JPH03252653A - Photochromic formation - Google Patents

Abstract

PURPOSE:To enhance durability of photochromic action by coating the surface of a thermosetting resin with a resin layer containing a specified photochromic compound and further coating the layer with a layer made of the hydrolyzate of an organic silicon compound. CONSTITUTION:The surface of the thermosetting resin is coated with the resin layer containing the 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 a norbornylidene or 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. The resin layer containing the photochromic compound is coated with the layer made of the hydrolyzate of the organic silicon compound.

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 with this property are
Called chromic compounds, compounds with various structures have been synthesized and proposed, but no particular common skeleton has been found in their structures.

As a result of research on a series of photochromic compounds, the present inventors succeeded in synthesizing a new chromene derivative having a chromene skeleton, and found that the chromene derivative has excellent photochromic action, and has already proposed (
Patent Application No. 1987-220387, Patent Application No. 1-141206
No. 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 thermosetting 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) The present invention has the following formula [A] However, R1 and R2 are the same or different alkyl groups, and these together are an optionally substituted norbornylidene group. or optionally substituted bicyclo [
3,3,1]9-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 2o Alkyl group, alkoxy group having 6 to 2 carbon atoms, -R5-8-R6 and -R5-X<R7 (wherein, R5 is an alkylene group or -(0-R8+).

(However, 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. ) A bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group having at least one substituent selected from the group consisting of:

A resin layer containing a photochromic compound represented by is coated on the surface of a thermosetting resin,
The photochromic molded article is further coated with a layer made of a hydrolyzate of an organosilicon compound.

In addition, in the present invention, R1 and R2 are respectively the same or different alkyl groups, and these together represent an optionally substituted norbornylidene group or an optionally substituted bicyclo[
It may constitute a 3,3,119-nonylidene group,
R3 and R4 are the same or different hydrogen atoms, aromatic hydrocarbon groups, or optionally substituted unsaturated heterocyclic groups; Alco6oxy group, -R5-5-R6 and -R5-X-R7 (wherein R5 is an alkylene group or +0-R8-)-.

(However, R8 is an alkylene group, n is a positive integer.), R6 and R7 are the same or different alkyl groups, respectively, and X is -N<, -P<, -P<. - or -〇-P<O-. ) 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 the surface of a thermosetting resin is impregnated with a photochromic compound represented by the formula, and a layer made of a hydrolyzate of an organosilicon compound is coated thereon.

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

In the above-mentioned -Noshiro CA), 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 -Noshiro (A), the number of carbon atoms is preferably 1 to 3, and particularly preferably 1. preferable. 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 -Noshiro (A) - together form a ring, and 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 %(2 (2), and the bicyclo(3,3,1)9-nonylidene group is represented by the following formula.These norbornylidene groups or bicyclo(3,3, 1) In the 9-nonylidene group, 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 group; Nitro group; Carboxyl group; Alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group; C1 to 4 group such as methoxy group, ethoxy group, propoxy group, butoxy group Alkoxy group; halogenoalkyl group with 1 to 4 carbon atoms such as trifluoromethyl group; aryl group with 6 to 10 carbon atoms such as phenyl group, tolyl group, naphthyl group; phenyloxy group, tolyloxy group, naphthyloxy group, etc. Aryloxy group having 6 to 10 carbon atoms; Aralkyl group having 7 to 10 carbon atoms such as Hensyl group, phenethyl group, phenylpropyl group; 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 groups, ethoxycarbonyl groups, etc. 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 to 10 carbon atoms. Aryl group, carbon number 7-1
0 aralkyl group, and dialkylamino group having 2 to 8 carbon atoms.

R3 and R4 in -Noshiro (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 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 heterocycles.The above-mentioned 4- to 7-membered monocyclic saturated heterocycles are represented by the following formula.

2 In the above formula, R9 is an alkylene group having 3 to 6 carbon atoms such as a tetramethylene group or a pentamethylene group 1-CHzC
HOCI(□-, -CH20CH2CH2-, -CH2
Oxyalkylene group having 3 to 6 carbon atoms such as CH□0CHzCHzH3 CH20(CH2) 3-1; -CHzSCHzCHz-, -CH2
Thioal CH having 3 to 6 carbon atoms such as S(CH2)3CH2CH2SCH2CH2-, C113 kylene group; -CLNCLCHz--CH□N(CHz
)+-CH.

Azoalkylene groups having 3 to 6 carbon atoms, such as CHzCHzNCH□CH2-, 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; 7 to 10 carbon atoms 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; pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring,
4 containing at least one nitrogen atom such as a thiazolidine ring, or containing a nitrogen atom and an oxygen atom or a sulfur atom
- A monovalent group derived from a 7-membered monocyclic saturated heterocycle can be mentioned.

Among these, R:I 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, and a dialkylamino group having 2 to 8 carbon atoms. , containing up to 2 nitrogen atoms, or 1 nitrogen atom and any 1 oxygen atom or sulfur atom
A monovalent group derived from a 5- or 6-membered monocyclic saturated heterocycle containing these is preferred. By selecting each R3 or R4 group, the fading rate of the -Noshiro (A) compound 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. Further, when R3 is a substituted amino group, the color-forming state of the trans form is stabilized by resonance, and while a high color density can be obtained, the fading rate is slightly slower. Furthermore, 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 - Noshiro [A) of the present invention, C
XI is a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group, each of which may have a substituent.

The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 14 carbon atoms. In particular, 2 derived from one benzene ring or 2 to 4 condensed rings thereof
Preferred are valence groups. Examples of rings forming such an aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a phenanthrene ring, and the like.

In addition, examples of the unsaturated heterocyclic group include a 5R ring or 6-membered monocyclic heterocyclic group containing 1 to 2 nitrogen atoms, acid pentatom atoms, and sulfur atoms, or a fused heterocyclic group in which a benzene ring is fused to these. The group 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.

The aromatic hydrocarbon group or unsaturated heterocyclic group represented by [ ] [ above may contain up to 5 substituents, preferably up to 3 substituents. Examples 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, ethyl, propyl, and butyl groups; methoxy and ethoxy groups; Alkoxy groups having 1 to 20 carbon atoms, such as, propoxy group, butoxy group; Aryl groups having 6 to 10 carbon atoms, such as phenyl group, tolyl group, naphthyl group; 1 to 20 carbon atoms, such as methylamino group, ethylamylo] group 4 alkylamino group; dialkylamino group having 2 to 8 carbon atoms such as dimethylamino group and diethylamino group; halogenoalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; thienyl group, furyl group, pyrrolyl group, pyridyl A 5-membered ring or 6-membered monocyclic heterocyclic group containing 1 to 2 sulfur atoms, oxygen atoms, or nitrogen atoms, such as groups, can be further described below.

When the above R1 and R together form a ring and constitute an optionally substituted norbornylidene group or an optionally substituted bicyclo(3,3,1)9-nonylidene group, , [] [represents a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a 6 to 20 carbon atoms
10 aryl groups, dialkylamino groups having 2 to 8 carbon atoms, halogenoalkyl groups having 1 to 4 carbon atoms, and monocyclic heterocyclic groups. It is preferably a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group.

In the above -Noshiro [A], R1 and R2 are optionally substituted with 20 alkyl groups, 1 to 3 alkoxy groups having 6 to 20 carbon atoms, in each case, 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
It is preferably a divalent group derived from a 5- or 6-membered monocyclic heterocycle containing two rings, or a fused heterocycle in which a benzene ring is fused to the monocyclic heterocycle.

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-R8-), r (however, 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 -N<, -P<.

A bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group having at least one substituent selected from the group consisting of:

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

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 a decyloxy group, an undecyloxy group, a dodecyloxy group, a 2-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'-9-R6÷0-R
8→□ (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:
The number of carbon atoms is not particularly limited and is generally selected from the range of 1 to 20, but in consideration of the durability of the resulting chromene derivative as a photochromic material, the number of carbon atoms is preferably in the range of 6 to 20. . Specific examples of alkylene groups include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, and dodecamethylene group. Examples include a methylene group, a tridecamethylene group, a pentadecamethylene group, an octadecamethylene group, and an eicosamethylene group.

In addition, n in ÷0-R8-+T represented by R5 may be a positive integer, but generally the number of carbon atoms in the chain represented by 10-R8+T is 1 to 20, preferably 6 to 20. For this purpose, n is generally 1.
-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 78th position of chromene are particularly suitable for use as photochromic materials because of their high color density.

The substituent of the monocyclic 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 -Noshiro (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 purposes such as ornaments, the compound of -Noshiro (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 preferred in the present invention because they can be adjusted to brown or gray tones when used in combination with the above-mentioned Noshiro (A) compound. used. The amount of the above-mentioned fulgide compound or fulgimide compound to be used can be selected as appropriate depending on the desired color tone (in general, in order to obtain a brown or gray color tone, - for 100 parts by weight of Noshiro (A) compound) 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 a compound having photochromic properties is employed without any restriction. Also, f(yA'I-
A compound having the structure shown by the radical ← 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.

In the formula, the divalent aromatic hydrocarbon group or the divalent unsaturated heterocyclic group R is a monovalent hydrocarbon group which may have a substituent or a monovalent mantylidene group, respectively, an oxygen atom, group"; N R2 group, 2=NAI B+ (8z+F-(
It represents a Bze-myo-R3 group, ;NA3-8, or a group;N-A3-Ra.

In the above-mentioned -Noshiro (1), it is a heterocyclic group, and these groups may have at most 5 substituents, preferably up to 3 substituents.

7 8 The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms,
Examples of rings forming such an aromatic hydrocarbon ring include a benzene ring,
Examples include naphthalene ring and phenanthrene ring.

Further, as the unsaturated heterocyclic group, a 5- or 6-membered monocyclic heterocyclic group containing at least one petro 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, hensifuran ring, and pyran ring; thiophene ring; Examples include sulfur-containing heterocycles such as hendithiophene 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; alkyl groups having 1 to 4 carbon atoms such as hydroxyl group; cyano group; nitro group; amino group; carboxyl group; methylamino group; diethylamino group. Amino group;
Methyl group, ethyl λ1 (lower alkyl group having 1 to 4 carbon atoms such as methyl group, t-butyl group; halogen atom such as trifluoromethyl group, 2-chloroethyl group)
3 halogenated lower alkyl groups; 1 lower alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, and L-butoxy; 1 aryl group having 6 to 10 carbon atoms such as phenyl, naphthyl, and tolyl; Aryloxy groups having 6 to 14 carbon atoms such as phenoxy group and 1-naphthoxy group; Aralkyl groups having 7 to 15 carbon atoms such as hensyl group, phenylethyl group and phenylpropyl group; benzyloxy group;
Examples thereof include an aralkoxy group having 7 to 15 carbon atoms such as a phenylpropoxy group, and an alkylthio group having 1 to 4 carbon atoms. These substituents may be the same or different, and their positions are not particularly limited.

90 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 alkyl 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 heterocycle or a fused heterocycle in which a Hensen ring or a cyclohexene ring is condensed to the heterocycle is preferred. It is also a preferred embodiment that these benzene rings, grassland heterocycles, or fused heterocycles contain one or two of the above-mentioned substituents.

R1 in the above-mentioned formula [I] is a monovalent hydrocarbon group or a monovalent heterocyclic group, each of which may have a substituent.

The hydrocarbon group for R3 may be any of aliphatic, alicyclic, or aromatic hydrocarbons, and specific examples include those having 1 to 1 carbon atoms such as methyl, ethyl, propyl, and butyl groups. 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.

Further, the heterocyclic group for R8 is a 5-membered or 6-membered ring containing 1 to 3, preferably 1 or 2, of at least 1 2 petro atoms such as nitrogen atoms, oxygen atoms, and sulfur atoms. A monocyclic heterocyclic group or a fused heterocyclic group in which Hensen is fused thereto is preferred. In addition to the examples of unsaturated heterocyclic groups explained in the definition, 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 the substituents that can be applied to a hydrocarbon group or a heterocyclic group include the same substituents as those described above, preferably containing at most 5, preferably 3.

The above R5 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 atom, carbon atom, and sulfur atom, or a fused heterocyclic group in which a benzene ring is fused to the heterocyclic group; groups, especially grassland heterocyclic groups.

Furthermore, particularly preferable as the above R1 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-mentioned formula (1) in the present invention means a rubornylidene 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 zyloxy group; phenoxy group;
Aryloxy group having 6 to 14 carbon atoms such as l-naphthoxy group; 1 to 14 carbon atoms such as methyl group, ethyl group, and butyl group
Lower alkyl group of 4; halogen atom such as fluorine, chlorine, oxaline; cyano group; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as 1-oxycarbonyl;
Halogen-substituted alkyl groups having 1 or 2 carbon atoms such as trifluoromethyl; nitro groups; aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl groups; 7 to 9 carbon atoms such as phenylethyl and phenylpropyl groups Examples include 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 aral group having 7 to 9 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

In the above-mentioned - binding margin (1) in the present invention, X is an oxygen atom (-0-), a group > N R2, a group; ;N-AI-A,
It also represents the group '>N-Al-R4.

In addition, in − binding margin (I), X is the base]:N At B+ (82) −5
+T R3, group〉N-83-A4 or group〉N-83
'R4, especially the group -; N A3 R4 or the group:,, N-At-B+ (112+-r-(Bze-
iR3 (wherein 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);

) is more preferable from the viewpoint of the durability of the photochromic properties of the resulting compound.

χ in the general formula CI) is the above group>NAI B+ (A2+F-(Bz+rR3
Among them, when R3 is a naphthyl group or a naphthylalkyl group, and when the group) NA:lA4,
Naphthyl group and imide group (〉N-
) is preferably in the range of 3 to 7 atoms in the main chain because a compound with excellent durability of photochromic action can be obtained.

Next, R2, R3, R,, A,, Az in the above X
, As, A4, 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 tart-butyl group, a pentyl group, a hexyl group, an octyl group, Among them, those with 1 to 20 carbon atoms,
Furthermore, those having 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.

AI, A2 and A3 may be the same or different, and represent an alkylene group, an alkylidene group,
It can be 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, 78 ethylene group, propylene group, butylene group, trimethylene group, tetramethylene group, or 2,2-dimethyltrimethylene group; ethylidene group; Algylidene 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,■-diyl group ( Examples thereof include alkylcycloalkane-diyl groups having 6 to 10 carbon atoms, such as (%). As A and A2, in particular, 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,
An alkylcycloalkane-diyl group having 6 to 7 carbon atoms is preferred.

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

9 ooo o.

1 or -NIIC m and n do not each independently represent O or 1,
When O is represented, (Ihe-V or (Bze, -) means a bond. When m is 0, rl 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 alkyl 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 R3 above, the same alkyl group as exemplified for R2 above can be used. Examples of the naphthylalkyl group include a naphthylmethyl group, a naphthyl ethyl group, a naphthylpropyl group, and a naphthylbutyl group.

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 cyan 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. It may be substituted with 1 to 3 atoms or groups 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 layer containing the photochromic compound,
Thermoplastic resins and thermosetting resins can be used as long as they adhere strongly to the surface of the thermosetting resin to be coated and the photochromic compound is uniformly dispersed therein. Generally, it is used for the purpose of improving the adhesion between the hydrolyzate film of an organosilicon compound and the thermosetting resin when forming the film of the hydrolyzate of the organosilicon compound on the surface of the thermosetting resin, which will be described later. Any primer can be used without any restriction. Such primers include, for example,
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin,
Epoxy resin primer having two or more epoxy groups in one molecule such as alicyclic epoxy resin; Tos Prime A
, Toss Prime B,) Su Prime C,) Su Prime D1
Silane primers such as Tos Prime E and YP9341 (trade names manufactured by Toshiba Silicone Co., Ltd.); Polysol F361, Polysol F341, Polysol FF-4
50, Kogum HW-7 (manufactured by Kobunshi Co., Ltd. in Showa 12: trade name), Cevian A317, Cevian A
4716, Cevian A46701, Cevian A 46
35, Cevian A 4730, Cevian A45000
, Cevian A4171 (manufactured by Daicel Chemical Industries, Ltd.; trade names), Nikazole F L-3000, Nikazole ME-702, Nikazole FX-201, Nikazole F
X-322, Nikazole FX-329, Nikazole TS
-444, Nikazole TS-501, Nikazole TS
-517, Nikazole TS-542, Niracera PC-5
01, Niracera PE-115, Niracera PE-118,
Examples include acrylic resin primers such as Niccera PE-121 (trade name, manufactured by Nippon Carbide Industries, Ltd.). Also, polyvinyl alcohol, poly(2-
Hydrophilic resins such as hydroxyethyl methacrylate), polyacrylonitrile, and cellulose-based natural polymers can also be used as resins for dispersing the above photochromic compounds.

The amount of the photochromic compound contained in these resins may be determined depending on the coloring density of the photochromic molded article obtained, and generally, the amount of the photochromic compound is 0.001 to 60 parts by weight, based on 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 may be determined depending on the color density of the resulting photochromic molded article, but is generally preferably in the range of 0.5 to 10 μm.

On the other hand, as a method for impregnating the surface of a thermosetting resin with a photochromic compound, a commonly used photochromic compound is heated above its melting point, melted, and the thermosetting resin is immersed in it for 1 to 60 minutes to impregnate the compound. A method is used to Alternatively, a method of dissolving a photochromic compound in a high-boiling inert liquid and immersing the thermosetting resin therein, as shown in JP-A No. 61-501145, can also be adopted. Here, silicone oil, perfluoro oil, etc. are used as the high boiling point inert liquid.
The photochromic compound may be dissolved in a high boiling inert liquid at a concentration of 0.1 to 50% by weight. Furthermore, a photochromic compound is dispersed in a commercially available lacquer as shown in JP-A-60-112880, and this is applied to a thermosetting resin.
A method of impregnating the surface by heating at 00 to 250°C for 1 to 60 minutes is also adopted. At this time, the photochromic compound concentration in the commercially available lacquer is 0.1 to 50.
Weight percent is preferred.

In the present invention, a layer containing a photochromic compound is formed on the surface or near the surface of the thermosetting resin by the method described above, and a layer containing a hydrolyzate of an organosilicon compound is further added on top of the layer to improve the durability of the photochromic property. A coating of different layers is carried out.

The hydrolyzate of the organosilicon compound is required to have strong adhesion to the resin layer containing the above-mentioned photochromic compound or to the surface of the thermosetting resin after impregnation with the photochromic compound. Furthermore, considering the durability of the photochromic compound and the surface hardness of the molded product, the coating of this hydrolyzate layer is uniform and its thickness is 0.2 to 10 μm.
It is preferable that

For forming such a film, a coating agent consisting of an organosilicon compound, a surface hardness improver, and a curing catalyst is suitably used.

First, the organosilicon compound which is the first component of the coating agent has the following formula (■) and/or (III) (where R6 is a vinyl group, a methacryloyloxy group,
is a hydrocarbon group having at least one group selected from the group consisting of lorcapto group, epoxy group, glycidoxy group, and amino group, or is an alkyl group, aryl group, or vinyl group, and R6 is an alkyl group and n is O or 1
, R1 is an alkyl group, an acetyl group or an alkoxyalkyl group. ) Organoalkoxysilane compound 5 (where A is a divalent hydrocarbon group whose main chain is linear and has at least 4 atoms, R8 and R7 are the same or different alkyl groups or alkoxyalkyl groups) Group, R.I.G.
and R1+ are the same or different alkyl groups, l and m are 0 or 1) are preferably used.

Among the organoalkoxysilane compounds represented by the above general formula (n), those in which R6 has 1 to 4 carbon atoms and Rヮ has 1 to 4 carbon atoms are generally used.

Specifically, methyltrimethoxysilane, dimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl Trismethoxyethoxysilane, T-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, T-mercaptopropyltrimethoxysilane, β-(3,4-epoxy Examples include cyclohexyl)ethyltrimethoxysilane and T-aminopropyltriethoxysilane.

Further, typical specific examples of the divalent hydrocarbon group represented by A in the disilane compound shown in the above-mentioned -Tsuriyo (III) are alkylene groups such as =C11□ell zcIl zcHzcH3 CIlzCHzCHCIl□-;
H2CH□0CH2CH2CH2CH2CH20CH2
General formula (CILz)po((Ct
h) an ether group represented by qo]r(Clhhi (where p, q are 2 or 3, and r is an integer of 0 or 1 or more); a spiro group represented by 2 or 3); 1 Cl(2CIl□CHzOCOCIIzGHzGHzGHz0) 111 CH□C)I 2CI(20COCI(ZC)I zO
cOcHzCH□CH2- etc. (However, R is CH2CH2O or CIIZC112
CI (20, S is an integer of O to 4; L is O when s=0, and 1 when s=1 to 4), and the like.

Furthermore, in addition to the above organosilicon compounds, neopentyl glycol diglycidyl ether, 1,6 hexanediol diglycidyl ether, 0-phthalic acid diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. An organic compound having two or more epoxy groups in one molecule can also be used in combination.

The second component of the coating agent is a tetraalkoxysilane compound represented by the following formula (%) (where R
I2 is recommended to be at least one selected from colloidal silica, a component obtained by hydrolyzing an alkyl group or an alkoxyalkyl group. - Tetraalkoxysilane compounds represented by the margin (IV) are those in which R1□ has 1 to 4 carbon atoms. Specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

Further, as the colloidal silica, fine silica powder having a particle size of 1 to 100 mμ manufactured by various conventionally known methods can be used as it is or in the form of a colloidal solution obtained by dispersing it in a polar solvent.

In the present invention, the colloidal solution prepared by dispersing the colloidal silica in a polar solvent, for example, water, methanol, or an alcoholic solvent such as isopropanol, is preferably adjusted to be weakly acidic.

The curing catalyst as the third component of the coating agent is used to lower the curing temperature and shorten the curing time of the coating,
Compounds known as curing catalysts in the hydrolysis of organosilicon compounds, such as hydrochloric acid, sulfuric acid, acetic acid/sodium acetate mixtures, tin chloride, perchloric acid, ammonium perchlorate, zinc perchlorate, magnesium perchlorate, etc. acid salt,
It is preferable to use acetylacetonate metal salts such as aluminum acetylacetonate, naphthenic acid metal salts, p-1-luenesulfonic acid, benzoic acid, alkali metal phosphates, sodium thiocyanate, and the like.

Furthermore, in addition to the above-mentioned components, a silicon-based or fluorine-based surfactant can be added in order to improve the smoothness of the obtained film and form a uniform film of the next inorganic hard material. In addition, various other additives such as ultraviolet absorbers, antioxidants, dyes and pigments, and organic carboxylic acids such as formic acid and acetic acid as gelling inhibitors can also be used.

The blending amount of each component of these coating agents is as follows:
00 parts by weight, the second component 10 to 100 parts by weight, the third component
Preferably, the amount of component is 1 to 10 parts by weight.

Thermosetting resins used in the present invention include ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate,
2.2-bis(4-methacryloyloxyethoxyphenyl)propane, 2.2-bis(3,5-dibromo-4
- Polyhydric acrylic acid and polyhydric methacrylic acid ester compounds such as (methacryloyloxyethoxyphenyl)propane, diaryl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexapthalate , diallyl carbonate,
Polyvalent allyl compounds such as allyl diglycol carbonate and trimethylolpropane triallyl carbonate; 1
, 2-bis(methacryloylthio)ethane, bis(2-
Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds such as acryloylthioethyl) ether and 1,4-bis(methacryloylthiomethyl)benzene; Polymers of radically polymerizable polyfunctional monomers such as divinylbenzene:
Or each of these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride; acrylic acids such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate; Methacrylic acid ester compounds; Fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; Thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate, and benzylthiomethacrylate; Styrene,
Chlorstyrene, methylstyrene, vinylnaphthalene,
Copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as bromostyrene; furthermore, ethanedithiol,
Nidiphenylethane diisocyanate, an addition copolymer of polyvalent thiol compounds such as propanetriol, hexanedithiol, penquerythritol tetrakisthioglycolate, di(2-mercaptoethyl) ether, and the above-mentioned radically polymerizable polyfunctional monomers, Polyvalent isocyanate compounds such as diisocyanate and p-phenylene diisocyanate, ethylene glycol, trimethylolpropane, pentaerythritol, and bisphenol A.
Examples include addition polymers with polyhydric alcohol compounds such as or the above-mentioned polyhydric thiol compounds.

These monomers can be used alone or in combination of two or more.

By incorporating an ultraviolet stabilizer into the resin layer containing the photochromic compound dispersed in the photochromic molded article of the present invention, or by impregnating the ultraviolet stabilizer together with the photochromic compound when impregnating the photochromic compound. , 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. More specific examples of these UV stabilizers include Sheasorb UV1084, Sheasorb 3346 (manufactured by American Cyanamid), and UV-Chek AMI.
OI, UV Check AM105 (manufactured by Ferro Corporation), Irgastab 2002, Tinuvin 765,
Tinuvin 144, Kimasorb 944, Tinuvin 622,
Irganox 1010, Irganox 245 (manufactured by Ciba Geigy), Lyrex NBC (manufactured by DuPont), Sheasorb 3346 (manufactured by American Cyanamid), Sanol LS-1114, Sanol LS-7
44, Sanol LS-2626 (manufactured by Tool Corporation), Sumilizer GA-80, Sumilizer GM, Sumilizer 88M-3, Sumilizer WX-R, Sumilizer S, Sumilizer BIT, Sumilizer TP-D,
Sumilizer TPL-R, Sumilizer TPS, Sumilizer MB (manufactured by Sumitomo Chemical Co., Ltd.), Mark AO-50
, mark AO-20, mark AO-30, mark AO-
330, Mark AO-23 (manufactured by Adeka Argus), Antioxidant HPM-12 (S, F, 0.
(manufactured by S company), 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 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 recording material. 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 cp-st: chlorstyrene TMP-TAC: I-limethylolpropane triallyl carbonate BADBP: 2,2-bis(4- Allyl carbonate ethoxy-3,5-dibromophenyl)propane ADC: Allyl diglycol carbonate DAP Nidialyl phthalate St: Styrene DCIPF Nidi(2-chloroisopropyl) fumarate EGDMA: Ethylene glycol dimethacrylate P
ETTP: Pentaerythritol tetrakis (β-thiopropionate) DMIl! Nizi(2-mercaptoethyl)ether DV
B: Divinylhenzene Libromobenzyl methacrylate HEMA: 2-hydroxyethyl methacrylate BMA: Benzyl methacrylate perbutyl ND: t-butyl peroxy-2-hexanate PVA: Polyvinyl alcohol PHEMA: Polyhydroxyethyl methacrylate P
AN: Polyacrylonitrile Production Example 1 1-hydroxy-2-acetonaphthone 1 og (0,05
4 mol) norkamph y-6.6g (0.06 mol)
A solution was prepared by dissolving 8 g (0,113 mol) of pyrrolidine and pyrrolidine in 300 cc of toluene. The mixture was boiled for 10 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 (hereinafter blank) 90 chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to obtain 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%, which is the calculated value for Cl9811IO, C B7.02%, H6, 87%, 06
．． It was in very good agreement with 12%. In addition, when proton nuclear magnetic resonance spectra were measured, δ7.2-8.3p
<6H peak based on the proton of the naphthalene ring near pm, <2H peak based on the alkene proton near δ5.6-6.7 ppm, δ1.2-2.5 ppm
A broad 10H peak based on the proton of the norbornylidene group was shown nearby. Furthermore, when the 13C-nuclear magnetic resonance spectrum was measured, a peak based on the carbon of the norbornylidene group was found at around 627 to 52 ppm, and a peak at δ110 to 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 110 ppm.

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
m01) and bicyclo(3,3,1)nonan-9-one 8
, 29 g (0.06 mol) and morpholine 8.7 g
(0.10 mol) was dissolved in 300 cc of toluene to prepare a solution. Boil this mixture for 5 hours,
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 dissolved in methanol 200 c
c and lithium aluminum hydride was added to obtain a chromanol compound. 6.49 g of this 12 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 a chromene of the following formula. 5.8 g of derivative was obtained.

The elemental analysis values of this compound are C86,81%, H7,6
2%, 05.57%, which is the calculated value for C2111°20 CB6.90%, H7,59%, 05
．． There was a very good agreement of 52%. In addition, when the proton nuclear magnetic resonance spectrum was measured, the results were 67.2 to 8.31.
6H peak based on the proton of the naphthalene ring near 1m, 66.0-7. It showed a <2H peak based on the alkene proton near Oppm, and a broad 14H peak based on the proI-n of the bicyclo(3,3,1)9-nonylidene group near 61.2 to 2.5 ppm. .

Furthermore, when we measured the C-Nuclear Magnetic Resonance spectrum, we found that bicyclo(3.3°1)
9-nonylidene group based on carbon, 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 110 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (2).

Production Example 3 3.06 g of a chromanone compound represented by the following formula was dissolved in 5 Qcc of anhydrous ether, the solution was cooled to 0°C, and freshly prepared Grini+- was dissolved in 50 cc of anhydrous ether.
Reagent C) IJgn (0,012 mol) was added dropwise to the solution of So34 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 6.6 g (0,
06 mol) and morpholine 8.7 g (0.10 mol)
l) 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 with amethane 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 C-nuclear magnetic resonance spectrum measurements,
1riLW confirmed that this compound was 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.

5 A Next, in the same manner as in Production Example 3, the generated chromanone compound was converted into a chromanol compound, subjected to a dehydration reaction, and after 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 m6 of toluene? A solution of debris was prepared. The mixture was boiled for 10 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in 100 mρ of methanol, and sodium borohydride was gradually added to form a chromanol compound.

This chromanol compound6. Og with 4.0 g of anhydrous copper sulfate in a stream of carbon dioxide at 150-160'C for 10
The brown viscous liquid was purified by chromatography on silica gel to obtain 3.8 g of a chromene derivative of the following formula.

As in Production Example 1, it was confirmed by elemental analysis, proton nuclear magnetic resonance spectrum, and 13C-nuclear magnetic resonance spectrum that this compound was a compound represented by the above structural formula (4).

Production Example 5 5-n-octyloxy-1-hydroxy-27 In the same manner as Production Example 1, elemental analysis, proton nuclear magnetic resonance spectrum, and +30-nuclear magnetic resonance spectrum revealed that this compound had the above structural formula (5 ) was confirmed to be a compound represented by 8.

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 method as in Production Example 1 to recognize Structure V1, 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) NHZ(JIzCOCl(z 1 ) was dissolved in toluene and heated at 50°C for 2 hours under a nitrogen atmosphere. After the reaction, the solvent was removed and the solution was dissolved in acetyl chloride and refluxed for 1 hour for cyclization. Obtained By refluxing the compound in 0-dichlorobenzene for 6 hours, it was rearranged to the following fulgimide compound (1). It was purified by chloroform and hexane as pale yellow needles in 27% yield. The elemental analysis of this compound was: C66,78% H6,09%, N3
．． 36%, O15.8%, 37.96%, which is the calculated value for C23H2SO4NS
67.15%, H6.08%, N 3.41%,
It matched extremely well with O15.6%37.79%. In addition, when proton nuclear magnetic resonance spectra were measured,
67.0-8. <2H peak based on aromatic protons near Oppm, at 62.7 ppm; c-
co.

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

Protons with 1 to 5 rearrangements at δ3 to 5 ppm and N-C
It showed a <3H peak based on H2-bonds.

Furthermore, +30-nuclear magnetic resonance spectrum (+3cmNMR
When measured, a peak based on the carbon of the adamantylidene group and the carbon of the methylene chain was observed at around 627 to 70 ppm2, a peak based on the carbon of the methyl group was around 615.6 ppm, and a peak based on the carbon of the thiophene ring was around 6110 to 160 ppm. A peak based on carbon of ≧C═O bond appears around δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was fulgimide compound Q51 represented by the following structural formula.

is dissolved in tetrahydrofuran, and 1 part of metallic potassium is added to this.
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 in dimethylformamide, the following fulgimide compound Q61 was obtained. This compound 34 was purified by a) chromatography on silica gel using chloroform and hexane as eluent;
Obtained in 57% yield as pale yellow crystals from hexane. The elemental analysis value of this compound is c 69.81%,
85.80%, N 7.44%, 08.50%,
38.46%, which is the calculated value for C2□H2□N20□S, C 69.84%, H5, 82%,
N 7.41%, 08.47%, 38.4
It was in very good agreement with 7%. In addition, when proton nuclear magnetic resonance spectra were measured, 67.0 to 7.5 pp
A <2I] peak based on the proton of the thiophene ring near m, around 64.5 ppm; a <2H peak based on the proton of the N -CH2CN bond, and a 1.5 rearranged proton around 63.7 ppm. Based on <IH peak, 6
The peak of <3I] based on the proton of -CH'1 bond is around 2.7 ppm, and the -
C1 (shows the 14H peak of the proton of the z-bond and the proton based on the 7 damantylidene group).

Furthermore, 13C-nuclear magnetic resonance spectrum (13cNMR)
When measured, there was a peak based on the carbon of the adamantylidene group 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 methyl group around 615.6 ppm.
Peak based on carbon of thiophene ring near ppm, 61
A peak based on carbon of the C═O bond appears around 60 to 170 ppm.

From the above results, it was confirmed that the isolated product was fulgimide compound α6) represented by the following structural formula.

5 6 Example 1 (1) Production of thermosetting resin Radical polymerization was initiated on a composition consisting of 70 parts of chlorstyrene and 30 parts of 2,2-bis(3,5-dibromo-4-methacryloyloxyethoxy-phenyl)propane. 1 part of Perbutyl N0 was added as an agent 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 is carried out in an air oven at 30°C to 90°C.
The temperature was gradually raised over 18 hours and maintained 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.

(2) Preparation of primer coating solution and coating curing 300 parts of the commercially available primer solution Sevian A46701 (manufactured by Daicel Chemical Industries, Ltd.; trade name) (the resin concentration was adjusted to 90% by weight) was added to the chromenene of Production Example 1. Derivative 3.
24 parts and 1.62 parts of the fulgimide compound of Production Example 15 were added and dissolved with thorough stirring. This primer solution was passed through a membrane filter with a pore size of 1μ, and applied to the substrate obtained in (1) by dipping, adjusting the pulling speed.
The primer film thickness after curing was set to 1 μm. After coating, it was dried at 60°C for 1 hour to obtain a photochromic substrate with a good appearance.

(3) Preparation of coating agent and application curing screw (
20 parts by weight of γ-triethoxysilylpropyl) carbonate, 1 part of T-glycidoxypropyltrimethoxysilane
0 parts by weight, 30 parts by weight of colloidal silica (methanol sol manufactured by Kaguchi Kagaku Co., Ltd.), 30 parts by weight of meticello, 10 parts by weight of 0.05N hydrochloric acid, 0 parts by weight of ammonium perchlorate as a curing catalyst
．． The photochromic substrate obtained in step (2) was coated by immersing it in a coating agent containing 25 parts by weight, which was thoroughly air-dried at room temperature and then cured at 130°C for 1 hour.

The photochromic properties of the molded article thus obtained were measured as follows. Xenon long life fade meter FAL-25A manufactured by Suga Test Instruments Co., Ltd.
Fatigue life was measured by X-HC.

In addition, changes in color tone were visually observed. Fatigue life (T
Iy□) 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 T and TI/□ is the value obtained by subtracting the absorbance of the unirradiated film at the maximum absorption wavelength based on the chromene derivative, and the absorbance of T was measured 60 seconds after light irradiation.

The results are shown in Table 3.

Further, the performance of the film made of the hydrolyzate of the organosilicon compound on the outermost surface of the thermosetting resin was evaluated as follows.

(1) Adhesion test Use a cutter knife with a sharp tip to cut 1 mm x 1 mm onto the surface of the sample.
After attaching 100 mm squares, apply commercially available cellophane tape and then quickly peel it off. Depending on the peeling condition of the film, the one with no peeling at all is 01, the one with some peeling is Δ,
Items that were completely peeled off were marked with an x.

(2) Scratch resistance test # 000 in a scratch resistance tester manufactured by Fukuda Machinery Co., Ltd.
After attaching No. 0 steel wool and reciprocating the sample surface 10 times under a load of 1 kg, the degree of damage to the surface was visually observed. The condition was evaluated as E and evaluated on a 5-grade scale from A to E.

(3) Hot water resistance test The film was left in boiling water for 2 hours, and the appearance of the film was visually observed. If the film had no cracks, peeling, blistering, whitening, etc. and had a good appearance, it was rated ◯, and if it was poor, it was rated ×. In addition, the adhesion test described above was conducted and evaluated using the same criteria.

The results are shown in Table 3.

Examples 2 to 14 Everything was carried out in the same manner as in Example 1, except that the coating agent containing the thermosetting resin, photochromic compound, brimer, and organosilicon compound used in Example 1 was changed to those shown in Table 3. Ta. The results are shown in Table 3. The types of coating agents containing organosilicon compounds are shown in Table 4.

Comparative Example 1 The same procedure as in Example 1 was carried out except that a film of a hydrolyzate of an organosilicon compound was not formed, and the results are also shown in Table 3.

Example 15 3 parts of diisopropyl peroxycarbonate as a radical polymerization initiator was added to 100 parts of allyl diglycol carbonate, thoroughly mixed, and polymerized in the same manner as in Example 1 to obtain a thermosetting resin. 5 parts of the chromene derivative obtained in Production Example 8 and 1 part of the fulgimide compound obtained in Production Example 25 were dispersed in 100 parts of silicone oil, and the mixture was applied to the surface of the poly(allyl diglycol carbonate) plate obtained above at 200°.
It was impregnated for 11 hours. Thereafter, this plate was cooled with cold water, washed with methanol and acetone, and in the same manner as in Example 1, a film made of a hydrolyzate of an organosilicon compound was formed on the surface of this plate. Further, evaluation of photochromic performance and evaluation of film performance of the film made of the hydrolyzate were performed in the same manner as in Example 1.

The results are shown in Table 5.

Examples 16 to 24 The same procedures as in Example 15 were carried out except that the thermosetting resin, photochromic compound, impregnating oil, and organosilicate metal used in Example 15 were changed.

The results are shown in Table 5.

Procedural amendment

Claims (2)

[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 resin layer containing a photochromic compound represented by is coated on the surface of a thermosetting resin,
The photochromic molded article is further coated with a layer made of a hydrolyzate of an organosilicon compound. (2) 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 impregnated with a photochromic compound represented by the formula above, and a layer made of a hydrolyzate of an organosilicon compound coated thereon.