JPH0913023A - Photochromic composition - Google Patents

Abstract

PURPOSE: To obtain a photochromic composition which changes color from initial colorlessness to halftones such as gray, brown and amber colors by mixing a specified flugimide compound with a specified chromene compound. CONSTITUTION: This photochromic composition is prepared by mixing a photochromic composition prepared by mixing 100 pts.wt. flugimide compound of formula I [wherein formula II is a bivalent aromatic hydrocarbon group or the like; formula III is norbonylidene, bicyclo(3,3,1)nonylidene or adamantylidene; R<1> is a monovalent hydrocarbon group or a monovalent heterocyclic group; and R<2> is a perhalogenoalkyl, cyano, an alkoxycarbonyl, an alkylcarbonyl, an arylcarbonyl, nitro, sulfonyl, an alkylsulfonyl, an arylsulfonyl or an aryloxycarbonyl] with 0.01-10,000 pts.wt. chromene compound of formula IV (wherein R<5> to R<8> are each H, a hydrocarbon group, a substituted amino, an aromatic hydrocarbon group, an unsaturated heterocyclic group or a saturated heterocyclic group) with a thermoplastic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composition which develops an intermediate colorless color such as gray, brown and amber from an initially colorless state upon irradiation with light including ultraviolet rays such as sunlight.

[0002]

2. Description of the Related 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 is rapidly changed and the light irradiation is performed. 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. A fulgide or fulgimide compound is known as a photochromic compound. The color tone of the fulgide or fulgimide compound at the time of color development is orange to blue. On the other hand, chromene compounds,
Alternatively, spirooxazine compounds are also well known as photochromic compounds, and the color tones of these compounds are generally orange to yellow for chromene compounds and reddish purple to blue for spirooxazine compounds.

However, when these compounds are used alone, the desired color tone may not be obtained. 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 with the above compounds alone.

[0004] Previously, in JP-A-2-28154, the inventors of the present invention mixed the above-mentioned fulgide or fulgimide compound with a chromene compound, and as a result, developed various intermediate colors such as gray, amber and brown. I succeeded in making it happen.

[0005]

However, Japanese Patent Application Laid-Open No.
The fulgimide compound of JP-A-28154 is a compound in which the maximum absorption wavelength at the time of color development is made longer, and accordingly,
It had a yellowish tint before absorbing ultraviolet rays (hereinafter referred to as initial coloring), and when used in a photochromic lens, it had a defect that the initial stage of the lens became yellow.

[0006]

[Means for Solving the Problems] Therefore, if a fulgimide compound that suppresses the initial coloration due to the increase in the maximum absorption wavelength can be made, by combining it with the above-mentioned chromene compound, the initial colorless state can be changed to gray, brown, amber, etc. I think that you can get something that develops in the intermediate color of
After a lot of diligent study.

As a result, by combining with a specific fulgimide compound and a chromene compound, or further with a spirooxazine compound, it succeeded in developing various intermediate colors such as gray, amber and brown from the initial colorless state. The present invention has been completed.

That is, the present invention provides (A) the following general formula (1)

[0009]

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However, the following formula (a)

[0011]

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Is optionally substituted 2
A divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group, represented by the following formula (b)

[0013]

[Chemical 6]

Is a norbornylidene group, a bicyclo [3.3.1] nonylidene group or an adamantylidene group, each of which may have a substituent, and R ¹ may each have a substituent of 1. A divalent hydrocarbon group or a monovalent heterocyclic group, R ² represents a perhalogenoalkyl group, a cyano group, an alkoxycarbonyl group which may have a substituent,
An alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, a nitro group, a sulfonyl group, an alkylsulfonyl group which may have a substituent,
100 parts by weight of a fulgimide compound represented by an arylsulfonyl group which may have a substituent or an aryloxycarbonyl group which may have a substituent, and (B) a chromene compound 0.01 to 1000
A photochromic composition comprising 0 parts by weight.

The present invention further comprises a spirooxazine compound of 0.01 to 100 in addition to the photochromic compound.
A photochromic composition containing 100 parts by weight is also provided.

The present invention further provides a photochromic composition containing 0.001 to 20 parts by weight of these photochromic compositions and 100 parts by weight of a polymerizable monomer,
A photochromic composition containing 0.001 to 20 parts by weight of the same photochromic composition and 100 parts by weight of a thermoplastic resin is also provided.

The component (A) in the photochromic composition of the present invention is a fulgimide compound.

In the above general formula (1)

[0019]

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Are each an aromatic hydrocarbon group or an unsaturated heterocyclic group which may have a substituent. These groups may have at most 5, preferably up to 3, substituents. The aromatic hydrocarbon group has 6 to 20 carbon atoms,
It preferably has 6 to 14 carbon atoms, and examples of the ring forming the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, a phenanthrene ring and the like.

The unsaturated heterocyclic group is a 5- or 6-membered mono-heterocyclic group containing at least one heteroatom such as nitrogen atom, oxygen atom and sulfur atom, or a benzene ring. Alternatively, a fused heterocyclic group in which a cyclohexene ring is fused is shown. Examples of the ring forming the heterocyclic group include nitrogen-containing heterocycles such as a pyrrole ring, a pyridine ring, a quinoline ring, an isoquinoline ring and an indole ring; a furan ring, a benzofuran ring, a pyran ring,
Oxygen-containing heterocycles such as tetrahydrobenzofuran ring; sulfur-containing heterocycles such as thiophene ring, benzothiophene ring and tetrahydrobenzothiophene ring.

Examples of the substituent which the aromatic hydrocarbon group or unsaturated heterocyclic group represented by the above formula (a) may have include a halogen atom such as fluorine, chlorine, bromine and iodine; hydroxyl. Group; cyano group; nitro group; amino group;
Carboxyl group; alkylamino group having 1 to 4 carbon atoms such as methylamino group and diethylamino group; lower alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and t-butyl group; trifluoromethyl group A halogen lower alkyl group having 1 to 3 halogen atoms such as a 2-chloroethyl group; a lower alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a t-butoxy group; a phenyl group, a naphthyl group, a toluyl group An aryl group having 6 to 10 carbon atoms such as: a phenoxy group, an aryloxy group having 6 to 14 carbon atoms such as a 1-naphthoxy group, an aralkyl group having 7 to 15 carbon atoms such as a benzyl group, a phenylethyl group, a phenylpropyl group An aralkoxy group having 7 to 15 carbon atoms such as a benzyloxy group or a phenylpropoxy group, and an alkyl group having 1 to 4 carbon atoms. Such as a group, and the like. These substituents may be the same or different, and the position is not particularly limited.

The group represented by the above formula (a) includes a halogen atom, a nitro group, a cyano group, an amino group, and a carbon number of 1 to 1.
A divalent group which may be substituted in each case by at least one atom or group selected from the group consisting of a C4 alkylthio group, a C1-4 alkyl group and a C1-4 alkoxy group. It is preferably an aromatic hydrocarbon group or a divalent unsaturated heterocyclic group.

The group represented by the above formula (a) is 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 A 5-membered or 6-membered monocyclic heterocyclic group having a nitrogen atom, an oxygen atom and a sulfur atom, or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed with the heterocyclic group is more preferable.

Further, as the group represented by the above formula (a), a benzene ring, a 5-membered or 6-membered monocyclic heterocycle containing 1 to 3 heteroatoms, or a benzene ring in the heterocycle or Preferred is a condensed heterocycle in which cyclohexene rings are condensed. The benzene ring, the monocyclic heterocyclic ring or the condensed heterocyclic ring, which contains one or two substituents described above, is also a preferable embodiment.

In the above general formula (1) in the present invention, the group of the above formula (b) is a norbornylidene group which may have a substituent, a bicyclo [3,3,1] nonylidene group or an adamantylidene group. Means As the norbornylidene group, the following formula (c)

[0027]

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A 7-norbornylidene group represented by the following formula is preferred, and a bicyclo [3,3,1] nonylidene group is represented by the following formula (d):

[0029]

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A bicyclo [3,3,1] 9-nonylidene group represented by the following is preferred, and an adamantylidene group is represented by the following formula (e):

[0031]

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A 2-adamantylidene group represented by: is preferred.

The above formulas have no substituents, 7-
1 shows a skeleton structure of a norbornylidene group, a bicyclo [3,3,1] 9-nonylidene group or a 2-adamantylidene group.

In these 7-norbornylidene group, bicyclo [3,3,1] 9-nonylidene group or 2-adamantylidene group, the hydrogen atom in the above formula may be substituted by a substituent, and the number thereof is 1 It may be individual or more. When it has a substituent, its type, number and position are arbitrarily selected depending on the purpose and application. When the compound has a plurality of substituents, the substituents may be the same or different.

Examples of the substituent of the 7-norbornylidene group, the bicyclo [3.3.1] 9-nonylidene group or the 2-adamantylidene group include a hydroxy group; a methylamino group, a diethylamino group and the like having 1 carbon atom. ~ 4 alkylamino group; methoxy group, ethoxy group, t-butoxy group, etc., C1-4 alkoxy group; benzyloxy group, etc., C7-15 aralkoxy group; phenoxy group, 1-naphthoxy group, etc. An aryloxy group having 6 to 14 carbon atoms; a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a t-butyl group; a halogen atom such as fluorine, chlorine and bromine; a cyano group; a carboxyl group; ethoxy Alkoxycarbonyl group having 2 to 10 carbon atoms such as carbonyl; Halogen-substituted alkyl group having 1 or 2 carbon atoms such as trifluoromethyl group; Nitro ; Phenyl group, the number 6 to 10 aryl group carbon atoms such as tolyl group, phenylethyl group, and aralkyl group having 7 to 9 carbon atoms such as phenylpropyl group.

Preferred examples of these substituents include a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms,
An alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

R ¹ in the general formula (1) is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent. Here, as the hydrocarbon group or the heterocyclic group, known ones can be used without any limitation. Specific examples of the hydrocarbon group may be an aliphatic, aromatic, or aromatic hydrocarbon group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. An alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms; an aryl group having 6 to 14 carbon atoms such as phenyl group, toluyl group, xylyl group, naphthyl group; carbon such as cyclopropyl group, cyclobutyl group, cyclopentyl group Examples of the number 3 to 7, especially a cycloalkyl group and the like, which is preferably a cyclopropyl group.

The heterocyclic group is not particularly limited, but is, for example, a 5-membered or 6-membered mono-heterocyclic ring containing at least 1 to 3 hetero atoms such as nitrogen atom, sulfur atom and oxygen atom. A cyclic group or the like is preferable. Examples of the ring forming this heterocyclic group include nitrogen-containing unsaturated heterocycles such as pyrrole rings and pyridine rings; oxygen-containing unsaturated heterocycles such as furan rings and pyran rings; sulfur-containing unsaturated rings such as thiophene rings. Saturated heterocycles are preferred. In addition, saturated heterocyclic groups such as saturated piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, indoline ring and chroman ring can also be used.

Specific examples of the substituent of each group of R ¹ include the same substituents as described in the above formula (a), and the number thereof is 1 or more. May be.

In the above general formula (1) in the present invention, R ² is a perhalogenoalkyl group, a cyano group, an alkoxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, or a substituent. An arylcarbonyl group which may have a group, a nitro group, a sulfonyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, or an optionally substituted group Indicates an aryloxycarbonyl group. Each of these groups is an electron-withdrawing group, and in the present invention, such a specific electron-withdrawing group has a structure in which it is directly bonded to an imide group constituting a fulgimide compound, whereby the initial coloration of the fulgimide compound is remarkably increased. To reduce.

In the above R ² , the perhalogenoalkyl group has 1 to 4 carbon atoms such as trichloromethyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group.
A perhalogenoalkyl group; as the alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group,
an alkoxycarbonyl group having 2 to 5 carbon atoms such as t-butoxycarbonyl group; as an alkylcarbonyl group,
An alkylcarbonyl group having 2 to 5 carbon atoms such as a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, and a t-butylcarbonyl group; an arylcarbonyl group such as a benzoyl group and a 1-naphthylcarbonyl group An arylcarbonyl group having 6 to 11 carbon atoms; an alkylsulfonyl group having 2 to 5 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and a t-butylsulfonyl group; an arylsulfonyl group Examples thereof include an arylsulfonyl group having 6 to 10 carbon atoms such as a phenylsulfonyl group and a 1-naphthylsulfonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group.

Of these R ² groups, an alkylcarbonyl group, an alkoxycarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group,
Specific examples of the substituent of the aryloxycarbonyl group include the same substituents as described in the above formula (a). And the number may be one or more. In particular, the group having this substituent is preferably a group substituted with a halogen atom or a cyano group. In addition, the group substituted with the halogen atom is preferably a group in which all of the alkoxy group, alkyl group or aryl group thereof is substituted with the halogen atom. Examples of the substituent include a perhalogenoalkoxycarbonyl group having 2 to 5 carbon atoms such as trichloromethoxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, heptafluoropropoxycarbonyl group, nonafluorobutoxycarbonyl group; trichloromethyl. Perhalogenoalkylcarbonyl group having 2 to 5 carbon atoms such as carbonyl group, trifluoromethylcarbonyl group, pentafluoroethylcarbonyl group, heptafluoropropylcarbonyl group, nonafluorobutylcarbonyl group; 7 carbon atoms such as pentafluorobenzoyl group And 11 perhalogenoarylcarbonyl groups.

In the general formula (1), the group represented by the above formula (b) is an optionally substituted 7-norbornylidene group, bicyclo [3.3.1] 9-nonylidene group or 2- Is an adamantylidene group, and R ² is a cyano group, a perhalogenoalkylcarbonyl group, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, particularly a cyano group and a substituent The arylcarbonyl group which may have is more preferable from the viewpoint of suppressing the initial coloration of the obtained compound.

Specific examples of the fulgimide compound preferably used in the present invention are as follows.

(1) N-cyano-4-cyclopropyl-
6,7-Dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2'-tricyclo [3.
3.1.1 ^3,7 ] decane) (2) N-acetyl-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2′-tricyclo [ 3.3.1.1
( ^3,7 ] Decane) (3) N-benzoyl-4-cyclopropyl-6,7-
Dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2′-tricyclo [3.3.1.
1 ^3,7 ] decane) (4) N-cyano-4-methyl-6,7-dihydro-2
-Phenylspiro (5,6-benzo [b] furandcarboximido-7,2'-tricyclo [3.3.1.1]
( ^3,7 ] decane) (5) N-methylsulfonyl-4-isopropyl-6,
7-Dihydro-N′-methylspiro (indoledicarboximido-7,2′-tricyclo [3.3.1.1
( ^3,7 ] decane) (6) 1 ', 5'-dichloro-1-ethyl-3,4-dihydro-7-methoxy-N-trichlorocarbonylspiro (dibenzo [5,6-b: d] thiophenedicarboxy Imido-4,2'-tricyclo [3.3.1.
1 ^3,7 ] decane) (7) 1-cyclopropyl-3,4-dihydro-N-phenylsulfonylspiro (6,7,8,9-tetrahydrodibenzo [5,6-b: d] thiophenedicarboximide -4,2 "-Tricyclo [3.3.1.1 ^3,7 ]
Decane) (8) 4-cyclopropyl-6,7-dihydro-1'-
Methyl-2-nitro-N-perfluorobenzoylspiro (5,6-benzo [b] thiophenedicarboximide-7,9'-bicyclo [3.3.1] nonane) (9) 4-butyl-6 7-dihydro-2-methoxy-
3 ', 3'-Dimethyl-N- (3 "-trifluoromethylphenylsulfonyl) spiro (5,6-benzo [b]
Frangicarboximide-7,9'-bicyclo [3.
3.1] Nonane) (10) 2-chloro-5,6-dihydro-N'-methyl-4-phenyl-N-trifluoromethylspiro (indolecarboximido-7,9 "-bicyclo [3.
(3.1] Nonane) (11) N-cyano-5,6-dihydro-4-furylspiro (5,6-benzo [b] furandcarboximido-7,7'-bicyclo [2.2.1] heptane) (12) 3,4-dihydro-1-npropyl-N-trichloromethanespiro (6,7,8,9-tetrahydrodibenzo [5,6-b: d] furandicarboximide-
4,7′-bicyclo [2.2.1] heptane) (13) 4,5-dihydro-2,7-dimethyl-6-methoxy-N-phenoxycarbonylspiro (3,4-benzo [b] thiophenedi Carboximide-5,2'-
Tricyclo [3.3.1.1 ^{3, 7]} decane) (14) N-cyano-4-methyl-6,7-dihydro-spiro (5,6-benzo [b] thiophene-dicarboximide -7,2 ' - tricyclo [3.3.1.1 ^{3, 7]} decane (15) N-cyano-4-cyclopropyl-6,7-dihydro-spiro (5,6-benzo [b] flange dicarboximide -7,2 ' -Tricyclo [3.3.1.
1 ^3,7 ] decane (16) 3,4-dihydro-5,7-dimethoxy-N-
Cyano-1-methylspiro (naphthalenedicarboximide-4,2′-tricyclo [3.3.1.1 ^3,7 ] decane (17) N-cyano-4-methyl-6,7-dihydrospiro (5 6-benzo [b] furandicarboximido-7,2′-tricyclo [3.3.1.1 ^3,7 ] decane The fulgimide compound represented by the general formula (1) is
It can be confirmed that the compound generally exists as a pale yellow solid at room temperature, and is generally a compound of the general formula (1) by the following means (a) to (c).

(A) Proton nuclear magnetic resonance spectrum ( ¹
The type and number of protons existing in the molecule can be known by measuring (1 H-NMR). That is, a peak due to an aromatic proton is present around δ7-8 ppm, a cyclopropyl group and a norbornylidene group, and bicyclo [3.3.1] around δ1.2-2.5 ppm.
A broad peak appears based on the protons derived from the nonylidene group or the adamantylidene group. In addition, the relative number of δ peak intensities can be compared to determine the number of protons in each bonding group.

(B) By elemental analysis, each weight% of carbon, hydrogen, nitrogen, sulfur and halogen can be determined. Further, the weight% of oxygen can be calculated by subtracting the sum of the recognized weight% of each element from 100. Thus, the composition of the corresponding product can be determined.

(C) ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR) makes it possible to know the type of carbon present in the molecule. Peaks derived from carbon of cyclopropyl group and norbornylidene group, bicyclo [3.3.1] nonylidene group or adamantylidene group around δ27-52ppm, aromatic hydrocarbon group or unsaturated heterocyclic group around δ110-150ppm The carbon-based peak of> C = 0 and a peak of> C = 0 based on the carbon appear in the vicinity of 160 to 170 ppm.

The fulgimide compound represented by the general formula (1) may be produced by any method,
The type of manufacturing method does not matter. However, although preferred and representative methods are described below, the present invention is not limited to these methods.

Process A: This process A is represented by the following general formula (2).

[0051]

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(In the formula

[0053]

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[0054]

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And R ¹ are the same as defined in the above general formula (1)) and are reacted with an amine corresponding to the above, and then cyclized to produce a fulgimide compound represented by the following general formula (1). Is the way.

The reaction in Process A is preferably carried out in a solvent, and examples of the solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran and 1,4-dioxane.

When the acid anhydride of the general formula (2) is directly cyclized, or when the acid anhydride and the amine compound are reacted and then cyclized, the cyclization reaction in both cases is performed under the same conditions. It can be carried out. For this cyclization reaction, for example, a method of heating to a temperature of 160 to 220 ° C., a combination of this heating and ultraviolet irradiation, or a method of contacting with a Lewis acid catalyst is suitably adopted. As the Lewis acid catalyst, known compounds such as SnCl ₄ , TiCl ₄ , Sb
Cl ₅ , AlCl _3, etc. can be used without any limitation. The amount of the Lewis acid catalyst used is not particularly limited, but it is usually preferably used in the range of 0.001 to 1 mol with respect to 1 mol of the compound to be cyclized.

In the process A, the general formula (2)
When the acid anhydride of (1) and the amine compound are reacted, the reaction ratio is adopted from a wide range, but in general, the molar ratio is 1:10 to 10: 1, preferably 1: 5 to 5: 1. It is suitable.

The above reaction is usually carried out at a temperature of 25 to 160.
It is carried out under conditions of a temperature of 1 to 24 hours. After completion of the reaction, the solvent is removed, dehydration is carried out with a dehydrating agent such as acetyl chloride or acetic anhydride, and the cyclization reaction of the obtained compound is carried out under the above conditions to obtain the compound of the general formula (1). be able to.

In the above process A, the acid anhydride of the general formula (2) used as a starting material can be produced, for example, by the following method.

That is, the following general formula (2-a)

[0062]

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(In the formula

[0064]

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And R ¹ are the same as defined in the above general formula (1)), and a carbonyl compound represented by the following general formula (2-b)

[0066]

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(In the formula

[0068]

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Is the same as defined in the general formula (1), and R ³ and R ⁴ are the same or different and have 1 to 6 carbon atoms.
Represents an alkyl group. The acid anhydride of the general formula (2) can be obtained by subjecting the succinic acid diester derivative represented by) to a condensation reaction and performing the treatment described below.

In the condensation reaction, the general formula (2-a)
The reaction ratio of the carbonyl compound of (4) and the succinic acid diester derivative of the general formula (2-b) may be in a wide range,
Generally, the molar ratio is in the range of 1:10 to 10: 1, preferably 1: 5 to 5: 1. The reaction is usually -20 ° C to 1
It is carried out at 10 ° C, preferably in the range of 0 ° C to 100 ° C. The reaction is suitably carried out using a solvent, and the solvent is preferably an aprotic solvent, and examples thereof include benzene, diethyl ether, toluene, tetrahydrofuran and the like.

This condensation reaction is generally carried out in the presence of a condensing agent such as sodium hydride, t-butoxide and sodium ethoxide. Such a condensing agent is usually 0.1 per mol of the carbonyl compound of the general formula (2-a).
It is used in the range of 10 to 10 mol.

After completion of the reaction, the obtained dicarboxylic acid diester is converted into a free dicarboxylic acid. For this reaction, the conditions for the hydrolysis reaction in the presence of a base which are generally known per se are used. For example, it is carried out at a temperature of 0 to 80 ° C. using a 10% ethanolic sodium hydroxide solution.

The dicarboxylic acid thus obtained can be converted into an acid anhydride according to a method known per se to obtain the acid anhydride of the general formula (2). The reaction to make an acid anhydride is
This is carried out by using a well-known reagent such as acetic anhydride and acetyl chloride.

Process B: This process B is represented by the following general formula (3).

[0075]

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(In the formula

[0077]

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[0078]

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And R ¹ is the same as defined in the general formula (1)), the imide compound is reacted with an alkali metal, and then the corresponding halogen compound is reacted with the imide compound. Is a method for producing a fulgimide compound.

As the alkali metal used in this process B, metal sodium, metal potassium, metal lithium and the like are used. The reaction ratio of the alkali metal is generally 1.0 to 1 mol of the compound represented by the general formula (3).
It is selected from the range of 10 mol. Further, the reaction ratio of the halogen compound is preferably selected from the range of 0.5 to 10 mol per 1 mol of the compound corresponding to (3) generally obtained by reacting with an alkali metal.

The solvent used in this reaction is the same as that described in the above process A. The reaction temperature is usually preferably in the range of 0 to 100 ° C.

The compound of the above-mentioned general formula (1) can be obtained by any of the above-mentioned processes A and B or by modification thereof.

The component (B) of claim 1 of the present invention is a chromene compound. The chromene compound has a chromene skeleton,
Known compounds having photochromic properties can be used without any limitation, and the chromene compound represented by the following general formula (4) is preferably used.

[0084]

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(Provided that R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different hydrogen atoms, hydrocarbon groups, substituted amino groups, aromatic hydrocarbon groups, unsaturated heterocycles, which may be substituted, respectively. A group or a saturated heterocyclic group, R ⁷ and R ⁸
May together form a ring,

[0086]

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The group represented by is an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group. ) In the above formula (4), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are
It is preferably a hydrogen atom, an alkyl group, an aryl group, a substituted amino group or a saturated heterocyclic group. Here, as the alkyl group and the aryl group, the alkyl group and the aryl group as described in the above formula (1) can be adopted, and the substituted amino group is
A substituted amino group in which at least one hydrogen atom is substituted in the alkyl group and the aryl group can be mentioned, and the saturated heterocyclic group is a nitrogen atom such as a pyrrolidine ring, an imidazoline ring, a piperidine ring, a piperazine ring, or a morpholine ring. Mention may be made of a monovalent group derived from a 5- or 6-membered ring containing 1 to 2 atoms, oxygen atoms or sulfur atoms as ring-constituting atoms.

In the above formula (4), the ring formed by R ⁷ and R ⁸ together includes a norbornylidene group, a bicyclo (3.3.1) nonylidene group and the like.

In the above formula (4),

[0090]

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The aromatic hydrocarbon group or unsaturated heterocyclic group represented by is the same as the group represented by the above formula (1),
The substituent of each of these groups is not particularly limited, but, for example,
Halogen atoms such as chlorine, bromine and iodine; C1-C20 alkyl groups such as methyl and ethyl groups; C1-C20 alkoxy groups such as methoxy and ethoxy groups; Phenyl, tolyl and xylyl groups And the like, an aryl group having 6 to 10 carbon atoms; an amino group; a nitro group; a cyano group and the like.

Among the chromene compounds represented by the above general formula (4), taking photochromic characteristics into consideration,
R ⁵ and R ⁶ are both hydrogen atoms, and R ⁷ and R ⁸ are
Each is an alkyl group, or these are taken together to form a bicyclo (3.3.1) nonylidene group or norbornylidene group,

[0093]

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The compound represented by the formula (1) is an optionally substituted naphthalene ring.

Specific examples of the chromene compounds that can be preferably used in the present invention include the following compounds.

Chromene compound: (1) Spiro (norbornane-2,2 '-(2H) benzo (h) chromene) (2) Spiro (bicyclo [3.3.1] nonane-9,
2 ′-(2H) benzo (h) chromene) (3) 7′-methoxyspiro (bicyclo (3.3.1)
Nonane-9,2 ′-(2H) benzo (h) chromene) (4) 7′-methoxyspiro (norbornane-2,2 ′)
-(2H) benzo (f) chromene) (5) 2,2-dimethyl-7-octoxy (2H) benzo (h) chromene) (6) 4'-methylspiro (bicyclo (3.3.1) nonane-9 , 2 ′-(2H) benzo (h) chromene) (7) 3′-methylspiro (bicyclo (3.3.1) nonane-9,2 ′-(2H) benzo (h) chromene) (8) spiro ( tricyclo [3.3.1.1 ^{3, 7]} decane -2, 2 '- (2H) benzo (h) chromene) (9) 4'Piperijinosupiro (bicyclo (3.3.
1) Nonane-9,2 '-(2H) benzo (h) chromene) (10) 2,2-Dimethyl-6-octoxy (2H) benzo (h) chromene) (11) Spiro (norbornane-)
2,2 ′-(2H) naphtho- (1,2-h) chromene) (12) 2,2-dimethyl-7- (ethylthiohexyl) oxy (2H) benzo (h) chromene) (13) 6- Chloro-2,2-dimethyl-7- (diisopropylphosphonohexyl) oxo (2H) benzo (h) chromene (14) 2,2-dimethyl (2H) pyrido (2,3-
h) chromene (15) 7-methoxy-2,2-dimethyl (2H) benzo (h) chromene (16) 7- (diethylaminooctyl) -2,2-dimethyl (2H) benzo (h) chromene In the present invention, The above-mentioned fulgimide compound and the mixing ratio of the chromene compound can be arbitrarily selected according to the intended color tone, but in order to adjust the color tone such as gray, brown, and amber, generally 100 parts by weight of the fulgimide compound is used. In contrast, 0.01 to 10,000 chromene compounds
It is suitable that the amount is, by weight, preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight. Further, two or more kinds of each of the fulgimide compound and the chromene compound may be added.

Further, the photochromic composition has a gray color,
In order to adjust the color tone of brown, amber, etc., a spirooxazine compound can be further used. As the spirooxazine compound, a known compound having a spirooxazine skeleton and having photochromic properties can be used without any limitation, and the spirooxazine compound represented by the following formula (5) is preferably used.

[0098]

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In the general formula (5), R ⁹ , R ¹⁰ and R
¹¹ are the same or different alkyl groups, cycloalkyl groups, alkoxy groups, alkyleneoxyalkyl groups,
Alkoxycarbonyl group, alkoxycarbonylalkyl group, aryl group, aralkyl group, aryloxy group,
It is an alkylenethioalkyl group, an acyl group, an acyloxy group, or an amino group, and R ¹⁰ and R ¹¹ may together form a ring, and R ⁹ , R ¹⁰ and R ¹¹ each have a substituent. In addition to the groups described above, examples of such a substituent include a halogen atom, a nitro group, a cyano group, a heterocyclic group, and the like. Also,

[0100]

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The group represented by is an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group,

[0102]

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The groups represented by are an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group. As the substituent, the same groups as those described above for R ⁹ , R ¹⁰ and R ¹¹ can be selected.

[0104]

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(Provided that R ¹² and R ¹³ are an optionally substituted alkyl group, an alkoxy group or an aryl group, and R ¹² and R ¹³ are bonded to each other and cyclized to form a nitrogen-containing heterocycle. The group represented by (1) is preferably used.

Among the spirooxazine compounds represented by the above formula (5), R ⁹ is an alkyl group or an alkoxycarbonylalkyl group, R ¹⁰ and R ¹¹ are cycloalkyl groups which together form a ring,

[0107]

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Is preferably an aromatic hydrocarbon group which may be partially or wholly substituted, and is an aromatic hydrocarbon group partially or wholly substituted with a halogen atom, especially fluorine. Preferably,

[0109]

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Is preferably an optionally substituted aromatic hydrocarbon group, particularly a naphthalene ring substituted with an amino group.

Specific examples of the spirooxazine compound that can be preferably used in the present invention include the following compounds.

Spirooxazine compound; (1) 1 ', 5'-dimethyl-6'-fluoro-6 "-
Morpholinodispiro (cyclohexane-1,3 '-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine (2) 6'-fluoro-1'-methoxycarbonylethyl-8" -methoxy -6 "-piperidinodisspiro (cyclohexane-1,3 '-(3H) indole-2'-
(2H), 3 "-(3H) naphtho (3,2-a) (1,
4) Oxazine (3) 1 '-(2- (dioxan-2-yl) ethyl)
-6′-Fluoro-6 ″-(4-methylpiperazino) disspiro (cyclohexane-1,3 ′-(3H) indole-2 ′-(2H), 3 ″-(3H) naphtho (3,2
-A) (1,4) Oxazine (4) 5 ', 7'-difluoro-1'-methyl-6 "-
Morpholinodispiro (cyclohexane-1,3 '-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine (5) 1'-isobutyl-5'-methyl-6'-fluoro-6 "-Morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(2H), 3 "-
(3H) Naphtho (3,2-a) (1,4) oxazine In the present invention, the mixing ratio of the photochromic composition and the spirooxazine compound can be arbitrarily selected according to the intended color tone, and gray or brown. In order to adjust the color tone such as Amber, generally 0.01 to 10000 parts by weight of the spirooxazine compound is added to 100 parts by weight of the photochromic composition comprising the fulgimide compound represented by the formula (1) and the chromene compound. Parts, preferably 0.1 to 1000 parts by weight, more preferably 1 to 500 parts by weight. Two or more spirooxazine compounds may be added.

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. Also,
A molded product such as a photochromic lens can be obtained by dispersing the polymerizable monomer in a polymer such as a thermosetting resin or a thermoplastic resin obtained by polymerization.

In this case, the addition amount of the photochromic composition comprising the fulgimide compound represented by the formula (1) and the chromene compound, or the photochromic composition obtained by mixing the spirooxazine compound with the photochromic compound is 100 parts by weight of the polymerizable monomer. Part or 100 parts by weight of the thermoplastic resin, 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight
Parts by weight.

As the thermosetting resin, any one can be used as long as the photochromic composition of the present invention is uniformly dispersed, and known ones can be used without any limitation.
Thermosetting resins that can be preferably used include ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) ) Polyvalent acrylic acid and polymethacrylic acid ester compounds such as propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl Polyhydric allyl compounds such as diglycol carbonate and trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bi (2 acryloylthioethyl)
Ether, 1,4-bis (methacryloylthiomethyl)
Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester such as benzene; glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl methacrylate,
Bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxymethacrylate, 3-
(Glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1
-Isopropyloxy) -2-hydroxypropyl acrylate, 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate, etc. methacrylate compounds or acrylate compounds;
A thermosetting resin obtained by polymerizing a radically polymerizable polyfunctional monomer such as divinylbenzene can be mentioned. Also,
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride of these monomers; acrylic acid and methacrylic acid such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate and 2-hydroxyethyl methacrylate. Fumarate compounds such as diethyl fumarate and diphenyl fumarate; Thioacrylic acid and thiomethacrylate compounds such as methylthioacrylate, benzylthioacrylate, and benzylthiomethacrylate; styrene, chlorostyrene, methylstyrene, vinylnaphthalene , Α-
Thermosetting resins obtained by copolymerization with radically polymerizable monofunctional monomers such as vinyl compounds such as methylstyrene dimer and bromostyrene are mentioned.

Furthermore, addition copolymerization of a polyvalent thiol compound such as ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakisthioglycolate, and di (2-mercaptoethyl) ether with the above radical-polymerizable polyfunctional monomer. Polymer: diphenylethane diisocyanate, xylylene diisocyanate, p
Examples thereof include thermosetting resins obtained by addition polymerization of a polyvalent isocyanate compound such as phenylene diisocyanate and a polyvalent alcohol compound such as ethylene glycol, trimethylolpropane, pentaerythritol and bisphenol A, or the above-mentioned polyvalent thiol compound. These polymerizable monomers can be used alone or in combination of two or more.

As a method for dispersing in a thermosetting resin,
There is no particular limitation and a general method can be used.
For example, after dissolving the photochromic composition in the polymerizable monomer, a polymerization catalyst is added and polymerized by heat or light,
A method of dispersing in a resin or a method of forming a surface of a thermosetting resin is adopted.

As the thermoplastic resin, any one can be used without any limitation as long as it can uniformly disperse the photochromic composition according to claim 1 or 2 of the present invention. To specifically exemplify, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane. , Polycarbonate, and the like.

There are no particular restrictions on the method for dispersing the resin in the thermoplastic resin, and a general method can be used. For example, a method in which a thermoplastic resin and a photochromic compound are melt-kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin can be used.

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

Considering the improvement of the durability of the compound in the present invention, among various ultraviolet stabilizers, the singlet oxygen quencher and the hindered amine light stabilizer can be publicly used.

The photochromic composition of the present invention can be used in a wide range of fields, for example, various recording memory materials, copying materials, printing photoconductors, cathode ray tube recording materials, laser light-sensitive materials and the like, which can replace silver salt light-sensitive materials. Can be used as various recording materials. In addition, the photochromic composition of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a light meter, a decoration, and the like.

For example, when it is used for a photochromic lens, it is not particularly limited as long as it is a method capable of obtaining uniform dimming performance. Specifically, the photochromic composition of the present invention is uniformly dispersed. A method of sandwiching a polymer film in the center of the lens, or a method of dissolving the photochromic composition and heat or a photoinitiator in a polymerizable monomer, and then curing by a predetermined method, or the photochromic composition of the present invention Is dissolved in, for example, silicone oil and heated at 150 to 200 ° C. for 10
There is a method in which the lens surface is impregnated for 60 minutes, and the surface is further coated with a curable substance to form a photochromic lens. Furthermore, a method of applying the above-mentioned polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens is also conceivable.

[0124]

As described above, the photochromic composition of the present invention has little initial coloration when uniformly dispersed in various resins, and does not emit light including ultraviolet rays such as sunlight or light of a mercury lamp. By irradiation, it develops various neutral colors such as gray, brown, and amber from a colorless state. Particularly when used as a photochromic lens, it is useful to exhibit color development from an initial colorless state to an intermediate color.

[0125]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. “Parts” in the examples is “parts by weight”.

Flugimide Compound (1) N-Cyano-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2′-tricyclo [3.3.1. 1
^3,7 ] decane)

[0127]

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[0128] (2) N-acetyl-4-cyclopropyl-6,7-dihydro-spiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 ^{3 , 7} ] decane)

[0129]

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[0130] (3) N-benzoyl-4-cyclopropyl-6,7-dihydro-spiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 ^{3 , 7} ] decane)

[0131]

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(4) N-cyano-4-methyl-6,7-
Dihydro-2-phenylspiro (5,6-benzo [b]
Furandicarboximide-7,2'-tricyclo [3.3.1.1 ^3,7 ] decane)

[0133]

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(5) N-methylsulfonyl-4-isopropyl-6,7-dihydro-N'-methylspiro (indoledicarboximido-7,2'-tricyclo [3.3.1.1 ^3,7 ] decane )

[0135]

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(6) 1 ', 5'-Dichloro-1-ethyl-3,4-dihydro-7-methoxy-N-trichlorocarbonylspiro (dibenzo [5,6-b: d] thiophenedicarboximide-4 , 2'-tricyclo [3.
3.1.1 ^3,7 ] decane)

[0137]

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(7) 1-Cyclopropyl-3,4-dihydro-N-phenylsulfonylspiro (6,7,8,9)
-Tetrahydrodibenzo [5,6-b: d] thiophenedicarboximide-4,2 "-tricyclo [3.3.
1.1 ^3,7 ] decane)

[0139]

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(8) 4-Cyclopropyl-6,7-dihydro-1'-methyl-2-nitro-N-perfluorobenzoylspiro (5,6-benzo [b] thiophenedicarboximide-7,9 ' -Bicyclo [3.3.1] nonane)

[0141]

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(9) 4-Butyl-6,7-dihydro-2
-Methoxy-3 ', 3'-dimethyl-N- (3 "-trifluoromethylphenylsulfonyl) spiro (5,6-
Benzo [b] furandicarboximido-7,9'-bicyclo [3.3.1] nonane)

[0143]

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(10) 2-chloro-5,6-dihydro-
N'-methyl-4-phenyl-N-trifluoromethyl spiro (indolecarboximido-7,9 "-bicyclo [3.3.1] nonane)

[0145]

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(11) N-cyano-5,6-dihydro-
4-furylspiro (5,6-benzo [b] furandcarboximido-7,7'-bicyclo [2.2.1] heptane)

[0147]

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(12) 3,4-dihydro-1-npropyl-N-trichloromethanespiro (6,7,8,9-tetrahydrodibenzo [5,6-b: d] furandicarboximide-4,7 '. -Bicyclo [2.2.1] heptane)

[0149]

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(13) 4,5-Dihydro-2,7-dimethyl-6-methoxy-N-phenoxycarbonylspiro (3,4-benzo [b] thiophenedicarboximide-5,2'-tricyclo [3. 3.1.1 ^3,7 ] decane)

[0151]

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(14) N-cyano-4-methyl-6,7
-Dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2'-tricyclo [3.3.
1.1 ^{3, 7} ] decane

[0153]

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(15) N-Cyano-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] furandcarboximido-7,2'-tricyclo [3.
3.1.1 ^3,7 ] decane

[0155]

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(16) 3,4-Dihydro-5,7-dimethoxy-N-cyano-1-methylspiro (naphthalenedicarboximido-4,2'-tricyclo [3.3.
1.1 ^{3, 7} ] decane

[0157]

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(17) N-cyano-4-methyl-6,7
-Dihydrospiro (5,6-benzo [b] furandcarboximido-7,2'-tricyclo [3.3.1.1]
^3,7 ] decane

[0159]

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Chromene compound: (1) Spiro (norbornane-2,2 '-(2H) benzo (h) chromene)

[0161]

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(2) 7'-methoxyspiro (bicyclo (3.3.1) nonane-9,2 '-(2H) benzo (f) chromene)

[0163]

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(3) 4'-methylspiro (bicyclo (3.3.1) nonane-9,2 '-(2H) benzo (h) chromene)

[0165]

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(4) 3'-methylspiro (bicyclo (3.3.1) nonane-9,2 '-(2H) benzo (h) chromene)

[0167]

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(5) 2,2-Dimethyl-7-octoxy (2H) benzo (h) chromene)

[0169]

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Spirooxazine compound; (1) 1 ', 5'-dimethyl-6'-fluoro-6 "-
Morpholinodispiro (cyclohexane-1,3 '-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine

[0171]

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(2) 6'-Fluoro-1'-methoxycarbonylethyl-8 "-methoxy-6" -piperidinodisspiro (cyclohexane-1,3 '-(3H) indole-2'-(2H), 3 "-(3H) naphtho (3,2-
a) (1,4) oxazine

[0173]

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(3) 1 '-(2- (dioxan-2-yl) ethyl) -6'-fluoro-6 "-(4-methylpiperazino) disspiro (cyclohexane-1,3'-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine

[0175]

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(4) 5 ', 7'-difluoro-1'-methyl-6 "-morpholinodispiro (cyclohexane-
1,3 '-(3H) indole-2'-(2H), 3 "
-(3H) naphtho (3,2-a) (1,4) oxazine

[0177]

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(5) 1'-isobutyl-5'-methyl-
6'-Fluoro-6 "-morpholino-disspiro (cyclohexane-1,3 '-(3H) indole-2'-(2
H), 3 "-(3H) naphtho (3,2-a) (1,4)
Oxazine

[0179]

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Example 1 0.1 part of the fulgimide compound (15), 0.05 part of the chromene compound (2), 70 parts of tetraethylene glycol dimethacrylate, 15 parts of triethylene glycol dimethacrylate, 10 parts of glycidyl methacrylate, 2-
5 parts of hydroxyethyl methacrylate and 1 part by weight of perbutyl ND as a polymerization catalyst were added, and they were sufficiently mixed until completely dissolved. This mixed solution was poured into a mold composed of a glass plate and a gasket composed of an ethylene-vinyl acetate copolymer, and the mixture was heated at 35 ° C to 90 ° C at 20 ° C in an air oven.
Polymerization was carried out by raising the temperature over time. After completion of the polymerization, the polymer was removed from the glass mold of the mold.

After the obtained polymer plate was irradiated with sunlight for 10 minutes, the color tone at that time was visually observed. Further, the YI of the obtained sample was measured with a color difference meter (SM-4 type) manufactured by Suga Test Instruments Co., Ltd. The results are shown in Table 1.

Examples 5 to 28 The same procedure as in Example 1 was carried out except that the composition shown in Table 1 was used instead of the fulgimide compound and the chromene compound in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 6 For comparison, a fulgimide compound represented by the following formula was used and combined with a chromene compound as shown in Table 1. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

[Table 1]

[0190]

[Table 2]

Example 29 0.08 part of the fulgimide compound (15), 0.05 part of the chromene compound (2), 0. 0 of the spirooxazine compound (1).
The same procedure as in Example 1 was carried out except that 04 parts were replaced with 70 parts of 2,2 bis (4-methacryloyloxyethoxyphenyl) propane, 20 parts of benzyl methacrylate, and 10 parts of glycidyl methacrylate. The results are shown in Table 2.

Examples 30 to 46 The same procedures as in Example 29 were carried out except that the compositions shown in Table 2 were used instead of the fulgimide compound, the chromene compound and the spirooxazine compound. The results are shown in Table 2.

Comparative Examples 7 to 9 For comparison, a fulgimide compound represented by the following formula was used and combined with a chromene compound as shown in Table 2. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[0194]

[Table 3]

Example 47 0.1 part of the fulgimide compound (15) and 0.1 part of the chromene compound (2) were adsorbed on the resin surface by dry blending with 100 parts of the polycarbonate resin. This resin was directly molded into a plate having a thickness of 2 mm by an injection molding machine. The molding temperature was 270 ° C. The molded plate thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Examples 48 to 56 Example 5 was repeated except that the compositions shown in Table 4 were used instead of the fulgimide compound and the chromene compound in Example 53.
Performed similarly to 3. The results are shown in Table 3.

Comparative Examples 10 to 11 For comparison, a fulgimide compound represented by the following formula was used and combined with a chromene compound as shown in Table 3. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

[0198]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 495/04 103 C07D 495/04 103 498/10 498/10 S

Claims (4)

[Claims] 1. (A) The following general formula (1): However, the following formula (a): Are each a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group, each represented by the following formula (b): Are each a norbornylidene group, a bicyclo [3.3.1] nonylidene group or an adamantylidene group which may have a substituent, and R ¹ is a monovalent carbon atom which may have a substituent. R ² is a hydrogen group or a monovalent heterocyclic group, R ² is a perhalogenoalkyl group, a cyano group, an alkoxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, a substituent An optionally substituted arylcarbonyl group, a nitro group, a sulfonyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, or an optionally substituted aryl 100 parts by weight of fulgimide compound represented by oxycarbonyl group and (B) chromene compound 0.01 to 1000
A photochromic composition comprising 0 parts by weight. 2. The photochromic composition according to claim 1, further comprising a spirooxazine compound 0.01 to 10000.
A photochromic composition containing parts by weight. 3. A photochromic composition comprising 0.001 to 20 parts by weight of the photochromic composition according to claim 1 or 2, and 100 parts by weight of a polymerizable monomer. 4. A photochromic composition comprising 0.001 to 20 parts by weight of the photochromic composition according to claim 1 or 2, and 100 parts by weight of a thermoplastic resin.