JPS6330584A - Photochromic substance - Google Patents

Abstract

PURPOSE:To obtain a photochromic substance which has a high capacity of absorbing the light in a long-wavelength region and excellent resistance to repeated use, and gives a photochromic optical material having an excellent light controlling function, by using a specified spironaphthoxazine compound. CONSTITUTION:A spironaphthoxazine compound of the formula (wherein R1 is H, a halogen, cyano, a 1-6C alkyl or 1-6C alkoxy; R2 is a substituted arylalkyl, a 1-6C alkyl, a 2-6C alkoxyalkyl, etc.) is used as a photochromic substance.A spironaphthoxazine compound of the formula is synthesized by reacting 2,6-dihydroxy-1,5-dinitrosonaphthalene with a corresponding indoline compound. A photochromic optical material having an excellent light controlling function can be obtained by incorporating this photochromic substance into a matrix comprising an optically transparent resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel photochromic material, and in particular, a non-colored material has high absorption characteristics for light in a long wavelength region of 35 On+a or more. The present invention relates to a photochromic substance made of a spironaphthoxazine compound that has excellent resistance to repeated use.

[Prior art]

Many compounds with photochromic properties have been found in inorganic and organic materials. Silver halide is a typical example of an inorganic photochromic substance, but silver halide requires a special glass as a matrix (medium) material, which limits its range of use. be. On the other hand, organic photochromic substances have advantages that inorganic photochromic substances do not have, such as vivid color development and a greater degree of freedom in selecting matrix materials, but they have very low resistance to repeated photochromic effects. This is a fatal flaw, and for this reason it is currently not in practical use.

Among various organic photochromic substances, spironaphthoxazine compounds are known as those with relatively good repetition resistance. 23
1.3.3-)limethylspiro[indoline-2,3'-( 3H)-naphtho(2,1-b)(I,
4) Oxazine] and its derivatives are disclosed,
Attempts have been made to improve the cycling resistance and absorption properties of colored species.

[Problem that the invention seeks to solve]

Although spironaphthoxazine compounds exhibit superior repetition resistance compared to other organic photochromic substances, they have the disadvantage that coloration at room temperature is not so great. This is because the rate of fading is extremely high, and the colored species reverts to non-colored species immediately after generation, making it impossible to obtain a state of sufficiently large coloring even when irradiated with ultraviolet rays.

This drawback is particularly noticeable when the amount of light emitted is not so large in the ultraviolet region (wavelength 400n+++ or less) such as sunlight, and for this reason, the photochromic material is not used, for example, for dimming. However, there was a problem in that the density at the time of coloring was low and a high light attenuation rate could not be obtained.

To address this problem, conventional methods have been to increase the absorption coefficient of colored species by introducing various substituents into the spironaphthoxazine compound, or to stabilize colored species by adding additives. It is being considered to increase the coloring density by this. However, the former method does not have such a great effect, and the latter method, although it does have some effect, suppresses the speed of fading that is characteristic of spironaphthoxazine and has a dimming effect. It cannot be said that it is an advantageous means for obtaining the desired photochromic substance.

[Means and actions for solving problems]

The present invention solves the above problems and provides a photochromic material having novel and excellent properties. The photochromic substance of the present invention is composed of a spironaphthoxazine compound represented by the following general formula (I).

[In the formula, R1 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R2 represents a variously substituted alkyl group or a cyano group having 1 to 6 carbon atoms. represents an alkyl group, an alkoxyalkyl group having 2 to 6 carbon atoms, or +CM, ±, 1COOR, provided that R
represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6. Representative examples of such spironaphthoxazine compounds include Ll', 3,3.3', 3" to Methyl dispiro [
Indoline-2,2°-(2H,8H)-naphtho(2,
1-b: 6°s-b”) (I,4) Dioxazine-8
°12"-indoline], 5.5"-dichloro-1,do,3,3.3',3'-hexamethyldispiro[indoline~2.2'-(2H,
8H)-naphthoC2,1-b:6.5-b”) (I,
4) Dioxazine-8゛,2''-indoline], 1.1'''', 3.3.3'', 3', 6.6''-octamethyldispiro[indoline-2,2''-(2H,8
H)-naphtho [2,1-b: 6.5-b')
(I,4) dioxazine-8°,2''-indoline], l,1@-dibenzyl-3,3,3'',3''-tetramethyldispiro[indoline-2,2°-(2H,8H)
-NaphthoC2,1-b: 6.5-b') (I,
4) Dioxazine -8°,2"-indoline], 1.1'-di(2-methoxyethyl") -3,3,3
”,3”-tetramethyldispiro[indoline-2,2
'-(2H.

8H)-naphtho(2+1-b:6+5-b'') (I,
4) Dioxazine-8'', 2''-indoline], and others, but are not limited to these.

The above spironaphthoxazine compound can be synthesized by reacting 2,6-cyhydroxy-1,5-dinitrosonaphthalene and the corresponding indoline compound. Specifically, the amount of the latter raw material at least twice that of the former raw material may be reacted by refluxing the boiling point in an appropriate solvent such as ethanol or toluene. Furthermore, instead of the indoline compound, a corresponding indolinium salt compound may be used.
As shown in Publication No. 18783, following the synthesis of indolinium salt, the resulting indolinium salt is isolated and
It is also possible to synthesize it without purification by reacting it with a nitrosated product of 2,6-naphdodiol. In these reactions, a base such as triethylamine can also be added as a catalyst. Furthermore, the synthesized spironaphthoxazine compound can be purified by techniques such as recrystallization, column separation, activated carbon treatment, etc. to obtain a pure product, if necessary.

The photochromic substance of the present invention comprising the above spironaphthoxazine compound can be made of optically favorable resins, such as polymers made from polyol (allyl carbonate) monomers, various acrylic resins such as polymethyl methacrylate, cellulose resins, polyacetic acid resins, etc. It is blended into a matrix made of polymers such as vinyl, polyvinyl alcohol, polyurethane, epoxy resin, polyester such as polystyrene and polyethylene terephthalate, epoxy resin, urethane resin, polyvinyl butyral, and nylon, which provides excellent light control function. A photochromic optical material is obtained.

Specifically, in order to obtain a photochromic optical material using the photochromic substance of the present invention, the photochromic substance is mixed with the above-mentioned resin and molded by casting or melting to form a film, plate, etc. A means for dyeing optical materials such as films and lenses made of various resins by immersing them in a solution of the photochromic substance, or a resin solution containing the photochromic substance for various substrates. A method of forming a photochromic layer by coating a photochromic substance, a method of laminating a film or the like containing the photochromic substance on a substrate, and other methods can be used. It is also possible to obtain a molded photochromic lens by mixing the photochromic substance with a monomer or thermosetting resin precursor that polymerizes to form a resin, and then directly cast-polymerize the mixture. . When obtaining these photochromic optical materials, it is also possible to coexist with the photochromic substance an antioxidant and an ultraviolet absorber for the purpose of blocking unnecessary light components in the short wavelength region.

These photochromic optical materials can be suitably used as optical materials for optical instruments such as various displays, memories, 8-round optical lens filters, light meters, etc.

Example 1 A) Bottom of 1,5-dinitroso-2,6-nafdodiol 2.8 g of 6-nafdodiol was dissolved in a mixed solvent of 100 m of acetic acid and 100 m of ethanol, and dissolved in a water bath for 5
A solution prepared by dissolving 13.8 g of sodium nitrite in 50 m7 of water was then added dropwise into the solution, which had been cooled to below 0.degree. C., over a period of 2 hours, and was stirred for an additional 4 hours to complete the reaction. This system was allowed to stand overnight, and the precipitate that precipitated was filtered off, and the resulting solid was washed with water and ethanol, and dried under vacuum at a temperature of 50° C. to obtain 5.7 g of product. This product was determined by thin layer chromatography and CHN elemental analysis to be 2.
．． It was found to be a mixture of mononitrosated, dinitrosated and unsubstituted 6-naphdodiol.

Note that this product was used in the subsequent steps without being purified.

4.36 g of the nitrosated product of 2,6-naphthodiol synthesized in Step A and 10.35 g of 1.3.3-)limethylindoline were dissolved in 50 tZ of absolute ethanol and refluxed for 2 hours in a nitrogen environment. After the reaction, concentrate the solvent, use silica gel as a carrier, and develop benzene? Column separation was performed using 8 soot.

After distilling off the solvent, the obtained solid was recrystallized from a mixed solvent of benzene and hexane to obtain 0.9 g of pale yellow powder.
I got it.

This product was analyzed by mass spectrometry, CIIN elemental analysis, NMR1
By infrared spectroscopy, 1.1", 3,3.3", 3'-hexamethyldispiro[indoline-2,2'-(2H
,8H)-naphtho(2,1-b :6+5-b') (
I,4) dioxazine-8',2''-indoline].

The results of elemental analysis are 77.21% by weight of carbon and 6% of hydrogen.
．． 26% by weight, and 10.20% by weight of nitrogen, but these values correspond to the theoretical values of 77.23% by weight of carbon and 6.11% of hydrogen.
% by weight, nitrogen was almost 10.60% by weight.

C] Application Example 1 part by weight of the compound obtained as described above and 20 parts by weight of polymethyl methacrylate were dissolved in 100 parts by weight of benzene to form a cast film with a thickness of 10 μm on a glass plate. This was placed in an oven at a temperature of 50°C to completely remove the residual solvent, and then returned to room temperature.

This film has excellent photochromic properties; it takes on a green color when exposed to sunlight, and quickly returns to its original colorless appearance when exposed to sunlight and placed in a dark place.

The absorption spectrum of this film in the visible and ultraviolet regions is shown by the solid line in Figure 1, and the spirooxazine compound 1,3.3-)limethylspiro[indoline-2,3゛-(3H)- The absorption spectrum of a film similarly prepared from 1 part by weight of naphtho(2,1-b)(I,4)oxazine] and 20 parts by weight of polymethyl methacrylate is shown by the broken line in Figure 1. From a comparison of these curves, As is clear, in the film made of the photochromic material of the present invention, the absorption in the ultraviolet region of the non-colored species is shifted to the longer wavelength side.

From this, it is recognized that this photochromic substance has considerably better dimming function due to sunlight than conventional spirooxazine compounds.

Example 2 2.18 g of the nitrosate of 2,6-naphthodiol synthesized in Step A of Example 1 and 5-chloro-1,3
, 3-) 6.2 g of dimethyl-2-methyleneindoline was dissolved in 50-g of absolute ethanol and refluxed for 20 hours in a nitrogen environment. After the reaction, the solvent was concentrated, and silica gel was used as a carrier and benzene was used as a developing solvent. Column separation was performed.

After distilling off the solvent, the obtained solid was recrystallized from a mixed solvent of benzene and hexane to obtain 0.5 g of pale yellow powder.

This product was determined by mass spectrometry and NMR1 infrared spectroscopy.
5.5″-dichloro-C1″, 3,3.3″, 3′-hexamethyldispiro[indoline-2,2′-(2H,
8H)-naphtho(2,1-b:6.5-b') (
I,4) dioxazine-8',2''-indoline].

The results of elemental analysis are 68.31% by weight of carbon and 5% by weight of hydrogen.
．． 21% by weight and 9.21% by weight of nitrogen, but these values are almost in agreement with the theoretical values of 68.34% by weight of carbon, 5.06% by weight of hydrogen, and 9.38% by weight of nitrogen.

The compound obtained as described above was dissolved in benzene together with polymethyl methacrylate in the same manner as in Example 1 to produce a cast film. When this film was exposed to sunlight, it immediately turned green, and when exposed to sunlight and left in a dark place, it quickly returned to its original colorless and bright state.

Example 3 15.9 g of 2.3.3-trimethylindolenine and 17.2 g of penzylfluoromide were dissolved in absolute ethanol, nitrogen was bubbled for 30 minutes, and then the boiling point was refluxed for 2 hours. This melt? After cooling overnight to a temperature near room temperature, 10.1 g of triethylamine, 50 g of absolute ethanol, and 5.5 g of the nitrosate of 2°6-naphthodiol synthesized in Step A of Example 1 were added, and further nitrogen was bubbled. The mixture was stirred at room temperature for 30 minutes. After boiling under reflux for 2 hours, the solvent was reduced by 7 hours, and column separation was performed using silica gel and benzene as a developing solvent.

After distilling off the solvent, the obtained solid was recrystallized from a mixed solvent of benzene and hexane to obtain 0.8 g of pale yellow powder.

This product was determined by mass spectrometry and NMR2 infrared spectroscopy.
1.1"-dibenzyl-3,3,3',3"-tetramethyldispiro[indoline-2,2'-(2H,8H)
-naphtho(2,1-b:6+5-b')(L4)dioxazine-8',2'-indoline].

The results of elemental analysis are 81.05% by weight of carbon and 6% by weight of hydrogen.
．． 01% by weight and 8.02% by weight of nitrogen, these values are almost in agreement with the theoretical values of 81.15% by weight of carbon, 5.92% by weight of hydrogen, and 8.23% by weight of nitrogen.

The compound obtained as described above was dissolved in benzene together with polymethyl methacrylate in the same manner as in Example 1 to produce a cast film. When this film was exposed to sunlight, it immediately turned green, and when exposed to sunlight and left in a dark place, it quickly returned to its original colorless and transparent film.

[Brief explanation of drawings]

FIG. 1 is a curve diagram showing the absorption spectrum of a spirooxazine compound in polymethyl methacrylate when colored, and the solid line is the photochromic material of the present invention, 1,1''.
,3,3.3'',3''-hexamethyldispiro[indoline-2,2'-(2H,8H)-naphtho[2゜1-
b: 5.5-b') (L4) Dioxazine-8°, 2
”-indoline] absorption spectrum, the dashed line is L3,3-
trinotylspiro [indoline-2,3'-(3H)-
The absorption spectrum of naphtho(2,1-b)(L4)oxazine] is shown.

Claims (1)

[Scope of Claims] 1) A photochromic substance comprising a spironaphthoxazine compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom, a halogen atom, a cyano group,
It represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R_2 is various substituted arylalkyl groups,
Indicates an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, or -(CH_2)-_nCOOR. However, R represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6. ]