JPH03252492A - Photochromic formed body - Google Patents

Abstract

PURPOSE:To obtain the subject formed body excellent in durability of photochromic action by dispersing resin particles containing a specific chromene derivative and having a specified particle diameter in a thermosetting resin. CONSTITUTION:The objective formed body obtained by dispersing resin particles, containing a chromene derivative expressed by formula I {R<1> and R<2> are alkyl, (substituted) norbornylidene or (substituted) bicyclo[3.3.1]9-nonylidene; R<3> and R<4> are H, alkyl, aryl, aralkyl or substituted amino; formula II is (substituted) aromatic hydrocarbon or (substituted) unsaturated heterocyclic ring} and having 0.01-100mum (preferably 0.1-20mum) average particle diameter in a thermosetting resin.

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.

It has been discovered that the chromene derivative has an excellent photochromic effect, and has already been proposed (Japanese Patent Application No. 63-2203).
No. 87, Japanese Patent Application No. 1-141206 and Japanese Patent Application No. 1-14
No. 3.011).

(Problems to be Solved by the Invention) Furthermore, the present inventors continued research on dispersing the above-mentioned chromene derivative in a thermosetting resin to produce a photochromic molded article typified by a photochromic lens. the 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, one object of the present invention is to obtain a photochromic molded article with excellent durability.

(Means for Solving the VS Problem) The present invention provides that R1 and R2 are respectively the same or different alkyl groups, and these are optionally substituted norbornylidene groups or Bicyclo optionally substituted with 1 [comprising a 3,3,119-nonylidene group]
Most preferably, R3 and R4 are the same or different hydrogen atoms, alkyl groups, aryl groups, aralkyl groups, or optionally 41-position unsaturated heterocyclic groups, and R1 and R2 are alkyl groups with 20 carbon atoms, 6 to 20 carbon atoms. alkoxy group, -R'-6-R" and -R'-X<.

(However, RM is an alkylene group or ÷O-R'+.

(However, R6 is an alkylene group, n is a positive integer.), Rm and R7 are the same or different alkyl groups, respectively, and X is -N<, -P<, -p< :z or -o-p < g II. ) 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 resin particles having an average particle diameter of 0.01 to 100 μm and containing a photochromic compound represented by the formula are dispersed in a thermosetting resin.

The photochromic compound in the present invention is a chromene derivative represented by the general formula (A).

In the general formula (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 photochromic properties of the compound represented by the general formula (A), the number of carbon atoms is preferably 1 to 3, and particularly preferably 1. Preferred alkyl groups are specifically methyl group, ethyl group, n-
Examples include propyl group and i-propyl group.

R' and R2 in the above-mentioned general 2 mA) are taken together to form a ring, and are an optionally substituted norbornylidene group or an optionally substituted bicyclo(3,3,
1:l 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, the type, number, and position 1 may be selected depending on the purpose and use; when a plurality of substituents are present, the same substituent may be used, or different substituents may be used. There may be.

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 Aryloxy group having 6 to 10 carbon atoms such as phenyloxy group, tolyloxy group, naphthyloxy group; benzyl group, phenethyl group, phenylpropyl group, etc. Aralkyl group having 7 to 10 carbon atoms; 7 to 10 carbon atoms such as benzyloxy group, phenethyloxy group, phenylpropyloxy group
~10 aralkoxy groups; C1-4 alkylamino groups such as methylamino and ethylamino groups; C2-8 dialkylamino groups such as dimethylamino and diethylamino groups; methoxycarbonyl and ethoxycarbonyl groups Examples include alkoxycarbonyl groups having 2 to 10 carbon atoms.

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.
~lO aryl group, aralkyl group having 7 to 10 carbon atoms,
It is a dialkylamino group having 2 to 8 carbon atoms.

R3 and R4 in the general formula (A) are each the same or different and are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a substituted amino group.

Here, the substituted amino 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 CI (zO(C
Hz) Oxydialkyl having 3 to 6 carbon atoms such as i-5 L/7
Group; -CH2SCHzCHz-, -CHzS(C!(z
) s-CHzCHzSCHtCIIz-, etc., carbon number 3
~6 thioal CHz CH3 kylene group; -CLNCLCL--CFIJ(CHx)
! An azoalkylene group having 3 to 6 carbon atoms, such as -H3 -CLCHJCLCL-, is 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
-1o aryl group; carbon number 7-1o such as benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group
Examples include aralkyl groups. In addition, examples of substituted amino groups include methylamino groups, ethylamino groups, etc. having 1 to 1 carbon atoms.
4 alkylamino'group; dialkylamino group having 2 to 8 carbon atoms such as dimethylamino group and diethylamino group; containing at least one nitrogen atom such as pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiazolidine ring, etc. or a monovalent group derived from a 4- to 7-membered monocyclic saturated heterocycle containing a nitrogen atom and an oxygen atom or a sulfur atom.

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 B 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, by selecting each group of Rs or R4, which is preferably a monovalent group derived from a 6-membered monocyclic saturated heterocycle, the fading rate of the compound of general formula (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, in the general formula [A] in the present invention, O
[II' is 2 which may each have a substituent
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 preferable. Examples of rings forming such an aromatic hydrocarbon group include a benzene ring, a naphthalene ring, etc. , phenanthrene ring, etc.

In addition, as unsaturated heterocyclic groups, nitrogen atoms, oxygen atoms,
A 5-membered or 6i4-ring monocyclic heterocyclic group containing 1 to 2 sulfur atoms, or a fused heterocyclic group in which a benzene ring is fused thereto is shown. Examples of rings forming such an unsaturated heterocyclic group include nitrogen-containing heterocycles such as pyridine ring, quinoline ring, and pyrrole ring; oxygen-containing heterocycles such as furan ring and benzofuran ring; thiophene ring and benzothiophene ring. Examples include sulfur-containing heterocycles such as.

) groups having 1 to 4 carbon atoms; dialkylamino groups having 2 to 8 carbon atoms such as dimethylamino and diethylamino groups; halogenoalkyl groups having 1 to 4 carbon atoms such as trifluoromethyl groups; thienyl groups , 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.

The above RL and R2 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 monocyclic heterocyclic groups. Preferably, it is a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group which may be substituted in each case by at least one member selected from the group.

In the general formula [A], R1 and R1 are each optionally substituted with 20 alkyl groups or 1 to 3 alkoxy groups having 6 to 20 carbon atoms, a benzene ring,
or a divalent group derived from 2 to 4 condensed benzene rings, or a divalent group derived from 2 to 4 condensed benzene rings, or 1 to 1 oxygen atom, sulfur atom, or nitrogen atom
A 5-membered ring containing two or 6j! 2 derived from a monocyclic heterocycle or a fused heterocycle with a benzene ring fused to the ring
Preferably, it is a valent group.

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'Jy (wherein, R1 is an alkylene group and n is a positive integer),
Rh and R1 are the same or different alkyl groups, respectively, and X is a bicyclic aromatic hydrocarbon group having at least one substituent selected from the group -N<, -p ( It is a cyclic 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, octadecyl group, eicosyl group, etc.

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, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, Examples include decyloxy group, undecyloxy group, dodecyloxy group, pentadecyloxy group, octadecyloxy group, and eicosyloxy group.

Furthermore, other substituents of the bicyclic aromatic hydrocarbon group or the bicyclic unsaturated heterocyclic group are -R'-5-R'+0-R
@++r (where RI' is an alkylene group and n is a positive integer), Rh and R'' are the same or different alkyl groups, respectively, and X is. The alkylene groups represented by R5 and R1 of the 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
Specific examples of the alkylene group, which preferably ranges from 20 to 20, include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

Pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group.

Examples include decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, pentadecamethylene group, octadecamethylene group, and eicosamethylene group. In addition, n in +O-R"-+-Ir represented by RS may be a positive integer, but the number of carbon atoms in the chain represented by 10-R"+-1r in the shell is 1 to 20, It is preferable to select n to be preferably 6 to 20, and for this purpose, n
is generally selected from the range of 1 to 20.

Further, the number of carbon atoms in the alkyl group represented by R6 and R7 is not particularly limited, but is preferably in the range of 1 to 4 from the viewpoint of fading speed 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.

The chromene derivative represented by the general formula (A) in the present invention generally develops a yellow to red color. Therefore, when the photochromic molded article of the present invention is used for applications such as ornaments, the compound of the general formula (A) may be used alone, and the photochromic molded article of the present invention is used for applications such as sunglasses. In some cases, 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. Other photochromic compounds are generally called fulgide compounds or fulgimide compounds. These compounds are preferably used in the present invention because they can be adjusted to brown or gray tones by using them in combination with the compound of general formula (A). The amount of the above-mentioned fulgide compound or fulgimide compound to be used may be appropriately selected depending on the required 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, based on 100 parts by weight of the compound.

The above-mentioned fulgide compound has the structure shown by the following formula, and a compound having photochromic properties is employed without any restriction. In addition, a compound having the structure shown in the following formula and having photochromic properties may 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 R3 may each have a substituent. monovalent hydrocarbon group or monovalent mantylidene group is an oxygen atom, Group>N Rz Group〉N-A1-Bl　-(Azh-(Br)r　R.

group) N-^, -A4 or Group'): represents N-A3-Ra.

In the general formula (1), these are heterocyclic groups, and these groups may have at most 5 substituents, preferably up to 3 substituents.

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 benzene ring, a naphthalene ring, and a phenanthrene ring. Examples include rings.

Further, as the unsaturated heterocyclic group, a 5- or 6-membered monocyclic heterocyclic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom, or a benzene 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 or unsaturated heterocyclic group may contain at most 5, preferably up to 3 substituents, examples of such substituents include fluorine, chlorine, bromine, iodine. halogen atom; hydroxyl group; cyano group; nitro group; carboxyl group; methylamino group; alkylamino group having 1 to 4 carbon atoms such as diethylamino group;
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 having 1 to 4 carbon atoms such as methoxy, ethoxy, and t-butoxy; aryl groups having 6 to 10 carbon atoms such as phenyl, naphthyl, and tolyl; phenoxy, 1-naphthoxy, etc. 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.

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 hetero N 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-membered ring or 6RN monocyclic heterocycle containing one elementary atom, or a fused heterocycle in which a benzene ring or a cyclohexene ring is fused to this heterocycle is preferable; these benzene rings, monocyclic heterocycles, or Similarly, it is a preferable embodiment that the fused heterocycle contains one or two of the above-mentioned substituents.

R1 in the general formula (1) is a monovalent hydrocarbon group or a monovalent heterocyclic group, each of which may have a substituent.

The hydrocarbon group for R1 may be an aliphatic, alicyclic, or aromatic hydrocarbon group, and specific examples include a hydrocarbon group having 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. 20, preferably an alkyl group having 1 to 6 carbon atoms; an aryl group having 6 to 14 carbon atoms such as a phenyl group, tolyl group, xylyl group, and naphthyl group; a carbon group such as a benzyl group, phenylethyl group, phenylpropyl group, and phenylbutyl group An aralkyl group having 1 to 10 alkylene groups, preferably 1 to 4 alkylene groups is suitable.

In addition, the heterocyclic group for R3 includes a small number of heteroatoms such as a nitrogen atom, an oxygen atom, and a sulfur atom (both with Ill being 1 to 1).
A 5-membered or 6-membered monocyclic heterocyclic group containing 3, preferably 1 or 2 rings, or a fused heterocyclic group in which benzene is fused thereto is preferred, as examples of the unsaturated heterocyclic group explained in the definition. In addition, saturated Bibe7+zine ring, piperazine ring, morpholine ring, pyrrolidine ring, indoline ring,
Saturated heterocyclic groups such as chroman rings can be mentioned.

The hydrocarbon group or heterocyclic group of R1 described above may have a W substituent, and there are at most 5 substituents, preferably at most 5, for the hydrocarbon group or heterocyclic group. The same substituents as those explained above may be exemplified, preferably containing up to three substituents.

The above R1 is preferably a halogen atom, 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, carbon, and sulfur atoms, or a fused heterocyclic group in which a benzene ring is fused to a heterocyclic group; , especially raminocycles.

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 IO carbon atoms.

In the general formula (1) in the present invention, it 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. These norbornylidene groups or adamantylidene groups may be substituted with a substituent, and the number of hydrogen atoms in the above formula may be one or more. The number and position are arbitrarily selected depending on the purpose and usage. 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 carbon group such as a methoxy group, an ethoxy group, and a tert-butoxy group. Alkoxy group having 1 to 4 carbon atoms; aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group; phenoxy group, 1-
Aryloxy group having 6 to 14 carbon atoms such as naphthoxy group;
Lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, and L-butyl group; halogen atoms such as fluorine, chlorine, and oxaline; cyano group; carboxyl 15: alkoxy having 2 to 10 carbon atoms such as ethoxycarbonyl Carbonyl group; halogen-substituted alkyl group with 1 or 2 carbon atoms such as trifluoromethyl group; Nitro group: aryl group with 6 to 10 carbon atoms such as phenyl group and tolyl group; carbon number such as phenylethyl group and phenylpropyl group Examples include 7 to 9 aralkyl groups.

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 aralkyl group having 7 to 9 carbon atoms, or an aralkyl group having 6 to 1 carbon atoms
It is an atom group of 0.

In the general formula (1) in the present invention, X represents an oxygen atom (-〇-), a group N-R1, a group ";
s, group; N -A x A 4 or group>NA
3 Indicates Ra.

Furthermore, in general formula (1), X is a group>NA+B+-(Azer-(Bz+rR),
Group〉N As A, or group”;NAx R
-, especially the group'; y-A, -Ra or the group>N A+ B+-(AJy (Bz+rRi
(However, R3 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.) This is more preferred from the viewpoint of the durability of the photochromic properties of the resulting compound.

X in general 2H) is the above-mentioned group>N Aa Bs (Jh+r-(Bz)i-R
3, when R8 is a naphthyl group or a naphthylalkyl group, and when the group) is y-jh-A,
The number of atoms in the main chain sandwiched between the naphthyl group represented by 6 or Ra and the imide group (> and This method is preferable because it provides a compound with a high temperature.

Next, Rz, Rs, R4, A+, A at the above x
! , As, Aa, B+, Bz, 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-1so- or tert-butyl group, a pentyl group, a hexyl group, an octyl group, Among them, those having 1 to 20 carbon atoms are preferred, and those having 1 to 10 carbon atoms are preferred. Examples of the aryl group include phenyl, tolyl, and naphthyl groups. Examples include those having 6 to 10 carbon atoms.

A, , Aa and A3 may be the same or different from each other, and represent an alkylene group, an alkylidene group,
cycloaJ lekylene group or alkylcycloalkane-
It can be a diyl group.

Specific examples of these include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, trimethylene group, tetramethylene group or 2,2-dimethyltrimethylene group; ethylidene group;
Flukylidene groups having 2 to 10 carbon atoms such as propylidene or isopropylidene groups; cycloalkylene groups having 3 to 10 carbon atoms such as cyclohexylene; 2-methylcyclohemethylcyclohexane-α,l-diyl group (-CN
Examples include a furkylcycloalkane-diyl group having 6 to 10 carbon atoms such as (3). As A1 and A, particularly preferred are 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, and 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.

ooo o.

■ or -NHC- m and n each independently represent 0 or 1,
When it represents 0, 1+Az-1T or 1B2 means a bond. Furthermore, when m is 0, n also represents 0.

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

The substituents of each of the above groups are not particularly limited, but the alkyl group may be disubstituted with 1 to 3 atoms or groups selected from the group consisting of a halogen atom, a cyano group, and a nitro group, In addition, the above naphthyl group or naphthylalkyl group is a halogen atom, a cyano group, a nitro group, or has a carbon number of 1.
1 to 3 atoms or groups selected from the group consisting of ~3 alkylamino groups, C1 to C3 alkyl groups, and C1 to C3 alkoxy groups, and r! It may be changed.

As the alkyl group represented by R5 above, the same alkyl group as exemplified for R2 above can be used. Further, examples of the naphthyl alkyl group include a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, a naphthylbutyl group, and the like.

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. 1 to 3 selected from the group consisting of
may be substituted with R
1 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.

The photochromink compound described above has an average particle size of 0.0
It is contained in resin particles of 1 to 100 μm, preferably 0.1 to 20 pm. The average particle size of resin particles is 0.01 μm
Smaller ones are difficult to manufacture, and 100 μm
If the size is larger than 100%, it is not preferable because it will cause uneven hue when dispersed in the thermosetting resin described below.

The type of resin constituting the resin particles may be either a thermoplastic resin or a thermosetting resin, and any known resin may be used without any restriction as long as it does not dissolve in the raw material monomer of the thermosetting resin described below.

For example, styrene, chlorstyrene, methylstyrene,
Polymers of radically polymerizable vinyl compounds such as vinylnaphthalene; Polymers of ester compounds of acrylic acid and methacrylic acid such as methyl acrylate and methyl methacrylate; Polymers of α-olefins such as polyethylene and polypropylene; Polyesters; Polyamides; Any resin can be used, such as polyurethane; phenol-formaldehyde resin; melamine resin.

In particular, when the resin particle size is in the range of 0.4 to 100 μm, it is preferable to use a resin with good transparency.
It is preferable to use a resin having a refractive index difference of 0.02 or less with respect to the thermosetting resin described later from the viewpoint of transparency of the resulting photochromic molded body.

In the production of resin particles containing a photochromink compound, the ratio of the photochromink compound to the resin may be determined depending on the coloring density of the desired photochromink molded article, but generally, 0,001 to 60 parts by weight, especially 0.1 parts by weight of the photochromink compound.
It is preferable to set it as the range of 40 parts by weight.

The method for producing resin particles containing a photochromic compound is not limited in any way, but examples include the following method.

■ 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 pulverized.

■ A method in which a thermoplastic resin is dissolved in an appropriate solvent, a photochromic compound is mixed therein, the solvent is removed by evaporation, etc., and the remaining resin film is crushed.

■ Mixing the raw material of thermoplastic resin or thermosetting resin with a photochromic compound and then polymerizing it,
How to crush if necessary.

According to emulsion polymerization or suspension polymerization, the average particle size is 0.01 to 10.
In some cases, it is not necessary to carry out pulverization because resin particles of 0 μm can be obtained.

■　Method using microencapsulation.

Known methods can be used for microencapsulation,
Interfacial polycondensation method (JP-A-61-33230), i
n 5itu method (Japanese Patent Application Laid-open No. 51-447
No. 08), an in-liquid curing coating method, a phase separation method from an organic solution, a melt dispersion cooling method, an air suspension coating method, a spray drying method, etc. can be suitably used.

The resin particles containing the photochromink compound thus obtained are dispersed in a thermosetting resin.

Examples of thermosetting resins include ethylene glycol diacrylate and diethylene glycol! J cold dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2.2-bis(4-methacryloyloxyethoxyphenyl)propane, 2.3
- Polyhydric acrylic acid and polyhydric methacrylic acid ester compounds such as bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane; diallyl phthalate,
Polyvalent allyl compounds such as diallyl terephthalate, diallyl isophthalate, diallyl tartrate, sialyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds such as 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl)ether, 1,4-bis(methacryloylthiomethyl)benzene, nidivinylbenzene Polymers of radically polymerizable polyfunctional monomers such as: or each of these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride; methyl acrylate, methyl methacrylate, benzyl methacrylate, Phenyl methacrylate, 2
-Acrylic acid and methacrylic acid ester compounds such as hydroxyethyl methacrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate, and benzylthiomethacrylate; Copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, and bromostyrene; furthermore, ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakisthioglycolate , diphenylethane diisocyanate, xylylene diisocyanate, p-phenyl diisocyanate, an addition copolymer of a polyvalent thiol compound such as di(2-mercaptoethyl) ether, and the above-mentioned radically polymerizable polyfunctional monomer. Examples thereof include addition polymers of polyvalent isocyanate compounds such as 1 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.

The dispersion of the resin particles containing the photochromink compound into the thermosetting resin described above is generally carried out by mixing the raw material of the thermosetting resin with the resin particles containing the photochromink compound, and then polymerizing the mixture. Adopted.

The amount of the resin particles containing the photochromink compound to be dispersed in the thermosetting resin is 0.1 to 50 parts by weight, preferably 1 to 301 parts by weight, based on 100 parts by weight of the thermosetting resin.
It is a quantity part.

The durability of photochromic properties can be further improved by incorporating an ultraviolet stabilizer into the resin layer containing a dispersed photochromic compound in the photochromic molded article of the present invention. As the ultraviolet stabilizer, known ultraviolet stabilizers 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 used. Preferably used. More specific examples of these UV stabilizers include Sheasorb LIV1084 and Sheasorb 3346 (
(Manufactured by American Cyanamid Co.), UV-Chek AM
IOI, UV-Chek AM105 (manufactured by Ferro Corporation), Irgastab 2002, Tinuvin 76
5, Tinuvin 144, Kimalyve 944, Tinuvin 62
2. Irganox l 010. Irganox 245
(manufactured by Ciba Geigy), Rylenx NBC (manufactured by DuPont), Sheasorb 3346 (manufactured by American Cyanamid), Sanol LS-1114, Sanol L
S-744, Sanol LS-2626 (manufactured by Sankyo Co., Ltd.), Sumilizer 0A-80, Sumilizer GM, Sumilizer BBM-S, Sumira 4f'-WX-R, x Miraizer-81 Sumilizer Bl (T, Sumilizer TP
-D, Sumilizer TPL-R, Sumilizer TPS,
Sumilizer MB (manufactured by Sumitomo Chemical Co., Ltd.) Mark AO-
50, mark AO-20, v-ri AO-30, mark A
O-330, Mark AO-23 (manufactured by Adeca Argus), Antioxidant HP M-12 (S, F
, manufactured by O, S Company). All of the above names are product names.

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

Therefore, the photochromink molded article of the present invention can be used in a wide range of fields, such as various recording and storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, and photosensitive materials for lasers. 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/cz-st:chlorstyrene/TMP-TAC: ) Limethylolbrobantriaryl carbonate/BADBP: 2. 2-bis(4-allyl carbonate ethoxy-3,5-dibromophenyl)propane/ADC: Allyl diglycol carbonate/DAP
Diaryl phthalate, St: Styrene, DCIPF Nidi(2-chloroisopropyl) fumarate, EGDMA: Ethylene glycol dimethacrylate, PETTP: Pentaerythritol tetrakis (β-thioprobionate), DME Nidi(2-mercaptoethyl) ether,
DVB Nidivinylbenzene/XIC: Xylylene diisocyanate/HPA
: 3-(2,4-dibromophenoxy)-2-hydroxypropyl acrylate/HMA : Methyl methacrylate/DECDMA
Nidiethylene glycol dimethacrylate/TBBM 1. 4. 5-) Libromobenzyl methacrylate・) IEMA: 2-Hydroxyethyl methacrylate・
BMA: Penzyl methacrylate/IPP
Nidiisopropyl peroxycarbonate/barbutyl ND: (manufactured by NOF ■) t-butyl peroxy-2-hexanate/SBC: sebacic acid dichloride/TMC:) rimesic acid trichloride/TPC: terephthalic acid dichloride/TMDI nitrimethyl hexanate Methylene diisocyanate/HMDI: Hexamethylene diisocyanate/I
PDI: Isophorone diisocyanate/EDA
: Ethylenediamine/HMDA : Hexamethylenediamine/DETA
Polyvalent isocyanate millionate MR-104 (manufactured by Nippon Polyurethane Kogyo) Polyvalent isocyanate millionate MR400 (manufactured by Nippon Polyurethane Kogyo)
: Polyvalent isocyanate/TDI: Toluene diisocyanate/Epicoat 834 (manufactured by Shell Oil Company): Epoxy resin/cured side U (manufactured by Shell Oil Company) : Amine adduct of epoxy resin/Milperesine 5M800 (manufactured by Showa Kobunshi): Melamine resin・Thermotite 8H5P (manufactured by Showa Kobunshi): Urea resin production example 1 1-hydroxy-2-acetonaphthone 1 og (0.05
4mol) norcampfy-6.6gC0.06mol)
A solution was prepared by dissolving 8 g (0,113@ol) of pyrrolidine and pyrrolidine in 300 cc of toluene. This mixture was boiled for 10 hours, and water was separated. After the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized with amethane. It was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. This chromanol compound 7.47
15 g with 4.5 g of anhydrous M copper in a stream of carbon dioxide.
The mixture was heated at 0-160° C. for 10 minutes and the brown viscous liquid was purified by chromatography on silica gel to obtain 6.3 g of a chromene derivative of the following formula.

The elemental analysis values of this compound are CB6.93%, H6.8
9%, 06.18%, which is the estimated true value for C1 drop H,,0.
It was in very good agreement with 12%. In addition, when proton nuclear magnetic resonance spectra were measured, δ7°2~8.3pp
A <6H peak based on the naphthalene ring proton near m, a <2H peak based on the alkene proton near δ5, 6 to 6.7 ppm, and a norbornylidene group proton near 61.2 to 2.5 ppm. It showed a broad peak of 10H based on Furthermore, when +3(- nuclear magnetic resonance spectrum was measured, there was a peak based on the carbon of the norbornylidene group in the vicinity of 627 to 52 pp-, δ110 to 160
Peak based on carbon of naphthalene ring near pp-, 68
A peak based on alkene carbon appears near 0 to 110 ppIII.

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

Production example 2 1-7 cetyl-2-naphthol 10 g < 0.05
4-of) and bicyclo(3,3,1)nonan-9-one8.29 g (0.06 mol) and morpholine8.
7g (0.10mol) and tonorenin 300c
Three times the solution was prepared by dissolving the solution in c. This mixture was boiled for 5 hours and the water was separated. After the reaction, toluene was removed under reduced pressure and the remaining chromanone compound was recrystallized with acetone. Next, this chromanone compound was dissolved in 200 cc of methanol. Lithium aluminum hydride was added 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 value of this compound is CB6.81%, H7.6
2%, 05.57%, which is the total summer value for Ct+Hz□0 CB6.90%, H7, 59%, 05.
There was a good agreement of 52%. In addition, when proton nuclear magnetic resonance spectrum was measured, 67.2 to 8.3 pp.
A peak of <6H due to the proton of the naphthalene ring near -, 66.0 to 7. A <2H peak based on alkene protons was shown near Opp-, and a 14H broad peak based on bicyclo(3,3,1)9-nonylidene protons was shown near 61.2 to 2.5 pp+n.

Furthermore, when we measured the '3C-Nuclear Magnetic Resonance vector, we found that it was around 627 to 55 pps.
9-nonylidene carbon-based peak, 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 can be concluded that the single larval parabolite is a compound represented by the above structural formula (2).
I got L'2.

Production Example 3 3.06 g of a chromanone compound represented by the following formula was dissolved in 50 cc of anhydrous ether, the solution was cooled to Q''C, and freshly prepared Glyni
The reagent CHzMg 12 (0,012 mol) was added dropwise into the solution over a period of about 1 hour. ’a After the bottom ends,
After stirring for another 2 hours at room temperature, gently pour the ether solution into cold water, extract the product with ether, dry the solution over magnesium sulfate, then remove the ether under reduced pressure and convert the chromanone compound to the chromanol compound. This chromanol compound was then heated at 200° C. for about 10 minutes with anhydrous copper plating in a stream of carbon dioxide, and a brown viscous liquid was chromatographed on silica gel to form a chromene derivative 2 of the formula .47 g was obtained.

Production example 4 1-acetyl-2-naphthol 10 g (0,054
mol) and norcampf-y-6,6g (0,06
5 mol) 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, toluene was removed under reduced pressure, and the remaining product was recrystallized with acetone to obtain compound 7 represented by the following formula. .53 g was obtained.

As in Production Example 1, by elemental analysis, proton nuclear magnetic resonance spectrum, and +30-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 mixed with 100 c of methanol.
By dissolving in c and reacting with methyl iodide,
6.95 g of a chromanone compound represented by the following formula was obtained.

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.

As in Production Example 1, this compound was confirmed to be a compound represented by the above structural formula (4) by elemental analysis, proton nuclear magnetic resonance spectrum, and +CoC nuclear magnetic resonance spectral measurements. .

Production Example 5 10 g (0,0318 sol) of 5-n-octyloxy-1-hydroxy-2-acetonaphthone, 2.77 g (0,0477 sol) of acetone, and 1.13 g (0,0159+mol) of pyrrolidine were added to 100 mf of toluene. A solution was prepared by dissolving . 1 of this mixture
After the reaction was completed by boiling for 0 hours and water was separated, toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in methanol 100a1, and sodium borohydride was gradually added to form a 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, the following formula 3.8 g of chromene derivative was obtained.

As in Production Example 1, it was determined by elemental analysis, proton nuclear magnetic resonance spectrum, and 12(-nuclear magnetic resonance spectrum) 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.
After a reaction in which NHzCHzCOCH* 1 (02 mol) was dissolved in toluene and heated at 50° C. for 2 hours under a nitrogen atmosphere, 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 refluxed in O-dichlorohenzene for 6 hours to rearrange to the following fulgimide compound (11). This compound was purified by chromatography on silica gel using benzene and ether as eluent. Obtained in 27% yield as pale yellow needles from chloroform and hexane. Elemental analysis of this compound was C66, 78%, H6
,09%, N 3.36%, OL5.8%, S
7.96%, which is the calculated value for CtsHzsO-NS, C67°15%, H6,08%,
N 3.41%, O 15.6%.

It was in excellent agreement with S 7.79%. In addition, when proton nuclear magnetic resonance spectra were measured, the results were 67.0 to 8.
．． Aromatic proton peak <2H near OppIIl, 62.7 ppm "::c-cH"
.

Based on the proton of the bond (C3H peak, 63°7pp
+1 <3H peak, δ] near m for the proton of the methyl group of the -COCHs bond, 14H peak δ based on the proton of the adamantylidene group at 2-2.5 pp+n
1 to 5 protons rearranged to 3 to 5 ppa+ and ≧N-C
Based on Hz-coupling, <3H peaks were shown.

Further +3(-nuclear magnetic resonance spectrum (IIc-NMR)
When measured, a peak based on the carbon of the adamantylidene group and the carbon of the methylene chain was found around 627 to 70 ppm.
A peak based on the carbon of the methyl group appears around 615.6 ppm, a peak based on the carbon of the thiophene ring appears around 6110 to 160 ppm, and a peak based on the carbon of the co bond appears around δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was the fulgimide compound QS) represented by the following structural formula.

was dissolved in tetrahydrofuran, and 1 g of metallic potassium was reacted with the solution 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 (0,01a
+ol) This and 1.2 g of bromoacetonitrile of the following formula
By reacting (0,01 mol) BrCt(,CN) in dimethylformamide, the following fulgimide compound Oe was obtained. This compound was purified by chromatography on silica gel using chloroform and hexane as eluent. was obtained in 57% yield as light yellow crystals from hexane.The elemental analysis of this compound was C69, 81%, 85.80%,
N 7.44%, 08.50%, 58.4
6%, calculated values for C22H2□NiO□S: C 69.84%, H5, 82%, N 7
．． 41%, 08.47%, and 58.47%. In addition, when proton nuclear magnetic resonance spectra were measured, there was a <2H peak based on the proton of the thiophene ring around 67.0 to 1-5 ppm+, and a peak of <2H at 64.0 to 1-5 ppm+.
A peak of <2H based on the proton of ≧N -CH2CN bond near 5 ppra, 1.5 near 63.7 ppm
<IH peak based on translocated protons, 62.7 p
-CH near pm.

<3H peak based on proton of bond, 61.3-2,
-CH around 5 ppm! - bond protons and 14H peaks of protons based on adamantylidene groups are shown.

Furthermore, +30-nuclear magnetic resonance spectrum (+3c-NMR
) was measured, and a peak based on the carbon of the adamantylidene group was found near 627-7 opplIl, 615, 6
Peak based on carbon of methyl group near ppm, 6110
A peak based on the carbon of the thiophene ring appears around ~160pp15, and a peak based on the carbon of the ';c=o bond appears around δ160-170pp.

From the above results, it was confirmed that the isolated product was fulgimide compound 0[0 shown by the following structural formula.

Example 1 Resin particles containing 4% by weight of the chromene compound of Production Example 1 and 2% by weight of the fulgimide compound of Production Example 15 (average particle size 0.1
μl11) was produced by an interfacial polycondensation method.

15 parts of the resin particles were mixed with 70 parts of chlorstyrene and 2°2-
The mixture was added to a composition consisting of 30 parts of bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane, and 1 part of Barbutyl ND as a radical polymerization initiator was added thereto and thoroughly mixed. This mixed solution was poured into a mold consisting of a glass plate and a gasket made of ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization was carried out using an air oven at 30° C. to 90° C. over 18 hours, gradually increasing the temperature and maintaining the temperature 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-25AX-HC manufactured by Suga Test Instruments Co., Ltd.

In addition, changes in color tone were visually observed. Fatigue life (T
I/2) was expressed as the time required for the absorbance at the maximum absorption wavelength based on the chromene derivative to decrease to 1/2 of the initial absorbance (To). However, the absorbance of To and T1/2 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 o was measured 60 seconds after light irradiation.

The results are shown in Table 3.

Examples 2 to 30 In Example 1, the production method, particle size, type, and amount of the resin particles used, as well as the types and amounts of the raw material monomers of the chromene derivative, fulgimide compound, and thermosetting resin, were changed to match the raw material monomers. Example 1 except that the polymerization was carried out by known means.
I did the same thing. 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 numerical formula, chemical formula, table, etc. ▼ is an optionally substituted aromatic hydrocarbon group or an optionally substituted unsaturated heterocyclic group When R^1 and R^2 are alkyl groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is an alkyl group having 6 to 20 carbon atoms, an alkoxy group having 6 to 20 carbon atoms, -R^ 5-S-R^5 and ▲ mathematical formula, chemical formula,
There are 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 resin particles having an average particle size of 0.01 to 100 μm and containing a photochromic compound represented by the formula are dispersed in a thermosetting resin.