JPH0826032B2 - Spironaphthoxazine compounds and photochromic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel spironaphthoxazine compound, and the spironaphthoxazine compound has excellent color-forming performance and excellent repetitive resistance to the color-forming action. And a good solubility in resin, the present invention relates to a photochromic material composed of the spironaphthoxazine compound.

[Conventional technology]

Conventionally, many compounds having photochromic properties have been found in inorganic substances and organic substances. A typical example of the inorganic photochromic substance is silver halide. However, silver halide requires a special glass as its matrix (medium) substance, and thus has a problem that its range of use is limited. On the other hand, the organic photochromic substance has advantages that the inorganic photochromic substance does not have, such as vivid color development and a large degree of freedom in selection of the matrix substance, but the repetition resistance of the photochromic action is very small. This is a fatal defect, and for this reason, it has not been put to practical use.

Among various conventionally known organic photochromic substances,
A spironaphthoxazine compound is known as a compound having relatively good repeated resistance to color development, and is disclosed, for example, in JP-B-45-28892, JP-B-49-48631, and JP-A-55-55.
-36284, JP60-53586A, JP61-53
No. 288 and JP-A-61-263982 disclose 1,3,3-trimethylspiro [indoline-2,3 ′-(3H) -naphtho (2,1
-B) (1,4) oxazine] and its derivatives are disclosed.

[Problems to be solved by the invention]

As shown in the above-mentioned publications, the spironaphthoxazine compounds are generally excellent in repeated resistance to color development as compared with other organic photochromic substances, and therefore, for various spironaphthoxazine compounds, Various studies have been conducted for the purpose of improving the coloring performance such as absorption characteristics of colored species, improving the repeated resistance of the coloring action, or improving the compatibility with resins.

However, to date, excellent color development performance,
There are few known spironaphthooxazine compounds that have a good balance of required properties such as good resistance to repeated color development and high compatibility with resins. From these facts, spironaphthoxazine compounds are practically effective as novel photochromic materials. The current situation is that they are required to appear.

[Means for solving problems]

The present invention responds to the above-mentioned demands, and a novel spironaphthoxazine compound and a photochromic compound having excellent balanced properties in terms of color-forming performance, repeated resistance of color-forming action and compatibility with resins. It provides the material.

The spironaphthoxazine compound of the present invention is a compound represented by the following general formula (I).

General formula (I) In the general formula (I), each of R ¹ , R ² , R ³ and R ⁴ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, which may be the same or different, and R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom or a hydroxy group, which may be the same or different, and R represents an unsubstituted phenyl group, or a phenyl group having a halogen atom or a hydroxy group as a substituent. , N represents an integer of 2 or more.

Further, in the above, the "lower alkyl group" means one having 3 or less carbon atoms, and the "lower alkoxy group" means one having 3 or less carbon atoms.

As typical examples of such spironaphthoxazine compounds, the following can be mentioned.

1- (2-phenoxyethyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b]
(1,4) Oxazine] 1- (3-phenoxypropyl) -3,3-dimethyl-spiro [indoline-2,3 '-(3H) -naphtho [2,1-
b] (1,4) oxazine] 1- (4-phenoxybutyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b]
(1,4) Oxazine] 1- [2- (p-bromophenoxy) ethyl] -3,
3-dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine] 1- (2-phenoxyethyl) -3,3,5-trimethylspiro [indoline -2,3 '-(3H) -naphtho [2,1-
b] (1,4) oxazine] 1- (3-phenoxypropyl) -3,3-dimethyl-5-chlorospiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1, 4) Oxazine] 1- (3-phenoxypropyl) -3,3-dimethyl-5-methoxyspiro [indoline-2,3 '-(3H)-
Naphtho [2,1-b] (1,4) oxazine] 9'-hydroxy-1- (3-phenoxypropyl) -3,3-dimethylspiro [indoline-2,3 '-(3
H) -naphtho [2,1-b] (1,4) oxazine] 9'-hydroxy-1- (4-phenoxybutyl)
-3,3-Dimethylspiro [indoline-2,3 '-(3H)-
Naphtho [2,1-b] (1,4) oxazine] 1- [2- (p-bromophenoxy) ethyl] -3,
3-dimethyl-8'-hydroxyspiro [indoline-
2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine] 1-3- (o-hydroxyphenoxy) propyl]
-3,3-Dimethylspiro [indoline-2,3 '-(3H)-
Naphtho [2,1-b] (1,4) oxazine] 1- [3- (3,5-dibromophenoxy) propyl] -3,3-dimethylspiro [indoline-2,3 '-(3
H) -naphtho [2,1-b] (1,4) oxazine] 1- [2- (pentafluorophenoxy) ethyl]
-3,3-Dimethylspiro [indoline-2,3 '-(3H)-
Naphtho [2,1-b] (1,4) oxazine] Of course, the compound according to the present invention is not limited to the above examples, and may be any one represented by the general formula (I).
And it is also possible to use two or more of them together.

The spironaphthoxazine compound of the present invention can be synthesized by reacting a 1-nitroso-2-naphthol derivative with a corresponding indoline compound to synthesize the desired compound. Specifically, both of them may be reacted by refluxing the boiling point thereof in an appropriate solvent such as ethanol or toluene. Instead of the indoline compound, a corresponding indolinium salt compound may be used. Further, JP-A-61-18783 and JP-A-61187
As disclosed in JP-A-165388, it is also possible to synthesize an indolinium salt by reacting the resulting indolinium salt with a 1-nitroso-2-naphthol derivative without isolation and purification. It is possible. In these reactions, a base such as triethylamine can be added as a catalyst. Further, the synthesized spironaphthoxazine compound can be purified by a method such as a recrystallization method, a column separation method, an activated carbon treatment method or the like, if necessary, to obtain a pure product.

The above spironaphtho oxazine compound, when receiving light from sunlight, an ultraviolet lamp, or other light source, colored species are generated by the light energy to generate color, and further, the repeated resistance of this color forming action is excellent. Even if it is used for a long period of time, there is only a slight decrease in the coloring performance, and it has a high compatibility with the resin and can be dissolved in a sufficient amount in a matrix composed of the resin. Therefore,
This spironaphthoxazine compound can be used very effectively in practice as a photochromic material for obtaining a resin optical product having an excellent photochromic action.

That is, the photochromic material of the present invention comprising the above-mentioned spironaphthoxazine compound is an optically transparent resin, for example, a polymer with a polyol (allyl carbonate) monomer, various acrylic resins such as polymethylmethacrylate, cellulose resin, poly By blending in a matrix composed of polymers such as vinyl acetate, polyvinyl alcohol, urethane resin, epoxy resin, polystyrene, polyester such as polyethylene terephthalate, polyvinyl butyral, nylon, etc. A photochromic optical material can be obtained.

More specifically, the photochromic material of the present invention is mixed with the resin as described above, and molded by a casting or melting method to obtain a film-shaped, plate-shaped or other molded product having a required shape, or , A solution obtained by dissolving the photochromic material of the present invention in a suitable solvent, by impregnating the material comprising the resin as described above,
A resin material having a photochromic effect can be obtained. Therefore, in order to obtain a photochromic optical material with the photochromic material of the present invention, a film made of various resins, an optical material such as a lens is directly dyed with the photochromic material by immersing it in a solution of the photochromic material. Means, a means for forming a photochromic layer by applying a resin solution containing the photochromic material to a base made of various optical materials, and a photochromic film made of a film containing the photochromic material is independently produced and laminated on the base. It is possible to use the means provided by the above, or other means.

It is also possible to directly obtain a molded photochromic lens by mixing the photochromic material with a monomer or a thermosetting resin precursor that is polymerized to form a resin, and casting polymerization the mixture. it can.

In the production of the above photochromic optical material, it is possible to coexist with the photochromic material, an ultraviolet absorber and other additives for the purpose of blocking an antioxidant and an unnecessary light component in the short wavelength region. .

These photochromic optical materials can be suitably used as optical materials for various displays, memories, photochromic lens filters, optical instruments such as photometers, and the like.

〔effect〕

INDUSTRIAL APPLICABILITY The spironaphthoxazine compound of the present invention has a good color-forming property and has CH _{2 n 2} O 3 in its molecular structure.
A spironaphthoxazine compound having no —R group (n is an integer of 2 or more, R is a phenyl group having a specific atom or a substituent or an unsubstituted phenyl group), For example, it has excellent resistance to repeated color development compared with a spironaphthoxazine compound having a hydrophilic polyalkoxyalkyl group, and has high compatibility with a resin, and has the greatest feature in this respect. Is. Therefore, when the spironaphthoxazine compound is used as a photochromic material, it is possible to uniformly contain the photochromic material in a matrix made of a resin at a high concentration, which results in good contrast and a large color density. Moreover, it is possible to obtain a photochromic resin material having excellent resistance to repeated color development. This photochromic resin material can be used alone as a light control material, but can also be used by being applied to an optical material in order to obtain a photochromic optical product.

〔Example〕

Examples of the present invention are described above, but the present invention is not limited to these.

Example 1 (A) 1- (2-phenoxyethyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-
b] (1,4) Oxazine] 1- (2-phenoxyethyl) -2,3,3-trimethylindolenium bromide 14.4 g and triethylamine
4,85 g and 1-nitroso-2-naphthol (6.9 g) were dissolved in 100 ml of ethanol, and this was dissolved under a nitrogen gas atmosphere to 3
The mixture was refluxed for boiling time and reacted.

After completion of the reaction, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and chloroform as a developing solvent. Then, the solvent was distilled off, and the obtained solid was purified by a recrystallization method using a mixed solvent of methylene chloride and hexane to obtain 1.1 g of a pale yellow powder. This compound is referred to as "spironaphthoxazine compound (1)".

This spironaphthoxazine compound (1) was analyzed by nuclear magnetic resonance analysis, infrared absorption spectrum analysis and CHN elemental analysis to give 1- (2-phenoxyethyl) -3,3
-Dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b (1,4) oxazine] was identified.

The results of elemental analysis were as follows: carbon 80.12% by weight, hydrogen 6.16.
% By weight and 6.33% by weight of nitrogen, which were almost in agreement with theoretical values of 80.16% by weight of carbon, 6.03% by weight of hydrogen and 6.45% by weight of nitrogen. The NMR spectra are 1.3 ppm (6H), 3.6 ppm (2H), 4.1 ppm (2H), 6.6 ~ in deuterated chloroform (CDCl ₃ ).
It was 8.7 ppm (16H).

(B) Application Example 6 parts by weight of the spironaphthoxazine compound (1) obtained as described above and polymethylmethacrylate 16
And 100 parts by weight of 2-butanone were dissolved to prepare a photochromic film forming liquid, and the photochromic film forming liquid was cast on a glass plate to form a cast film having a thickness of 2 μm. This was dried in an oven at a temperature of 50 ° C. to completely remove the residual solvent, and then cooled to room temperature to form a photochromic film.

The photochromic film formed here has an excellent photochromic action, and turned dark blue when exposed to sunlight, and quickly returned to the original colorless and transparent state when left in the dark except for light.

In addition, when using this photochromic film as a sample, an accelerated exposure test was carried out with a weather meter "Super Long Life Sunshine Weather Meter" (manufactured by Suga Test Instruments Co., Ltd.), it was still 80% or more of the initial value even after 60 hours had passed. It was observed that the photochromic effect of the above was exhibited, and that excellent weather resistance, that is, repeated resistance of the color forming effect was obtained.

Comparative Example 1 Instead of 6 parts by weight of the spironaphthoxazine compound (1) in Example 1, the group bonded to the nitrogen atom was a methyl group instead of a 2-phenoxyethyl group.
1,3,3-Trimethylspiro [indoline-2,3 '-(3H)
A photochromic film was prepared in exactly the same manner as in Example 1 except that 2 parts by weight of naphtho [2,1-b] (1,4) oxazine] was used.

When this photochromic film was subjected to the accelerated exposure test with the same weather meter as in Example 1,
After 60 hours, only 50% of the initial photochromic effect was obtained.

Comparative Example 2 Instead of 6 parts by weight of the spironaphthoxazine compound (1) in Example 1, the group bonded to the nitrogen atom was a methyl group instead of a 2-phenoxyethyl group.
1,3,3-Trimethylspiro [indoline-2,3 '-(3H)
-A photochromic film was prepared in exactly the same manner as in Example 1 except that 6 parts by weight of naphtho [2,1-b] (1,4) oxazine] was used. Precipitates were generated during drying, and the formed film became cloudy.

Example 2 (A) 9'-Hydroxy-1- (3-phenoxypropyl) -3,3-dimethylspiro [indoline-2,3 '-(3
H) -Synthesis of naphtho [2,1-b] (1,4) oxazine] 1- (3-phenoxypropyl) -3,3-dimethyl-
11.74 g of 2-methylene indoline and 1-nitroso-2,7
-7.53 g of dihydroxynaphthalene was dissolved in 100 ml of ethanol, and this was reacted by boiling under reflux for 3 hours in a nitrogen gas atmosphere.

After completion of the reaction, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and an equal volume mixture of acetone and methylene chloride as a developing solvent. Then, the solvent was distilled off to obtain 2.6 g of a green paste. This compound is referred to as "spironaphthoxazine compound (2)".

This spironaphthoxazine compound (2) was analyzed by nuclear magnetic resonance analysis, ultraviolet absorption spectrum analysis and CHN elemental analysis to obtain 9'-hydroxy-1- (3-phenoxypropyl) -3,3-dimethylspiro [indoline. −
It was identified as 2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine].

The results of elemental analysis were as follows: carbon 77.53% by weight, hydrogen 6.15.
% By weight, 6.15% by weight nitrogen, which was almost the same as the theoretical values of 77.56% by weight carbon, 6.08% by weight hydrogen, and 0.03% by weight nitrogen. The NMR spectra are 1.2ppm (6H), 2.0ppm (2H), 3.2ppm (2H), 3.9ppm in deuterated dimethyl sulfoxide.
(2H), 6.5-7.7ppm (15H), 9.7ppm (1H).

(B) Application Example 10 parts by weight of the spironaphthoxazine compound (2) obtained as described above and 48 parts by weight of an epoxy resin precursor "Eponics # 1100 clear" (manufactured by Dainippon Paint Co., Ltd.) Was dissolved in 100 parts by weight of methyl ethyl ketone to prepare a photochromic film forming liquid, and the photochromic film forming liquid was applied on a slide glass by a dipping method.
This was heat-cured at a temperature of 80 ° C. for 16 hours to form a photochromic film having a thickness of 10 μm.

The photochromic film formed here has an excellent photochromic action, and turned dark blue when exposed to sunlight, and quickly returned to the original colorless and transparent state when left in the dark except for light.

Further, this photochromic film had excellent solvent resistance, and no change was observed in the photochromic action even when acetone was blown at room temperature.

Further, when this photochromic film was subjected to the accelerated exposure test by the same weather meter as in Example 1, it showed an excellent photochromic action of 70% or more of the initial value after 60 hours had passed.

Comparative Example 3 Instead of 10 parts by weight of the spironaphthoxazine compound (2) in Example 2, 9'-hydroxy-1,3 in which the group bonded to the nitrogen atom was a methyl group instead of a 3-phenoxypropyl group. In exactly the same manner as in Example 2 except that 4 parts by weight of 3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine] was used. A photochromic film was manufactured.

When this photochromic film was subjected to the accelerated exposure test with the same weather meter as in Example 1,
After 60 hours, only 38% of the initial photochromic effect was obtained.

Comparative Example 4 Instead of 10 parts by weight of the spironaphthoxazine compound (2) in Example 2, 9'-hydroxy-1,3 in which the group bonded to the nitrogen atom was a methyl group instead of a 3-phenoxypropyl group. Example 2 except that 10 parts by weight of 3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine] were used.
An attempt was made to produce a photochromic film in exactly the same manner as above, but a precipitate was generated during drying in an oven at 50 ° C, and the formed film became cloudy.

Example 3 (A) 1- (4-phenoxybutyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-
b] Synthesis of (1,4) oxazine] 7.96 g of 2,3,3-trimethylindolenine and 12.03 g of 4-phenoxybutyl bromide were dissolved in 100 ml of ethanol, and this was dissolved in a nitrogen gas atmosphere for 2 hours. Brought to reflux. Then, 50 ml of ethanol and 5.3 g of triethylamine
Was added and stirred for 30 minutes, and 8.66 g of 1-nitroso-2-naphthol was added and dissolved therein, and then the mixture was refluxed at the boiling point for 3 hours again in a nitrogen gas atmosphere.

After completion of the reaction, the solvent was concentrated to remove the generated triethylamine bromate, and then separation was performed by column chromatography using silica gel as a carrier and chloroform as a developing solvent. Then, the solvent was distilled off to obtain 1.9 g of a yellowish green paste. This compound is referred to as "spironaphthoxazine compound (3)".

This spironaphthoxazine compound (3) was analyzed by nuclear magnetic resonance analysis, infrared absorption spectrum analysis and CHN elemental analysis to give 1- (4-phenoxybutyl) -3,3
-Dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine].

The results of elemental analysis were as follows: carbon 80.41% by weight, hydrogen 6.78
% By weight and 5.88% by weight nitrogen, which were almost the same as the theoretical values of 80.49% by weight carbon, 6.54% by weight hydrogen and 6.06% by weight nitrogen. The NMR spectrum is 1.3 ppm (6
H), 1.7ppm (2H), 2.0ppm (2H), 3.5ppm (2H), 4.0
It was ppm (2H) and 6.6-8.7ppm (16H).

(B) Application Example A photochromic film was formed in the same manner as in the application example of Example 1 using the spironaphthoxazine compound (3) obtained as described above.

The photochromic film formed here has an excellent photochromic action, and turned dark blue when exposed to sunlight, and quickly returned to the original colorless and transparent state when left in the dark except for light.

Further, when this photochromic film was subjected to an accelerated exposure test using a weather meter similar to that in Example 1, it showed a photochromic effect of 67% or more of the initial level after 60 hours had passed.

Example 4 (A) 1- [2- (p-bromophenoxy) ethyl]-
Synthesis of 3,3-dimethylspiro [indoline-2,3 '-(3H) -naphtho [2,1-b] (1,4) oxazine] 1- [2- (p-bromophenoxy) ethyl] -2 , 3,
17.57 g of 3-trimethylindolenium bromide, 4.85 g of triethylamine, and 6.9 g of 1-nitroso-2-naphthol were dissolved in 150 ml of ethanol, and this was refluxed for 3 hours in a nitrogen gas atmosphere for reaction.

After completion of the reaction, the solvent was concentrated, and separation was performed by column chromatography using silica gel as a carrier and chloroform as a developing solvent. Then, the solvent was distilled off, and the obtained solid was purified by a recrystallization method using methylene chloride to obtain 1.5 g of a yellowish green powder. This compound is referred to as "spironaphthoxazine compound (4)".

This spironaphthoxazine compound (4) was analyzed by 1- [2- (p-bromophenoxy)) by nuclear magnetic resonance analysis, infrared absorption spectrum analysis and CHN elemental analysis.
Ethyl] -3,3-dimethylspiro [indoline-2,3'-
It was identified as (3H) -naphtho [2,1-b] (1,4) oxazine].

The results of elemental analysis were as follows: carbon 67.43% by weight, hydrogen 5.11
% By weight, 5.31% by weight of nitrogen, which were almost the same as the theoretical values of 67.84% by weight of carbon, 4.91% by weight of hydrogen, and 5.46% by weight of nitrogen. The NMR spectrum is 1.3 ppm (6
H), 3.6ppm (2H), 4.1ppm (2H), 6.6 ~ 8.7ppm (15
H).

(B) Application Example 2 parts by weight of the spironaphthoxazine compound (4) obtained as described above and polymethylmethacrylate 16
And 100 parts by weight of 2-butanone were dissolved, and a photochromic film was formed in the same manner as in the application example of Example 1.

The photochromic film formed here has an excellent photochromic action, and turned dark blue when exposed to sunlight, and quickly returned to the original colorless and transparent state when left in the dark except for light.

Further, when this photochromic film was subjected to the accelerated exposure test by the same weather meter as in Example 1, it showed an excellent photochromic action of 75% or more of the initial value after 60 hours had passed.

Claims (2)

[Claims] 1. A spironaphthoxazine compound represented by the following general formula (I): General formula (I) (In the formula, R ^{1 to} R ⁴ : hydrogen atom, lower alkyl group, lower alkoxy group or halogen atom R ^{5 to} R ⁷ : hydrogen atom or hydroxy group R: unsubstituted phenyl group, or halogen atom or hydroxy group as a substituent A phenyl group having a group n: an integer of 2 or more.) 2. A photochromic material comprising a spironaphthoxazine compound represented by the following general formula (I). General formula (I) (In the formula, R ^{1 to} R ⁴ : hydrogen atom, lower alkyl group, lower alkoxy group or halogen atom R ^{5 to} R ⁷ : hydrogen atom or hydroxy group R: unsubstituted phenyl group, or halogen atom or hydroxy group as a substituent A phenyl group having a group n: an integer of 2 or more.)