JPH04136085A - Photochromic material - Google Patents

Abstract

PURPOSE:To obtain a photochromic material which consists of a compd. of a specified formula, is rich in hue by exhibiting redish color, exhibits high coloring density, has excellent durability in repeated color development and fading and light resistance. CONSTITUTION:A photochromic material consists of a compd. of formula I [wherein the ring alpha is a five- or six-membered ring contg. an N atom, or a five- or six-membered ring contg. an N atom and condensed to a benzene ring, a naphthalene ring or a pyridine ring and at least one of the N atoms has a bond of formula II (wherein R<1> is a 1-20C alkyl, a 7-20C aralkyl or a 6-19C aryl); R<2> and R<3> are each OH, NH, a 1-20C alkoxy, a 1-20C alkyl, a 6-14C aryl, a halogeno, CN, COOH, NO2, etc., and R<2> contains H too; X is O or S; R is H, a 1-20C alkyl, a 7-20C aralkyl, a 6-19C aryl, a 1-20C acyl, etc.; n is 0-3; the ring beta is a 3-18C ring condensed to a benzoxazine ring, and cases where the ring beta is absent are included]. This compd. is obtd. by reacting a hydroxy arom. compd. of formula III, a compd. represented by R<4>XH and a methyleneindoline compd. of formula IV.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to photochromic materials,
It is particularly suitable for use in printing, optical equipment, recording materials, clothing, and decorative materials.

[Prior Art] Spirooxazine compounds are conventionally known as photochromic compounds. For example, JP-A-1-1631
No. 84 discloses a compound having the following structure.

[Problem to be Solved by the Invention J] However, conventional spirooxazine compounds have a color tone of reddish-purple to blue-green, which is a color-forming type, and lack richness in hue. Furthermore, although there are some blue spirooxazine compounds that have excellent fatigue resistance, there have been no reddish-purple to purple spirooxazine compounds that have excellent fatigue resistance. Furthermore, the color density of conventional spirooxazine compounds was not necessarily sufficient for practical use.

The present invention aims to solve the drawbacks of the prior art, and aims to provide a photochromic material that has excellent fatigue resistance due to repeated coloring and fading, is rich in hue, and has sufficient coloring density. shall be.

[Means for Solving the Problems] In order to solve the problems, the photochromic material of the present invention has the following configuration.

``-A photochromic material comprising a compound represented by (I).

R3, , or one type selected from 6-membered rings, and at least one nitrogen atom in the α ring is organic/.

Here, R1 is an alkyl group having 1 to 20 carbon atoms, and 7 to 20 carbon atoms.
represents a substituent selected from 20 aralkyl groups and aryl groups having 6 to 19 carbon atoms.

R2 and R3 are hydroxy group, amino group, carbon number 1-20
alkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, 7 to 15 carbon atoms
15 aralkyl groups, aryl groups with 6 to 14 carbon atoms, halogeno groups, cyano groups, carboxy groups, nitro groups, acyl groups with 1 to 2 carbon atoms, alkoxycarbonyl groups with 2 to 2 carbon atoms, 1 to 2 carbon atoms represents a substituent selected from 20 carbamoyl groups, and R2 also includes hydrogen.

X represents oxygen or sulfur.

R4 is hydrogen, an alkyl group having 1 to 2 carbon atoms, and 7 to 2 carbon atoms;
20 aralkyl group, C6-19 aryl group, C1-2o acyl group, C2-20 alkoxycarbonyl group, C1-20 carbamoyl group, C2-20 Alkylthiocarbonyl group, carbon number 1~
2o sulfonyl group, carbon number 1-20 sulfinyl group, carbon number 1-20 sulfenyl group, carbon number 1-2o
represents a substituent selected from sulfamoyl groups.

n represents an integer of O to 3.

The β ring represents a ring having 3 to 18 carbon atoms condensed to a benzoxazine ring, and includes cases where there is no β ring. ]” The α ring in the general formula (1) of the present invention is a 5-membered ring containing one nitrogen atom or a 6-membered ring containing one nitrogen atom, and is fused to a benzene ring, a naphthalene ring or a pyridine ring. One type selected from a 5-membered ring or a 6-membered ring containing one nitrogen atom, and at least one nitrogen atom in the α ring
One is an organic group/ Preferred specific examples of the α ring in general formula (I) are:
Examples include pyrrolidine ring, pyrrole ring, piperidine ring, tetrahydropyridine ring, dihydropyridine ring, indoline ring, benzindoline ring, tetrahydroquinoline ring, acridine ring, benzothiazoline ring, benzoxazoline ring, and pyridopyridine ring.

The organic group R bonded to the nitrogen atom contained in the α ring has 1 carbon number
It represents a substituent selected from an alkyl group having ~20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 19 carbon atoms, and preferable specific examples thereof include a methyl group, a propyl group, an octadecyl group, etc. chain alkyl group; te
Branched alkyl groups such as rt-butyl group and 2-ethylhexyl group; cycloalkyl groups such as dichlorohexyl group, norbornyl group and adamantyl group; vinyl group, allyl group, isopropenyl group, 1,3-butadienyl group, etc. Aralkyl groups such as alkenyl groups, benzyl groups, phenethyl groups, and (2-naphthyl)methyl groups; aryl groups such as phenyl groups and 1-naphthyl groups; and the like.

When R1 is substituted, specific examples of the substituent include:
Hydroxy group niamino group, dibenzylamino group, (2-
Amino groups such as methacryloyloxyethyl) amino group and piperidino group; methoxy group, ethoxy group, tert-
Alkoxy groups such as butoxy group, glycidyloxy group, vinyloxy group, allyloxy group; aralkoxy group such as benzyloxy group, phenethyloxy group; phenoxy group,
Aryloxy groups such as 2-naphthyloxy group; Acyloxy groups such as formyloxy group, acetoxy group, benzoyloxy group, (meth)acryloyloxy group; N-phenylcarbamoyloxy group, N(2-methacryloyloxyethyl)carbamoyloxy group, etc. Carbamoyloxy group: Alkyl group such as methyl group, isopropyl group, trifluoromethyl group, glycidyl group; benzyl group, (
Aralkyl groups such as 2-naphthyl) methyl groups; Aryl groups such as phenyl and 1-naphthyl groups; Alkenyl groups such as vinyl, allyl, ■, and 3-butadienyl groups; Halogen groups such as chloro and bromo groups; Cyano group; carboxylic acid group, carboxylic acid group such as sodium carboxylate group; ethoxycarbonyl group, (2,2,6,6-tetramethyl-
Alkoxycarbonyl groups such as 4-piperidyl)oxycarbonyl groups; Nitro groups; Acyl groups such as formyl groups, acetyl groups, benzoyl groups, and (meth)acryloyl groups;
Examples include carbamoyl groups such as N-methylcarbamoyl group and N-phenylcarbamoyl group; sulfonic acid groups such as sodium sulfonate group and sulfonic acid group; and sulfamoyl group.

When the α ring is substituted, preferred specific examples of the substituent include R2. The same substituents as the specific examples of R3 can be mentioned.

Among these α rings, an indoline ring having a substituent and a benzoindoline ring having a substituent are preferred from the viewpoint of ease of synthesis, high sensitivity to visible light, and high light resistance. Particularly preferred is an indoline ring having one substituent at the 1st position and two substituents at the 3rd position, with the carbon at the 2nd position being a spiro atom. In this case, this indoline ring may have substituents at other positions, and the two substituents at the 3-position may be combined to form a ring.

R2 and R3 are hydroxy group, amino group, carbon number 1-20
alkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, 7 to 15 carbon atoms
15 aralkyl groups, aryl groups having 6 to 14 carbon atoms, halogeno groups, cyano groups, carboxy groups, nitro groups, acyl groups having 1 to 20 carbon atoms, and alkoxycarbonyl groups having 2 to 20 carbon atoms. , and R2 also includes hydrogen; preferred specific examples thereof include a hydroxy group; an amino group, a diethylamino group, a piperidino group,
Amino groups such as (2-methacryloyloxyethyl) amino groups; alkoxy groups such as methoxy, ethoxy, tert-butoxy, glycidyloxy, vinyloxy, and allyloxy groups; aralkoxy groups such as benzyloxy and phenethyloxy groups; phenoxy group, aryloxy group such as 2-naphthyloxy group; formyloxy group,
Acyloxy groups such as acetoxy, benzoyloxy and (meth)acryloyloxy groups; Chain alkyl groups such as methyl, propyl and octadecyl groups; Branched alkyl groups such as isopropyl and 2-ethylhexyl groups;
Cycloalkyl groups such as cyclohexyl group, norbornyl group, adamantyl group; Alkenyl groups such as vinyl group, allyl group, isopropenyl group, 1,3-butadienyl group; benzyl group, phenethyl group, (2-naphthyl)methyl group, etc. Aryl groups such as aralkyl groups, phenyl groups, and 1-naphthyl groups; halogen groups such as chloro groups and bromo groups; cyano groups; carboxylic acid groups such as carboxylic acid groups and sodium carboxylic acid groups; nitro groups; formyl groups and acetyl groups , benzoyl group, acyl group such as (meth)acryloyl group;
Ethoxycarbonyl group, isopropoxycarbonyl group,
Alkoxycarbonyl groups such as (2,2°6.6-tetramethyl-4-piperidyl)oxycarbonyl group; carbamoyl groups such as carbamoyl group and N-propylcarbamoyl group; R2 may be hydrogen. When R2 or R3 is further substituted, specific examples of the substituent include the same examples of the substituent when R1 is further substituted.

X represents oxygen or sulfur.

R4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 7 to 20 carbon atoms.
20 aralkyl group, aryl group having 6 to 19 carbon atoms, acyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbamoyl group having 1 to 20 carbon atoms, alkylthiocarbonyl group having 2 to 20 carbon atoms group, carbon number 1-2
It represents a substituent selected from a sulfonyl group having 0 carbon atoms, a sulfinyl group having 1 to 20 carbon atoms, a sulfenyl group having 1 to 20 carbon atoms, and a sulfamoyl group having 1 to 20 carbon atoms. ; Alkyl groups such as methyl group, propyl group, octadecyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, vinyl group, allyl group, glycidyl group, 2-(meth)acryloyloxyethyl group; benzyl group, phenethyl group aralkyl groups such as (2-naphthyl)methyl groups; aryl groups such as phenyl groups and 1-naphthyl groups; acyl groups such as formyl groups, acetyl groups, benzoyl groups, and (meth)acryloyl groups;
Ethoxycarbonyl group, benzyloxycarbonyl group,
Alkoxycarbonyl groups such as (2,2,6,6-tetramethyl-4-piperidyl)oxycarbonyl group; Carbamoyl groups such as carbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group; propylthiocarbonyl group, phenyl Alkylthiocarbonyl groups such as thiocarbonyl groups; Sulfonyl groups such as methanesulfonyl groups, propanesulfonyl groups, and benzenesulfonyl groups; Sulfenyl groups such as methanesulfenyl groups, propanesulfenyl groups, and benzenesulfenyl groups;
Sulfinyl groups such as methanesulfinyl group, propanesulfinyl group, and benzenesulfinyl group; sulfamoyl groups such as sulfamoyl group, N-propylsulfamoyl group, and N-phenylsulfamoyl group; and the like. When R4 is further substituted, specific examples of the substituent include those similar to the specific examples of the substituent when R1 is substituted.

Specific examples of the ring represented by formula (I) include a naphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, an acephenanthrylene ring, an indene ring, a fluorene ring, a quinoline ring, a quinoxaline ring, a penzofuran ring, Examples include a benzothiophene ring, a dibenzofuran ring, a coumarin ring, a chroman ring, a carbazole ring, a tetrahydronaphthalene ring, a dihydroanthracene ring, and the present invention also includes cases where there is no β ring and only a benzene ring is used.

When the β ring is substituted, preferred examples of the substituent include the same substituents as those for R2 and R3.

One of the methods for producing the compound represented by the general formula (I) of the present invention is to prepare a hydroxy aromatic compound represented by the following formula (A) using nitrous acid in the presence of divalent copper ions. A method of reacting a compound obtained by nitrosation, a compound represented by R4XH, and a 2-methyleneindoline compound represented by the following -killing (B) α ρ=CH-R2 (B) can be mentioned.

In addition, as an example of another production method, a method in which a nitrosohydroxy aromatic compound represented by -killing below, a compound represented by R4XH, and a compound of formula (B) are reacted in the presence of divalent copper ions. Can be mentioned.

In any reaction, if a basic substance such as sodium hydroxide or sodium methoxide is present, the reaction proceeds smoothly.

When R4 in the compound represented by general formula (I) is hydrogen, the -XH group can be further modified to easily convert into another substituent.

Preferred examples of purification methods in the production stage include recrystallization using various solvents, column chromatography using silica gel, solvent extraction, and activated carbon treatment.

The otochromic materials of the present invention are preferably used in combination with optically transparent resins. Examples of such resins include diethylene glycol bisallyl carbonate polymer; (meth)acrylic polymer; cellulose; polyvinyl acetate, polyvinyl alcohol,
polyvinyl butyral, polystyrene, polyethylene,
Olefinic polymers such as poly(4-methylpentene), polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride; polyester resins such as polyethylene terephthalate; polycarbonate resins: eboxy resins; nylon resins; polyurethane resins: (halogenated) bisphenol A Examples include di(meth)acrylate polymers, urethane-modified di(meth)acrylate polymers of (halogenated) bisphenol A, and copolymers and alloys of these resins are also preferably used.

Further, the compound represented by the general formula (I) of the present invention may have a polymerizable functional group. Examples of the polymerizable functional group include a hydroxy group, an amino group, a carboxyl group, a (meth)acryloyl group, a vinyl group, an allyl group, a glycidyl group, and an organic group containing these groups. Among these, radically polymerizable functional groups such as (meth)acryloyl groups, vinyl groups, allyl groups, and organic groups containing these groups are preferable in terms of ease of polymerization reaction. Taking this into consideration, a (meth)acryloyl group and an organic group containing a (meth)acryloyl group are more preferred.

Specific examples of organic groups containing a (meth)acryloyl group include an acryloyloxy group, an acryloylthio group,
N-acryloylamino group, 4-acryloyloxypiperidino group, 2-acryloyloxyethyl group, 3-acryloyloxypropyl group, 4-acryloyloxybutyl group, 6-acryloyloxyhexyl group, 8-acryloyloxyoctyl group, 11-acryloyloxyundecyl group, (2-acryloyloxyethyl)oxy group, (2-acryloyloxyethyl)thio group, (
2-acryloyloxyethyl)amino group, N-(2-
acryloyloxyethyl)carbamoyl group, N-(2
-acryloyloxyethyl)carbamoyloxy group,
and those in which the acryloyl group portion of the above substituents is replaced with a methacryloyl group. of course,(
The organic group containing the meth)acryloyl group is not limited to these.

These polymerizable functional groups are preferably included as R1, R3, R4, substituents on the α ring, and substituents on the β ring from the viewpoint of ease of synthesis. Further, from the viewpoint of increasing the coloring density, it is preferable to include R4 as a substituent on the α ring and a substituent on the β ring.

When the compound represented by general formula (1) has a polymerizable functional group, it can be polymerized alone or with other polymerizable compounds such as acrylic monomers, styrene monomers, vinyl acetate monomers, epoxy monomers, It can also be used in the form of a copolymer copolymerized with a silane compound having an organic polymerizable functional group.

When polymerized alone or copolymerized with other monomers, durability against photodeterioration is greatly improved.

The photochromic material of the present invention, or a material made by combining the photochromic material of the present invention with other resins, includes:
It can be used as a coating composition in the form of a polymer solution, or it can be made into an emulsion and applied to various substrates by various printing methods such as screen printing and gravure printing. Furthermore, various coating methods can be employed, such as dip coating, spin coating, and roll coating.

When combined with other resins, the content of the photochromic material of the present invention should be determined depending on the purpose and method of use, but from the viewpoint of visual sensitivity, it should be 0001 to 20% by weight of the other resins. is preferred.

Furthermore, from the standpoint of improving the repeated durability of the photochromic material of the present invention, it is particularly effective to block oxygen and water during use. Furthermore, for the purpose of improving durability, known additives such as singlet oxygen quenchers represented by nickel salts, antioxidants represented by hindered amine compounds or their polymers, ultraviolet absorbers, and triple light quenchers are added. Available for use.

In particular, the uses of the photochromic material of the present invention include:
Examples include use as an optical element that changes color due to light. Optical elements include sunglass lenses, ski goggles, safety glasses lenses, curtains, clothing,
Suitable examples include automobile windows such as windshields and sunroofs, toys, cosmetics, and writing instruments.

[Example] Next, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Nitrosation of 2-naphthol 14.4 g of 2-naphthol was dissolved in a mixture of 50 ml of ethanol/50 ml of glacial acetic acid/50 ml of water. An appropriate amount of sodium acetate was added to this to adjust the pH to 4.2.

Put 300 ml of water in another container, dissolve 9.6 g of anhydrous copper sulfate therein, and then add 10.0 ml of sodium nitrite.
4g was added and dissolved. This aqueous solution was added dropwise over 30 minutes to the previously prepared 2-naphthol solution that was being vigorously stirred. During this time, add sodium acetate as needed and p
H was kept at 4.2. After the addition was completed, stirring was continued for another 10 minutes, and the precipitate was collected by filtration, washed with water, and dried to obtain 18.6 g of a brown nitrosate.

■ Synthesis of the compound of the following formula (D) 2.04 g of the nitrosate of 2-naphthol obtained by the method of Example 1-■ was added to 40 ml of absolute ethanol at reflux temperature in the presence of 0.54 g of sodium methoxide. The reaction was allowed to proceed for 3 hours. A solution of 1.50 g of 1,3°3-trimethyl-2-methyleneindoline dissolved in 10 ml of absolute ethanol was added to the mixture, and the mixture was further refluxed for 20 hours.

This reaction mixture was filtered while hot to remove insoluble materials, and then the solvent was distilled off. This was separated and purified by column chromatography using silica gel as a support carrier, once using toluene as a developing solvent, and once using an ethyl acetate/hexane mixed solvent as a developing solvent. This was further recrystallized from an ethanol solvent to obtain pale yellow crystals of the compound of formula (D).

■ Analysis results The analysis results of the compound of formula (D) are shown.

(Elemental analysis value) Actual value (%) Calculated value (%) C7
7,277,4 H6,86,5 N 7. 3 7. 5 (melting point)
174-175°C Further, the infrared absorption spectrum of the compound of formula (D) is shown in FIG. 1, and the IH nuclear magnetic resonance absorption spectrum is shown in FIG.

(2) Application Example A compound of formula (D) was dissolved in a 30% by weight toluene solution of poly(n-butyl methacrylate) at a concentration of 5 mol%. After applying this solution onto a glass slide, toluene was removed by heating to produce a film. The obtained film had a pale reddish-purple color. When the film was irradiated with ultraviolet light, it turned deep reddish-purple. When the visible absorption spectrum of the film was measured, it was found that λma of the colored species
X was 566 nm.

When the irradiation with ultraviolet light was stopped, the films changed in color by these methods quickly returned to their original pale reddish-purple color at room temperature. Furthermore, when this yellow film was irradiated with ultraviolet light, it developed a deep color again, and these changes could be repeated any number of times.

Example 2 (1) Nitrosation of 2,7-dihydroxynaphthalene A nitrosated product was obtained in the same manner as in Example 1-2, except that 1.60 g of 2,7-dihydroxynaphthalene was used instead of 2-naphthol.

■ Synthesis of the compound of the following formula (E) Instead of the nitrosate of 2-naphthol, Example 2-
Using 2.2 g of the nitrosated product of 2,7-dihydroxynaphthalene obtained by method (1), 1. 3゜3-trimethyl-
1. instead of 2-methyleneindoline. 3. The formula (
Compound E) was obtained. The compound of formula (E) was purified by silica gel column chromatography using a mixed solvent of ethyl acetate/hexane as a developing solvent.

■ Synthesis of compound of formula (F) below 2.3 g of compound of formula (E), 4.0 g of triethylamine
2.0 g of methacrylic acid chloride is added to a solution of 2.0 g and 50 ml of methylene chloride being stirred at room temperature.
A solution consisting of 10 ml of methylene chloride was added dropwise over 20 minutes. After the dropwise addition was completed, stirring was continued for an additional 30 minutes. After the reaction was completed, the solvent was distilled off, and silica gel column chromatography was performed using silica gel as a support carrier and an ethyl acetate/hexane mixed solvent as a developing solvent to obtain a compound of formula (F).

■ Analysis results The analysis results of the compound of formula (F) are shown.

(Elemental analysis value) Actual value (%) Calculated value (%) C6
4,364,OH5,25,ON5. 0 5. 3CI
13.8 13.5 ■ Application example 1 equivalent of the compound of formula (F) and 50 equivalents of methyl methacrylate are polymerized by a normal radical polymerization method using azobisisobutyronitrile as a polymerization initiator, and purified by a reprecipitation method. A copolymer was obtained.

A solution of this copolymer in toluene was applied onto a slide glass and dried to obtain a film.

When the film was irradiated with ultraviolet light, it developed a red color, and when the irradiation was stopped, the color disappeared. This change could be repeated many times.

Example 3 ■ Synthesis of the compound of the following formula CG) 2.04 g of the nitrosated product of 2-naphthol obtained by the method of Example 1-■ and 1.86 g of ethylene glycol were mixed in 30 ml in the presence of 0.54 g of sodium methoxide. The mixture was reacted in toluene at reflux temperature for 3 hours. This includes 1.3.
A solution of 2.4 g of 3-trimethyl-2methylene-4,6-dichloroindoline dissolved in 10 ml of toluene was added, and the mixture was further refluxed for 20 hours. This reaction mixture was filtered while hot to remove insoluble materials, and then the solvent was distilled off. This was separated and purified by column chromatography once using silica gel as a support carrier and toluene as a developing solvent.
The reaction was carried out once using an ethyl acetate/hexane mixed solvent as a developing solvent to obtain a compound of formula (G).

■ Synthesis of compound of formula (H) below Instead of compound of formula (E), compound 2.6 of formula (G)
A compound of formula (H) was obtained in the same manner as in Example 2-2, except that g was used.

■ Analysis results The analysis results of the compound of formula (H) are shown.

(Elemental analysis value) Actual value (%) Calculated value (%) C6
3,764,OH5,15,ON5. 2 5. 3CA'
13.2 13.5■ Application example The same procedure as in Example 2-■ was carried out except that the compound of formula (H) was used instead of the compound of formula (F).
− Changes similar to ■ could be observed.

Example 4 ■ Synthesis of the compound of the following formula (I) 2.04 g of nitrosated 2-naphthol obtained by the method of Example 1-■, 0.40 g of sodium hydroxide, 15 g of water
ml and 40 ml of toluene into a reaction vessel,
The reaction was carried out at reflux temperature for 3 hours while stirring. 1 for this
．． 3.34limethyl-2=methyleneindoline 1.50
A solution prepared by dissolving G in toluene (10 ml) was added thereto, and the mixture was further refluxed for 20 hours. After the reaction was completed, an appropriate amount of water was added to the reaction mixture, and then extracted with toluene. The extract was dried over anhydrous sodium sulfate, and then toluene was distilled off. Separation and purification of this by column chromatography,
Using silica gel as a support carrier, the reaction was carried out once using toluene as a developing solvent and twice using an ethyl acetate/hexane mixed solvent as a developing solvent to obtain a compound of formula (1).

■ Analysis results The analysis results of the compound of formula (1) are shown.

(Elemental analysis value) Actual value (%) Calculated value (%) C7
7, 176, 7 H5, 85, 9 N 8. 0 8.1 ■ Formula (
Compound J) was obtained.

(2) Application example A film was prepared in the same manner as in Example 2-(2) except that the compound of formula (H) was used instead of the compound of formula (F).

When the film was irradiated with ultraviolet light, it developed a color, and when the irradiation was stopped, the color disappeared. This change could be repeated many times.

Example 5 ■ Synthesis of compound of the following formula (K) 6.1 g of dodecanethiol instead of ethylene glycol
using 1.3.34limethyl-2methylene-4,6-
A compound of formula (K) was obtained in the same manner as in Example 3-2, except that 1.5 g of 1.3.3-)rifthyl-2-methyleneindoline was used instead of dichloroindoline. The compound develops color when irradiated with ultraviolet light in an acetone solution,
The color disappeared when the irradiation was stopped. This change could be repeated any number of times.

■ Analysis results The analysis results of the compound of formula (K) are shown.

(Elemental analysis value) Actual value (%) Calculated value (%) C7
7,077,2 H8,18,4 N 5. 2 5. 3S
5. 9 6. 1 Example 6 ■ Nitrosation of p-nitrophenol Glacial acetic acid 90ml
p-nitrophenol in a mixture of 150 ml/water.
7g was dissolved. Add an appropriate amount of sodium acetate to this,
The pH was adjusted to 4.2. 1500ml water in another container
was added and 23.9 g of anhydrous copper sulfate was dissolved therein, and then 51.8 g of sodium nitrite was further added and dissolved. This aqueous solution was added to the above phenol solution and reacted at 60°C for 12 hours. After cooling to room temperature, collect the precipitate by filtration.
After washing with water, it was dried to obtain a black nitrosate.

■ Synthesis of the compound of the following formula (L) Instead of the nitrosate of 2-naphthol, Example 6-■
Nitrosated product of p-nitrophenol obtained by the method 2.
0g and 0.78g of 2-mercaptoethanol in place of ethylene glycol; 1. 3. In the same manner as in Example 3-■, except that 1.5 g of 1.3゜3-trimethyl-2-methyleneindoline was used instead of 3-4trimethyl-2-methylene-4,6-dichloroindoline, the formula Compound (L) was obtained.

■ Synthesis of compound of formula (M) below Instead of compound of formula (E), compound 2.1 of formula (L)
A compound of formula (M) was obtained in the same manner as in Example 2-2 except that g was used.

■ Analysis results The analysis results of the compound of formula (M) are shown.

(Elemental analysis value) Actual value (%) Calculated value (%) C6
2,462,6 H5,15,3 N 9. 0 8. 8S
6. 8 6. 7 Comparative Example 1 A compound of formula (D) and a compound represented by the following formula (N)L-r″3 were separately added to a 30% toluene solution of poly(n-butyl methacrylate) at a concentration of 5 mol%. After each solution was applied to a slide glass so that the film thickness was equal, toluene was removed by heating to create a film.When the two obtained films were irradiated with ultraviolet light under the same conditions, The film containing the compound of formula (D) was more deeply colored.The time required for decolorization was also longer for the film containing the compound of formula (D).

Comparative Example 2 A compound of formula (D) and a compound represented by formula (0) below were separately dissolved in a 30% toluene solution of poly(n-butyl methacrylate) at a concentration of 5 mol%. After each solution was applied onto a slide glass so that the film thickness was equal, toluene was removed by heating to prepare a film. The two obtained films were subjected to a light resistance test by irradiating them with ultraviolet rays for 20 hours using a carbon arc fade meter. The film containing the compound of formula (D) showed no difference in color development before and after the test, but the film containing the compound of formula (0) only slightly remained in color development after the test. It had deteriorated to such an extent.

[Effects of the Invention] The photochromic material of the present invention is characterized in that it has a rich range of hues, such as a red color, and a high color density. Moreover, the photochromic material of the present invention had excellent durability against repeated color development and fading, and excellent light resistance, compared to conventional spirooxazines that exhibit reddish-purple color development.

[Brief explanation of drawings]

FIG. 1 is a drawing showing an infrared absorption spectrum of the compound of formula (D) obtained in Example 1. Figure 2 shows the compound of formula (D) obtained in Example 1! H
It is a drawing showing a nuclear magnetic resonance absorption spectrum. Patent Applicant Toshi Co., Ltd. Figure 2

Claims (1)

[Claims] (1) A photochromic material comprising a compound represented by general formula (I). ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, α ring is a 5- or 6-membered ring containing one nitrogen atom, and a nitrogen atom fused to a benzene ring, naphthalene ring, or pyridine ring. one type selected from a 5-membered ring or a 6-membered ring containing one nitrogen atom, and at least one nitrogen atom in the α ring exists bonded to an organic group R^1, and ▲ mathematical formula, chemical formula, table etc. It is represented by ▼. Here, R^1 is an alkyl group having 1 to 20 carbon atoms, and 7 carbon atoms.
Represents a substituent selected from an aralkyl group having ~20 carbon atoms and an aryl group having 6 to 19 carbon atoms. R^2, R^3 are hydroxy group, amino group, carbon number 1~
20 alkoxy group, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, Selected from an aryl group having 6 to 14 carbon atoms, a halogeno group, a cyano group, a carboxy group, a nitro group, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a carbamoyl group having 1 to 20 carbon atoms. R^2 also includes hydrogen. X represents oxygen or sulfur. R^4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 7 carbon atoms.
~20 aralkyl group, C6-19 aryl group,
Acyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbamoyl group having 1 to 20 carbon atoms, alkylthiocarbonyl group having 2 to 20 carbon atoms, 1 to 20 carbon atoms
20 sulfonyl group, sulfinyl group having 1 to 20 carbon atoms, sulfenyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
represents a substituent selected from sulfamoyl groups. n represents an integer of 0 to 3. The β ring represents a ring having 3 to 18 carbon atoms condensed to a benzoxazine ring, and includes cases where there is no β ring. ]