Process for production of photochromic cured product

A process for producing a photochromic cured product by allowing an unpurified, impurities-containing polyfunctional (meth)acrylate monomer such as unpurified polyalkylene glycol dimethacrylate and a photochromic spirooxazine compound to contain a compound having at least one epoxy group in the molecule such as glycidyl methacrylate and then polymerizing the resulting composition. The process can provide a spirooxazine-based photochromic cured product which hardy undergoes initial coloring and is superior in initial color-developing performance.

This application is a 371 of PCT/JP96/61386 filed May 24, 1996 
TECHNICAL FIELD 
The present invention relates to a process for producing a cured product 
superior in photochromism. 
BACKGROUND ART 
Photochromism is a phenomenon which has drawn attention in the last several 
years, and is a reversible reaction in which a certain compound quickly 
changes its color when irradiated with an ultraviolet-containing light 
such as sunlight or a light emitted from a mercury lamp and, when the 
light irradiation is stopped and the compound is placed in a dark room, 
returns the original color. Compounds capable of photochromism are called 
photochromic compounds, and photochromic compounds having various 
structures have heretofore been synthesized. These conventional 
photochromic compounds have poor durability. 
There are known novel photochromic compounds having improved durability, 
such as spirooxazine-based photochromic compounds (hereinafter referred to 
simply as oxazine compound), fulgimide-based photochromic compounds 
(hereinafter referred to simply as fulgimide compound), chromene-based 
photochromic compounds (hereinafter referred to simply as chromene 
compound) and the like. See U.S. Pat. Nos. 4,882,438, 4,960,678, 
5,130,058 and 5,106,998; and Japanese Kokai (Laid-Open) Patent Application 
Nos. 62-288830, 2-28154, 3-11074 and 3-133988!. 
Also in Japanese Kokai (Laid-Open) Patent Application No. 5-306392 is 
proposed combination use of a compound having an epoxy group(s) as a 
component for further improving the durability of fulgide compound. 
Japanese Kokai (Laid-Open) Patent Application No. 187784/1987 discloses a 
process for producing a photochromic resin, in which a highly reactive 
polyfunctional (meth)acrylate monomer is used and the concentration of 
polymerization initiator is specified, in order to prevent the degradation 
of an oxazine compound caused by polymerization initiator when the oxazine 
compound is mixed with and dissolved in a radically polymerizable monomer 
(hereinafter referred to simply as monomer) and curing is conducted in the 
presence of a polymerization initiator. 
The above-mentioned photochromic compounds show excellent reversible 
durability. Among them, the oxazine compound is known as compound which 
generally hardly undergoes photodegradation, and when subjected to 
continuous irradiation with sunlight or a light similar thereto, shows a 
small reduction in initial color-developing performance and hence, 
exhibits excellent performance in light resistance. However, in order to 
easily produce a cured product by a method comprising mixing and 
dissolving the above photochromic compound and a monomer and subsequently 
subjecting to polymerization for curing (hereinafter referred to simply as 
a knead-mixing method) and use the cured product in various applications, 
it is necessary to develop a process for producing a cured product, in 
which the characteristic properties of the above oxazine compound can be 
exhibited fully. 
For example, a cured product obtained by knead-mixing diethylene glycol 
bisallylcarbonate with the above-mentioned photochromic compound, which is 
widely used as a spectacle lens, has a problem in that the photochromic 
compound is degraded by the action of radical seed in curing and 
consequently, the cured product has a reduced initial color-developing 
performance. 
In the process disclosed in Japanese Kokai (Laid-Open) Patent Application 
No. 62-187784 disclosing a method comprising curing a polyfunctional 
(meth)acrylate monomer and an oxazine compound at a polymerization 
initiator concentration specified in the literature by the knead-mixing 
method, a cured product capable of exhibiting sufficient photochromic 
performance can be obtained when a fully purified polyfunctional 
(meth)acrylate monomer is used. When a polyfunctional (meth)acrylate 
monomer generally available in the market and an oxazine compound are 
mixed, however, the resulting solution is strikingly colored, and when the 
solution is cured according to the process described in the literature, 
the resulting cured product not only is strikingly colored but also 
exhibits extraordinarily reduced color-developing performance. 
As described above, a photochromic cured product produced according to the 
knead-mixing method, using an oxazine compound and an insufficiently 
purified commercial polyfunctional (meth)acrylate monomer has not 
exhibited satisfactory performance. 
DISCLOSURE OF THE INVENTION 
The present invention provides a process for producing a cured product 
having an excellent photochromic performance from an oxazine compound and 
a polyfunctional (meth)acrylate monomer available in the market, which is 
not purified in advance, by the simple knead-mixing method. 
The present inventors made an extensive study on (1) preparation of a cured 
product by the knead-mixing method from an oxazine compound and a 
commercially available polyfunctional (meth)acrylate monomer which is used 
directly without subjecting to troublesome purification and on (2) 
production of photochromic cured product of excellent photochromic 
performance, typified by a spectacle lens. As a result, the present 
inventors found that in production of a photochromic cured product from a 
composition containing a polyfunctional (meth)acrylate monomer and an 
oxazine compound, when the composition is allowed to further contain a 
compound having at least one epoxy group in the molecule, incorporation of 
the oxazine compound into the polyfunctional (meth)acrylate monomer causes 
no striking coloring and the resulting photochromic cured product is 
almost free from initial coloring and superior in initial color-developing 
performance and durability in photochromism. The present invention has 
been accomplished based on the above finding. 
That is, the present invention relates to a process for producing a 
photochromic cured product by polymerizing a composition containing a 
polyfunctional (meth)acrylate monomer, a photochromic spirooxazine 
compound and a polymerization initiator, wherein the composition is 
allowed to further contain a compound having at least one epoxy group in 
the molecule. 
The polyfunctional (meth)acrylate monomer used in the present invention is 
such polyfunctional (meth)acrylate monomers available in the market that 
is difficult to industrially purify by distillation because they have a 
high boiling point at ordinary pressures and hence, cause polymerization 
when subjected to purification by distillation this monomer is 
hereinafter referred to simply as polyfunctional (meth)acrylate!. General 
polyfunctional (meth)acrylates contain a trace amount of impurities such 
as those derived from raw material polyalcohol or from esterification, 
polymerization initiator and the like and, when an oxazine compound is 
mixed with and dissolved in such a polyfunctional (meth)acrylate, the 
resulting solution has striking coloring. When this colored solution is 
cured, the resulting cured product has striking coloring and is reduced in 
initial color-developing performance. However, when an epoxy compound is 
added to the above colored solution and then is stirred, the coloring is 
gradually reduced though the acting mechanism therefor is unknown, whereby 
there can be obtained a cured product free of coloring and having good 
color-developing performance. It is presumed that the trace amount of 
impurities contained in the polyfunctional (meth)acrylate exerts an action 
on the coloring in solution state and degradation during curing of the 
oxazine compound, based on a fact that when an oxazine compound is mixed 
with and dissolved in a distillation-purified monofunctional 
(meth)acrylate monomer (e.g. methyl methacrylate or benzyl methacrylate) 
having a structure similar to that of polyfunctional (meth)acrylates, or a 
sufficiently purified polyfunctional (meth)acrylate monomer, there occurs 
no striking coloring in the solution and that the resulting cured product 
exhibits sufficient initial photochromic performance. Further, when 
purification is not completely performed and removal of impurities is not 
sufficient, the resulting cured product has coloring and sufficient 
initial color-developing performance can not be achieved even though 
coloring in the solution state is not caused. Therefore, when a 
photochromic cured product is produced from a polyfunctional 
(meth)acrylate in the absence of an epoxy compound, the quality of the 
polyfunctional (meth)acrylate need to be of a high purity. 
In the present production process and in the preparation of a composition 
by mixing the above components, individual components may be mixed in any 
order. However, when the oxazine compound and the polyfunctional 
(meth)acrylate are mixed first, the resulting solution has coloring and 
the oxazine compound in a colored state is liable to be degraded by the 
influence of a light or impurities such as oxygen or the like contained in 
the solution. It is preferable, therefore, to first mix the polyfunctional 
(meth)acrylate and the epoxy compound sufficiently and then add the 
oxazine compound thereto. Thereby, the striking coloring of the oxazine 
compound in the composition can be prevented. 
The polyfunctional (meth)acrylate used in the present invention contains, 
as impurities, chemical substances capable of allowing an oxazine compound 
to have coloring. It includes a polyfunctional (meth)acrylate generally 
available in the market, which is a known polyfunctional (meth)acrylate 
not sufficiently purified. 
Typical examples of the polyfunctional (meth)acrylate includes monomers 
represented by the following general formula (1): 
##STR1## 
wherein R.sup.1 is a hydrogen atom or a methyl group, R.sup.2 is an 
alkylene group having 2 to 4 carbon atoms, and a is an integer of 1 to 10, 
monomers represented by the following formula (2): 
##STR2## 
wherein R.sup.1 is a hydrogen atom or a methyl group; R.sup.3 is an 
ethylene group or a propylene group; b, c, d and e are each an integer of 
0 to 10; when b, c, d or e is 
##STR3## 
is a single bond; R.sup.4 is an alkylene group having 3 to 10 carbon atoms 
or a group represented by the following formula 
##STR4## 
(in which R.sup.5, R.sup.6, R.sup.7 and R.sup.8 may be the same or 
different and are each a hydrogen atom or a halogen atom other than 
fluorine), and 
monomers represented by the following formula (3): 
##STR5## 
wherein R.sup.1 is a hydrogen atom or a methyl group; R.sup.3 is an 
ethylene group or a propylene group; f is an integer of 0 to 10; g is 0 or 
1; when f or g is 0, --(R.sup.3 O).sub.f -- or --(CH.sub.2).sub.g -- is a 
single bond; h is an integer of 0-2; R.sup.9 is a hydrogen atom, a 
hydroxymethyl group or an alkyl group such as methyl, ethyl or the like). 
Specific examples of the polyfunctional (meth)acrylates represented by the 
general formulas (1), (2) and (3) include ethylene glycol 
di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol 
di((meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene 
glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene 
glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 
tetrapropylene glycol di(meth)acrylate, polypropylene glycol 
di(meth)acrylate, polybutylene glycol di(meth)acrylate, 1,6-hexanediol 
di(meth)acrylate, neopentyl glycol di(meth)acrylate, acrylate or 
methacrylate compound of 2,2'-bis(4-methacryloyloxyethoxyphenyl)propane, 
acrylate or methacrylate compound of 2,2'-bis(4-methacryloyloxy 
polyethoxyphenyl)propane, acrylate or methacrylate compound of 
2,2'-bis(4-methacryloyloxypropoxyphenyl)propane, acrylate or methacrylate 
compound of 2,2'-bis(4-methacryloyloxypolypropoxyphenyl)propane, acrylate 
or methacrylate compound of 
2,2'-bis(3,5-dibromo-4-methacryloyloxyethoxy)propane, acrylate or 
methacrylate compound of addition product of hydrogenated bisphenol A with 
ethylene oxide or propylene oxide, dimethyloltricyclodecane 
di(meth)acrylate, dimethyloltricyclodecane polyethoxydi(meth)acrylate, 
trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 
a reaction product of ethylene glycol or polyethylene glycol and glycidyl 
(meth)acrylate, a reaction product of propylene glycol or polypropylene 
glycol and glycidyl (meth)acrylate, a reaction product of glycidyl 
(meth)acrylate and addition product of bisphenol A with ethylene oxide or 
propylene oxide, and a reaction product of glycidyl (meth)acrylate with 
addition product of hydrogenated bisphenol A with ethylene oxide or 
propylene oxide. These polyfunctional (meth)acrylates can be used singly 
or in combination of two or more. In the present invention, (meth)acrylate 
is a generic for methacrylate compound and acrylate compound. 
As the compound having at least one epoxy group in the molecule 
(hereinafter referred to as epoxy compound) to be used in the present 
invention, any known compound can be used without limitation. It includes, 
for example, reaction products between epichlorohydrin and alcoholic 
hydroxyl group-containing compound such as mono-, di- or tri-hydric 
alcohol or phenolic hydroxyl group-containing compound such as phenol or 
hydroquinone, and reaction products between epichlorohydrin and carboxylic 
acid such as benzoic acid or terephthalic acid. Typical epoxy compounds 
can be represented by the following general formula (4). 
##STR6## 
wherein A is a residue of an n-valent alcoholic hydroxyl group-containing 
compound, a residue of an n-valent phenolic hydroxyl group-containing 
compound, or a residue of an n-valent carboxylic acid; R.sup.1 is a 
hydrogen atom or a methyl group; and n is an inter of 1 to 4. 
The epoxy compound of the present invention preferably has further at least 
one unsaturated double bond group in the molecule. By using such a 
compound having an unsaturated double bond group and an epoxy group and 
polymerizing a composition containing the above compound and a 
photochromic compound to produce a photochromic cured product, the 
compound having at least one unsaturated double bond group and at least 
one epoxy group in the molecule is polymerized to form a polymer matrix to 
fix the compounds and in consequence, even though such a compound is used 
in a large amount, it does not impair the properties of the photochromic 
resin obtained. 
Examples of the unsaturated double bond group includes a vinyl group, an 
allyl group, an acryloyl group and a methacryloyl group. An acryloyl group 
or a methacryloyl group is preferred to obtain a cured product of good 
photochromic properties. 
As the epoxy compound having no unsaturated double bond group, there are 
mentioned compounds of the above general formula in which n is 1 or 2 and 
A is, when n is 1, an alkyl group of 2 to 20 carbon atoms which may be 
substituted with a hydroxyl group(s), a group represented by 
--R--(OR).sub.m --OH (in which R is an alkylene group of 2 to 4 carbon 
atoms, and m is an integer of 1 to 20), a cycloalkyl group of 6 to 7 
carbon atoms which may be substituted with a hydroxyl group(s), a phenyl 
group which may be substituted with a hydroxyl group(s), or a benzoyl 
group which may be substituted with a carboxyl group(s); and when n is 2, 
an alkylene group of 2 to 20 carbon atoms which may be substituted with a 
hydroxyl group(s), a group represented by --R--(OR).sub.m -- (in which R 
is an alkylene group of 2 to 4 carbon atoms, and m is an integer of 1 to 
20), a cycloalkylene group of 6 to 7 carbon atoms which may be substituted 
with a hydroxyl group(s), a phenylene group which may be substituted with 
a hydroxyl group(s), a phthaloyl, isophthaloyl or terephthaloyl group 
which may be substituted with a hydroxyl group(s), or a group represented 
by the following formula: 
##STR7## 
As the epoxy compound having at least one unsaturated double bond group, 
there can be mentioned compounds represented by the following general 
formula (5) which are typical compounds preferably used in the present 
invention: 
##STR8## 
wherein R.sup.1 and R.sup.12 are each a hydrogen atom or a methyl group; 
R.sup.10 and R.sup.11 may be the same or different and are each an 
alkylene group of 1 to 4 carbon atoms which may be substituted with a 
hydroxyl group(s), or a group represented by the following formula 
##STR9## 
and m and n are each 0 or 1. 
In the above formula, the alkylene group represented by R.sup.10 can be 
exemplified by methylene group, ethylene group, propylene group, butylene 
group, trimethylene group and tetramethylene group. 
Specific examples of the epoxy compound preferably usable in the present 
invention are as follows. 
Examples of the compound having, in the molecule, at least one epoxy group 
but no unsaturated double bond group are ethylene glycol glycidyl ether, 
propylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerol 
polyglycidyl ether, sorbitol polyglycidyl ether, butyl glycidyl ether, 
phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene 
glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol 
diglycidyl ether, adduct of propylene oxide to bisphenol A or hydrogenated 
bisphenol A, diglycidyl terephthalate, spiroglycol diglycidyl ether and 
hydroquinone diglycidyl ether. 
Examples of the compound having, in the molecule, at least one epoxy group 
and at least one unsaturated double bond group are acrylate or 
methacrylate compounds such as glycidyl acrylate, glycidyl methacrylate, 
.beta.-methylglycidyl acrylate, .beta.-methylglycidyl methacrylate, 
bisphenol A-monoglycidyl ether methacrylate, 4-glycidyloxybutyl 
methacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 
3-(glycidyloxy-1-isopropyloxy)-2-hydroxypropyl acrylate, 
3-(glycidyloxy-2-hydroxypropyloxy)-2-hydroxypropyl acrylate and the like. 
In the composition of the present invention, the amount of the epoxy 
compound used cannot be specified generally because it varies depending 
upon the amount of the impurities contained in the polyfunctional 
(meth)acrylate. When a general polyfunctional (meth)acrylate in the market 
is used, use of the epoxy compound in an amount of 1 part by weight or 
more per 100 parts by weight of the whole monomer can suppress the 
coloring of the cured product obtained. Generally, even if up to 30 parts 
by weight of an epoxy compound is blended, a cured product of sufficient 
strength can be obtained. In the case of an epoxy compound having no 
unsaturated double bond group, however, it is used in an amount of 
preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by 
weight, per 100 parts by weight of the whole monomer because too large an 
amount of such compound prevent curing of a cured product. 
The above-mentioned whole monomer refer to the compounds having an epoxy 
group(s) and/or an unsaturated double bond group(s), capable of giving 
rise to radical polymerization, and includes all of the polyfunctional 
(meth)acrylate, the epoxy compound and other monomer added as necessary 
(described later). The same applies hereinafter. 
The oxazine compound used in the present invention can be any known 
compound having a spirooxazine skeleton and having photochromic 
properties. It is preferably a spirooxazine compound represented by the 
following general formula (6): 
##STR10## 
In the above general formula (6), R.sup.13, R.sup.14 and R.sup.15 may be 
the same or different and are each an alkyl group, a cycloalkyl group, a 
cycloaralkyl group, an alkoxy group, an alkyleneoxyalkyl group, an 
alkoxycarbonyl group, an alkoxycarbonylalkyl group, an aryl group, an 
aralkyl group, an aryloxy group, an alkylenethioalkyl group, an acyl 
group, an acyloxy group or an amino group, R.sup.14 and R.sup.15 may 
together form a ring, and R.sup.13, R.sup.14 and R.sup.15 may each have a 
substituent(s). The substituent(s) includes (include), besides the 
above-mentioned groups, halogen atom, nitro group, cyano group, 
heterocyclic group and the like. The group represented by 
##STR11## 
is a substituted or unsubstituted bivalent aromatic hydrocarbon group or a 
substituted or unsubstituted bivalent unsaturated heterocyclic group. The 
group represented by 
##STR12## 
is a substituted or unsubstituted bivalent aromatic hydrocarbon group or a 
substituted or unsubstituted bivalent unsaturated heterocyclic group. The 
bivalent aromatic hydrocarbon or bivalent unsaturated heterocyclic group 
includes, for example, bivalent groups derived from a benzene ring or from 
a fused ring of 2 or 3 benzene rings. The bivalent unsaturated 
heterocyclic ring includes, for example, bivalent groups derived from a 5- 
to 7-membered ring containing 1 or 2 oxygen, nitrogen or sulfur atoms as 
the ring-forming atom(s), or from a fused ring of the above 5- to 
7-membered ring and a benzene ring. 
Specific examples of the bivalent aromatic hydrocarbon group are groups of 
6 to 14 carbon atoms derived from benzene ring, naphthalene ring, 
phenanthrene ring, anthracene ring or the like. Specific examples of the 
bivalent unsaturated heterocyclic group are groups of 4 to 9 carbon atoms 
derived from furan ring, benzofuran ring, pyridine ring, quinoline ring, 
isoquinoline ring, pyrrole ring, thiophene ring, thiophene ring, 
benzothiophene ring or the like. The substituents can be selected from the 
same groups as mentioned above with respect to R.sup.13, R.sup.14 and 
R.sup.15. In particular, an oxazine compound substituted with a group 
represented by 
EQU --NR.sup.16 R.sup.17 
wherein R.sup.16 and R.sup.17 are each an alkyl group, an alkoxy group, an 
allyl group or the like, each of which may be substituted; and R.sup.16 
and R.sup.17 may be bonded and cyclized with each other to form a 
nitrogen-containing heterocyclic ring, 
is preferable from the standpoint of high density of its developed color in 
the initial photochromic performance. 
Specific examples of the oxazine compound, preferably usable in the present 
invention are as follows. 
(1) 
6'-Fluoro-1'-methyl-8"-methoxy-6"-morpholinodispiro-(cyclohexane-1,3'-(3H) 
indole-2'-(2H),3"-(3H)naphtho(3,2a)(1,4)oxazine) 
(2) 
1'-Methoxycarbonylmethyl-8"-methoxy-6"-(4-methylpiperazino)dispiro(cyclohe 
xane-1,3'-(3H)indole-2'-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
(3) 
5'-Fluoro-1'-methyl-6"-piperidinodispiro(cyclohexane-1,3'-(3H)indole-2'-(2 
H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
(4) 
1'-Methyl-8"-methoxydispiro(cyclohexane-1,3'-(3H)indole-2'-(2H),3"-(3H)nap 
htho(2,3-a)(1,4)oxazine) 
(5) 
6'-Fluoro-1',7'-dimethyl-6"-morpholinodispiro(cyclo-hexane-1,3'-(3H)indole 
-2'-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
(6) 
6'-Fluoro-1',5'-dimethyl-6"-morpholinodispiro(cyclo-hexane-1,3'-(3H)indole 
-2'-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
(7) 
6'-Fluoro-1'-isobutyl-6"-morpholinodispiro(cyclohexane-1,3'-(3H)indole-2'- 
(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
(8) 
6'-Fluoro-5'-methyl-1'-isobutyl-6"-morpholinodispiro(cyclohexane-1,3'-(3H) 
indole-2'-(2H),3"-(3H)naphtho(3,2a)(1,4)oxazine) 
(9) 
6'-Fluoro-5'-methyl-1'-neopentyl-6"-morpholinodispiro(cyclohexane-1,3'-(3H 
)indole-2'-(2H),3"-(3H)naphtho(3,2a)(1,4)oxazine) 
(10) 
1',3',3'-Trimethyl-6"-piperinospiro((3H)indole-2'-(2H),3"-(3H)naphtho(3,2- 
a)(1,4)oxazine) 
(11) 
3',3'-Dimethyl-1'-isobutyl-spiro((3H)indole-2'-(2H),3"-(3H)naphtho(3,2-a)( 
1,4)oxazine) 
(12) 
1',3',3'-Trimethyl-spiro((3H)indole-2'-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxaz 
ine) 
In the present invention, by containing the epoxy compound in the 
composition, coloring of the oxazine compound does not occur, the 
composition shows reduced coloring and the cured product has improved 
initial color-developing performance. Therefore, the amount of the oxazine 
compound used can be determined from a wide range. However, when the 
amount of the oxazine compound is too small, no sufficient initial 
color-developing performance is obtained, while the amount is too large, 
the oxazine compound causes cohesion, resulting in sharp reduction in 
durability of photochromic properties. Hence, the oxazine compound is used 
in an amount of preferably 0.001 to 10 parts by weight, more preferably 
0.01 to 5 parts by weight, particularly preferably 0.01 to 1 part by 
weight, per 100 parts by weight of the whole monomer. 
In the present invention, by using other two types of photochromic 
compounds, i.e. a chromene compound and a fulgide compound in combination 
with the oxazine compound, there can be obtained a photochromic cured 
product of higher degree of completeness suited for the intended 
application. For example, it is known that oxazine compounds mainly 
develop a blue-line color, but when it is intended to use a photochromic 
cured product obtained by the present invention for obtaining a spectacle 
lens having a neutral color of gray or brown, a cured product capable of 
developing a neutral gray or brown color and superior in durability can be 
produced by combination use of a chromene compound and a fulgimide 
compound with the oxazine compound. The chromene compound is a compound 
mainly developing a yellow color and is needed to procure a neutral color 
in combination with a blue color and the fulgimide compound develop a blue 
color similarly to the oxazine compound, but show wider absorption for 
visible light than the oxazine compound. Accordingly, it is possible to 
obtain a deeper color. As the above fulgide compound and chromene 
compound, there can be suitably used known compounds described in, for 
example, U.S. Pat. Nos. 4,882,438, 4,960,678, 5,130,058, 5,106,998 and the 
other. 
The fulgide-based photochromic compounds suitably used in the present 
invention can be represented by the following general formula (7): 
##STR13## 
wherein the group represented by the following formula 
##STR14## 
is a substituted or unsubstituted bivalent aromatic hydrocarbon group or a 
substituted or unsubstituted bivalent unsaturated heterocyclic group; 
R.sup.18 is an alkyl group, an aryl group, a cyclopropyl group which may 
be substituted, or a monovalent heterocyclic group; the group represented 
by the following formula: 
##STR15## 
is a norbornylidene group or an adamantylidene group; and X is an oxygen 
atom, a group represented by &gt;N--R.sup.19, a group represented by 
&gt;N--A.sub.1 --B.sub.1 --(A.sub.2).sub.k --(B.sub.2).sub.l --R.sup.20, a 
group represented by &gt;N--A.sub.3 --A.sub.4 or a group represented by 
&gt;N--A.sub.3 --R.sup.21 (in which R.sup.19 is a hydrogen atom, an alkyl 
group or an aryl group; R.sup.20 is an alkyl group, a naphthyl group or a 
naphthylalkyl group; R.sup.21 is a halogen atom, a cyano group or a nitro 
group; A.sub.1, A.sub.2 and A.sub.3 may be the same or different and are 
each an alkylene group, an alkylidene group, a cycloalkylene group or an 
alkylcycloalkan-diyl group; A.sub.4 is a naphthyl group; B.sub.1 and 
B.sub.2 may be the same or different and are each a group represented by 
the following group: 
##STR16## 
and k and l are each independently 0 or 1 with a proviso that when k is 0, 
l is 0)!. 
In the general formula (7), the bivalent aromatic hydrocarbon group 
represented by the following formula: 
##STR17## 
includes, for example, bivalent groups derived from a benzene ring or from 
a fused ring of 2 or 3 benzene rings. The bivalent unsaturated 
heterocyclic ring includes, for example, bivalent groups derived from a 5- 
to 7-membered ring containing 1 or 2 oxygen, nitrogen or sulfur atoms as 
the ring-forming atom(s), or from a fused ring of the above 5- to 
7-membered ring and a benzene ring. 
Specific examples of the bivalent aromatic hydrocarbon group are groups of 
6 to 14 carbon atoms derived from benzene ring, naphthalene ring, 
phenanthrene ring, anthracene ring or the like. Specific examples of the 
bivalent unsaturated heterocyclic group are groups of 4 to 9 carbon atoms 
derived from furan ring, benzofuran ring, pyridine ring, quinoline ring, 
isoquinoline ring, pyrrole ring, thiophene ring, thiophene ring, 
benzothiophene ring or the like. The bivalent aromatic hydrocarbon group 
or bivalent unsaturated heterocyclic group may have a substituent(s). The 
substituent(s) is (are) not particularly restricted and can be exemplified 
by halogen atoms such as chlorine, bromine, iodine and the like; alkyl 
groups of 1 to 4 carbon atoms such as methyl group, ethyl group and the 
like; alkoxy groups of 1 to 4 carbon atoms such as methoxy group, ethoxy 
group and the like; aryl groups of 6 to 10 carbon atoms such as phenyl 
group, tolyl group, xylyl group and the like; alkoxyaryl groups of 7 to 14 
carbon atoms (aryl groups of 6 to 10 carbon atoms each substituted with an 
alkoxy group of 1 to 4 carbon atoms); amino group; nitro group; and cyano 
group. 
In the general formula (7), the alkyl group, aryl group and heterocyclic 
group represented by R.sup.18 can be exemplified by the same groups as 
mentioned with respect to the above substituents, and include alkyl groups 
of 1 to 4 carbon atoms, aryl groups of 6 to 10 carbon atoms, and 
monovalent groups each derived from a 5- to 7-membered ring containing 1 
or 2 oxygen, nitrogen or sulfur atoms as the ring-forming atom(s), or from 
a fused ring of the above 5- to 7-membered ring and a benzene ring. 
The alkyl group and aryl group represented by R.sup.19 when X is a 
nitrogen-containing group, can be exemplified by the same groups as 
mentioned with respect to R.sup.18. The alkylene group represented by 
A.sub.1, A.sub.2 and A.sub.3 when X is a nitrogen-containing group, is 
preferably a group of 1 to 4 carbon atoms such as methylene group, 
ethylene group, propylene group, trimethylene group, tetramethylene group 
or the like; the alkylidene group is preferably a group of 2 to 4 carbon 
atoms such as ethylidene group, propylidene group, isopropylidene group or 
the like; the cycloalkylene group is preferably a cyclohexylene group; and 
the alkylcycloalkan-diyl group is preferably a dimethylcyclohexan-diyl 
group. The alkyl group represented by R.sup.20 is the same as mentioned 
with respect to R.sup.18 ; and the naphthylalkyl group is preferably a 
group of 11 to 14 carbon atoms such as naphthylmethyl group, naphthylethyl 
group or the like. 
Of the fulgide-based photochromic compounds represented by the general 
formula (7), there is preferred, in view of the durability in 
photochromism, etc., a compound of the formula (7) in which R.sup.18 is an 
alkyl group or a cyclopropyl group; X is &gt;N--R in which R is a cyanoalkyl 
group of 1 to 4 carbon atoms, a nitroalkyl group of 1 to 4 carbon atoms or 
an alkoxycarbonylalkyl group of 3 to 9 carbon atoms (containing an alkoxy 
group of 1 to 4 carbon atoms and an alkylene group of 1 to 4 carbon 
atoms), the group represented by the following formula: 
##STR18## 
is an adamantylidene group, and the group represented by the following 
formula: 
##STR19## 
is a heterocyclic group which may be substituted with an aryl group of 6 
to 10 carbon atoms or an alkoxyaryl group of 7 to 14 carbon atoms (an aryl 
group of 6 to 10 carbon atoms substituted with an alkoxy group of 1 to 4 
carbon atoms), particularly a group derived from a thiophene ring. 
The chromene compounds suitably used in the present invention can be 
represented by the following general formula (8): 
##STR20## 
wherein R.sup.22, R.sup.23, R.sup.24 and R.sup.25 may be the same or 
different and are each a hydrogen atom, an alkyl group, an aryl group, a 
substituted amino group or a saturated heterocyclic group and R.sup.24 and 
R.sup.25 may form a ring together; and the group represented by the 
following formula: 
##STR21## 
is a substituted or unsubstituted bivalent aromatic hydrocarbon group or a 
substituted or unsubstituted bivalent unsaturated heterocyclic group. 
In the general formula (8), the alkyl group and aryl group represented by 
R.sup.22, R.sup.23, R.sup.24 and R.sup.25 can be the same alkyl groups and 
aryl groups as mentioned with respect to the general formula (7); the 
substituted amino group includes amino groups in which at least one of the 
hydrogen atoms is substituted with the above-mentioned alkyl group(s) or 
aryl group(s); the saturated heterocyclic group includes monovalent groups 
each derived from a 5- to 6-membered ring containing, as a ring-forming 
atom, 1 or 2 nitrogen, oxygen or sulfur atoms, such as pyrrolidine ring, 
imidazolidine ring, piperidine ring, piperazine ring, morpholine ring or 
the like. 
In the general formula (8), the ring which R.sup.24 and R.sup.25 form 
together includes a norbornylidene group, a bicyclo3.3.1!9-nonylidene 
group, etc. 
In the general formula (8), the bivalent aromatic hydrocarbon group or 
bivalent unsaturated heterocyclic group represented by the following 
formula: 
##STR22## 
can be exemplified by the same groups as mentioned with respect to the 
general formula (7). These groups may each have a substituent(s). The 
substituent(s) is (are) not particularly restricted and can be exemplified 
by halogen atoms such as chlorine, bromine, iodine and the like; alkyl 
groups of 1 to 20 carbon atoms such as methyl group, ethyl group and the 
like; alkoxy groups of 1 to 20 carbon atoms such as methoxy group, ethoxy 
group and the like; aryl groups of 6 to 10 carbon atoms such as phenyl 
group, tolyl group, xylyl group and the like; amino group; nitro group; 
and cyano group. 
Of the above-mentioned chromene-based photochromic compounds, particularly 
suitable is a compound of general formula (8) in which R.sup.22 and 
R.sup.23 are each a hydrogen atom; R.sup.24 and R.sup.25 may be the same 
or different and are each an alkyl group of 1 to 4 carbon atoms, or may 
together form a bicyclo3.3.1!-nonylidene group or a norbornylidene group; 
and the group represented by the following formula 
##STR23## 
is a group derived from a naphthalene ring which may be substituted with 
an alkyl group(s) of 1 to 20 carbon atoms or an alkoxy group(s) of 1 to 20 
carbon atoms. 
Specific examples of the fulgide compound and chromene compound, which can 
be suitably used in the present invention, are as follows. 
Fulgide compounds 
(1) 
N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzob!thiophenedica 
rboxyimido-7,2-tricyclo3.3.1.1!decane) 
(2) 
N-cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl)-4-methylspiro(5,6-benzob!th 
iophenedicarboxyimido-7,2-tricyclo3.3.1.1!decane) 
(3) 
N-cyanomethyl-6,7-dihydro-4-methylspiro(5,6-benzob!thiophenedicarboxyimid 
o-7,2-tricyclo-3.3.1.1!decane) 
(4) 
6,7-dihydro-N-methoxycarbonylmethyl-4-methyl-2-phenylspiro(5,6-benzob!thi 
ophenedicarboxyimido-7,2-tricyclo3.3.1.1!decane) 
(5) 
6,7-dihydro-4-methyl-2-(p-methylphenyl)-N-nitromethylspiro(5,6-benzob!thi 
ophenedicarboxyimido-7,2-tricyclo3.3.1.1!decane) 
(6) 
N-cyanomethyl-6,7-dihydro-4-cyclopropyl-3-methyl-spiro(5,6-benzob!thiophe 
nedicarboxyimido-7,2-tricyclo3.3.1.1!decane) 
(7) 
N-cyanomethyl-6,7-dihydro-4-cyclopropyl-spiro(5,6-benzob!thiophenedicarbo 
xyimido-7,2-tricyclo3.3.1.1!decane) 
Chromene compounds 
(1) spironorbornane-2,2'-2H!benzoh!chromene! 
(2) spirobicyclo3.3.1!nonane-9,2'-2H!benzoh!chromene! 
(3) 7'-methoxyspirobicyclo3.3.1!nonane-9,2'-2H!benzoh!chromene! 
(4) 7'-methoxyspironorbornane-2,3'-3H!benzof!chromene! 
(5) 2,2-dimethyl-7-octoxy2H!benzoh!chromene 
In the present invention, the chromene or fulgide compound is used in the 
range of generally 0.001 to 10 parts by weight, preferably 0.01 to 1 part 
by weight per 100 parts by weight of the whole monomer. In this range, the 
best photochromic performance can be achieved. 
In the present invention, in addition to the polyfunctional (meth)acrylate, 
other known unsaturated monomers can be added, as required, to obtain a 
cured product. Examples of other monomer suitably used are monofunctional 
(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl 
(meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl 
(meth)acrylate, tribromophenyl (meth)acrylate, 2-hydroxyethyl 
(meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol 
(meth)acrylate, alkoxypolyethylene glycol (meth)acrylate, 
alkoxypolypropylene glycol (meth)acrylate and the like; and aromatic vinyl 
compounds such as styrene, chlorostyrene, .alpha.-methylstyrene dimer, 
vinylnaphthalene, isopropenylnaphthalene, bromostyrene, divinylbenzene and 
the like. These monomers can be used in the composition of the present 
invention singly or in combination of two or more. The amount of other 
monomer used can be determined depending upon the application of the 
resulting cured product, but is generally 0.5 to 80 parts by weight and, 
in view of the heat resistance of the resulting photochromic resin, 0.5 to 
30 parts by weight per 100 parts by weight of the whole monomer. 
The polymerization initiator used in the present invention is not 
particularly limited and a known polymerization initiator may be used. 
Typical examples thereof are diacyl peroxides such as benzoyl peroxide, 
p-chlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, acetyl 
peroxide and the like; peroxy esters such as t-butyl 
peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, cumyl 
peroxyneodecanoate, t-butyl peroxybenzoate and the like; percarbonates 
such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate and 
the like; and azo compounds such as azobisisobutyronitrile and the like. 
The amount of the polymerization initiator used varies depending upon the 
polymerization conditions employed, the kinds of initiator used and the 
composition of monomers used, and cannot be specified generally. However, 
the suitable amount is generally 0.001 to 10 parts by weight, preferably 
0.01 to 5 parts by weight, per 100 parts by weight of the whole monomer. 
The polymerization process for obtaining a cured product from the 
polymerizable composition of the present invention is not particularly 
limited, and a known radical polymerization process can be used. The 
polymerization can be initiated by the use of a variety of radical 
polymerization initiators such as peroxides, azo compounds or the like, or 
by irradiation of ultraviolet light, .alpha.-ray, .beta.-ray, .gamma.-ray 
or the like, or by the combination use of the above two means. As the 
typical polymerization process, cast polymerization can be employed; that 
is, the photochromic composition of the present invention containing a 
radical polymerization initiator is poured into a mold held by an 
elastomer gasket or spacer, the mold is placed in a heating furnace to 
carry out polymerization of the composition, and then the resulting 
polymer is taken out. 
Of the polymerization conditions, the polymerization temperature, in 
particular, exerts an influence on the properties of the photochromic 
cured product to be obtained. The temperature condition varies depending 
upon the kind and amount of initiator used and the kinds of monomers used 
and cannot be specified generally. However, it is generally preferred to 
conduct so-called tapered type two-stage polymerization wherein 
polymerization is initiated at a relatively low temperature, the 
temperature is increased gradually and, upon the completion of 
polymerization, curing is conducted at a high temperature. The 
polymerization time also varies depending upon various factors similarly 
to the polymerization temperature. Therefore, it is preferred to 
determine, in advance, an optimum polymerization time to meet the 
conditions, while it is preferable that the conditions are selected so as 
to complete the polymerization generally in 2 to 40 hours. 
In the polymerization, it is of course possible to add, as necessary, 
various stabilizers and additives such as mold-releasing agent, 
ultraviolet absorber, ultraviolet stabilizer, antioxidant, coloring 
inhibitor, antistatic agent, fluorescent dye, dye, pigment, odorant or the 
like. 
In the photochromic composition of the present invention, addition of the 
ultraviolet stabilizer is preferred because the durability of the 
photochromic compound used in the composition can be further improved 
thereby. Particularly, a fulgide compound shows large improvement in 
durability by the presence of an ultraviolet stabilizer and hence, in the 
case where a mixture of the aforesaid oxazine compound, fulgide compound 
and chromene compound is used, addition of an ultraviolet stabilizer 
serves to favorably prevent the neutral color developed by these compounds 
from changing with time. 
As the ultraviolet stabilizer, there can be preferably used a hindered 
amine light stabilizer, a hindered phenol light stabilizer, a sulfur-based 
antioxidant and a phosphorous acid ester compound. Particularly preferred 
is a hindered amine light stabilizer having a hindered amine structure in 
the molecule. 
The amount of the ultraviolet stabilizer used is not particularly 
restricted, but a preferable amount is generally 0.01 to 5 parts by 
weight, preferably 0.02 to 1 part by weight, per 100 parts by weight of 
the whole monomer. 
When an infrared absorber is used in the present composition, there can be 
obtained a photochromic cured product having not only photochromism but 
also infrared absorptivity. There can be used, as the infrared absorber, a 
polymethine compound, a diimmonium compound, a cyanine compound, 
ananthraquinone compound and an aluminum compound. A diimmonium compound 
is preferred because it has a high molecular absorptivity coefficient and 
can show an effect in a small amount. 
The amount of the infrared absorber used is preferably 0.0001 to 1 part by 
weight, more preferably 0.001 to 0.01 part by weight, per 100 parts by 
weight of the whole monomer. 
The photochromic cured product obtained as above can be subjected to the 
following treatments, depending upon the application. That is, to the 
cured product can be applied processing and secondary treatments such as 
dyeing by the use of a dye such as dispersed dye or the like; a treatment 
by a silane coupling agent or a hard-coat agent containing, as the main 
component, a sol of silicon, zirconium, antimony, aluminum, tin, tungsten 
or the like; an anti-reflection treatment by formation of a thin film of a 
metal oxide (e.g. SiO.sub.2, TiO.sub.2 or ZrO.sub.2) by vapor deposition; 
an antistatic treatment by coating of a thin film of an organic polymer; 
and so forth. 
The present process can produce a photochromic cured product which is 
almost free of initial coloring and superior in initial color-developing 
performance and durability of photochromic properties. The present 
invention has made it possible to produce a photochromic cured product 
containing an oxazine compound, which is a thermosetting resin usable as a 
photochromic lens or the like, by the simple knead-mixing method.

EXAMPLES 
The present invention is hereinafter explained specifically by way of 
Examples. However, the present invention is not restricted to these 
Examples. 
The compounds used in the following Examples are as follows. 
Compounds having at least one epoxy group in the molecule! 
GMA: glycidyl methacrylate 
GA: glycidyl acrylate 
MGMA: .beta.-methylglycidyl dimethacrylate 
MGA: .beta.-methylglycidyl acrylate 
BPMGMA: bisphenol A-monoglycidyl ether methacrylate 
GBMA: 4-glycidyloxybutyl methacrylate 
GEHPMA: 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate 
GIHPA: 3-(glycidyloxy-1-isopropyloxy)-2-hydroxypropylacrylate 
EGGE: ethylene glycol glycidyl ether 
PGGE: propylene glycol glycidyl ether 
FDGE: diglycidyl terephthalate 
HDGE: hydroquinone diglycidyl ether 
BGE: butyl glycidyl ether 
HDGE: 1,6-hexanediol diglycidyl ether 
Polyfunctional (meth)acrylates! 
3G: triethylene glycol dimethacrylate NK Ester 3G (trade name), a product 
of Shin-Nakamura Chemical Co., Ltd.! 
4G: tetraethylene glycol dimethacrylate (a monomer mixture of polyethylene 
glycol having four (on an average) moles of ethylene oxide chains NK 
Ester 4G (trade name), a product of Shin-Nakamura Chemical Co., Ltd.! 
3PG: tripropylene glycol dimethacrylate NK Ester 3PG (trade name), a 
product of Shin-Nakamura Chemical Co., Ltd.! 
4PG: tetrapropylene glycol dimethacrylate (a monomer mixture of 
polypropylene glycol having four (on an average) moles of propylene oxide 
chains NK Ester 4PG (trade name), a product of Shin-Nakamura Chemical 
Co., Ltd.! 
BP-2EM: 2,2'-bis(4-methacryloyloxypolyethoxyphenyl)-propane methacrylate (a 
mixture having 2.2 (on an average) moles of ethylene oxide chains) Light 
Ester BP-2EM (trade name), a product of Kyoeisha Chemical Co., Ltd.! 
BR-MA: 2,2'-bis(3,5-dibromo-4-methacryloyloxy-ethoxy)-propane methacrylate 
Light Ester BR-MA (trade name), a product of Kyoeisha Chemical Co., Ltd.! 
TEGDMA: triethylene glycol dimethacrylate TEGDMA (trade name), a product 
of Mitsubishi Gas Chemical Co., Ltd.! 
3EG: triethylene glycol dimethacrylate Light Ester 3EG (trade name), a 
product of Kyoeisha Chemical Co., Ltd.! 
PRO-631: 2,2'-bis(4methacryloyloxypolyethoxyphenyl)-propane methacrylate 
PRO-631 (trade name), a product of Sartomer Co., Ltd.! 
Other monomers! 
MMA: methyl methacrylate 
MS: .alpha.-methylstyrene 
MSD: .alpha.-methylstyrene dimer 
BzMA: benzyl methacrylate 
HEMA: 2-hydroxyethyl methacrylate 
Purified polyfunctional (meth)acrylates! 
P1-3G: triethylene glycol dimethacrylate NK Ester 3G (trade name), a 
product of Shin-Nakamura Chemical Co., Ltd.! washed twice each with a 1N 
aqueous hydrochloric acid solution, a 10% (by weight) aqueous sodium 
carbonate solution and pure water. 
P2-3G: 20 g of triethylene glycol dimethacrylate which was first fractioned 
out of the colume when 500 g of triethylene glycol dimethacrylate NK 
Ester 3G (trade name), a product of Shin-Nakamura Chemical Co., Ltd.! was 
passed through a column filled with alumina. 
Spirooxazine compounds! 
SP1: 
6'-fluoro-1'-methyl-8"-methoxy-6"-morpholino-dispiro(cyclohexane-1,3'-(3H) 
indole-2'-(2H),3"-(3H)naphtho(3,2a)(1,4)oxazine) 
SP2: 
1'-methoxycarbonylmethyl-8"-methoxy-6"-(4-methylpiperazino)dispiro(cyclohe 
xane-1,3'-(3H)indole-2'-(2H),3"-(3H)naphtho(3,2a)(1,4)oxazine) 
SP3: 
5'-fluoro-1'-methyl-6"-piperidinodispiro(cyclo-hexane-1,3'-(3H)indole-2'-( 
2H),3"-(3H)naphtho (3,2-a)(1,4)oxazine) 
SP4: 
1'-methyl-8"-methoxydispiro(cyclohexane-1,3'-(3H)indole-2'-(2H),3"-(3H)nap 
htho(2,3-a)(1,4)oxazine) 
SP5: 6'-fluoro-1',7'-dimethyl-6"-morpholinodispiro 
(cyclohexane-1,3'-(3H)indole-2'-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
SP6: 6'-fluoro-1',5'-dimethyl-6"-morpholinodispiro 
(cyclohexane-1,3'-(3H)indole-2'-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
SP7: 
6'-fluoro-1'-isobutyl-6"-morpholinodispiro-(cyclohexane-1,3'-(3H)indole-2' 
-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
SP8: 
6'-fluoro-5'-methyl-1'-isobutyl-6"-morpholinodispiro(cyclohexane-1,3'-(3H- 
)indole-2'-(1'H),3"-(3H)naphtho(3,2a)(2H)oxazine) 
SP9: 
6'-fluoro-5'-methyl-1'-neopentyl-6"-morpholinodispiro(cyclohexane-1,3'-(3H 
)indole-2'-(2H),3"-(3H)naphtho(3,2a)(1,4)oxazine) 
SP10: 1',3',3'-trimethyl-6"-piperidinospiro 
((3H)indole-2'-(2H),3"-(3H)naphtho(3,2-a)(1,4)oxazine) 
SP11: 
3',3'-dimethyl-1'-isobutyl-spiro((3H)indole-2'-(2H),3"-(3H)naphtho(3,2-a)( 
1,4)oxazine) 
SP12: 
1',3',3'-trimethyl-spiro((3H)indole-2'-(2H),3"-3H)naphtho(3,2-a)(1,4)oxazi 
ne) 
Fulgide compounds! 
F1: 
N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzob!thiophenedica 
rboxyimido-7,2-tricyclo3.3.1.1!-decane) 
F2: 
N-cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl)-4-methylspiro(5,6-benzob!th 
iophenedicarboxyimido-7,2-tricyclo3.3.1.1!decane) 
F3: 
N-cyanomethyl-6,7-dihydro-4-methylspiro(5,6-benzob!thiophenedicarboxyimid 
o-7,2-tricyclo3.3.1.1!decane) 
Chromene compounds! 
C1: spironorbornane-2,2'-2H!benzoh!chromene! 
C2: spirobicyclo3.3.1!nonane-9,2'-2H!benzoh!chromene! 
C3: 7'-methoxyspirobicyclo3.3.1.!nonane-9,2'-2H!benzoh!chromene! 
Example 1 
Various epoxy compounds and monomers polyfunctional (meth)acrylates and 
other monomers! shown in Table 1 were each stirred at room temperature for 
2 hours. To the resulting solution were added 0.04 part by weight of an 
oxazine compound SP5: 
6'-fluoro-1',7'-dimethyl-6"-morpholinodispiro(cyclohexane-1,3'-(3H)indole- 
2'-(1'H),3"-(3H)naphtho(3,2-a)(1,4)oxazine)! and 1 part by weight of 
t-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator, and 
the mixture was stirred sufficiently. The mixture solution in which the 
oxazine compound was dissolved had almost no change in color. The mixture 
solution was poured into a mold constituted by a glass sheet and a gasket 
composed of an ethylene-vinyl acetate copolymer, and cast polymerization 
was conducted. In the polymerization, an air oven was employed. 
Temperature was elevated gradually from 30.degree. C. to 90.degree. C. 
over 18 hours and was kept at 90.degree. C. for 2 hours. After the 
completion of polymerization, the mold was taken out of the air oven and 
allowed to cool. Then, a cured product was taken out of the glass mold. 
Each photochromic cured product(thickness: 2 mm)obtained above was measured 
for photochromic properties by the following methods, and the results are 
shown in Table 1. 
(1) Density of developed color 
The thus-obtained cured product(thickness: 2 mm) was irradiated with a beam 
emitted from a xenon lamp L-2480 (300 W) SHL-100, a product of Hamamatsu 
Photonics Co., Ltd.! through Aero Mass Filter (a product of Corning Co., 
Ltd.) at 20.degree. C..+-.1.degree. C. with beam intensities of 2.4 
mW/cm.sup.2 (at 365 nm) and 24 :W/cm.sup.2 (at 245 nm) on the surface of 
the cured product for 30 seconds or 120 seconds, to give rise to color 
development. Then,.epsilon.(30 or 120)-.epsilon.(0)! was determined and 
used as the density of developed color of the cured product. In this case, 
.epsilon.(30 or 120) is an absorbance of the photochromic compound at its 
maximum absorption wavelength when the compound was irradiated for 30 
seconds or 120 seconds under the above conditions to give rise to color 
development; and .epsilon.(0) is an absorbance of the photochromic 
compound before irradiation at the same wavelength. The initial density of 
developed color and initial developed color before a life test was 
conducted, were expressed by T.sub.o. 
(2) Initial coloring 
Expressed by .epsilon.(0) which was measured under the above conditions. 
Incidentally, in the blue region of visible light, coloring can generally 
be clearly recognized by naked eyes when the absorbance exceeds 0.1. 
(3) Durability 
Fatigue durability was measured with a xenon fadeometer (FA-25AX-HC, a 
product of Suga Shikenki Co., Ltd.). Fatigue durability was expressed by a 
ratio of the absorbance of the products after irradiation at its maximum 
absorption wavelength when the cured products were irradiated with a xenon 
fadeometer for 200 hours and then allowed to develop a color by the method 
mentioned in the above (1), to the absorbance of the cured products before 
irradiation. In Table 1, the values of A.sub.200 /A.sub.o (%) of the 
T.sub.200 corresponds to this fatigue durability. 
TABLE 1 
__________________________________________________________________________ 
Epoxy T.sub.0 Initial coloring 
Compound Radical-polymerizablem monomers (parts by weight) 
Density of 
T.sub.200 
Color of 
(Parts by 
Polyfunctional 
Other developed 
Developed 
A.sub.200 /A.sub.0 
initial 
No. 
weight) 
(meth)acrylate(s) 
monomers color 
color 
(%) .epsilon. (0) 
coloring 
__________________________________________________________________________ 
1 GMA:10 
3G:90 -- 0.42 Purple 
82.3 
0.06 
No color 
2 GMA:1 4G:99 -- 0.56 Purple 
80.2 
0.05 
No color 
3 GMA:30 
3PG:70 -- 0.68 Purple 
78.5 
0.04 
No color 
4 GMA:9 3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.48 Purple 
85.0 
0.04 
No color 
5 GMA:9 3G:35, BP-2EM:48 
MS:7, MSD:1 
0.48 Purple 
88.0 
0.05 
No color 
6 GMA:10 
3G:40, BR-MA:20 
MS:9, MSD:1, BzMA:20 
0.45 Purple 
78.0 
0.05 
No color 
7 GMA:10 
4G:40, BR-MA:20 
MS:9, MSD:1, BzMA:20 
0.50 Purple 
79.3 
0.05 
No color 
8 GMA:10 
3PG:60 MMA:22, MS:7, MSD:1 
0.42 Purple 
80.3 
0.05 
No color 
9 GA:9 3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.48 Purple 
85.0 
0.04 
No color 
10 MGMA:9 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.48 Purple 
85.0 
0.04 
No color 
11 MGA:9 3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.48 Purple 
85.0 
0.04 
No color 
12 BPMGMA:9 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.46 Purple 
85.0 
0.04 
No color 
13 GBMA:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.48 Purple 
85.0 
0.04 
No color 
14 GEHPMA:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.48 Purple 
85.0 
0.04 
No color 
15 GIHPA:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.48 Purple 
85.0 
0.04 
No color 
16 EGGE:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.52 Purple 
85.0 
0.04 
No color 
17 PGGE:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.52 Purple 
85.0 
0.04 
No color 
18 FDGE:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.50 Purple 
85.0 
0.04 
No color 
19 HDGE:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.50 Purple 
85.0 
0.04 
No color 
20 BGE:4 3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.52 Purple 
85.0 
0.04 
No color 
21 HDGE:4 
3G:15, 4G:65 
MS:8, MSD:1, HEMA:2 
0.52 Purple 
85.0 
0.04 
No color 
22 GMA:10 
3G:45, TEGDMA:45 
-- 0.42 Purple 
82.0 
0.06 
No color 
23 GMA:10 
TEGDMA:45, 3EG:45 
-- 0.42 Purple 
82.5 
0.05 
No color 
24 GMA:10 
BP-2EM:45, PRO-631:45 
-- 0.48 Purple 
78.1 
0.07 
No color 
__________________________________________________________________________ 
*Density of developed color is a value after 30 seconds irradiation with 
xenon lamp. 
Example 2 
The same operation as in Example 1 was conducted except that there were 
used the monomers and epoxy compound shown in No. 4 of Table 1 and the 
oxazine compound used in Example 1 was changed to an oxazine compound 
shown in Table 2. The results are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Initial coloring 
Spiro- Amount of spiro- 
T.sub.0 T.sub.200 
Color of 
oxazine 
oxazine added 
Density of 
Developed 
A.sub.200 /A.sub.0 
initial 
No. 
compound 
(parts by weight) 
developed color 
color (%) .epsilon. (0) 
coloring 
__________________________________________________________________________ 
1 SP1 0.04 0.56 Blue purple 
81.5 
0.04 
No color 
2 SP2 0.04 0.53 Blue purple 
84.2 
0.1 
Light blue 
3 SP3 0.04 0.54 Purple 
80.5 
0.04 
No color 
4 SP4 0.04 0.41 Blue 78.8 
0.04 
No color 
5 SP6 0.04 0.40 Purple 
83.7 
0.04 
No color 
6 SP7 0.04 0.50 Purple 
81.0 
0.06 
No color 
7 SP8 0.04 0.54 Blue purple 
81.4 
0.1 
Light blue 
8 SP9 0.04 0.58 Blue purple 
82.0 
0.1 
Light blue 
9 SP10 0.04 0.71 Purple 
82.0 
0.15 
Purple 
10 SP11 0.04 0.35 Blue 82.0 
0.03 
No color 
11 SP12 0.04 0.30 Blue 82.0 
0.04 
No color 
12 SP1 0.01 0.08 Blue purple 
85.0 
0.01 
No color 
13 SP1 0.15 0.70 Blue purple 
68.1 
0.07 
Light blue 
__________________________________________________________________________ 
*Density of developed color is a value after 30 seconds irradiation with 
xenon lamp. 
Example 3 
The same operation as in Example 1 was conducted except that there were 
used the monomers and epoxy compound shown in No. 4 of Table 1 and the 
photochromic compound used in Example 1 was changed to an oxazine 
compound, a fulgimide compound and a chromene compound all shown in Table 
3. The results are shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Amount Amount Amount 
of spiro- of fulgide 
of chromene 
T.sub.0 
Spiro- 
oxazine added added Density of 
T.sub.200 
Initial 
oxazine 
added (parts 
Fulgide 
(parts 
Chromene 
(parts 
developed 
Developed 
A.sub.200 /A.sub.0 
coloring 
No. 
compound 
by weight) 
compound 
by weight) 
compound 
by weight) 
color 
color 
(%) .epsilon. (0) 
__________________________________________________________________________ 
1 SP5 0.03 F2 0.1 C2 0.04 0.83 Gray 75.2 
0.03 
2 SP6 0.03 F2 0.1 C2 0.02 0.80 Gray 70.5 
0.03 
3 SP8 0.05 F1 0.03 C1 0.04 0.70 Brown 
77.5 
0.1 
4 SP9 0.03 F3 0.05 C3 0.05 0.77 Brown 
73.5 
0.11 
__________________________________________________________________________ 
*Density of developed color is a value after 120 seconds irradiation with 
a xenon lamp. 
Example 4 
The same operation as in Example 1 was conducted except that there were 
used the monomers and epoxy compound shown in No. 5 of Table 1 and the 
photochromic compound used in Example 1 was changed to an oxazine 
compound, a fulgimide compound and a chromene compound all shown in Table 
4. The results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Amount Amount Amount 
of spiro- of fulgide 
of chromene 
T.sub.0 
Spiro- 
oxazine added added Density of 
T.sub.200 
Initial 
oxazine 
added (parts 
Fulgide 
(parts 
Chromene 
(parts 
developed 
Developed 
A.sub.200 /A.sub.0 
coloring 
No. 
compound 
by weight) 
compound 
by weight) 
compound 
by weight) 
color 
color 
(%) .epsilon. (0) 
__________________________________________________________________________ 
1 SP5 0.05 F1 0.08 C2 0.09 0.71 Brown 
80.2 
0.05 
2 SP6 0.05 F2 0.05 C2 0.04 0.88 Gray 78.3 
0.04 
3 SP8 0.04 F2 0.04 C1 0.05 0.80 Gray 78.5 
0.13 
4 SP9 0.03 F3 0.05 C3 0.05 0.80 Brown 
73.5 
0.11 
__________________________________________________________________________ 
*Density of developed color is a value after 120 seconds irradiation with 
a xenon lamp. 
Example 5 
The same operation as in Example 1 was conducted except that there were 
used the monomers and epoxy compound shown in No. 6 of Table 1 and the 
photochromic compound used in Example 1 was changed to an oxazine 
compound, a fulgimide compound and a chromene compound all shown in Table 
5. The results are shown in Table 5. 
TABLE 5 
__________________________________________________________________________ 
Amount Amount Amount 
of spiro- of fulgide 
of chromene 
T.sub.0 
Spiro- 
oxazine added added Density of 
T.sub.200 
Initial 
oxazine 
added (parts 
Fulgide 
(parts 
Chromene 
(parts 
developed 
Developed 
A.sub.200 /A.sub.0 
coloring 
No. 
compound 
by weight) 
compound 
by weight) 
compound 
by weight) 
color 
color 
(%) .epsilon. (0) 
__________________________________________________________________________ 
1 SP5 0.05 F1 0.08 C2 0.09 0.64 Brown 
78.2 
0.06 
2 SP6 0.05 F2 0.05 C2 0.04 0.78 Gray 75.7 
0.06 
3 SP8 0.04 F2 0.04 C1 0.05 0.75 Gray 74.5 
0.13 
4 SP9 0.03 F3 0.05 C3 0.03 0.76 Brown 
72.5 
0.09 
__________________________________________________________________________ 
*Density of developed color is a value after 120 seconds irradiation with 
a xenon lamp. 
Comparative Example 1 
The same procedure as in Example 1 was repeated using 0.04 part by weight 
of an oxazine compound shown in Table 6, except that no epoxy compound was 
used. In each of the composition Nos. 1-7 shown in Table 6, striking 
coloring occurred as a result of the mixing of an oxazine compound and a 
polyfunctional (meth)acrylate(s). The results are shown in Table 6. 
TABLE 6 
__________________________________________________________________________ 
Amount of 
spiro- 
Radical-polymerizable monomers 
T.sub.0 Initial coloring 
Spiro- oxazine 
(parts by weight) Density of Color of 
oxazine 
added (parts 
Polyfunctional 
Other developed 
Developed 
initial 
No. 
compound 
by weight) 
(meth)acrylate(s) 
monomer 
color 
color .epsilon. (0) 
coloring 
__________________________________________________________________________ 
1 SP5 0.04 3G:100 -- Impossible 
No color 
0.85 
Red purple 
to measure 
development 
2 SP5 0.04 4G:100 -- Impossible 
No color 
0.90 
Red purple 
to measure 
development 
3 SP5 0.04 3PG:70 MMA:30 
Impossible 
No color 
1.0 
Red purple 
to measure 
development 
4 SP9 0.04 3G:100 -- Impossible 
No color 
1.0 
Purple 
to measure 
development 
5 SP5 0.04 3G:50, TEGDMA:50 
-- Impossible 
No color 
0.90 
Red purple 
to measure 
development 
6 SP5 0.04 TEGDMA:50, 3EG:50 
-- Impossible 
No color 
0.95 
Red purple 
to measure 
development 
7 SP5 0.04 BP-2EM:50, PRO-631:50 
-- Impossible 
No color 
0.83 
Red purple 
to measure 
development 
8 SP5 0.04 -- MMA:100 
0.6 Purple 
0.03 
No color 
9 SP5 0.04 -- BzMA:100 
0.6 Purple 
0.04 
No color 
__________________________________________________________________________ 
*Density of developed color is a value after 30 seconds irradiation with 
xenon lamp. 
Comparative Example 2 
The same procedure as in Example 1 was repeated using 0.04 part by weight 
of an oxazine compound shown in Table 7, except that a purified 
polyfunctional (meth)acrylate was used and there was used no epoxy 
compound having at least one epoxy group in the molecule. In the 
composition No. 1 shown in Table 1, the mixing of an oxazine compound and 
a purified polyfunctional (meth)acrylate had no coloring, but its cured 
product had coloring. The results are shown in Table 7. 
TABLE 7 
__________________________________________________________________________ 
Amount of 
Purified 
T.sub.0 
spirooxazine 
Polyfunctional 
Density of 
Initial coloring 
Spirooxazine 
added (meth)acrylate 
developed 
Developed 
Color of 
No. 
compound 
(parts by weight) 
(parts by weight) 
color 
color 
.epsilon. (0) 
initial coloring 
__________________________________________________________________________ 
1 SP5 0.04 P1-3G:100 
0.15 Purple 
0.63 
Blue 
2 SP5 0.04 P2-3G:100 
0.40 Purple 
0.06 
No color 
__________________________________________________________________________ 
*Density of developed color is a value after 30 seconds irradiation with 
xenon lamp.