of at least two adjacent R3s to each other and
by including the carbon atom to which R3 is bonded, wherein the aromatic
ring group or non-aromatic ring group includes one ring or two
5 annelated rings which may include a heteroatom selected from the group
consisting of oxygen, sulfur, and nitrogen;
1 is an integer 0 to 2; and
m is an integer 0 to 4.
10 13. The process for producing photochromic optical materials
according to Claim 12,
wherein the photochromic compound (C) is represented by the
following general formula (9);
(9)
15
wherein, in formula (9), each of R1, R2, and R3 has the same meaning
as that in formula (7);
A represents an annelated ring represented by the above formula (A2 )
20
83
wherein, in these annelated rings, a dotted line represents a
C5-C6 bond of the naphthopyran ring in general formula (9);
an a bond of an annelated ring (A4 ) can be normally bonded to the
5 C5 or C6 of the naphthopyran ring in general formula {9);
R4 's are 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
group (CO);
10 R5 represents a 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 which
is substituted with 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 substituted or unsubstituted phenyl or benzyl group, wherein the
substituted phenyl or the substituted benzyl group 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 R2 groups in general
20 formula (9) independently corresponds to an aryl or heteroaryl group;
-NH2 or -NHR, wherein R is a linear or branched alkyl group having
1 to 6 carbon atoms;
a substituted or unsubstituted phenoxy or naphthoxy group, wherein
84
the substituted phenoxy or the substituted naphthoxy group 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, wherein R9 represents a linear or
5 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 , wherein the substituted phenyl or the substituted
benzyl group has at least one of substituents described above in the
definition of R1 and R2 groups as a substituent in a case where each
10 of R1 and R2 groups in general formula ( 9) independently corresponds
to an aryl or heteroaryl group; and
in a case where A represents (A4), n is an integer of 0 to 2, pis
an integer of 0 to 4, and in a case where A represents (A2), n is
an integer of 0 to 2.
15
14. A photochromic optical material obtained by the process
according to any one of Claims 1 to 13.
15. A plastic lens formed of the optical material according to Claim
20 14.