JP2692115B2 - Photochromic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photochromic material comprising a spirobenzoxazine compound, and particularly to printing,
The present invention relates to a photochromic compound useful as a material for optical devices, recording materials, medicine, decorations, and the like.

[Prior Art] Conventionally, spirooxazine compounds have been known as photochromic compounds having excellent fatigue resistance.

For example, a spironaphthoxazine compound having a basic skeleton represented by the following formula (F) is disclosed in JP-A-61-276833, and is represented by the following formulas (G), (H) and (I). Each of spirooxazine compounds having a skeleton is disclosed in
62-153292, JP-A-62-72778, JP-A-62
-164685 gazette.

Further, 1,3,3-trimethyl derivatives of spirobenzoxazine are described in GH Brown, "Photochromism", pages 54, 92 and 244.

[Problems to be Solved by the Invention] The spirooxazine compounds represented by the formulas (F) to (I) have a drawback that the hue of the coloring species is purple to blue, and the richness of hue is insufficient. Had. Further, the color developability near room temperature (15 to 30 ° C) was also insufficient.

In addition, 1,3,3-trimethyl derivative of spirobenzoxazine is known to be colored yellow in dioxane, but it does not develop color at around room temperature and is not practical for optical devices. There was a problem that it was a thing.

The present invention is intended to solve the drawbacks of the prior art, and an object of the present invention is to provide a photochromic material having abundant hues and excellent color development even at room temperature.

[Means for Solving the Problems] The present invention has the following configurations in order to achieve the above object.

That is, the present invention is a photochromic material comprising spirobenzoxazine represented by the general formula (A). (Wherein the α ring is one selected from a five-membered ring containing one nitrogen atom, a five-membered ring containing one nitrogen atom linked to a benzene ring or a naphthalene ring, and a six-membered ring containing one nitrogen atom. And the nitrogen atom in the α ring is bonded to the organic group R ¹ represented by N—R ¹ .

Here, R ¹ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms,
It represents a substituent selected from an unsubstituted or substituted aryl group having 6 to 19 carbon atoms.

R is a hydroxy group, an unsubstituted or substituted amino group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an alcyoxy group having 2 to 20 carbon atoms, and a carbon number. 1 to 20 alkyl group, 7 to 7 carbon atoms
15 aralkyl groups, C6-C14 aryl groups, halogen groups, cyano groups, carboxy groups, nitro groups, C2-C2
It represents a substituent selected from an acyl group having 20 and an alkoxycarbonyl group having 2 to 20 carbon atoms. l represents an integer of 1 to 4. ), The following compounds (B) to
It consists of the compound represented by (D). (A) General formula (B)
A spirobenzoxazine compound represented by.

(In the formula, R ¹ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms,
It represents a substituent selected from an unsubstituted or substituted aryl group having 6 to 19 carbon atoms.

R represents an unsubstituted or substituted amino group, and l represents an integer of 1 to 4. ) R ² and R ³ are, independently, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 19 carbon atoms Represents a substituent selected from the above, and when not independent, represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms including the carbon at the 3'position.

X represents a halogen group. m represents an integer of 1 to 4. (2) A spirobenzoxazine compound represented by the general formula (C).

(In the formula, R ¹ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms,
It represents a substituent selected from an unsubstituted or substituted aryl group having 6 to 19 carbon atoms.

R is a hydroxy group, an unsubstituted or substituted amino group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, and a carbon number. 1 to 20 alkyl group, 7 to 7 carbon atoms
15 aralkyl groups, C6-C14 aryl groups, halogen groups, cyano groups, carboxy groups, nitro groups, C2-C2
It represents a substituent selected from an acyl group having 20 and an alkoxycarbonyl group having 2 to 20 carbon atoms. Represents an integer of 1 to 4. ) R ² and R ³ are, independently, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 19 carbon atoms Represents a substituent selected from the above, and when not independent, represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms including the carbon at the 3'position.

R ⁴ is a hydroxy group, an unsubstituted or substituted amino group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, Alkyl group having 1 to 20 carbon atoms, 7 carbon atoms
~ 15 aralkyl groups, C6-14 aryl groups, halogen groups, cyano groups, carboxy groups, nitro groups, 2 carbon atoms
Represents a substituent selected from an acyl group having 20 to 20 and an alkoxycarbonyl group having 2 to 20 carbon atoms. m represents an integer of 0 to 4. ) R ⁵ is a hydroxy group, an unsubstituted or substituted amino group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms. , An alkyl group having 1 to 20 carbon atoms, and 7 carbon atoms
~ 15 aralkyl groups, C6-14 aryl groups, halogen groups, cyano groups, carboxy groups, nitro groups, 2 carbon atoms
Represents a substituent selected from an acyl group having 20 to 20 and an alkoxycarbonyl group having 2 to 20 carbon atoms. (3) A spirobenzoxazine compound represented by the general formula (D).

(In the formula, R, l, and R ¹ are the same as those described in claim (2).

R ² , R ³ , R ⁴ and m have the same meanings as in claim (2).

R ⁵ and n are the same as those described in claim (2).

The α-ring of the present invention may be a five-membered ring or a six-membered ring containing one nitrogen atom, or the five-membered ring linked to a benzene ring or a naphthalene ring, which are the above specific examples. As is clear from the general formulas (B) to (E), specific examples thereof include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, a benzindoline ring, a tetrahydroquinoline ring, and an acridine. Examples include rings.

Next, specific examples of the substituent R in the general formula (A) include hydroxy group, amino group, dimethylamino group, diethylamino group, methylethylamino group, di-tert-butylamino group, dibenzylamino group, diphenylamino. Group, acetylamino group, benzoylamino group, organic substituted amino group such as methylacetylamino group, methoxy group,
Ethoxy, tert-butoxy and other C1-20 alkoxy groups, benzyloxy and other C7-15 aralkoxy groups, phenoxy and other C6-14 aryloxy groups, methyl and trifluoromethyl Group, hexyl group, alkyl group having 1 to 20 carbon atoms such as 3-ethyloctadecyl group, benzyl group, 3-methylbenzyl group, 2,4-
Aralkyl group having 7 to 15 carbon atoms such as dichlorobenzyl group, 2-naphthylethyl group, phenyl group, 3-chloro-2
-Aryl group having 6 to 14 carbon atoms such as naphthyl group, halogen group such as fluoro group, chloro group and bromo group, alkoxycarbonyl group having 2 to 20 carbon atoms such as cyano group, carboxy group and ethoxycarbonyl group, acetyl group , A benzoyl group, a methacryl group, or another acyl group having 2 to 20 carbon atoms,
2 to 20 carbon atoms such as benzoyloxy group and acryloxy group
And acyloxy groups, nitro groups and the like.

In particular, among such substituents as R, an organic-substituted amino group is preferable for imparting the color forming property at a high temperature, and an aryl group such as a phenyl group is preferable for imparting the color forming property at a low temperature.
Particularly in the formula (B), R represents an unsubstituted or substituted amino group among the substituents shown above. However, it may further have the above-mentioned other substituents.

On the other hand, alpha ring is a five- or six-membered ring containing a nitrogen atom, a nitrogen atom contained in the alpha ring is present in combination with the organic group R ¹ represented by N-R ^1.

Here, specific examples of the substituent R ¹ include a chain alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and an octadecyl group, and a branched alkyl group having 3 to 20 carbon atoms such as a 2-methylpentyl group. C3-C10 cycloalkyl groups such as alkyl groups and cyclohexyl groups; C7-C20 aralkyl groups such as benzyl and phenethyl groups; C6-C19 aryl groups such as phenyl groups and 2-naphthyl groups. Is mentioned.

When R ¹ is substituted, specific examples of the substituent include:
Hydroxy group, amino group, organic substituted amino group, alkoxy group, aralkoxy group, aryloxy group, halogen group,
Examples thereof include a cyano group, a carboxy group, an alkoxycarbonyl group, an acyl group and a nitro group, and when R ¹ is a cycloalkyl group, an aralkyl group or an aryl group, an alkyl group, an aralkyl group and an aryl group can be mentioned.

Further, specific examples of R ² and R ³ in the spirobenzoxazine compound in the general formulas (B), (C) and (D) include a methyl group, an ethyl group, an octadecyl group when R ² and R ³ are independent. A chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms such as 2-methylpentyl group, a cycloalkyl group having 3 to 10 carbon atoms such as cyclohexyl group, a benzyl group, a phenethyl group 7 to 20 carbon atoms
Examples of the aralkyl group, phenyl group and the like having 6 to 19 carbon atoms include a cycloalkyl group having 3 to 10 carbon atoms such as cyclohexyl group, when not independent. If R ^2, R ³ are substituted, the substituents R ^2, R ³ are the same as the substituents for the above-described R ^1. The compound of the general formula (A) of the present invention is produced, for example, by the following production method.

General formula (I) A methylene compound represented by the general formula (II) A compound of formula (A) is produced by reacting a 2-nitrosophenol compound represented by

 It is also manufactured by the following manufacturing method.

General formula (III) A compound represented by the formula (A), a quaternizing agent R ¹ -X (X is an anionic leaving group), a basic substance and the compound of the general formula (II) are added in any order and reacted. The compound is prepared.

 Furthermore, the following method can also be mentioned.

A product obtained by reacting the compound of the general formula (I) with sulfurous acid, and a general formula (IV) A compound of formula (A) is produced by reacting a 2-aminophenol compound represented by

In addition, the product of the reaction of the compound of formula (III) with sulfurous acid, the quaternizing agent R ¹ -X, the basic substance and the general formula (I
The compound of formula (A) can be prepared by adding and reacting the compound of V) in any order.

Furthermore, the general formula (V) A compound of formula (A) can also be produced by adding a basic substance and a compound of general formula (IV) in an arbitrary order and reacting with the product of the reaction of the compound represented by with sulfurous acid.

Preferable examples of the purification method in the production stage include recrystallization with various solvents, column chromatography separation using a silica column or the like, solvent extraction, or activated carbon treatment.

The photochromic compound of the present invention is an optically transparent resin, for example, diethylene glycol bisallyl carbonate polymer, (meth) acrylic polymer and copolymers thereof, celluloses, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyester resin, Polycarbonate, polystyrene and copolymers thereof, epoxy resin, (halogenated) bisphenol A di (meth) acrylate polymer and copolymers thereof,
It is preferably used by being blended with a (halogenated) urethane-modified di (meth) acrylate polymer of bisphenol A, a copolymer thereof, a nylon resin, a polyurethane or the like. The compounded resins can be used as an optical element having discoloration by light. Suitable examples of the optical element include a sunglass lens, ski goggles, protective eyeglass lenses, curtains, clothes, toys, and the like.

Various methods, such as a dyeing method, a casting method, and a coating method of a compounded polymer solution, can be applied to the method of compounding the photochromic compound of the present invention with resins.

In addition, the amount to be added to the resin should be determined according to the purpose and the method of use, but from the viewpoint of visual sensitivity, an addition amount of 0.01 to 20% by weight is preferable.

[Examples] Next, examples will be described, but the present invention is not limited thereto.

Example 1 (1) Synthesis of Spirobenzoxazine of Formula (J) 10 g of 1,3,3-trimethyl-2-methylene-5-chloroindoline and 10 g of 2-nitroso-5-dimethylaminophenol were dissolved in 100 ml of ethanol and refluxed in a nitrogen stream for 2 hours. After the reaction, the mixture was concentrated and subjected to Soxhlet extraction using hexane as an extraction solvent. The hexane layer was concentrated and crystals were deposited when left at room temperature. The obtained crude crystals were recrystallized from methanol to obtain yellow crystals of spirobenzoxazine of the formula (J).

(NMR) 1.3ppm (6H) 2.7ppm (3H) 2.9ppm (6H) 6.4 ~ 7.4ppm (7H) (3) Application Example This compound was dissolved in methyl methacrylate at a concentration of 0.5% by weight, and azobisisobutyrate was added. Cast polymerization was performed using ronitrile as a polymerization initiator to prepare a polymethylmethacrylate plate containing the present compound. This plate turned red when exposed to ultraviolet rays, and quickly returned to its original color when left in the dark except for the light. Further, when the weather resistance was examined by irradiating this with a fade meter for 20 hours, the photochromic characteristics were exactly the same as before being put in the fade meter, and the fatigue resistance was excellent.

Further, this plate turned red when exposed to ultraviolet rays even at 50 ° C, and the color development temperature was 50 ° C or higher.

When the absorption of this plate at the time of color development was measured, it was λmax = 545 nm.

Comparative Example 1 (1) Synthesis of Spirobenzoxazine of Formula (K) 2-nitroso-5-diethylaminophenol instead of 2-nitroso-5-dimethylaminophenol, 1,
Yellow crystals were obtained in the same manner as in Example 1 except that 1,3,3-trimethyl-2-methyleneindoline was used instead of 3,3-trimethyl-2-methylene-5-chloroindoline.

(NMR) 1.1ppm (6H) 1.3ppm (6H) 2.8ppm (3H) 3.3ppm (4H) 6.0-7.4ppm (8H) (3) Application example Polyvinyl butyral in which this compound was dissolved at a concentration of 0.5% by weight / A butanol solution was applied onto a glass plate and dried to prepare a polyvinyl butyral plate containing the present compound. This plate turned red-purple upon irradiation with ultraviolet rays, and quickly returned to its original colorless state when left in the dark except for the light. Further, this plate was colored reddish purple even when irradiated with ultraviolet rays even at 50 ° C, and the color development temperature was 50 ° C or higher.

Example 2 (1) Synthesis of Spirobenzoxazine of Formula (L) 1- (2,4-dichlorobenzyl) -3,3-dimethyl-2
10 g of methylene-5,6-dichloroindoline and 10 g of 2-nitroso-5-dimethylaminophenol were dissolved in 100 ml of benzene and refluxed in a nitrogen stream for 2 hours. After the reaction, the mixture was concentrated and extracted with water / hexane as a solvent. The hexane layer was concentrated and 50 ml of ethanol was added. This solution was heated to 60 ° C., 3 g of activated carbon was added, and the mixture was stirred for 10 minutes. Then, when the mixture was filtered, the filtrate was concentrated and allowed to stand at room temperature, crystals began to precipitate. The obtained crude crystals were recrystallized from petroleum ether to obtain yellow crystals of spirobenzoxazine of the formula (L).

(NMR) 1.1ppm (6H) 1.3ppm (6H) 3.3ppm (4H) 4.3ppm (2H) 6.0 to 7.4ppm (9H) (3) Application Example Polymethyl of the present compound formulation prepared in the same manner as in Example 1 The methacrylate plate turned vermilion when irradiated with ultraviolet rays, and quickly returned to its original colorlessness when left in the dark except for the light. When the absorption of this plate during color development was measured, λmax = 518
nm.

Comparative Example 2 (1) Synthesis of Spirobenzoxazine of Formula (M) 2-nitroso-5-acetylaminophenol in place of 2-nitroso-5-dimethylaminophenol, 1,
Except for using 1,3,3-trimethyl-2-methyleneindoline in place of 3,3-trimethyl-2-methylene-5-chloroindoline, the same procedure as in Example 1 was carried out,
Yellow crystals were obtained.

(2) Application Example A polyvinyl butyral plate containing the present compound prepared in the same manner as in Comparative Example 1 becomes bluish purple when irradiated with ultraviolet rays, and quickly returns to its original colorlessness when left in a dark place except for light. It was

Comparative Example 3 (1) Synthesis of Spirobenzoxazine of Formula (N) 1,2,3,3-Tetramethylindolenium iodide 1
A solution prepared by dissolving 0 g in 50 ml of 50% acetic acid aqueous solution was cooled to 10 ° C. or lower, and 50 ml of 20% sodium sulfite aqueous solution was added dropwise thereto over 30 minutes. After the dropping was completed, the temperature was kept below 10 ° C. and stirring was continued for 1 hour. The precipitated solid was filtered, washed with water, and dried. The product thus obtained and 2
10 g of -amino-4-phenylphenol was dissolved in 50 ml of isopropanol and heated at 70 ° C. 5 g of triethylamine was added dropwise to this solution over 10 minutes. Thereafter, the mixture was refluxed for 1 hour in a nitrogen stream. The reaction solution was concentrated and subjected to column chromatography separation using silica gel as a support carrier and chloroform as a developing solvent. The chloroform layer was concentrated and left at room temperature to precipitate crystals. The obtained crude crystals were recrystallized from hexane to give white crystals of 1 ', 3', 3'-trimethyl-6-phenylspiro [2H- (1,4) -benzoxazine-2,2'-indoline]. Obtained.

(2) Application Example An acetone solution in which the present compound was dissolved in a concentration of 2% by weight turned blue when irradiated with ultraviolet rays, and when it was left in a dark place except for light, it quickly returned to the original colorless state.

Example 3 (1) Synthesis of Spirobenzoxazine of Formula (O) 2-nitroso-5-dibenzylaminophenol instead of 2-nitroso-5-dimethylaminophenol,
White crystals were obtained in the same manner as in Example 1 except that 1,3,3-trimethyl-2-methylene-5-chloroindoline was replaced with 1,3,3-trimethyl-2-methylene-indoline. .

(NMR) 1.3ppm (6H) 2.8ppm (3H) 4.6ppm (4H) 6.1-7.4ppm (18H) (3) Application Example The polymethylmethacrylate plate containing this compound prepared in the same manner as in Example 1 was When it was exposed to light, it turned reddish purple, and when it was left in the dark except for the light, it immediately returned to its original colorlessness.

When the absorption of this plate during color development is measured, it is λmax = 545nm
Met.

Comparative Example 4 (1) Synthesis of Spirobenzoxazine of Formula (P) 2-nitroso-5-methylaminophenol instead of 2-nitroso-5-dimethylaminophenol, 1,3,
Light yellow crystals were obtained in the same manner as in Example 1 except that 1,3,3-trimethyl-2-methyleneindoline was used instead of 3-trimethyl-2-methylene-5-chloroindoline.

(2) Application Example A polyvinyl butyral plate containing the present compound prepared in the same manner as in Comparative Example 1 turned purple when irradiated with ultraviolet rays, and quickly returned to the original colorless state when left in the dark except for light.

Example 4 Synthesis of 2,3,3-trimethylbenz (g) indolenine 5 g of sulfuric acid was added dropwise to 10 g of 1-naphthylhydrazine hydrochloride and 30 g of methylisopropylketone. Then 2
The reaction was carried out at reflux temperature for an hour and then neutralized with a 20% aqueous sodium hydroxide solution. The mixture was extracted with water / ether, and the ether layer was concentrated to obtain 8 g of 2,3,3-trimethylbenz (g) indolenine.

Synthesis of 1,2,3,3-tetramethylbenz (g) indolenium iodide A solution of 2,3,3-trimethylbenz (g) indolenine 2g and methyliodide 25g was reacted at reflux temperature for 30 minutes. It was The deposited precipitate was filtered and washed with acetone to obtain 12 g of white crystals.

Synthesis of compound of formula (Q) 1,2,3,3-Tetramethylbenz (g) 12 g of indolenium iodide and 10 g of 2-nitroso-5-dibenzylaminophenol dissolved in 50 ml of isopropanol were heated to 50 ° C, and 6 g of triethylamine was added. It was Then, the reaction was carried out at the reflux temperature for 1 hour. After the reaction,
After concentration, column chromatography was performed using silica gel as a support and a mixed solvent of petroleum ether / methyl isobutyl ketone as a developing solvent. The solvent was distilled off to obtain a pink solid. The solid was recrystallized from methanol to obtain 2.6 g of spirobenzoxazine of formula (Q) as pale pink crystals.

(NMR) 1.4ppm (6H), 3.4ppm (3H), 4.6ppm (4
H), 6.4 to 8.7 ppm (20H) Application Example A coating solution prepared by dissolving 0.1 g of the present compound in 100 g of 10% polyvinyl butyral butanol solution was applied to two glass plates. After drying, attach the resin surfaces of the two glass plates,
Heated. The photochromic laminated glass thus produced turned purple when irradiated with ultraviolet rays, and returned to the original colorless state when left in a dark place except for light. Moreover, when the weather resistance was examined by irradiating this with a fade meter for 20 hours, the photochromic characteristics were exactly the same as those before putting it in the fade meter, and the fatigue resistance was excellent. In addition, a sufficient color density was obtained even when UV irradiation was performed at 30 ° C.

Example 5 Synthesis of compound of formula (R) 2-nitroso-5-benzylaminophenol
Synthesis was performed in the same manner as in Example 4 except that nitroso-5-diethylaminophenol was used instead.

(NMR) 1.1ppm (6H), 1.4ppm (6H), 3.3ppm (4
H), 3.4 ppm (3H), 6.4 to 8.7 ppm (10H) Example 6 Synthesis of compound of formula (S) 1,2,3,3-Tetramethylbenz (g) indolenium iodide was added to 1- (p-methoxybenzyl) -2,3,3
Synthesis was carried out in the same manner as in Example 4 except that trimethylbenz (g) indolenium iodide was replaced with 2-nitroso-5-dibenzylaminophenol instead of 2-nitroso-5-diethylaminophenol.

Application Example A photochromic laminated glass plate prepared in the same manner as in Example 4 was colored blue-violet when irradiated with ultraviolet rays, and returned to the original colorless state when left in a dark place except for light.

Example 7 Synthesis of 2,3,3-trimethylbenz (f) indolenine The same procedure as in Example 4 was repeated except that 10 g of 2-naphthylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride. , 6 g of product was obtained.

Synthesis of compounds of formula (T) 6 g of 2,3,3-trimethylbenz (f) indolenine and 10 g of methyl tosylate were dissolved in ethanol and reacted at reflux temperature for 2 hours. Then, set the temperature of the reaction solution to 50 ° C.
2 g of triethylamine and 2-nitroso-5
-Add 10 g of dimethylaminophenol and add 2 at reflux temperature.
A time reaction was performed. Subsequent operations were performed in the same manner as in Example 4 to obtain 0.4 g of yellow crystals.

Application Example A photochromic laminated glass plate produced in the same manner as in Example 4 is colored purple when irradiated with ultraviolet rays,
When left in a dark place except for light, it returned to its original colorless state.

Examples 13 to 30 (1) In the same manner as in Example 4, except that the compounds shown in column A of Table 1 were used instead of 1-naphthylhydrazine hydrochloride.
The same procedure as in Example 1 was performed to obtain the compounds described in the column B of Table 1.

(2) In the place of 1,2,3,3-tetramethylbenz (g) indolenium iodide, a compound was used in column B of Table 1, and in place of 2-nitroso-5-dibenzylaminophenol, the compound of Table 1 was used. The procedure described in Example 4 was repeated except that the compounds listed in column C were used to give the compounds listed in column D of Table 1.

(3) Application Example The photochromic aerated glass produced by using the compound described in the column D of Table 1 in the same manner as in Example 4 was colored with the color described in Table 1 when exposed to ultraviolet rays, When left in a dark place except for, the original colorless color was restored. This change could be repeated many times.

[Effects of the Invention] The compound of the present invention is colorless in a general state regardless of the type of solvent and matrix polymer, but when it is irradiated with ultraviolet rays, it immediately changes into a compound that absorbs in the visible light region. It is a photochromic compound that quickly returns to its original colorless state when the irradiation of is stopped and has the following characteristics.

 Rich in hue of coloring species.

 High color development temperature.

 Very good fatigue resistance.

Claims (3)

(57) [Claims] 1. A photochromic material comprising a spirobenzoxazine compound represented by the general formula (B). (In the formula, R ¹ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms,
It represents a substituent selected from an unsubstituted or substituted aryl group having 6 to 19 carbon atoms. R represents an unsubstituted or substituted amino group, and l represents an integer of 1 to 4. ) R ² and R ³ are, independently, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 19 carbon atoms Represents a substituent selected from the above, and when not independent, represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms including the carbon at the 3'position. X represents a halogen group. m represents an integer of 1 to 4. ) 2. A photochromic material comprising a spirobenzoxazine compound represented by the general formula (C). (In the formula, R ¹ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms,
It represents a substituent selected from an unsubstituted or substituted aryl group having 6 to 19 carbon atoms. R is an unsubstituted or substituted amino group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, and 6 to 6 carbon atoms.
An aryloxy group having 14 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms,
It represents a substituent selected from a halogen group and a cyano group. l represents an integer of 1 to 4. ) R ² and R ³ are, independently, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, an unsubstituted or substituted aryl group having 6 to 19 carbon atoms Represents a substituent selected from the above, and when not independent, represents a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms including the carbon at the 3'position. R ⁴ is a substituent selected from an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, a halogen group and a cyano group. Represents a group. m represents an integer of 0 to 4. ) R ⁵ is selected from an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, a halogen group and a cyano group. Represents a substituent. n represents the integer of 0-2. ) 3. A photochromic material comprising a spirobenzoxazine compound represented by the general formula (D). (In the formula, R, 1, R ¹ are the same as those described in claim (2). R ² , R ³ , R ⁴ , and m are the same as those described in claim (2). R ⁵ and n are the same as those described in claim (2).)