JP2512583B2 - Photochromic composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photochromic composition having various tones such as gray, brown and amber.

(Prior art) Photochromism is a phenomenon that has been attracting attention for several years, and when a compound is irradiated with light including ultraviolet rays such as sunlight or light from a mercury lamp, the color of the compound rapidly changes, and the irradiation of light is prevented. It is a reversible action that returns to the original color when stopped and placed in the dark. A compound having this property is called a photochromic compound, and compounds having various structures have been conventionally synthesized and proposed, but no special common skeleton is recognized in the structure.

As a photochromic compound, chromene or its derivative is known. The color tone of chromene or its derivative is orange to yellow. On the other hand, fulgide compounds or fulgimide compounds are also well known as photochromic compounds, and the color tones of these compounds are orange to blue.

(Problems to be Solved by the Invention) However, when these compounds are used alone, a desired color tone may not be obtained in some cases. In particular,
When used as a photochromic lens, color tones such as gray, amber and brown are preferred, but these color tones cannot be obtained by the above compounds alone.

Therefore, the present inventors have conducted extensive studies to develop various intermediate colors such as gray, amber, and brown.

(Means for Solving the Invention) As a result, as a result of mixing the novel chromene derivative synthesized by the present inventors with a fulgide compound or an argimide compound, including gray, amber, and brown,
In addition, they succeeded in developing various intermediate colors and completed the present invention.

That is, the present invention provides (a) the following formula [A] The photochromic composition comprises 100 parts by weight of the chromene derivative represented by the formula (b) and 0.01 to 10,000 parts by weight of the fulgide compound or the fulgimide compound (b).

The component (a) of the photochromic composition in the present invention is the chromene derivative represented by the above general formula [A].

In the general formula [A], R ¹ and R ² are the same or different alkyl groups. The number of carbon atoms of the alkyl group is not particularly limited, but from the viewpoint of the photochromic property of the compound represented by the general formula [A], the number of carbon atoms is preferably 1 to 3, and particularly preferably 1. preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group and an i-propyl group.

Further, R ¹ and R ² in the general formula [A] together form a ring, and may have an optionally substituted norbornylidene group or an optionally substituted bicyclo [3.3.1] 9
-A nonylidene group may be constituted.

The norbornylidene group has the following formula The bicyclo [3.3.1] 9-nonylidene group is represented by the following formula: Is represented by In these norbornylidene group or bicyclo [3.3.1] 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, and is preferably 1 to 3. When it has a substituent, its type, number and position may be selected according to the purpose and application. When it has a plurality of substituents, it may be the same substituent or different substituents.

The above norbornylidene group or bicyclo [3.3.1]
As the substituent of the 9-nonylidene group, for example, fluorine,
Halogen atom such as chlorine and chlorine; hydroxyl group; cyano group; nitro group; carboxyl group; alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and butyl group; methoxy group, ethoxy group, propoxy group Group, butoxy group and other C1-4 alkoxy group; trifluoromethyl group and other C1-4 halogenoalkyl group; phenyl group, tolyl group, naphthyl group and other C6-10 aryl group An aryloxy group having 6 to 10 carbon atoms such as a phenyloxy group, a tolyloxy group and a naphthyloxy group; a carbon number 7 to 7 such as a benzyl group, a phenethyl group and a phenylpropyl group
Aralkyl group having 10 to 10 carbon atoms; aralkoxy group having 7 to 10 carbon atoms such as benzyloxy group, phenethyloxy group and phenylpropyloxy group; alkylamino group having 1 to 4 carbon atoms such as methylamino group and ethylamino group; dimethylamino group And a dialkylamino group having 2 to 8 carbon atoms such as diethylamino group; an alkoxycarbonyl group having 2 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group.

Preferred examples of these substituents are 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 an aryl group having 6 to 10 carbon atoms. A group, an aralkyl group having 7 to 10 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms.

R ³ and R ⁴ in the general formula [A] are the same or different, and each represent a hydrogen atom, an alkyl group, an aryl group,
It is 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 heterocycle containing at least one nitrogen atom or containing a nitrogen atom and an oxygen atom or a sulfur atom. A monovalent group derived from a ring may be mentioned. The above 4- to 7-membered monocyclic saturated heterocycle is represented by the following formula.

In the above formula, R ⁹ is an alkylene group having 3 to 6 carbon atoms such as a tetramethylene group or a pentamethylene group; _{-CH 2 OCH 2 CH 2 -,} - CH 2 CH 2 OCH 2 CH 2 -, - CH 2 O (CH 2) 3
-, An oxyalkylene group having 3 to 6 carbon atoms such as; -CH ₂ S
A thioalkylene group having 3 to 6 carbon atoms, such as CH ₂ CH ₂ —, —CH ₂ S (CH ₂ ) ₃ —, —CH ₂ CH ₂ SCH ₂ CH ₂ —; An azoalkylene group having 3 to 6 carbon atoms and the like are preferably used.

Specific examples of the groups represented by R ³ and R ⁴ include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group and a decyl group; phenyl 6 to 6 carbon atoms such as group, tolyl group and naphthyl group
10 aryl groups; benzyl, phenethyl, phenylpropyl, phenylbutyl, and other aralkyl groups having 7 to 10 carbon atoms. Further, as the substituted amino group,
An alkylamino group having 1 to 4 carbon atoms such as methylamino group and ethylamino group; a dialkylamino group having 2 to 8 carbon atoms such as dimethylamino group and diethylamino group; pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiazolidine 4 to 7 containing at least one nitrogen atom such as a ring or containing a nitrogen atom and an oxygen atom or a sulfur atom
A monovalent group derived from a monocyclic saturated plural ring of a member ring and the like can be mentioned.

Of these, R ³ and R ⁴ are hydrogen atoms and have 1 carbon atom.
-20 alkyl group, 6-10 carbon aryl group, 7-10 carbon aralkyl group, 2-8 carbon dialkylamino group, containing up to 2 nitrogen atoms or 1 nitrogen atom and oxygen A monovalent group derived from a 5-membered or 6-membered monocyclic saturated heterocycle containing either one atom or a sulfur atom is preferred. By selecting each group of R ³ or R ⁴ , the fading rate of the compound of the general formula [A] can be changed. For example, if R ³ and R ⁴ are alkyl groups, then perhaps
It seems that it is difficult to take the trans type of the coloring state, but a high fading speed can be obtained. Further, when R ³ is a substituted amino group, the trans-form in the color-developed state is stabilized by resonance and a high color-developing density can be obtained, but the fading speed is slightly slowed. Furthermore, a compound in which both R ³ and R ⁴ are hydrogen atoms has a feature that it develops a particularly deep color and has a fast fading rate.

Next, in the general formula [A] in the present invention, Are each a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 carbon atoms.
It has ~ 14 pieces. Particularly, a divalent group derived from one benzene ring or two to four condensed rings thereof is preferable. Examples of the ring forming such an aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a phenanthrene ring, and the like.

Further, as the unsaturated heterocyclic group, a 5-membered or 6-membered monocyclic heterocyclic group containing 1 to 2 nitrogen atoms, oxygen atoms, and sulfur atoms, or a condensed heterocyclic group in which a benzene ring is condensed with these Is shown. Examples of the ring 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. And sulfur-containing heterocycles.

Above The aromatic hydrocarbon group or unsaturated heterocyclic group represented by may contain at most 5, preferably up to 3, substituents. Examples of such substituents include halogen atoms such as fluorine, chlorine and iodine; hydroxyl group; cyano group; nitro group; alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group and butyl group. 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, ethylamino group Etc., such as an alkylamino group having 1 to 4 carbon atoms; dimethylamino group, diethylamino group, etc., having 2 carbon atoms
A dialkylamino group having 1 to 8; a halogenoalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a sulfur atom, an oxygen atom, and a nitrogen atom such as a thienyl group, a furyl group, a pyrrolyl group, and a pyridyl group; 5-membered or 6-membered monocyclic heterocyclic group, further-R ⁵ -S-R ⁶ or And so on.

Above And when R ¹ and R ² together form a ring and constitute an optionally substituted norbornylidene group or an optionally substituted bicyclo [3.3.1] 9-nonylidene group, Halogen atom, hydroxyl group, cyano group,
Nitro group, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C10 aryl group, C2-C2
A divalent aromatic carbon which may in each case be substituted by at least one selected from the group consisting of a dialkylamino group of 8, a halogenoalkyl group of 1 to 4 carbon atoms and a monocyclic heterocyclic group. It is preferably a hydrogen group or a divalent unsaturated heterocyclic group.

Also, Is a divalent group derived from a benzene ring which may be substituted in each case by 1 to 3 of each substituent described above, or a condensed ring of 2 to 4 benzene rings, or
It is preferably a divalent group derived from a 5-membered or 6-membered monocyclic heterocycle containing 1 to 2 oxygen atoms, sulfur atoms or nitrogen atoms, or a condensed heterocycle in which a benzene ring is condensed with these.

Furthermore, Is a benzene ring, naphthalene ring, which may be substituted in each case by 1 to 3 of the above-mentioned substituents,
A divalent group derived from a phenanthrene ring, a pyridine ring, a quinoline ring, a pyrrole ring, a furan ring, a benzofuran ring, a thiophene ring, or a benzothiophene ring is preferable.

In the general formula [A], when R ¹ and R ² are alkyl groups, Is an alkyl group having 6 to 20 carbon atoms, an alkoxy group having 6 to 20 carbon atoms, -R ⁵ -S-R ⁶ and (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 respectively the same or different alkyl groups, and X is Is. And a bicyclic aromatic hydrocarbon group or a bicyclic unsaturated heterocyclic group having at least one kind of substituent selected from the group consisting of

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

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

Furthermore, the other substituents of the bicyclic aromatic hydrocarbon group or the bicyclic unsaturated heterocyclic group are -R ⁵ -S-R ⁶ and (However, R ⁵ is an alkylene group or O—R ⁸ _n (provided that R _{8 is}
Is an alkylene group, and n is a positive integer. ), R ⁶ and R ⁷ are the same or different alkyl groups, and X is Is. ). The alkylene group represented by R ⁵ and R ⁶ of these two substituents is not particularly limited in carbon number and is generally selected from the range of 1 to 20, but the durability of the resulting chromene derivative as a photochromic material is improved. Considering this, the carbon number is preferably in the range of 6 to 20.
Specific examples of the alkylene group 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. , Dodecamethylene group, tridecamethylene group, gentadecamethylene group, octadecamethylene group, eicosamethylene group and the like. Also,
_N of O—R ⁸ _{n represented} by R ⁵ may be a positive integer, but generally, the number of carbon atoms of the chain represented by O—R ⁸ _n is 1 to 1
It is preferably chosen to be 20, preferably 6-20, for which n is generally chosen in the range 1-20.

Further, the carbon number of the alkyl group represented by R ⁶ and R ⁷ is not particularly limited, but it is preferably in the range of 1 to 4 from the viewpoint of the fading rate of the obtained chromene derivative as a photochromic material.

The above-mentioned various substituents may be substituted on the bicyclic aromatic hydrocarbon group or the bicyclic unsaturated heterocyclic group up to a maximum of 6, but usually 1 to 3 for reasons such as ease of production. Substitution within the range is preferred.

The bicyclic aromatic hydrocarbon group or the bicyclic unsaturated heterocyclic group substituted with the above-mentioned various substituents is a 5-membered ring among the above-mentioned aromatic hydrocarbon group or unsaturated heterocyclic group. A condensed 6-membered ring is adopted. Especially, as a condensation position, a chromene derivative in which an aromatic ring is condensed at the 7- and 8-positions of chromene is particularly suitable for use as a photochromic material because of its high coloring density.

The substituent of the bicyclic aromatic hydrocarbon group or the bicyclic unsaturated heterocyclic group is an alkyl group having 6 to 20 carbon atoms or 6 to 20 carbon atoms.
When it contains the alkoxy group, the obtained chromene derivative becomes a photochromic material having excellent durability. on the other hand,
The substituent of the bicyclic aromatic hydrocarbon group or the bicyclic unsaturated heterocyclic group is -R ⁵ S-R ⁶ or In the case of containing, the resulting chromene derivative becomes a photochromic material having a high fading rate.

The component (b) of the photochromic composition of the present invention is a fulgide compound or a fulgimide compound. The fulgimide compound has the following formula A compound having a structure represented by and having photochromic properties is adopted without any limitation. The fulgimide compound has the following formula A compound having a structure represented by and having photochromic properties is adopted without any limitation.

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

In the formula Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group R ₁ may be a monovalent hydrocarbon group which may have a substituent, or Monovalent heterocyclic group Is a norbornylidene group or an adamantylidene group which may have a substituent, X is an oxygen atom, a group N—R ₂ group N—A ₁ —B ₁ — (A _{2 m} (B _{2 n} R ₃ group shows the N-a ₃ -A ₄ or a group N-a ₃ -R _4.

In the general formula [I], Is an aromatic hydrocarbon group or an unsaturated heterocyclic group,
These groups may have at most 5, preferably up to 3, substituents. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 14 carbon atoms, and examples of the ring forming the aromatic hydrocarbon group include a benzene ring, a naphthalene ring and a phenanthrene ring. A ring is included.

Further, as the unsaturated heterocyclic group, at least one kind of hetero atom such as nitrogen atom, oxygen atom and sulfur atom is
A 5-membered or 6-membered monocyclic heterocyclic group containing 5 or 6 members, or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed therewith. Examples of the ring forming the 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 pyran ring; thiophene ring, Examples thereof include sulfur-containing heterocycles such as benzothiophene ring.

As previously mentioned, The aromatic hydrocarbon group or unsaturated heterocyclic group represented by may contain at most 5, preferably up to 3, substituents. Examples of such substituents are halogen atoms such as fluorine, chlorine, bromine and iodine; hydroxyl group; cyano group; nitro group; amino group; carboxyl group; methylamino group; carbon number 1 such as diethylamino group.
An alkylamino group having 1 to 8; a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a t-butyl group; a halogen atom having 1 to 3 halogen atoms such as a trifluoromethyl group and a 2-chloroethyl group. Halogenated lower alkyl group having 1 to 2 carbon atoms; lower alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group and t-butoxy group; phenyl group
Aryl group having 6 to 10 carbon atoms such as naphthyl group and tolyl group; 6 to 10 carbon atoms such as phenoxy group and 1-naphthoxy group
14 aryloxy group; aralkyl group having 7 to 15 carbon atoms such as benzyl group, phenylethyl group and phenylpropyl group; aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group and phenylpropoxy group and 1 to 4 carbon atoms And an alkylthio group. These substituents may be the same or different and the position is not particularly limited.

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

Also, Contains an aryl group having 6 to 14 carbon atoms which may be substituted in each case by 1 to 3 of the above-mentioned substituents, or one nitrogen atom, oxygen atom and sulfur atom 5
A monocyclic heterocyclic group having a six-membered ring or a six-membered ring or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed with the heterocyclic group is more preferable.

Further above Is preferably a divalent benzene ring, a 5-membered or 6-membered monocyclic heterocycle containing one heteroatom, or a condensed heterocycle in which a benzene ring or a cyclohexene ring is condensed with this heterocycle. . The benzene ring, monocyclic heterocycle or condensed heterocycle containing one or two of the above-mentioned substituents is also a preferred embodiment.

Each R ₁ in the above general formula [I] is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent.

The hydrocarbon group of R ₁ may be any of an aliphatic, alicyclic or aromatic hydrocarbon group, and specific examples include a carbon number such as a methyl group, an ethyl group, a propyl group and a butyl group. 1 to 20, preferably 1 to 6 alkyl group; aryl group having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group and naphthyl group; benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group Such an aralkyl group having 7 to 16 carbon atoms having an alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms is suitable.

As the heterocyclic group for R ₁ , at least one heteroatom such as nitrogen atom, oxygen atom and sulfur atom is 1 to 3
A 5-membered or 6-membered monocyclic heterocyclic group containing 1 or 2, preferably 1 or 2, or a condensed heterocyclic group in which benzene is condensed thereto is preferable. Specific examples of such a heterocyclic group include In addition to the examples of the unsaturated heterocyclic group described in the definition of 1, saturated saturated heterocyclic groups such as a piperidine ring, a piperazine ring, a morpholine ring, a pyrrolidine ring, an indoline ring and a chroman ring can be mentioned.

The hydrocarbon group or heterocyclic group for R ₁ described above may have a substituent, which is not critical. The number of such substituents is preferably at most 5, preferably up to 3, with respect to the hydrocarbon group or the heterocyclic group. Specific examples of the substituents include the above. The same substituents as those described above can be exemplified.

The above R ₁ is preferably a halogen atom or having 1 carbon atom.
To C4 alkyl group optionally substituted with an alkoxy group having 4 to 4 carbon atoms; an aryl group having 6 to 10 carbon atoms optionally substituted with a halogen atom or an alkoxy group having 1 to 4 carbon atoms Or a 5-membered or 6-membered monocyclic heterocyclic group containing 1 to 3, especially 1 nitrogen atom, carbon atom and sulfur atom, or a condensed heterocyclic group in which a benzene ring is fused to the heterocyclic group , Especially monocyclic heterocyclic groups.

Furthermore, it is particularly preferable that R _{1 be 1 to} 6 carbon atoms.
Is an alkyl group, a C7-10 aralkyl group, or a C6-10 aryl group.

In the above general formula [I] in the present invention, Means a norbornylidene group or an adamantylidene group, each of which may have a substituent. Here, the norbornylidene group is represented by the following formula And the adamantylidene group is represented by the following formula.

The above formulas show the skeleton structures of the norbornylidene group and the adamantylidene group, each of which has no substituent. In these norbornylidene group or adamantylidene group, the hydrogen atom in the above formula may be substituted with a substituent, and the number thereof may be one or more. When it has a substituent, its type, number and position are arbitrarily selected depending on the purpose and application. When it has a plurality of substituents, it may be the same or different.

Examples of the substituent of the above norbornylidene group or adamantylidene group include a hydroxy group; an alkylamino group having 1 to 8 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. An alkoxy group having 1 to 4 carbon atoms; an aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group; an aroxy group having 6 to 14 carbon atoms such as phenoxy group, 1-naphthoxy group; methyl group, ethyl group, t-butyl group Etc., a lower alkyl group having 1 to 4 carbon atoms; a halogen atom such as fluorine, chlorine, and iodine;
Cyano group; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl; halogen-substituted alkyl group having 1 to 3 halogen atoms and 1 to 2 carbon atoms such as trifluoromethyl group; nitro group; phenyl group, Examples thereof include an aryl group having 6 to 10 carbon atoms such as a tolyl group; and an aralkyl group having 7 to 9 carbon atoms such as a phenylethyl group and a phenylpropyl group.

Preferred examples of these substituents include a halogen atom,
Hydroxy group, C1-C4 alkyl group, C1-C1
A C4 alkoxy group, a C2-10 alkoxycarbonyl group, a C7-9 aralkyl group or a C6-10
Is an aryl group.

In the above general formula [I] of the present invention, X is an oxygen atom (—O—), a group N—R ₂ , a group N—A ₁ —B ₁ — (A _2
m (B _{2 n} R _3, a group N-A ₃ -A ₄ or a group N-A ₃ -R _4.

Further, in the general formula [I], X is a group N-A ₁ -B _1-
(A _{2 m} (B _{2 n} R ₃ , group N-A ₃ -A ₄ or group N-A ₃
-R ₄ , especially the group N-A ₃ -R ₄ or the group N-A ₁ -B _1- (A _2
m (B _{2 n} R ₃ (wherein R ₃ is alkyl having 1 to 10 carbon atoms which may be substituted with 1 to 3 atoms or groups selected from the group consisting of halogen atom, cyano group and nitro group) It is more preferable that it is a group.) From the viewpoint of durability of photochromic property of the obtained compound.

X in the general formula [I] is the above-mentioned group N-A ₁ -B _1-
(A _{2 m} (B _{2 n} R ₃ , when R ₃ is a naphthyl group or a naphthylalkyl group, and when it is a group N-A ₃ -A ₄ , a naphthyl group represented by R ₃ or R ₄ It is preferable that the number of main chain atoms sandwiched between the and the imide group (N-) is in the range of 3 to 7 since a compound excellent in durability of photochromic action can be obtained.

Next, in the above X, R ₂ , R ₃ , R ₄ , A ₁ , A ₂ , A ₃ , A ₄ ,
The definitions of B ₁ , B ₂ , m and n will be described in detail.

R ₂ 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, n-, iso- or tert-butyl group,
Examples thereof include a pentyl group, a hexyl group, an octyl group and a decyl group. Among these, those having 1 to 20 carbon atoms, and those having 1 to 10 carbon atoms are preferable. Examples of the aryl group include those having 6 to 10 carbon atoms such as phenyl group, tolyl group and naphthyl group.

A ₁ , A ₂ and A ₃ may be the same as or different from each other and can be an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group. Specific examples thereof include, for example, methylene group, ethylene group, propylene group, butylene group, trimethylene group, tetramethylene group or alkylene group having 1 to 10 carbon atoms such as 2,2-dimethyltrimethylene group; ethylidene group, Alkylidene group having 2 to 10 carbon atoms such as propylidene group or isopropylidene group; Cycloalkylene group having 3 to 10 carbon atoms such as cyclohexylene group; 2
-Methylcyclohexane-α, 1-diyl group 4-methylcyclohexane-α, 1-diyl group And an alkylcycloalkane-diyl group having 6 to 10 carbon atoms such as As A ₁ and A ₂ , particularly 1 to ₂ carbon atoms
An alkylene group having 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 are preferable.

B ₁ and B ₂ may be the same as or different from each other, and are selected from the seven groups in the following group.

m and n each independently represent 0 or 1, and when 0 is represented, A _{2 m} or B _{2 n} means a bond. Further, when m is 0, n is also 0.

R ₃ represents an alkyl group which may have a substituent, a naphthyl group or a naphthylalkyl group. The number of carbon atoms of the above alkyl group is not particularly limited, but it is preferably 1 to 10, and the number of carbon atoms of the alkyl group of the naphthylalkyl group is preferably 1 to 4.

The substituent of each of the above groups is not particularly limited, but the alkyl group 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 naphthyl group or naphthylalkyl group is selected from the group consisting of 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. It may be substituted with only 1 to 3 atoms or groups. As the alkyl group represented by R ₃ , the same alkyl groups as those exemplified for R ₂ can be used. Examples of the naphthylalkyl group include naphthylmethyl group, naphthylethyl group, naphthylpropyl group, naphthylbutyl group and the like.

A ₄ represents a naphthyl group which may have a substituent.
The kind of the substituent is not particularly limited, but the naphthyl group is 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. It may be substituted with 1 to 3 atoms or groups selected from the group consisting of: R ₄ represents a halogen atom, a cyano group or a nitro group.

In the above definition of R ₃ and A ₄ , the halogen atom may be fluorine, chlorine or bromine.

In the present invention, the above-mentioned chromene derivative and the mixing ratio of the fulgide compound or the fulgimide compound can be arbitrarily selected according to the intended color tone, but in order to adjust the color tone such as brown, gray and amber, generally, Is relative to 100 parts by weight of the chromene derivative, 0.01-10000 parts by weight of the fulgide compound or fulgimide compound, preferably 0.0
It is preferable that the amount is 5 to 200 parts by weight.

The photochromic composition of the present invention can be made into a photochromic fluid that can be used for applications such as decoration by dispersing it in an organic solvent. Further, by dispersing the photochromic composition of the present invention in a polymer such as a thermoplastic resin or a thermosetting resin, a molded product such as photochromic glass or photochromic lens can be obtained.

The thermoplastic resin may be any one that can uniformly disperse the chromene derivative and the fulgide compound or the fulgimide compound. Optically preferably, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polymethacryl Examples thereof include ethyl acid, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

Dispersion of the photochromic composition of the present invention in a thermoplastic resin is a method of synthesizing a thermoplastic resin, that is, a method of performing polymerization in the presence of the photochromic composition, or a thermoplastic resin and a photochromic composition of a thermoplastic resin. A method of melting and kneading at a melting temperature or higher can be mentioned.

Next, as the thermosetting resin, ethylene glycol diacrylate, diethylene glycol dimethacrylate,
Ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2
-Polyvalent acrylic acid and polyvalent methacrylic acid ester compounds such as bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl Polyvalent allyl compounds such as fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ) Ethers, polyvalent thioacrylic acid such as 1,4-bis (methacryloylthiomethyl) benzene and polyvalent thiomethacrylic acid ester compounds; Polymers of radically polymerizable polyfunctional monomers such as divinylbenzene: Is an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or maleic anhydride; acrylic acid such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate or 2-hydroxyethyl methacrylate; Methacrylic acid ester compounds; diethyl fumarate, diphenyl fumarate, and other fumaric acid ester compounds; methylthioacrylate, benzylthioacrylate, benzylthiomethacrylate, and other thioacrylic acid and thiomethacrylic acid ester compounds; styrene, chlorostyrene, methylstyrene, vinyl Copolymers with vinyl-polymerizable monofunctional monomers such as naphthalene and bromostyrene: ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakis Addition copolymers of polyvalent thiol compounds such as thioglycolate and di (2-mercaptoethyl) ether with the above radically polymerizable polyfunctional monomers: diphenylethane diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate and the like. Examples thereof include addition polymers of a polyvalent isocyanate compound and a polyhydric alcohol compound such as ethylene glycol, trimethylolpropane, pentaerythritol, and bisphenol A, or the above-mentioned polyvalent thiol compound. These raw material monomers can be used alone or in combination of two or more.

To disperse the photochromic composition in the thermosetting resin described above, a method in which the raw material monomer of the thermosetting resin and the photochromic composition are mixed and then polymerized is generally adopted.

The addition amount of the photochromic composition of the present invention dispersed in such a polymer is 0.0 with respect to 100 parts by weight of the polymer.
The amount is 01 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

By adding an ultraviolet stabilizer to the composition of the present invention, the durability of photochromic property can be further improved. As the ultraviolet stabilizer, known ultraviolet stabilizers added to various plastics can be used without any limitation.

In the present invention, considering the improvement of durability of the photochromic compound, among various ultraviolet stabilizers, singlet oxygen quencher, hindered amine light stabilizer, hindered phenol antioxidant, and sulfur-based antioxidant are preferably used. To be done. More specific examples of these ultraviolet stabilizers, Ciasorb UV1084, Ciasorb 3346 (above, American Cyanamid Co., Ltd.); UV-Chek AM101, UV-Chek AM105 (above, Ferro Corporation, Inc.); Irgastab 2002, Tinuvin 765, Tinuvin 144, Kima Sorb 94
4, Chinubin 622, Irganox 1010, Irganox 245
(Above, manufactured by Ciba Geigy); Relex NBC (manufactured by DuPont); Ciasorb 3346 (manufactured by American Cyanamid); Sanol LS-1114, Sanol LS-744, Sanol L
S-2626 (above, Sankyo Co., Ltd.); Sumilizer GA-8
0, Sumilizer GM, Sumilizer BBM-S, Sumilizer WX
-R, Sumilizer S, Sumilizer BHT, Sumilizer TP-
D, Sumilizer TPL-R, Sumilizer TPS, Sumilizer M
B (above, manufactured by Sumitomo Chemical Co., Ltd.); Mark AO-50, Mark AO-2
0, Mark AO-30, Mark AO-330, Mark AO-23 (above,
Adeka Argus)); Antioxidant HPM-12
(Manufactured by SFOS) and the like. All the above names are product names.

The mixing ratio of the ultraviolet stabilizer is preferably 0.01 to 10000 parts by weight with respect to the total amount of 100 parts by weight of the chromene derivative and the fulgide compound or the fulgimide compound, and in particular, the photochromic composition of the obtained photochromic composition. From the viewpoint of properties, the ultraviolet stabilizer is preferably in the range of 10 to 500 parts by weight.

(Effect) As described above, the photochromic composition of the present invention changes from colorless to colored or dark colored form by sunlight or light containing ultraviolet rays such as light of a mercury lamp, and the change is reversible. Shows excellent dimmability. In addition, the present invention has succeeded in easily obtaining various intermediate colors such as gray, brown, and amber by using a chromene derivative and a frigide compound or a fulgimide compound in combination.

Therefore, the photochromic composition of the present invention can be used in a wide range of fields, for example, various recording memory materials replacing silver salt photosensitive materials, copying materials, photoconductors for printing, recording materials for cathode ray tubes, and photosensitive materials for lasers. Can be used as various recording materials. In addition, the photochromic composition of the present invention is a photochromic lens material, an optical filter material,
It can also be used as a material for display materials such as photometers and decorations.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. “Parts” in the examples is “parts by weight”.

The symbols and trade names of UV stabilizers in the following examples indicate the following compounds.

・ BMDBP: 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane ・ Cl-St: chlorostyrene ・ TMP-TAC: trimethylolpropane triallyl carbonate ・ BADBP: 2,2-bis ( 4-allylcarbonate ethoxy-3,5-dibromophenyl) propane-ADC: allyl diglycol carbonate-DAP: diallyl phthalate-St: styrene-DCIPF: di (2-chloroisopropyl) fumarate-EGDMA: ethylene glycol dimethacrylate-PETTP : Pentaerythritol tetrakis (β-thiopropionate) ・ DME: Di (2-mercaptoethyl) ether ・ DVB: Divinylbenzene ・ XIC: Xylylene diisocyanate ・ HPA: 3- (2,4-Dibromophenoxy) -2- Hydroxypropyl acrylate ・ MMA: methyl methacrylate ・ DEGDMA: diethylene glycol Dimethacrylate-TBBM: 3,4,5-tribromobenzyl methacrylate-HEMA: 2-Hydroxyethyl methacrylate-BMA: Benzyl methacrylate-IPP: Diisopropyl peroxycarbonate-Perbutyl ND: t-butyl (manufactured by NOF Corporation) Peroxy-2-hexanate-BPO: Benzoyl peroxide-Sanol LS-744 (Product name: Sankyosha) ・ MARK LA-82 (Product name: ADEKA ARGUS) ・ MARK LA-87 (Product name: ADEKA ARGUS) ・ Sanol LS-2626 (Product name: Sankyo Co., Ltd.) ・ Sumilyzer GA-80 (Product name: Sumitomo Chemical Co., Ltd.) ・ Irganox 1010 (Product name: Ciba Geigy) ・ Cyasorb UV1084 (Product name: American Cyanamid) ・ Tinuvin 765 (Product name: Ciba Geigy) ・ UV-Chek AM101 (Product name: Ferro Corporation) ・ MARK AO-20 (Product name: ADEKA ARGUS) ・ Sumilyzer TP-D (Product name: Sumitomo Chemical Co., Ltd.) (H ₂₅ C ₁₂ SCH ₂ CH ₂ COOCH ₂ ) ₄ C ・ Sanol LS-1114 (Product name: Sankyosha) Production Example 1 1-hydroxy-2-acetonaphthone 10 g (0.054 mo
l) and norcamphor 6.6g (0.06mol) and pyrrolidine 8g
(0.113 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized with acetone. Next, this 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 g) was heated in a carbon dioxide stream with anhydrous copper sulfate (4.5 g) at 150 to 160 ° C for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to give the chromene compound of the following formula. 6.3 g of the derivative was obtained.

The elemental analysis value of this compound is C 86.93%, H 6.89%, O
6.18%, which is the calculated value for C ₁₉ H ₁₈ O, C 87.0
2%, H 6.87% and O 6.12% were extremely well matched. Also, when the proton nuclear magnetic resonance spectrum was measured,
Based on the naphthalene ring protons around δ7.2-8.3 ppm 6
The peak of H, the peak of 2H based on the alkene proton near δ5.6 to 6.7ppm, and the broad peak of 10H based on the proton of the norbornylidene group around δ1.2 to 2.5ppm. Furthermore, when ¹³ C-nuclear magnetic resonance spectrum was measured, a peak based on the carbon of the norbornylidene group around δ27 to 52 ppm, a peak based on the carbon of the naphthalene ring near δ110 to 160 ppm, and a peak based on the carbon of the alkene near δ80 to 110 ppm. Appears. From the above results, it was confirmed that the isolated product was the compound represented by the structural formula (1).

Production Example 2 A solution of 10 g (0.054 mol) of 1-acetyl-2-naphthol, 8.29 g (0.06 mol) of bicyclo [3.3.1] nonan-9-one and 8.7 g (0.10 mol) of morpholine in 300 cc of toluene was prepared. Prepared. The mixture was boiled for 5 hours and the water was separated. After completion of 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, and lithium aluminum hydride was added to obtain a chromanol compound. This chromanol compound 6.49 g was heated with anhydrous copper sulfate in a carbon dioxide stream at 170 to 180 ° C. for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain 5.8 g of the chromene derivative of the following formula. It was

The elemental analysis values of this compound are C 86.81%, H 7.62%, O
5.57%, which is the calculated value for C ₂₁ H ₂₂ O, C 86.9
Very good agreement with 0%, H 7.59%, and O 5.52%. Also, when the proton nuclear magnetic resonance spectrum was measured,
Based on the naphthalene ring protons around δ7.2-8.3 ppm 6
H peak, 2H peak due to alkene protons at δ 6.0 to 7.0 ppm, and bicyclo (3.
3.1] It showed a broad peak of 14H based on the proton of the 9-nonylidene group. Furthermore, when ¹³ C-nuclear magnetic resonance spectrum was measured, bicyclo (3.3.
1] carbon-based peak of 9-nonylidene group, δ 110-16
A peak based on the carbon of the naphthalene ring near 0 ppm, δ80-
A peak based on carbon of alkene appears at around 110 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the structural formula (2).

Production Example 3 3.06 g (0.01 mol) of a chromanone compound represented by the following formula Was dissolved in 50 cc of anhydrous ether, the solution was cooled to 0 ° C., and Grignard reagent CH ₃ Mgl (0.012 mol) newly prepared in 50 cc of anhydrous ether was added dropwise to the solution over about 1 hour. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours, then the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, and the ether was removed under reduced pressure to remove chromanone. The compound was changed to a chromanol compound. Next, this chromanol compound was mixed with anhydrous copper sulfate in a carbon dioxide stream at 200 ° C for about 1
Heat for 0 minutes to produce a brown viscous liquid by chromatography on silica gel, the chromene derivative of the formula
2.47 g was obtained.

By elemental analysis, proton nuclear magnetic resonance spectrum, and ¹³ C-nuclear magnetic resonance spectrum measurement in the same manner as in Production Example 1,
It was confirmed that this compound was the compound represented by the structural formula (3).

Production Example 4 10 g (0.054 mol) of 1-acetyl-2-naphthol, 6.6 g (0.06 mol) of norcamphor and 8.7 g (0.10 m) of morpholine
was dissolved in 300 cc of toluene and boiled for 15 hours to separate water. After completion of the reaction, toluene was removed under reduced pressure,
The remaining product was recrystallized from acetone to obtain 7.53 g of a compound represented by the following formula.

Next, 7.53 g of this compound was dissolved in 100 cc of methanol and reacted with methyl iodide to obtain 6.95 g of a chromanone compound represented by the following formula.

Then, the produced chromanone compound was replaced with a chromanol compound in the same manner as in Production Example 3 to carry out a dehydration reaction, and after separation and purification, 5.84 g of a chromene derivative represented by the following formula was obtained.

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

Production Example 5 5-n-octyloxy-1-hydroxy-2-acetonaphthone 10 g (0.0318 mol) and acetone 2.77 g (0.0477 m
ol) and 1.13 g (0.0159 mol) of pyrrolidine in 100 ml of toluene.
A solution dissolved in was prepared. The mixture was boiled for 10 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in 100 ml of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. 6.0g of this chromanol compound together with 4.0g of anhydrous copper sulfate in a carbon dioxide stream at 150-160 ℃
After heating for 10 minutes, the brown viscous liquid was purified by chromatography on silica gel to obtain 3.8 g of the chromene derivative of the following formula.

As in Production Example 1, it was confirmed by elemental analysis, proton nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum measurement that this compound was the compound represented by the structural formula (5).

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

The obtained product was subjected to structural analysis using the same means for structural confirmation as in Production Example 1, and as a result, it was confirmed to be 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 glycine-methyl ester of the following formula 17.8 g (0.02 mol) Was dissolved in toluene and heated at 50 ° C. for 2 hours under a nitrogen atmosphere. After the reaction, remove the solvent and dissolve in acetyl chloride,
The mixture was refluxed for 1 hour and cyclized. The obtained compound was refluxed in O-dichlorobenzene for 6 hours to be transferred to the following fulgimide compound (15). This compound was purified by chromatography on silica gel using benzene and ether as eluents and was obtained in 27% yield as pale yellow needles from chloroform and hexane. The elemental analysis value of this compound is C 66.78%, H 6.09%, N
3.36%, O 15.8%, S 7.96%, which are calculated values for C ₂₃ H ₂₅ O ₄ NS C 67.15%, H 6.08%, N 3.41%, O 15.6
%, S 7.79%. Also, when the proton nuclear magnetic resonance spectrum was measured, it was δ 7.0 to 8.0 ppm.
2H peak due to aromatic protons,
The peak of 3H based on the proton of C-CH ₃ bond at δ2.7ppm, around δ3.7ppm 3H peak due to the proton of the bound methyl group, δ1.2
14H based on adamantylidene group protons to ~ 2.5ppm
Of 1 to 5 rearranged in the peak of δ3-5ppm and N
-CH ₂ - and a peak of 3H based on binding.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR was measured to find that the peak due to the carbon of the adamantylidene group and the carbon of the methylene chain was around δ27 to 70 ppm, and the peak around the carbon of the methyl group was around δ15.6 ppm. , A peak based on carbon of thiophene ring near δ110-160ppm, δ160-170pp
A peak based on the carbon of the C = 0 bond appears near m.

From the above results, it was confirmed that the isolated product was a fulgimide compound (15) represented by the following structural formula.

Production Example 16 3.4 g (0.01 mol) of a fulgimide compound represented by the following formula Is dissolved in tetrahydrofuran and 1 g of metallic potassium is added to it.
Was reacted at room temperature to obtain 3 g of imide potassium having the following formula.

This was reacted with 1.2 g (0.01 mol) of BrCH ₂ CN represented by the following formula in dimethylformamide to obtain the following fulgimide compound (16). This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained in 57% yield as pale yellow crystals from hexane. The elemental analysis values of this compound are C 69.81%, H 5.80%, N 7.44%, O 8.50
%, S 8.46% and calculated value for C ₂₂ H ₂₂ N ₂ O ₂ S C 69.84%, H 5.82%, N 7.41%, O 8.47%, S 8.47%
Was very well matched. Further, when the proton nuclear magnetic resonance spectrum was measured, a peak of 2H based on the proton of the thiophene ring was observed around δ7.0 to 7.5 ppm, a peak of 2H based on the proton of the N-CH ₂ CN bond was observed around δ4.5 ppm, and δ3. .7
1H peak due to protons translocated to around 1.5 ppm, δ
A peak of 3H based on a proton of a —CH ₃ bond was shown near 2.7 ppm, and a peak of 14H of a proton based on a —CH ₂ — bond and a proton based on an adamantylidene group was observed around δ1.3 to 2.5 ppm.

Furthermore, when ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured, a peak due to the carbon of the adamantylidene group at δ 27 to 70 ppm, a peak due to the carbon of the methyl group at δ 15.6 ppm, and δ 110 to 160 ppm. A peak based on the carbon of the thiophene ring, C = 0 near δ160-170 ppm
A peak based on the carbon of the bond appears.

From the above results, it was confirmed that the isolated product was a fulgimide compound (16) represented by the following structural formula.

Example 1 70 parts of chlorostyrene, 2,2-bis (3,5-dibromo-4)
-Methacryloyloxyethoxyphenyl) propane 30
0.4 parts of the chromene derivative of Production Example 1 in a composition consisting of
0.2 part of the fulgimide compound of Production Example 15 was added, and further 1 part of perbutyl ND as a radical polymerization initiator was added and mixed sufficiently. This mixed solution was poured into a mold composed of a gasket composed of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was carried out. Polymerization was carried out at 30 ° C. to 90 ° C. for 18 hours using an air furnace, the temperature was gradually raised, and the temperature was kept at 90 ° C. for 2 hours. After the polymerization was completed, the mold was taken out of the air furnace, and after standing to cool, the polymer was removed from the glass of the mold. The fatigue life of the obtained molded product was measured with a xenon long life fade meter FAL-25AX-HC manufactured by Suga Test Instruments Co., Ltd.

In addition, the change in color tone was visually observed. Fatigue life (T _1/2 ) is the time required for the absorbance of the chromene derivative and the fulgide compound or the fulgimide compound to decrease to 1/2 of the initial (T ₀ ) absorbance at the maximum absorption wavelength of each compound. Represented. However, T ₀ and T _1/2
Is the value obtained by subtracting the absorbance of the unirradiated molded article at the maximum absorption wavelength based on each compound,
The T ₀ absorbance was measured 60 seconds after light irradiation.

 The results are shown in Table 3.

Examples 2 to 30 Monomers used in Example 1, chromene derivatives,
The same procedure as in Example 1 was carried out except that the type and amount of the fulgimide compound were changed and the polymerization was carried out by a known means depending on the monomer. The results are shown in Table 3.

Example 21 2,2-bis- (4-methacryloyloxyethoxy-
3,5-dibromophenyl) propane 40 parts, styrene 60 parts in a composition 0.4 parts of the chromene derivative of Production Example 1, 0.2 parts of the fulgimide compound of Production Example 16, 0.6 parts of Sanol LS-744 as a UV stabilizer, radicals 1 part of perbutyl ND was added as a polymerization initiator and mixed thoroughly.

The obtained mixed liquid was polymerized in the same manner as in Example 1 to obtain a molded article, and its photochromic performance was measured.

The results are shown in Table 4. During Table 4, the color tone at T _1/2 is the tone in the T _1/2 of chromene derivatives.

Examples 22-40 Monomers used in Example 21, chromene derivatives,
The same procedure as in Example 21 was carried out except that the amounts and types and amounts of the fulgimide compound and the ultraviolet stabilizer were changed, and polymerization was performed by a known means depending on the monomer. The results are shown in Table 4.

Example 41 To 100 parts by weight of chloroform, 0.8 g of the chromene compound of Production Example 1 and 0.9 g of the fulgimide compound of Production Example 33 were added and dissolved. This solution was placed in a quartz cell (1 cm × 1 cm × 4 cm) and irradiated with stirring with the xenon lamp of the fade meter described in Example 1.

As a result of visually observing the change in color tone, the color changed rapidly from colorless to gray.

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Claims (2)

(57) [Claims] 1. (a) The following formula A photochromic composition comprising 100 parts by weight of the chromene derivative represented by the formula (b) and 0.01 to 10000 parts by weight of the fulgide compound or the fulgimide compound (b). 2. A polymer composition comprising 100 parts by weight of the polymer and 0.001 to 20 parts by weight of the photochromic composition according to claim (1).