JPH03252654A - Photochromic formation - Google Patents

Abstract

PURPOSE:To enhance durability of photochromic action by coating both the sides of a resin layer containing a specified photochromic dispersed in it with thermosetting resin layers. CONSTITUTION:The thermosetting resin layers are laminated on both the sides of the resin layer containing the dispersed photochromic compound represented by formula I in which each of R<1> and R<2> is alkyl or both may combine with each other to form a ring, such as norbornylidene bicyclo[3,3,1]9-nonylidene group; each of R<3> and R<4> is H, alkyl, or the like; and the ring containing Y is an aromatic hydrocarbon group or an unsaturated heterocyclic group, thus permitting the durability of the photochromic action to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photochromic molded article with excellent durability of photochromic action.

(Prior art) Photochromism is a phenomenon that has attracted attention over the past few years.When a certain compound is irradiated with light containing ultraviolet rays, such as sunlight or light from a mercury lamp, the color changes immediately, and when the compound is irradiated with light, it changes color. This is a reversible effect that returns to the original color when you stop using it and leave it in a dark place. Compounds having this property are called photochromic compounds, and although compounds with various structures have been synthesized and proposed, no particular common skeleton has been found in their structures.

As a result of continuing research on a series of photochromic compounds, the present inventors succeeded in synthesizing a new chromene derivative having a chromene skeleton, and discovered that the chromene derivative has excellent photochromic effects, which have already been proposed. (Patent Application No. 1987-220387, Patent Application No. 1-1
No. 41206 and Japanese Patent Application No. 1-143011).

(Problems to be Solved by the Invention) Furthermore, the present inventors continued research on dispersing the above-mentioned chromene derivative in a resin to produce a photochromic molded article, typified by a photochromic lens. As a result, it has been found that the durability of the photochromic action of the chromene derivative can be improved depending on how the chromene derivative is present in the resin.

Therefore, an object of the present invention is to obtain a photochromic molded article with excellent durability.

(Means for Solving the Problems) In the present invention, R1 and R2 are the same or different alkyl groups, respectively, and these together are an optionally substituted norbornylidene group or a substituted Moyoi Bicyclo [
It may constitute a 3,3,1co9-nonylidene group,
R3 and R4 are the same or different hydrogen atoms, alkyl groups, aryl groups, aralkyl groups, optionally substituted aromatic hydrocarbon groups, or optionally substituted unsaturated heterocyclic groups, and R1 and R2 are 20 Alkyl group, alkoxy group having 6 to 20 carbon atoms, -R'-8-R' and -R'-X<R.

(However, R8 is an alkylene group or +0-R8+.

(However, R6 is an alkylene group, and n is a positive integer.), R6 and R7 are the same or different alkyl groups, respectively, and X is 0- 0- -N<, -P< , −P<. -or-o-p<. − is. ) A bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group having at least one substituent selected from the group consisting of:

This is a photochromic molded article in which thermosetting resin layers are laminated on both sides of a resin layer containing a dispersed photochromic compound represented by:

The photochromic compound in the present invention is a chromene derivative represented by the above-mentioned -tsujiyome (A).

In the above-mentioned binding margin [A), R1 and R2 are the same or different alkyl groups, respectively. The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of the photochromic properties of the compound represented by the above-mentioned -bond margin (A), the number of carbon atoms is preferably 1 to 3, particularly 1. is preferred. Specific examples of alkyl groups include methyl group, ethyl group, n-
Examples include propyl group and i-propyl group.

Moreover, R1 and R2 in the above-mentioned - binding margin (A) are - together to form a ring, and are an optionally substituted norbornylidene group or an optionally substituted bicyclo (3,3,
1) It may constitute a 9-nonylidene group.

The norbornylidene group is represented by the following formula, and the bicyclo(3,3,1)9-nonylidene group is represented by the following formula. In these norbornylidene groups or bicyclo[3,3,1)9-nonylidene groups, the hydrogen atom in the above formula may be substituted with a substituent.

The number of substituents may be one or more, preferably 1 to 3. When a substituent is present, its type, number and position may be selected depending on the purpose and use. Moreover, when it has a plurality of substituents, they may be the same substituent or different types of substituents.

The above norbornylidene group or bicyclo(3,3,1
) Examples of substituents for the 9-nonylidene group include halogen atoms such as fluorine, chlorine, and oxaline; hydroxyl groups; cyano groups; nitro groups; carboxyl groups; carbon atoms such as methyl groups, ethyl groups, propyl groups, and butyl groups. Alkyl group having 1 to 4 carbon atoms; alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group; halogenoalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; phenyl group, tolyl Aryl groups having 6 to 10 carbon atoms such as phenylene, tolyloxy, and naphthyloxy groups; Aryloxy groups having 6 to 1 degrees of carbon atoms such as phenyloxy, tolyluoxy, and naphthyloxy groups; carbon atoms such as hensyl, phenethyl, and phenylpropyl groups 7-10 aralgyl group; carbon number 7 such as hensyloxy group, phenethyloxy group, phenylpropyloxy group
~10 aralkoxy groups; C1-C4 alkylamino groups such as methylamino and ethylamino groups; C2-8 dialkylamino groups such as dimethylamino and diethylamino groups; methoxycarbonyl groups, Examples include alkoxycarbonyl groups having 2 to 10 carbon atoms, such as oxycarbonyl groups.

Preferred examples of these substituents include a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, and a halogen alkyl group having 6 carbon atoms.
-10 aryl group, C7-10 aralkyl group,
It is a dialkylamino group having 2 to 8 carbon atoms.

R3 and R4 in the above-mentioned binding margin [A] are the same or different, and are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a substituted amine group.

Here, the substituted amine group is an alkylamino group, a dialkylamino group, or a 4- to 7-membered monocyclic saturated heterocyclic ring containing at least one nitrogen atom or containing a nitrogen atom and an oxygen atom or a sulfur atom. Examples include monovalent groups derived from a ring. The above 4- to 7-membered monocyclic saturated heterocycle is represented by the following formula.

In the above formula, R9 is an alkylene CH20 (CH
z) An oxyalkylene group having 3 to 6 carbon atoms such as 3-1, -C1l. SC: H2CH2-, -CH□5(CH2
) I-, CH2CH25CH2C)+2-, etc., thioal having 3 to 6 carbon atoms CH3CH: 1 Kylene group; -CHzNCHz(Jlz--CHIN(
CH2) zCJI.

-CHzCHzNCJIzCHz-, etc. with 3 to 6 carbon atoms
Azoalkylene groups and the like are preferably employed.

Specific examples of each group represented by R3 and R4 include:
Alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, and decyl groups; 6 carbon atoms such as phenyl, tolyl, and naphthyl groups
-10 aryl group; carbon number 7-10 such as Hensyl group, phenethyl group, phenylpropyl group, phenylbutyl group
Examples include aralkyl groups. In addition, as substituted amino groups, alkylamino groups having 1 to 4 carbon atoms such as 0 methylamino group and ethylamino group; dialkylamino groups having 2 to 8 carbon atoms such as dimethylamino group and diethylamino group; pyrrolidine ring, piperidine A monovalent ring derived from a 4- to 7-membered monocyclic saturated heterocycle containing at least one nitrogen atom or containing a nitrogen atom and an oxygen atom or a sulfur atom, such as a ring, a piperazine ring, a morpholine ring, a thiazolidine ring, etc. Examples include the following groups.

Among these, R3 and R4 are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms,
an aralkyl group having 7 to 10 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a 5-membered ring containing up to 2 nitrogen atoms or containing 1 nitrogen atom and either an oxygen atom or a sulfur atom; Alternatively, a monovalent group derived from a 6-membered monocyclic saturated heterocycle is preferable. By selecting each group of R3 or R4, the fading rate of the compound of -Tsuriyo (A) can be changed. For example, when R3 and R4 are alkyl groups, a fast color fading rate can be obtained, probably because it becomes difficult to take the trans form of the coloring state. or,
When R3 is a substituted amino group, the color-forming trans form is stabilized by resonance, and while a high color density can be obtained, the fading rate is slightly slow. moreover,
A compound in which both R3 and R4 are hydrogen atoms has the advantage of developing a particularly deep color and fading quickly.

Next, the above-mentioned binding margin (A) in the present invention has a good smell.
It is a valent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 14 carbon atoms. In particular, a divalent group derived from one benzene ring or 2 to 4 condensed rings thereof is preferred. Examples of rings forming such an aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a phenanthrene ring, and the like.

Examples of unsaturated heterocyclic groups include 5- or 6-membered monocyclic heterocyclic groups containing 1 to 2 nitrogen atoms, acid 2 atoms, and sulfur atoms, or fused heterocyclic groups in which a benzene ring is fused to these 5- or 6-membered monocyclic heterocyclic groups. A ring group is shown. Examples of rings forming such unsaturated heterocyclic groups include nitrogen-containing heterocycles such as pyridine ring, quinoline ring, and virole ring; oxygen-containing heterocycles such as furan ring and benzofuran ring; thiophene ring and benzothiophene ring. Examples include sulfur-containing heterocycles such as.

Alkylamino groups having 1 to 4 carbon atoms, such as a group; dialkylamino groups having 2 to 8 carbon atoms, such as a dimethylamino group and diethylamino group; halogenoalkyl groups having 1 to 4 carbon atoms, such as a trifluoromethyl group; thienyl group , a 5- or 6-membered monocyclic heterocyclic group containing 1 to 2 sulfur atoms, oxygen atoms, or nitrogen atoms, such as furyl group, pyrrolyl group, or pyridyl group; is at most 5,
Preferably up to 3 substituents may be contained.

Examples of such substituents include halogen atoms such as fluorine, chlorine, and oxaline; hydroxyl groups; cyano groups; nitro groups; alkyl groups having 1 to 20 carbon atoms such as methyl groups, ethyl groups, propyl groups, and butyl groups. Group; Alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group; Aryl group having 6 to 10 carbon atoms such as phenyl group, tolyl group, naphthyl group; Methylamino group, ethylamine group can.

R1 and R2 described above together form a ring,
The optionally substituted norbornylidene group or the optionally substituted bicyclo(3,3,1) is a halogen atom, a hydroxyl group, a cyano group, a nitro group, or a group having 1 to 1 carbon atoms.
20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, dialkylamino groups having 2 to 8 carbon atoms, halogenoalkyl groups having 1 to 4 carbon atoms, and 34 monocyclic heterocycles. It is preferable that it is a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group which may be substituted in each case with at least one selected from the group consisting of:

In the above-mentioned margin [A], when R1 and R2 are an alkyl group, [][ is an alkyl group having 6 to 20 carbon atoms,
A benzene ring which may be substituted in each case by 1 to 3 alkoxy groups having 6 to 2 o carbon atoms, or a divalent group derived from a condensed ring of 2 to 4 benzene rings, or an oxygen atom or a sulfur atom , 5 containing 1 to 2 nitrogen atoms
It is preferably a divalent group derived from a membered or 6-membered monocyclic heterocycle, or a fused heterocycle in which a benzene ring is fused thereto.

Preference is given to a benzene ring, a naphthalene ring, a phenanthrene ring, a pyridine ring, a quinoline ring, a virole ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, which may be substituted in each case by 1 to 3 rings. .

is an alkylene group or 10-R”+tr (however, R6
is an alkylene group, and n is a positive integer. ), R6 and R7 are the same or different alkyl groups, respectively, and X is a bicyclic aromatic carbide having at least one substituent selected from the group -N<, -P< It is a hydrogen group or a bicyclic unsaturated heterocyclic group.

Examples of the alkyl group having 6 to 20 carbon atoms as a substituent of a bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, and undecyl group. , dodecyl group, tridecyl group, pentadecyl group, ophtade56yl group, eicosyl group, and the like.

Further, as the alkoxy group having 6 to 20 carbon atoms which is a substituent of a bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group, examples include hexyloxy group, 3heptyloxy group, octyloxy group, nonyloxy group, Examples include a decyloxy group, an undecyloxy group, a dodecyloxy group, a pentadecyloxy group, an octadecyloxy group, and an eicosyloxy group.

Furthermore, other substituents of the bicyclic aromatic hydrocarbon group or the bicyclic unsaturated heterocyclic group are -R'-3-R6÷o-R
8-k (wherein, R8 is an alkylene group, and n is a positive integer), R6 and R7 are the same or different alkyl groups, respectively, and X is. ). The alkylene groups represented by R5 and R1+ of these two substituents are not particularly limited in carbon number and are generally selected from the range of 1 to 20, but considering the durability of the resulting chromene derivative as a photochromic material. , its carbon number is 6~
A range of 20 is preferred. Specific examples of alkylene groups include methylene group, ethylene group, propylene group,
trimethylene group, tetramethylene group, pentamethylene group,
Examples include hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, pentadecamethylene group, octadecamethylene group, and eicosamethylene group. In addition, n in the +0-R sequence represented by R5 may be a positive integer, but generally 1+-o-R
It is preferred that the number of carbon atoms in the chain represented by "-+T" be from 1 to 20, preferably from 6 to 20; for this purpose, n is generally selected from the range from 1 to 20.

Further, the number of carbon atoms in the alkyl group represented by R6 and R7 is not particularly limited, but it is preferably in the range of 1 to 4 from the 7 8 point of fading rate of the obtained chromene derivative as a photochromic material.

Up to six of the above-mentioned substituents can be substituted on a bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group,
For reasons such as ease of production, it is usually preferable to substitute in the range of 1 to 3.

The bicyclic aromatic hydrocarbon group or bicyclic unsaturated heterocyclic group substituted with the various substituents described above is a 5-membered ring or A ring in which two six-membered rings are condensed is used. In particular, chromene derivatives in which an aromatic ring is condensed at the 7° and 8-positions of chromene are particularly suitable for use as photochromic materials because of their high color density.

The substituent of the bicyclic aromatic hydrocarbon group or bicyclic unsaturated heterocyclic group is an alkyl group having 6 to 20 carbon atoms or 6 to 2 carbon atoms
When the chromene derivative contains 0 alkoxy groups, the resulting chromene derivative becomes a photochromic material with excellent durability. On the other hand, a chromene derivative in which a substituent of a bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group is removed becomes a photochromic material with a fast discoloration rate.

In the present invention, the chromene derivative represented by the above-mentioned "A" generally develops a color from yellow to red. Therefore, when the photochromic molded article of the present invention is used for purposes such as ornaments, the above compound (A) may be used alone. Furthermore, when the photochromic molded article of the present invention is used for applications such as sunglasses, brown or gray color tone is generally preferred, so it is preferable to use it in combination with other photochromic compounds to adjust the color tone. As other photochromic compounds, those generally referred to as fulgide compounds or fulgimide compounds are suitable in the present invention because they can be adjusted to brown or gray tones when used in combination with the above-mentioned compound (A). used for. The amount of the above-mentioned fulgide compound or fulgimide compound to be used may be selected as appropriate depending on the desired color tone. It is preferable to select from the range of 0.01 to 10,000 parts by weight, preferably 0.05 to 200 parts by weight.

The above-mentioned fulgide compound has the structure shown by the following formula, and any compound having photochromic properties is employed without any restriction. Also, Fu (yA Ding #:
A compound having the structure shown by h and having photochromic properties can be employed without any restriction.

In the present invention, a compound represented by the following formula is generally used as the fulgide compound or fulgimide compound.

During the ceremony divalent aromatic hydrocarbon group or Divalent unsaturated heterocyclic group 1 2 R.

is a monovalent hydrocarbon group, a monovalent norbornylidene group, or an adamantylidene group, each of which may have a substituent, is an oxygen atom, P3 group, ;NA,
-A, or a group; n-A3-R.

In CI), these are heterocyclic groups, and these groups may have at most 5 substituents, preferably up to 3 substituents.

3 4 The aromatic hydrocarbon group has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, and examples of rings forming such an aromatic hydrocarbon ring include a Hensen ring and a naphthalene ring. , a phenanthrene ring.

In addition, as the unsaturated heterocyclic group, a 5- or 6-membered monocyclic heterocyclic group containing at least one type of petro atom such as nitrogen atom, oxygen atom, and sulfur atom, or a Hensen ring or cyclohexene A fused heterocyclic group is shown in which the rings are fused.

Examples of the rings forming such a heterocyclic group include nitrogen-containing heterocycles such as pyrrole ring, pyridine ring, quinoline ring, and isoquinoline ring; oxygen-containing heterocycles such as furan ring, benzofuran ring, and biran ring; thiophene ring; Examples include sulfur-containing heterocycles such as benzothiophene rings.

The hydrogenated group or unsaturated heterocyclic group may contain at most 5, preferably up to 3 substituents. Examples of such substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl monodyano group; nitro group; amino group; carboxyl group; methylamino group; alkylamino having 1 to 4 carbon atoms such as diethylamino group. Base;
Lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, and t-butyl group; halogenated lower alkyl groups having 1 to 3 halogen atoms such as trifluoromethyl group and 2-chloroethyl group; Lower alkoxy groups with 1 to 4 carbon atoms such as methoxy, ethoxy, and t-butoxy; aryl groups with 6 to 1 o of carbon atoms such as phenyl, naphthyl, and tolyl; such as phenoxy and 1-naphthoxy groups Aryloxy group having 6 to 14 carbon atoms; aralkyl group having 7 to 15 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group; aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group, phenylpropoxy group; Examples include alkylthio groups of numbers 1 to 4. These substituents may be the same or different, and their positions are not particularly limited.

5 6 cyano group, amino group, alkylthio group having 1 to 4 carbon atoms,
A divalent aromatic hydrocarbon which may be substituted in each case by at least one atom or group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. or a divalent unsaturated heterocyclic group.

an aryl group having 6 to 14 carbon atoms or a 5- or 6-membered monocyclic heterocyclic group containing one nitrogen atom, one oxygen atom and one sulfur atom, which may be substituted in each case by ~3 More preferably, it is a fused heterocyclic group in which a benzene ring or a cyclohexene ring is fused to the heterocyclic group.

A 5-shell or 6-membered monocyclic heterocycle containing one elementary atom, or a fused heterocycle in which a benzene ring or a cyclohexene ring is fused to the heterocycle is preferred. It is also a preferred embodiment that these benzene rings, monocyclic heterocycles, or fused heterocycles contain one or two of the above-mentioned substituents.

R in the above-mentioned -tsuzuri allowance [1] is a monovalent hydrocarbon group or a monovalent heterocyclic group, each of which may have a substituent.

The hydrocarbon group for R may be any of aliphatic, alicyclic, or aromatic hydrocarbons, and specific examples include methyl, ethyl, propyl, and butyl groups having 1 carbon number. ~20, preferably 1 to 6 alkyl groups; C6 to C14 aryl groups such as phenyl, tolyl, xylyl, and naphthyl; benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups; An aralkyl group having an alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms is suitable.

The heterocyclic group for R1 is a 5- or 6-membered ring containing 1 to 3, preferably 1 or 2, of at least 8 heteroatoms such as nitrogen, oxygen, and sulfur atoms. A ring heterocyclic group or a condensed heterocyclic group in which benzene is condensed thereto is preferred. In addition to the examples of unsaturated heterocyclic groups explained in the above definitions, saturated heterocyclic groups such as saturated piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, indoline ring, and chroman ring can be mentioned.

There is no particular problem even if the hydrocarbon group or heterocyclic group of R1 described above has a substituent. Examples of such substituents include the same substituents as those explained above, in which the hydrocarbon group or the heterocyclic group preferably contains at most 5, preferably 3.

The above R is preferably a halogen atom, a carbon number 1
C1-C20 alkyl group optionally substituted with ~4 alkoxy group or phenyl group: C6-C10 aryl group optionally substituted with a halogen atom or C1-4 alkoxy group ; or a 5- or 6-membered monocyclic heterocyclic group containing 1 to 3, especially 1 nitrogen atom, carbon atom, and sulfur atom, or a fused heterocyclic group in which a benzene ring is fused to the heterocyclic group; , especially monocyclic heterocyclic groups.

Furthermore, particularly preferred among the above R is a carbon number of 1 to 6.
an alkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

The above general 2N) in the present invention means a rubonylidene group or an adamantylidene group. Here, the norbornylidene group is represented by the following formula, and the adamantylidene group is represented by the following formula.

\ / The above formula shows the skeletal structure of a norbornylidene group and an adamantylidene group, both of which have no substituents. In these norbornylidene groups or adamantylidene groups, the hydrogen atom of the above formula may be substituted with a substituent, and the number thereof may be one or more. When a substituent is present, its type, number and position are arbitrarily selected depending on the purpose and use. Moreover, when it has a plurality of substituents, they may be the same substituent or different types of substituents.

Substituents for the norbornylidene group or adamantylidene group include, for example, a hydroxy group; an alkylamino group having 1 to 4 carbon atoms such as a methylamino group and a diethylamino group; a methoxy group, an ethoxy group, a tert-butoxy group, etc. Alkoxy group having 1 to 4 carbon atoms; aralkoxy group having 7 to 15 carbon atoms such as hensyloxy group: phenoxy group, 1
-Aryloxy group having 6 to 14 carbon atoms such as naphthoxy group; 1 to 4 carbon atoms such as methyl group, ethyl group, L-butyl group
Lower alkyl group: halogen atom such as atom, chlorine, oxal, etc.; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl; halogen substitution having 1 or 2 carbon atoms such as trifluoromethyl group Alkyl groups; nitro groups; aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl groups; aralkyl groups having 7 to 9 carbon atoms such as phenylethyl and phenylpropyl groups; and the like.

Preferred examples of these substituents include halogen atoms, hydroxy groups, alkyl groups having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
an alkoxy group having 2 to 10 carbon atoms, an aral 12kyl group having 7 to 9 carbon atoms, or an aral group having 6 to IO carbon atoms.

In the above-mentioned binding margin (1) in the present invention, X is an oxygen atom (-〇-), a group N-R2, %:;
Group: ;NA, -A, or group>N-8, -R4.

Also, in - Tsuzuriyo (1), X is the base: >N At B+ (82 Uichikoku - (
B2)-GoR3, the group: ;N A3 Aa or the group '/N-A3-R4, especially the group '; N-A3-R, or the group ";
However, R1 is 1 to 3 atoms selected from the group consisting of a halogen atom, a cyano group, and a nitro group, or an optionally substituted alkyl group having 1 to 10 carbon atoms. ) is more preferable from the viewpoint of the durability of photochromic properties of the resulting compound.

X in general formula (1) represents the above group>N-8+ 8+ (A2+F-(Bz+-rR3
Among them, when R1 is a naphthyl group or a naphthylalkyl group, and when the group is :;N A3 Aa, the naphthyl group and imide group (〉
It is preferable that the number of atoms in the main chain sandwiched between N- and N- is in the range of 3 to 7 because a compound with excellent durability of photochromic action can be obtained.

Next, R in the above χ, , R3, R4, A, , A2
, A3, 'A4, B+, B2, m and n will be explained in detail.

R2 represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-5iso- or tart-butyl group, a pentyl group, a hekynyl group, an octyl group, Examples include decyl groups, among which those with 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, are preferred. Examples of the aryl group include those having 6 to 10 carbon atoms, such as phenyl, tolyl, and naphthyl groups.

A9, Am and A may be the same or different and can be an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group.

Specific examples of these include alkylene groups having 1 to 10 carbon atoms such as methylene group, 34 ethylene group, propylene group, butylene group, trimethylene group, tetramethylene group or 2,2-dimethyltrimethylene group; ethylidene group; Alkylidene group having 2 to 10 carbon atoms such as propylidene group or isopropylidene group; cycloalkylene group having 3 to 10 carbon atoms such as cyclohexylene group; 2-methylcyclohemethylcyclohexane-α,l-diyl group (
Examples include alkylcycloalkane-diyl groups having 6 to 10 carbon atoms, such as -co2%). A.

And A2 is particularly preferably an alkylene group having 1 to 6 carbon atoms, an alkylidene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, or an alkylcycloalkane-diyl group having 6 to 7 carbon atoms.

B and B2 may be the same (or different) and are selected from the following seven bonding groups.

5 ooo o.

1 or -NIIC- m and n each independently represent 0 or],
When it represents O, (A2);- or (Bztsui- means a bond. When m is 0, r! also represents 0.

R3 represents an alkyl group, a naphthyl group, or a naphthylalkyl group, each of which may have a substituent. Although the number of carbon atoms in the above alkyl group is not particularly limited, it is preferably 1 to 10, and the number of carbon atoms in the alkyl group of the naphthylalkyl group is preferably 1 to 4.

The substituents of each group described above are not particularly limited, but the alkyl group described above may be substituted with 1 to 3 atoms or groups selected from the group consisting of a halogen atom, a cyano group, and a nitro group, and The above naphthyl group or naphthylalkyl group is a halogen atom, a cyano group, a nitro group, and has a carbon number of 1
~3 alkyl6-ruamino groups, alkyl groups having 1 to 3 carbon atoms, and 1 to 3 carbon atoms
may be substituted with 1 to 3 atoms or groups selected from the group consisting of 3 alkoxy groups.

As the alkyl group represented by R above, the same alkyl group as exemplified for R2 above can be used. Examples of the naphthylalkyl group include naphthylmethyl, naphthyl ethyl, naphthylpropyl, and naphthylbutyl groups.

A4 represents a naphthyl group which may have a substituent.

The type of substituent is not particularly limited, but the naphthyl group includes a halogen atom, a cyano group, a nitro group, an alkylamino group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. may be substituted with 1 to 3 atoms or 1 selected from the group consisting of: Further, R4 represents a halogen atom, a cyano group or a nitro group.

In the above definitions of R3 and A4, examples of the halogen atom include fluorine, chlorine, and bromine.

As the resin for the resin layer containing the photochromic compound dispersed therein, a resin in which the photochromic compound can be uniformly dispersed and which does not swell or dissolve in the thermosetting resin monomer is preferably used. More specific examples of such resins include hydrophilic resins such as polyvinyl alcohol, polyvinyl butyral, polyhydroxyethyl methacrylate, polyacrylonitrile, and cellulose; polyolefin resins such as polyethylene and polypropylene; polytetrafluoroethylene, polyvinyl chloride, etc. halogen-containing resin; examples include thermosetting resins described below.

The blending ratio of the above-mentioned resin and photochromic compound may be determined depending on the color density of the desired photochromic molded article, but in general, 0.001 to 60 parts by weight of the photochromic compound is added to 100 parts by weight of the resin. ,
In particular, it is preferably in the range of 0.1 to 40 parts by weight.

The thickness of the resin layer containing the photochromic compound is not particularly limited, but from the viewpoint of color density and durability of photochromic properties of the photochromic molded article, it is generally 0.01 to 2 mm, preferably 0.02 to 1 mm.
mtn range.

Although the method for producing the resin layer containing the photochromic compound is not limited in any way, for example, the following method can be mentioned.

■ A method in which a thermoplastic resin and a photochromic compound are melted and kneaded at a temperature higher than the melting point of the thermoplastic resin, and then extruded.

■ A method in which a thermoplastic resin is dissolved in a suitable solvent, a photochromic compound is mixed therein, and then the solvent is removed by evaporation or the like.

■ A method of mixing raw material monomers of thermoplastic resins or thermosetting resins with photochromic compounds, subjecting them to emulsion polymerization or suspension polymerization, and forming a film on the surface of the thermosetting resin with the resulting emulsion or suspension as described below. .

■ A method in which a thermoplastic resin or thermosetting resin raw material and a photochromic compound are mixed and cast polymerization is performed.

Next, as the thermosetting resin, ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis(4-methacryloyloxyethoxyphenyl)propane, 2.
Polyhydric acrylic acid and polyhydric methacrylic acid ester compounds such as 2-bis(3,5 dibromo-4-methacryloyloxyethoxyphenyl)propane; diallyl phthalate,
Polyvalent allyl compounds such as diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1. Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds such as 2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl)ether, and 1,4-bis(methacryloylthiomethyl)benzene; divinylbenzene, etc. Polymers of radically polymerizable polyfunctional monomers: or each of these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride; methyl acrylate, methyl methacrylate,
Acrylic acid and methacrylic acid ester compounds such as hensyl methacrylate, phenyl methacrylate, and 2-hydroxyethyl methacrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; Acrylic acid and thiomethacrylic acid ester compounds; copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, and bromostyrene; furthermore, ethanedithiol, propanetriol, Addition copolymers of polyvalent thiol compounds such as hexanedithiol, pentaerythritol tetrakisthioglycolate, di(2-mercaptoethyl)ether and the above radically polymerizable polyfunctional monomers; diphenylethane diisocyanate, xylylene diisocyanate, Examples include addition polymers of polyvalent isocyanate compounds such as p-phenylene diisocyanate and polyhydric alcohol compounds such as ethylene glycol, trimethylolpropane, pentaerythritol, and bisphenol A, or the above-mentioned polyvalent thiol compounds. These monomers can be used alone or in combination of two or more.

As a method for molding the photochromic molded body, any known method may be used as long as a resin layer containing a dispersed photochromic compound is laminated between thermosetting resins. A method of injecting raw material monomers of a thermosetting resin onto both sides of a resin layer containing a dispersed compound, and then heating and curing the thermosetting resin, using an appropriate adhesive on both sides of a resin layer containing a photochromic compound. The method of laminating layers is to adhere a resin layer containing a dispersed photochromic compound onto a thermosetting resin molded body using an appropriate adhesive, then pour the raw material monomer of the thermosetting resin onto it and heat cure it. Examples include a method of stacking the layers. In addition, in order to improve the adhesion between the thermosetting resin and the resin layer containing dispersed photochromic compounds,
The surface of the resin layer may be coated with an adhesive reinforcing coat. Examples of the adhesive reinforcing coating agent include epoxy primers, polyurethane primers, silicone primers, and polyalcohol primers.

By incorporating an ultraviolet stabilizer into the resin layer containing a dispersed photochromic compound in the photochromic molded article of the present invention, the durability of photochromic properties can be further improved. As the UV stabilizer, any known UV stabilizer added to various plastics can be used without any limitations.

In the present invention, considering the improvement in the durability of the photochromic compound, among various UV stabilizers, - doublet oxygen quenchers, hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants are preferred. used. A more specific example of these UV stabilizers is Sheasorb UV1084. Sheasorb 3346
(manufactured by American Cyanamid), UV-Chek AMIOI, IIV-Chek AM105 (manufactured by Ferro Corporation), Irgastab 2002. Tinuvin 765. Tinuvin 144 Kinsobu 944. Tinuvin 622. Irganox 1010° Irganox 245 (manufactured by Ciba Geigy), Lilex NB
C (manufactured by DuPont), Sheasorb 3346 (manufactured by American Cyanamid), Sanol LS1114, Su/-
Le I, s-744, S/-le LS-2626 (manufactured by Tool ■), Sumilizer GA-80, Sumilizer GM, Sumilizer BBM-3, Sumilizer WX-
11° Sumilizer S, Sumilizer B) IT, Sumilizer TP-D, Sumilizer TPL-R, Sumilizer TPS, Sumilizer MB (manufactured by Sumitomo Chemical Co., Ltd.), Mark A0-50. Ma=io-20, Mark AO
-30,7-ri AO-330, Mark AO-23, (manufactured by Adeca Argus), Antioxidant HPM
-12 (S, F.

(manufactured by OOS), etc. All of the above names are product names.

(Effects) In the photochromic molded article of the present invention, the durability of the photochromic compound is improved depending on how the photochromic compound is present in the resin.

The photochromic molded article of the present invention can be used in a wide range of fields, such as various recording memory materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, etc. It can be used as a variety of recording materials. In addition, the photochromic molded article of the present invention can also be used as a material for photochromic lenses, optical filter materials, display materials, photometers, decorations, and the like.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

"Parts" in Examples are "parts by weight."

In addition, the symbols in the following examples indicate the following compounds.

・BMDBP: 2.2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane・cI! , -st: Chlorstyrene・TMP-TAC: ) Limethylolpropane triallyl carbonate・BADBP: 2,2-bis(4-allyl carbonate ethoxy-3,5-dibromophenyl)propane・^DC: Allyl diglycol carbonate・DAP
Diaryl phthalate, St: Styrene, DCIPF Nidi(2-chloroisopropyl) fumarate, EGDMA: Ethylene glycol dimethacrylate, PETTP: Pentaerythritol tetrakis (β-thiopropionate), DME Nidi(2-mercaptoethyl) ether, I
IVB Nidivinylbenzene/XIC: Xylylene diisocyanate/HPA:
3-(2,4-dibromophenoxy)-2hydroxypropyl acrylate/MMA: Methyl methacrylate 56/DECDMA Nidiethylene glycol dimethacrylate/TBBM: 3,4.5-toIJ bromohensyl methacrylate/HEMA: 2-hydroxy Ethyl methacrylate/BMA: Penzyl methacrylate/PVA:
Polyvinyl alcohol/PHE'MA: Polyhydroxyethyl methacrylate/PAN: Polyacrylonitrile Production example 1 1-hydroxy-2-acetonaphthone 10g (0,Q5
4mol) Norcamphor 6.6g (0.06mol)
A solution was prepared by dissolving 8 g (0,113 mol) of pyrrolidine and pyrrolidine in 300 cc of toluene. 1 of this mixture
It was boiled for 0 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized from acetone. Next, this chromanone compound (hereinafter referred to as blank space) 7 was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to form a chromanol compound. This chromanol compound 7.47
1 g with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide.
Heating at 50-160° C. for 10 minutes and purifying the brown viscous liquid by chromatography on silica gel gave 6.3 g of a chromene derivative of the following formula.

The elemental analysis values of this compound are C86,93%, H6,8
9%, 06.18% Teatte, Cl98180 Calculated value for C 87.02%, H6.8T%, 0
It was in very good agreement with 6.12%. In addition, when proton nuclear magnetic resonance spectra were measured, the results were 67.2 to 8.3.
A peak of <6H based on the proton of the naphthalene ring near ppm, a peak of <2H based on the proton of the alkene near δ5.6 to 6.7 ppm, and a peak of <2H based on the proton of the norbornylidene group near 61.2 to 2.5 ppm. It showed a broad peak of 10H. Furthermore, when I'3C-nuclear magnetic resonance spectrum was measured, a peak based on the carbon of the norbornylidene group was found around 627-52 ppm, and a peak based on the carbon of the norbornylidene group at 6110-1
A peak based on the carbon of the naphthalene ring around 60 ppm,
A peak based on the carbon of the alkene appears around δ80 to x1 oppm.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (1).

Production example 2 1-acetyl-2-naphthol 10 g (0,054
mol ) and bicyclo(3,3,1)nonan-9-one 8.29 g (0.06 mol) and morpholine 8.7
g (0.10 mol) and 300 cc of toluene
To? 8. A solution was prepared. The mixture was boiled for 5 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was mixed with methanol 20
0 cc and added lithium aluminum hydride to form a chromanol compound. 6.49 g of this chromanol compound was heated with anhydrous copper sulfate in a stream of carbon dioxide at 170-180°C for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain the chromene derivative 5. 8g was obtained.

The elemental analysis values of this compound are CB6.81%, H7,6
2%, 05.57%, calculated values for C2182□0 CB6.90%, H7,59%, 05.
There was a very good agreement of 52%. In addition, when proton nuclear magnetic resonance spectra were measured, δ7.2-8.3pp
<6H peak based on the proton of the naphthalene ring near m, 66.0 to 7. <2H peak based on alkene proton near Oppm, 61.2-2.5 pptn
A broad peak of 14H based on the proton of the bicyclo(3,3,1) 9-nonylidene group was shown nearby.

Furthermore, when the l″C-nuclear magnetic resonance spectrum was measured, bicyclo(3.3°1) was found around δ27-55ppm.
Peak based on carbon of 9-nonylidene group, δ110-1
A peak based on the carbon of the naphthalene ring around 60 ppm,
A peak based on alkene carbon appears around 680 to 110 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).
child.

Production Example 3 3.06 g of a chromanone compound represented by the following formula was dissolved in 50 cc of anhydrous ether, and the solution was cooled to 0°C.
Freshly prepared Grignard reagent CH,Mg 1 (0,012 mol) in 5 Qec of anhydrous ether was added dropwise to the solution of SO 1 2 over a period of about 1 hour. After the addition was completed, the ether solution was stirred for another 2 hours at room temperature, the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, the ether was removed under reduced pressure, and the chromanone The compound was changed to a chromanol compound.

This chromanol compound was then heated at 200°C for about 10 minutes with anhydrous copper sulfate in a stream of carbon dioxide, and a brown viscous liquid was produced by chromatography on silica gel to obtain 2.47 g of a chromene derivative of the following formula. Ta.

Production example 4 1-acetyl-2-naphthol 10 g (0,054
mol ) and norkampf y-6,6g (0,06m
ol) and morpholine 8.7 g (0.10 mol)
was dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining product was recrystallized from acetone to obtain 7.53 g of a compound represented by the following formula.

As in Production Example 1, by elemental analysis, proton nuclear magnetic resonance spectrum, and I″C-nuclear magnetic resonance spectrum measurements,
This compound was confirmed to be a compound represented by the above structural formula (3).

Next, 7.53 g of this compound was added to 100 cc of methanol.
6.95 g of a chromanone compound represented by the following formula was obtained by dissolving it in the solution and reacting it with methyl iodide.

Next, the generated chromanone compound was converted into a chromanol compound in the same manner as in Production Example 3, and after dehydration reaction, separation and purification, a chromene derivative 5.84 of the following formula was obtained.
I got g.

10 g (0,0318 mol) of acetonaphthone, 2.77 g (0,0477 mol) of acetone, and 1,13 g (0,0159 mol) of pyrrolidine in 100 m7 of toluene! To? A solution of debris was prepared. The mixture was boiled for 10 hours and the water was separated. After the reaction is complete,
Toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in 100 mρ of methanol, and sodium borohydride was gradually added to give the chromanol compound.

By heating 6.0 g of this chromanol compound with 4.0 g of anhydrous copper sulfate at 150 to 160°C for 10 minutes in a carbon dioxide stream, and purifying the brown viscous liquid by chromatography on silica gel, 3.8 g of a chromene derivative of the formula was obtained.

As in Production Example 1, it was confirmed by elemental analysis, proton nuclear magnetic resonance spectrum, and +3C+*N gas resonance spectrum that this compound was a compound represented by the above structural formula (4).

Production Example 5 5-n-octyloxy-1-hydroxy-2 Production Example 1
as well as elemental analysis, proton nuclear magnetic resonance spectroscopy,
By measurement of 13C-nuclear magnetic resonance spectrum, it was confirmed that this compound was a compound represented by the above structural formula (5).

Production Examples 6-14 The chromene derivatives shown in Table 1 were synthesized in the same manner as in Production Examples 1-5.

As a result of structural analysis of the obtained product using the same structural confirmation method as in Production Example 1, it was confirmed that it was a compound represented by the structural formula shown in Table 1.

Production Example 15 3.4 g (0.01 mol) of 3-thienylethylidene-2-adamantylidene succinic anhydride of the following formula and 17.8 g (0.01 mol) of glycine-methyl ester of the following formula.
02 mol) NH□C11zCOCt13 1 was dissolved in toluene and heated at 50°C for 2 hours under nitrogen atmosphere. After the reaction, the solvent was removed, the solution was dissolved in acetyl chloride, and the mixture was refluxed for 1 hour for cyclization. The obtained compound was rearranged to the following fulgimide compound (1) by refluxing it in O-dichlorobenzene for 6 hours. The compound was purified by chromatography on silica gel using benzene and 9-methyl as eluent and was obtained as light yellow needles from chloroform and hexane in 27% yield. The elemental analysis values of this compound are C66.78%, H6.09%, N3
．． 36%, O15.8%, 37.96%, which is the calculated value for Cz3HzsOJS
．． 15%, H6.08%, N 3.41%, 01
The results were in excellent agreement with 5.6% and 37.79%. In addition, when proton nuclear magnetic resonance spectra were measured, δ7.
0-8. <2H peak based on aromatic protons near Oppm, at 62.7 ppm; c-cH
.

<3H peak based on proton of bond, δ3.7ppm
There is a <3H peak based on the proton of the methyl group of the -COCHz bond in the vicinity, and a 14H peak based on the proton of the adamantylidene group at 61.2 to 2.5 ppm.

Proton N-c with 1-5 rearrangements at δ3-5 ppm
It showed a <3H peak based on the o2-bond.

Furthermore, 13C-nuclear magnetic resonance spectrum (13C-NMR)
When measured, there was a peak based on the carbon of the adamantylidene group and the carbon of the methylene chain at around 627 to 70 ppm, a peak based on the carbon of the methyl group around 615.6 ppm, and a peak based on the carbon of the thiophene ring around 6110 to 160 ppm. A peak based on the carbon of the C-0 bond appears near δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was fulgimide compound θ shown by the following structural formula.

was dissolved in tetrahydrofuran, and 1 part of metallic potassium was added to the solution.
g was reacted at room temperature to obtain 3 g of imido potash having the following formula.

Production Example 16 Fulgimide compound of the following formula 3.4 g (0.01 mo
l) This and 1.2 g of bromoacetonitrile (0
,01 mol) BrCHzCN was reacted in dimethylformamide to obtain the following fulgimide compound. This compound 1 2 was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained as pale yellow crystals from hexane in 57% yield. The elemental analysis value of this compound is C69, 81%, 85
．． 80%, N 7.44%, 08.50%, 38
．． 46%, which is the calculated value for 02□H2□N20□S 69.84%, 85.82%,
There was excellent agreement with N 7.41%, 08.47%, and 38.47%. In addition, when proton nuclear magnetic resonance spectrum was measured, there was a <2H peak based on the proton of the thiophene ring at around 67.0 to 7.5 ppm, and a peak of <2H at 64.0 to 7.5 ppm.
<2H peak based on proton of ≧N-CH2CN bond near 5 ppm, <IH peak based on 1.5 rearranged proton near δ3.7 ppm, 62.7 ppm
-CM nearby.

<3H peak based on proton of bond, 61.3-2,
The 14H peak of the proton of the -CH,- bond and the proton based on the adamantylidene group was shown around 5 ppm.

Furthermore, 130-nuclear magnetic resonance spectrum (Ilc-NMR)
) was measured, and a peak based on the carbon of the adamantylidene group was observed at around 627 to 70 ppm, and a peak at δ15.6 ppm was observed.
Nearby peaks based on carbon of methyl group, 6110-16
A peak based on the carbon of the thiophene ring near 0 ppm, 6
A peak based on carbon of ≧C=0 bond appears around 160 to 170 ppm.

From the above results, it was confirmed that the isolated product was fulgimide compound 061 shown by the following structural formula.

3 Example 1 A polyvinyl alcohol film (thickness 0.2 mm) in which 5% by weight of the photochromic compound of Production Example 1 and 3% by weight of the fulgimide compound of Production Example 15 were dispersed was coated with an adhesive reinforcing coating in advance and was bonded to a glass plate. It was set in the center of a mold made of a gasket made of ethylene-vinyl acetate copolymer, and allyl diglycol carbonate containing 3.0% by weight of isopropyl bar carbonate was injected into the cavities on both sides to perform cast polymerization. went. Polymerization was carried out using an air oven at 30°C to 90°C over 18 hours, gradually increasing the temperature and holding at 90°C for 2 hours.

After the polymerization was completed, the mold was taken out from the air oven, and after cooling, the polymer was removed from the glass mold. The fatigue life of the obtained molded product was measured using a xenon long life fade meter FAL-25AXHC manufactured by Suga Test Instruments Co., Ltd.

In addition, changes in color tone were visually observed. Fatigue life (T
+/l) was expressed as the time required for the absorbance at the maximum absorption wavelength of the chromene derivative to decrease to 1/2 of the initial absorbance (To). However, T.

The absorbance of and TI/2 is the value obtained by subtracting the absorbance of the unirradiated molded product at the maximum absorption wavelength based on the chromene derivative, and the absorbance of To was measured 60 seconds after light irradiation.

The results are shown in Table 3.

Examples 2 to 21 In Example 1, the types and amounts of the raw material monomers of the resin containing the photochromic compound dispersed therein, the photochromic compound, and the thermosetting resin used were changed, and polymerization was carried out by known means according to the raw material monomers. The same procedure as in Example 1 was carried out except that. The results are shown in Table 3.

Comparative Example 1 The fatigue life of the polyvinyl alcohol film containing the photochromic compound obtained in Example 1 dispersed therein was measured in the same manner as in Example 1. The results are shown in Table 3.

Procedural amendment

Claims (1)

[Claims] (1) The following formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A] However, R^1 and R^2 are the same or different alkyl groups, respectively, and these are substituted together. may constitute an optionally substituted norbornylidene group or an optionally substituted bicyclo[3.3.1]9-nonylidene group, and R^3 and R^4 are respectively the same or different hydrogen atoms,
It is an alkyl group, aryl group, aralkyl group, or substituted amino group, and ▲ has a mathematical formula, chemical formula, table, etc. ▼ is an optionally substituted aromatic hydrocarbon group or an optionally substituted unsaturated heterocyclic group. Yes, when R^1 and R^2 are alkyl groups, there are ▲mathematical formulas, chemical formulas, tables, etc.▼,
There are alkyl groups with 6 to 20 carbon atoms, alkoxy groups with 6 to 20 carbon atoms, -R^5-S-R^6, and ▲mathematical formulas, chemical formulas, tables, etc.▼ (However, R^5 is an alkylene group or ■ O-R^8■_n
(However, R^8 is an alkylene group, and n is a positive integer.), R^6 and R^7 are the same or different alkyl groups, respectively, and X is ▲ mathematical formula, chemical formula, There are tables, etc. ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) A bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group having at least one substituent selected from the group consisting of: A photochromic molded article comprising a thermosetting resin layer laminated on both sides of a resin layer containing a dispersed photochromic compound represented by: