JPH03281689A - Photochromic composition - Google Patents

Abstract

PURPOSE:To obtain a photochromic composition which can maintain its photochromic property for a prolonged period of time and undergo discoloration rapidly by mixing a fulgi(mi)de compound containing no halogen atom and a compound containing a halogen atom in each molecule at a specific mixing ratio. CONSTITUTION:A fulgide compound of formula I which exhibits photochromic property and contains no halogen atom or a fulgimide compound of formula II which exhibits photochromic property and contains no halogen atom; 0.01 to 1000mol, per mol of the fulgi(mi)de compound, of a compound that contains at least one halogen atom in each molecule [e.g. poly(1- bromomethylmethacrylate)] and optionally a UV stabilizer are blended to obtain a photochromic composition. 0.001 to 20 parts by weight of this photochromic composition is blended with 100 parts by weight of a polymer such as a thermoplastic resin or a thermosetting resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photochromic composition that has good durability of photochromic action and fast fading speed.

(Question B to be solved by the prior art and the invention) Photochromism is a phenomenon that has attracted attention over the past few years. When a certain compound is irradiated with light containing ultraviolet rays, such as sunlight or light from a mercury lamp, photochromism immediately This is a reversible effect in which the color changes and returns to the original color when the light is removed and placed in a dark place. Compounds having this property are called photochromic compounds, and various compounds have been synthesized to date, but no particular commonality is recognized in their structures.

As photochromic compounds, fulgide compounds and fulgimide compounds are known. In order to improve the fading speed when returning to the original colorless state after stopping ultraviolet irradiation to these fulgide compounds or fulgimide compounds,
It is known to introduce norbornylidene groups into these compounds (JP-A-2-28154). However, in order to put these compounds into practical use, photochromic properties with even faster fading rates are desired.

(Means for Solving the Problems) As a result of intensive research aimed at further speeding up the fading speed of the photochromic properties of fulgide or fulgimide compounds, the present inventors found that 1 halogen atom
It was discovered that the progress of chromaticity can be significantly accelerated by combining one or more compounds in the molecule, and the present invention was completed.

That is, the present invention comprises: (a) a fulgide compound having no halogen atom or a fulgimide compound having no halogen atom; and (b) a compound having one or more halogen atoms in one molecule; This is a photochromink composition characterized in that (b) consists of 0.01 to 1000 moles as a halogen atom.

One component of the photochromink composition of the present invention is a fulgide compound that does not have a halogen atom or a fulgimide compound that does not have a halogen atom. The above fulgide compound is
A compound containing a halogen atom, having a structure represented by the following formula, and having photochromic properties may be employed without any restriction. Further, as the above-mentioned fulgimide compound, a compound that does not have a halogen atom, has a structure represented by the following formula, and has photochromic properties is employed without any restriction.

In the present invention, a compound represented by the following formula is generally used as a fulgide compound having no halogen atom or a fulgimide compound having no halogen atom.

During the ceremony teeth, divalent aromatic hydrocarbon group or Divalent unsaturated heterocyclic group Each may have a substituent. monovalent hydrocarbon group or monovalent heterocyclic group teeth, mantylidene group oxygen atom Group〉N-Rz Group〉N　AIB+　(Az product (Bz+-r-R3 group N-A3-A.

or base /NA, -R.

shows.

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

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

Further, as the unsaturated heterocyclic group, 5j! contains at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom. A ring or a 6-membered monocyclic heterocyclic group, or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed thereto is shown.

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

As mentioned above, the aromatic hydrocarbon group or unsaturated heterocyclic group represented by OII may contain at most 5 substituents, preferably up to 3 substituents. Examples of such substituents include hydroxyl group; cyano group; nitro group; amino group; carboxyl group; methylamino group; alkylamino group having 1 to 4 carbon atoms such as diethylamino group;
Lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, and t-butyl group; Lower alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, and t-butoxy group; phenyl group; Aryl group with 6 to 10 carbon atoms such as naphthyl group and tolyl group: Aryloxy group with 6 to 14 carbon atoms such as phenoxy group and 1-naphthoxy group: 7 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group ~15 aralkyl groups; examples include aralkoxy groups having 7 to 15 carbon atoms, such as benzyloxy groups and phenylpropoxy groups, and alkylthio groups having 1 to 4 carbon atoms. These substituents may be the same or different, and their positions are not particularly limited.

The above OII is an atom or group selected from the group consisting of 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. Preference is given to divalent aromatic hydrocarbon radicals or divalent unsaturated heterocyclic radicals which may be substituted in each case by at least one radical.

In addition, the above [■ has 6 to 6 carbon atoms, which may be substituted with 1 to 3 of the above-mentioned substituents in each case.
14 aryl groups or a 5-membered or 6-ring monocyclic heterocyclic group containing one nitrogen atom, oxygen atom, and sulfur atom, or a fused heterocyclic group in which a benzene ring or a cyclohexene ring is fused to the heterocyclic group is even more preferable.

Furthermore, the above [f is a divalent benzene ring, a heterocyclic group
These benzene rings, monocyclic heterocycles, or fused heterocycles are preferably fused heterocycles in which a benzene ring or cyclohexene ring is fused to the heterocycle. It is also a preferable embodiment that 1 to 2 of the above-mentioned substituents are included.

R8 in the general formula CI) is a monovalent hydrocarbon group or a monovalent heterocyclic group, each of which may have a substituent.

The hydrocarbon group for R3 may be any of aliphatic, alicyclic, or aromatic hydrocarbons, and specific examples include those having 1 to 1 carbon atoms such as methyl, ethyl, propyl, and butyl groups. 20, preferably 1 to 6 alkyl groups: aryl groups having 6 to 14 carbon atoms such as phenyl, tolyl, xylyl, and naphthyl groups; carbon atoms such as benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups An aralkyl group having a number of 1 to 101, preferably 1 to 4 alkylene groups is suitable.

Further, as the heterocyclic group for R8, at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom is selected from 1 to 3.
A 5- or 6-membered monocyclic heterocyclic group, preferably 1 or 2, or a fused heterocyclic group in which a benzene ring is fused thereto is preferred.

Specific examples of such heterocyclic groups include, in addition to the unsaturated heterocyclic groups explained in the definition of 0 above, saturated piperidine rings, piperazine rings, morpholine rings, pyrrolidine rings, indoline rings, chroman rings, etc. Mention may be made of saturated heterocyclic groups.

There is no particular problem even if the hydrocarbon group or heterocyclic group of R described above has a substituent. It is preferable that the hydrocarbon group or heterocyclic group contains at most 5, preferably 3 such substituents, and specific examples of the substituents include the same substituents as those explained in [r] can be exemplified.

The above R3 is preferably a C1-C4 alkoxy group or a C1-C4 alkoxy group optionally substituted with a phenyl group.
~20 alkyl group: an aryl group having 6 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms; or an aryl group having 1 to 3 nitrogen atoms, carbon atoms and sulfur atoms, especially 1
or a fused heterocyclic group in which a benzene ring is fused to the heterocyclic group, particularly a monocyclic heterocyclic group.

Furthermore, particularly preferable as the above R1 is a carbon number of 1 to 6.
an alkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

In the general formula (1) in the present invention, it means a lupolnylidene group or an adamantylidene group. Here, the norbornylidene group is represented by the following formula, and the adamantylidene group is represented by the following formula.

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

Substituents for the norbornylidene group or adamantylidene group include, for example, a hydroxy group; an alkylamino group having 1 to 4 carbon atoms such as a methylamino group and a diethylamino group; a carbon group such as a methoxy group, an ethoxy group, and a tert-butoxy group. Alkoxy group having 1 to 4 carbon atoms; aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group; phenoxy group, 1-
Aryloxy group having 6 to 14 carbon atoms such as naphthoxy group;
Lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and t-butyl group; cyano group; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl; nitro group; phenyl group, tolyl group etc. carbon number 6-1
0 aryl group; Examples include aralkyl groups having 7 to 9 carbon atoms such as phenylethyl group and phenylpropyl group.

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

In the general formula (I) according to the present invention, X represents an oxygen atom (-0-), a group N-R,,
Group N As A4 or group〉N -A3- Ra
shows.

In general formula [1], X is a group>N-At-B+-(At(Bz+-r-Ri
, group〉N-^, -A4 or group〉N As-Ra, especially group)N Az R4 or group "iN A + 8 + (A zt (Bz product Rf
f (wherein R1 is an optionally substituted alkyl group having 1 to 10 carbon atoms or 1 to 3 atoms selected from the group consisting of a cyano group and a nitro group) is obtained. This is more preferred from the viewpoint of the durability of the photochromic properties of the compound.

X in general formula (1) represents the above group>N At B+ (AzhHBz+T-R3
Among them, when R1 is a naphthyl group or a naphthylalkyl group, and when the group>N-/h-R4, R
Naphthyl group and imide group (N-) represented by 2 or R4
It is preferable that the number of atoms in the main chain sandwiched between the two is in the range of 3 to 7 because a compound with excellent durability of photochromic action can be obtained.

Next, Rt -Rz -R4, At, A in the above X
! , As , A4 , B+ , B! , m and n will be explained in detail.

Ro represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-1 iso- or tert-butyl group, a pentyl group, a hexyl group, an octyl group, Among these, those having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, are exemplified. Examples of the aryl group include those having 6 to 10 carbon atoms, such as phenyl, tolyl, and naphthyl groups.

At, At and A may be the same or different from each other (and can be an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group).

Specific examples of these include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, trimethylene group, tetramethylene group or 2,2-dimethyltrimethylene group; ethylidene group;
An alkylidene group having 2 to 10 carbon atoms such as a propylidene group or an isopropylidene group; a carbon atom such as a 34-methylcyclohexane-α,1-diyl group (-C1(,÷(a)←) such as a dichlorohexylene group; Examples include 6 to 10 alkylcycloalkane-diyl groups. A I
And A2 is particularly preferably an alkylene group having 1 to 6 carbon atoms, an alkylidene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, or an alkylcycloalkane-diyl group having 6 to 7 carbon atoms.

B1 and B2 may be the same or different and are selected from the following seven bonding groups.

m and n each independently represent O or 1,
When it represents 0, +1h)=- or +th)i means a bond. Further, when m is 00, n also represents O.

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

The substituents of each of the above groups are not particularly limited, but the alkyl group may be substituted with 1 to 3 atoms or groups selected from the group consisting of a cyano group and a nitro group,
The naphthyl group or naphthylalkyl group is one selected from the group consisting of 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. As the alkyl group represented by R3 above, which may be substituted with ~3 atoms or groups, the same alkyl groups as exemplified for R2 above can be used. Further, examples of the naphthyl alkyl group include a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, a naphthylbutyl group, and the like.

A4 represents a naphthyl group which may have a substituent.

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

The other component of the photochromink composition of the present invention is a compound having one or more halogen atoms in the molecule. As such a compound, any known compound can be used without any restriction, regardless of whether it is a low-molecular compound or a high-molecular compound.

- When a polymer compound is used as the compound having one or more halogen atoms in the molecule, the cough polymer compound may also serve as the polymer described later in the description of the polymer matrix in which the photochromic composition of the present invention is dispersed. can.

That is, the effects of the present invention can be obtained even if the fulgide compound and the fulgide compound are dispersed in a polymer having one or more halogen atoms in one molecule.

Specific examples of compounds that can be suitably used as compounds having one or more halogen atoms in one molecule in the present invention are as follows. Examples of polymer compounds include 2-chloroethyl acrylate, 1-bromomethyl methacrylate, tribromophenyl methacrylate, 3-(2,4
Acrylic monomers such as -dibromophenoxy)-2-hydroxylpropyl acrylate, 3,4.54ribromobenzyl methacrylate, 2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane; p - Styrenic monomers such as chlorstyrene and tribromostyrene; Allyl monomers such as 2゜2-bis(4-allylcarbonateethoxy-3゜5-dibromophenyl)propane; Vinylidene chloride; Vinyl chloride, etc. Examples include homopolymers or copolymers of various monomers: chlorinated vinyl chloride resins: chlorinated olefin resins such as chlorinated polyethylene and chlorinated polypropylene: chlorinated phenoxy resins.

In addition, examples of low molecular weight compounds include chloroform, carbon tetrachloride L1,2-dibromoethane, 2-bromopentane, allyl bromide, 1-bromo-2-chloroethane, bromocyclohexane, 1,2-dibromo-3-chloropropane, 1 - Halogenated aliphatic hydrocarbons such as bromoadamantane; halogenated aromatic hydrocarbons such as chlorobenzene, O-dichlorobenzene, 4-bromotoluene, α-bromotoluene, tetrabromodiphenyl, hexabromobenzene, P-promochlorobenzene; Halogenated ether compounds such as P-bromoanisole, 2,2-bis(4-allyloxy-3,5-dibromophenyl)-propane, octabromodiphenyl ether, trichlorophenylallyl ether; tetrabromobisphenol A,
2. Halogenated hydroxy compounds such as 4-dichlorophenol and pentabromophenol; halogenated carboxylic acids or esters such as tetrabromophthalic anhydride and 2,2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane Compound; halogenated carbonate compound such as 4-bromodiphenyl carbonate;
Halogenated thioether compounds such as para-bromothioanisole, trichlorophenylallyl thioether, octabromodiphenylthioether;
, 5-dibromo-methacryloylthiooxyethoxyphenyl)propane, 4-bromobenzylthioacrylate, and other halogenated thioester compounds; tris(bromocresyl)phosphate, tris(2,3-dibromopropyl)phosphate, and other halogenated phosphorus compounds Examples include halogenated nitrogen-containing compounds such as 2-bromo-1-aminoethane, 3-bromo-1-aminopropane, 4-bromoaniline, and 5,7-dipromo-8-hydroxyquinoline. In addition, compounds obtained by substituting the above-mentioned fulgide compound or fulgimide compound with a halogen atom may also be used. Among these, in consideration of the durability of photochromic properties, compounds that are solid at around room temperature are more preferably used.

In the present invention, the mixing ratio of the fulgide compound without a halogen atom or the fulgimide compound without a halogen atom and the compound having one or more halogen atoms in one molecule is determined according to the desired rate of discoloration. Although it can be arbitrarily selected depending on the situation, in general, a compound having one or more halogen atoms in one molecule is used as a halogen atom for 1 mole of a fulgide compound having no halogen atom or a fulgimide compound having no halogen atom. The range is from 0.01 to 1000 mol, and more preferably from 0.1 to 500 mol. If the amount of the compound having one or more halogen atoms in one molecule is less than 0.01 mole in terms of halogen atoms, the effect of improving the fading speed of the fulgide compound or fulgimide compound is not sufficient; on the contrary, if it exceeds 1000 moles, Although it is possible to improve the fading speed, this is not preferable because it adversely affects the durability of photochromic properties.

By dispersing the photochromink composition of the present invention in an organic solvent, it can be made into a photochromink fluid that can be used for purposes such as decoration.

Furthermore, by dispersing the photochromink composition of the present invention in a polymer such as a thermoplastic resin or a thermosetting resin,
Molded objects such as photochromic glass and photochromic lenses can be obtained.

Any thermoplastic resin may be used as long as it can uniformly disperse a fulgide compound that does not have a halogen atom or a fulgimide compound that does not have a halogen atom, and optically preferably, for example, polymethyl acrylate, polyacrylic acid, etc. Examples include ethyl, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly(2-hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

Dispersion of the photochromink composition of the present invention in a thermoplastic resin can be carried out by a method of synthesizing the thermoplastic resin, that is, by performing polymerization in the presence of the photochromink composition, or by a method in which the thermoplastic resin and the photochromink composition are synthesized. and a method of melt-kneading the thermoplastic resin at a temperature higher than the melting temperature of the thermoplastic resin.

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

For dispersing the photochromic composition in the above-mentioned thermosetting resin, a method is generally adopted in which a raw material of the thermosetting resin and a photochromic composition are mixed and then polymerized.

The amount of the photochromink composition of the present invention to be dispersed in such a polymer is 0 to 100 parts by weight of the polymer.
．． 0.001 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

By incorporating an ultraviolet stabilizer into the composition of the present invention, the durability of photochromic properties can be improved.

As the UV stabilizer, any known UV stabilizer added to various plastics can be used without any limitations.

In the present invention, considering the improvement in the durability of photochromink compounds, among various UV stabilizers, -heavycyclic oxygen quenchers, hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants are used. Preferably used. More specific examples of these UV stabilizers include Sheasorb UV1084 and Sheasorb 3346 (
(manufactured by American Cyanamid Company); UV-Chek A
M101, UV-Cheku AM105 (manufactured by Ferro Corporation); Irgastab 2002, Tinuvin 765, Tinuvin 144, Kimasorb 944, Tinuvin 622, Irganox 1010, Irganox 24
5 (all manufactured by Ciba Geigy); Lilex NBC
(manufactured by DuPont); Sheasorb 3346 (manufactured by American Cyanamid); Sanol LS-1114, Sanol LS-744, Sanol LS-2626 (manufactured by Sankyo); Sumilizer GA-80, Sumilizer G
M, Sumilizer BBM-3, Sumilizer WX-R.

Sumilizer S, Sumilizer BHT, Sumilizer T
P-D, Sumilizer TPL-R, Sumilizer TPS
, Sumilizer MB (manufactured by Sumima Kagaku Co., Ltd.); Mark AO-50, Mark AO-20, Mark AO-30, Mark AO-330, Mark AO-23 (manufactured by Adeka Co., Ltd.);
Manufactured by Argus); Antioxidant HP M-12
(manufactured by S, F, O, S companies), etc. All of the above names are product names.

The blending ratio of the UV stabilizer is 0.01 to 100 parts by weight per 100 parts by weight of the fulgide compound that does not have a halogen atom or the fulgimide compound that does not have a halogen atom.
The amount of the ultraviolet stabilizer is preferably in the range of 10 to 500 parts by weight, particularly from the viewpoint of photochromic properties of the resulting photochromic composition.

(Effects) As explained above, the photochromic composition of the present invention changes from colorless to colored form when exposed to sunlight or light containing ultraviolet rays such as light from a mercury lamp, and this change is reversible and has an excellent effect. Shows dimmability. In addition, the present invention provides a method for reducing photochromic fading by using a fulgide compound that does not have a halogen atom or a fulgide compound that does not have a halogen atom together with a compound that has one or more halogen atoms in one molecule. This succeeded in significantly increasing the speed.

Therefore, the photochromink composition of the present invention can be used in a wide range of fields, such as various recording memory materials in place of silver salt photosensitive materials, copying materials, window light materials for printing, recording materials for cathode ray tubes, and laser materials. It can be used as various recording materials such as photosensitive materials. In addition, the photochromic composition of the present invention can also be used as a material for photochromic lenses, optical filter materials, display materials, photometers, decorations, and the like.

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

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

In addition, symbols and trade names of ultraviolet stabilizers in the following examples indicate the following compounds.

BMDBP: 2. 2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane・lower-8t:chlorstyrene・↑MP-TAC: )limethylolpropane triallyl carbonate BADBP: 2. 2-bis(4-allylcarbonate ethoxy-3,5-dibromophenyl)propane ADC: Allyl diglycol carbonate DAP Nidialyl phthalate St: Styrene DCIPF Nidi(2-chloroisopropyl) fumarate EGDMA: Ethylene glycol dimethacrylate P
HTTP: Pentaerythritol tetrakis (β-thiopropionate) DME Ni(2-mercaptoethyl)ether DV
B Nidivinylbenzene nc: xylylene diisocyanate HPA:
3- ('2.4-dibromophenoxy)2-hydroxypropyl acrylate? IMA: methyl methacrylate/DECDMA diethylene glycol dimethacrylate TBBM: 3. 4. 5-) Ribromobenzyl methacrylate HEMA: 2-hydroxyethyl methacrylate BMA: Penzyl methacrylate IPP Nidiisopropyl peroxycarbonate perbutyl ND: (manufactured by NOF ■) t-butyl peroxy-2-hexanate BPO: Benzoyl peroxide production Example 1 3.4 g (0.01 mol) of 3-thienylethylidene-2-adamantylidene succinic anhydride of the following formula and 17.8 g (0.01 mol) of glycine-methyl ester of the following formula
2 mol) NHzCHzCOCHs was dissolved in toluene and heated at 50° C. for 2 hours under a nitrogen atmosphere. After the reaction, the solvent was removed, the solution was dissolved in acetyl chloride, and the mixture was refluxed for 1 hour for cyclization. The obtained compound was rearranged to the following fulgimide compound (1) by refluxing it in O-dichlorobenzene for 6 hours. The compound was purified by chromatography on silica gel using benzene and ether as eluent and was obtained as pale yellow needles from chloroform and hexane in 27% yield. The elemental analysis values of this compound are C66, 78%, H6
,09%, N3.36%, O15,8%, 37.96%
The calculated values for CχxHzsOaNS are C67.15%, H6.08%, N3.41%, C15
, 6%, and 37.79%. In addition, when proton nuclear magnetic resonance spectrum was measured, it was found to be 67.
0-8. <2H peak based on aromatic protons near Opp->c-cHs at 62.7 ppm
Based on the protons of the bond <3H based on the protons of U
14H based on the proton of the adamantylidene group of pp-
, and a peak of <3H based on protons transferred from 1 to 5 to δ3 to 5pp- and >c-CB, - bonds.

Furthermore, '3C-Nuclear Magnetic Resonance Vector (+30-NMR)
When measured, a peak based on the carbon of the adamantylidene group and the carbon of the methylene chain was found around δ27-70pp■,
A peak based on the carbon of the methyl group near 615.6pp-, a peak based on the carbon of the thiophene ring near 6110-160pp-, and a peak based on the carbon of the thiophene ring near 6160-170ppm+〉C=
A peak based on 0-bond carbon appears.

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

Manufacturing example 2 Full gimme of the following formula Compound 3.4g (0,01 餠 o1) Dissolve in tetrahydrofuran, This is metal potash. 1 g of rum is reacted at room temperature, I of the following formula ( Dokari 3g was obtained.

This and 1.2 g of bromoacetonitrile (0,0
The following fulgimide compound (2) was obtained by reacting 1 mol) BrCH, CN in dimethylformamide. The compound was purified by chromatography on silica gel using chloroform and hexane as eluent and was obtained as pale yellow crystals from hexane in 57% yield. The elemental analysis values of this compound are C69, 81%, 85.80%, N
7.44%, 08°50%, 38.46%, C
2□Hz t O! Calculated values for NtS: C 69.84%, H5, 82%, N7.41%, 08
．． 47% and 38.47%, which showed very good agreement. Also,
When proton nuclear magnetic resonance spectrum was measured, 67
．． 0-7. <2H peak based on the proton of the thiophene ring near spp■, 64, 5>C-C near 5 pp-)
1. <2H peak based on proton of cN bond, 63.
<IH based on 1.5 protons rearranged around 7 ppf
peak, 62.71) peak of <3H based on proton of -GHz bond near p-, 61.3-2.5 ppm
A proton of a -CH2- bond and a 14H peak of a proton based on an adamantylidene group were shown nearby.

Furthermore, '3C-Nuclear Magnetic Resonance Vector (IfC-NMR)
When measured, there was a peak based on the carbon of the adamantylidene group at around 627 to 70 ppm, a peak based on the carbon of the methyl group around δ15.6pp-, and a peak based on the carbon of the methyl group around δ110 to 16o.
Peak based on carbon of thiophene ring near pp-, 61
A peak based on carbon of the >C=0 bond appears near 60-17Opp steel.

From the above results, it was confirmed that the isolated product was fulgimide compound (2) represented by the following structural formula.

Production Examples 3 to 15 In the same manner as Production Examples 1 to 2, fulgide compounds having no halogen atom or fulgide compounds having no halogen atom shown in Table 1 were synthesized.

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

Example 1 To a composition consisting of 70 parts of chlorstyrene and 30 parts of 2,2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane, 0.2 parts of the fulgimide compound of Production Example 1 was added, and Barbutyl NDI portion was added as a radical polymerization initiator and thoroughly mixed. This mixed solution was injected into a mold consisting of a gasket made of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed at 30 to 90 °C using an air furnace. The temperature was gradually raised over 18 hours and maintained at 90°C for 2 hours. After the polymerization was completed, the mold was taken out from the air oven, and after cooling, the polymer was removed from the glass mold.

A mercury lamp 5HL-100 manufactured by Toshiba ■ was attached to the obtained molded product.
was irradiated at 25° C.±1° C. for 60 seconds at a distance of 10 cm to develop color, and the photochromic properties were measured. The photochromic properties were expressed as follows. The results are shown in Table 2.

Maximum absorption wavelength (λIIIX); ■ λ and □ of this coloring film were determined using a spectrophotometer 22OA manufactured by Hitachi, Ltd.

ε (60 seconds): Absorbance of this film at the maximum absorption wavelength after 60 seconds of light irradiation under the above conditions.

ε (0 seconds); at the maximum absorption wavelength after light irradiation,
Absorbance of unirradiated film.

Half-life 11/! : Time required for the absorbance of the film to decrease to 2 (ε (60 seconds) - ε (0 seconds)) after stopping light irradiation for 50 seconds.

Examples 2 to 20 and Comparative Example 1 Examples except that in Example 1, the type and amount of the monomer, fulgide compound, or fulgide compound used were changed, and polymerization was carried out by known means according to the monomer. Same as 1.

The results are shown in Table 2.

Claims (1)

[Claims] (1) Consisting of (a) a fulgide compound that does not have a halogen atom or a fulgimide compound that does not have a halogen atom, and (b) a compound that has one or more halogen atoms in one molecule, based on 1 mole of (a) A photochromic composition characterized in that (b) consists of 0.01 to 1000 moles of halogen atoms.