JPH0559355A - Photochromic material - Google Patents

Abstract

PURPOSE:To obtain a photochromic material, composed of a spiroxazine compound having a specific structure, useful for printing, optical instruments, recording materials, etc., excellent in fatigue resistance of coloring and decoloring with light and absorption wavelength of coloring species hardly affected by matrices. CONSTITUTION:A photochromic material is composed of a spiroxazine compound expressed by the formula (R<2> to R<5> are 1-40C alkenyl, 1-2C halogen-substituted alkyl, 1-4C alkoxy, halogen or nitro; n and q are 0-2; m and t are 0-4; R<1> is 1-20C alkyl, 3-10C cycloalkyl, 7-20C aralkyl or 6-14C aryl).

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photochromic compound useful as a photochromic material for printing, a photochromic material for optical devices, a photochromic material for recording materials or clothing, and a photochromic material for ornaments.

[0002]

2. Description of the Related Art A typical photochromic compound is a spiropyran compound, and many compounds are known (G.H. Brown, "Photochromism", Willy Interscience, New York).
(GH Brown, “Photochromis
m ”, Wiley Interscience, New
York (1971)).

As spirooxazine compounds, JP-B-45-28892, JP-B-49-48631, JP-A-48-23787 and JP-A-55-3.
6284, East German Patent 0153-690, East German Patent 1563-72.

[0004]

[Problems to be Solved by the Invention] The spiropyran compound has a problem in fatigue resistance in repeated use of photo-bleaching. Further, the fatigue resistance of the known spirooxazine compound is improved as compared with the above compounds.

However, conventional coloring species of spiropyran and spirooxazine compounds have a large matrix effect, and the absorption wavelength largely changes depending on the polarity of the solvent, for example. Therefore, the types of matrices that can be automatically used when the color tone of the coloring species is determined are limited.

[0006]

The present invention relates to a photochromic material for solving the above problems. That is, the photochromic material provided by the present invention is represented by the following general formula (A).

[0007]

[Chemical 2] (In the formula, R ² , R ³ , R ⁴ , and R ⁵ are alkyl groups having 1 to 4 carbon atoms, halogen-substituted alkyl groups having 1 or 2 carbon atoms,
Represents a substituent selected from an alkoxy group having 1 to 4 carbon atoms, a halogen group and a nitro group, n is an integer of 0 to 2, m and t are an integer of 0 to 4, and q is an integer of 0 to 2. , R ² ,
R ³ , R ⁴ and R ⁵ may be the same or different. R ¹ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, and an unsubstituted or substituted aralkyl group having 6 to 14 carbon atoms. It represents a substituent selected from a substituted or substituted aryl group. ) Specific examples of the substituent R ¹ in the formula (A) include a chain alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, octyl group, hexadecyl group and eicosyl group; iso-propyl Group, tert-butyl group, 4,4-dimethylhexyl group,
Branched alkyl group having 3 to 20 carbon atoms such as 5,7-diethylhexadyl group; 3 carbon atoms such as cyclopropyl group, cyclohexyl group, cyclooctyl group and cyclodecyl group
Cycloalkyl group of 10; benzyl group, 2-phenylethyl group, (1-naphthyl) methyl group, 2- (1-naphthyl) ethyl group, (2-naphthyl) methyl group, 2- (2
-Naphthyl) ethyl group, (9-anthracyl) methyl group, (9-phenanthryl) methyl group, (5-naphthacyl) ethyl group and other aralkyl groups having 7 to 20 carbon atoms; phenyl group, 1-naphthyl group, 2- Examples thereof include aryl groups having 6 to 14 carbon atoms such as naphthyl group and 9-anthracyl group. When R ¹ is an acyclic alkyl group, specific examples of the substituent contained in the substituent derivative include a hydroxy group; an amino group; an organic substituted amino group such as a methylamino group and a diethylamino group; a methoxy group, an ethoxy group. Base,
C1-C4 alkoxy group such as tert-butoxy group;
Aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group; C6 to carbon atoms such as phenoxy group and 1-naphthoxy group
14 aryloxy group; halogen group such as fluoro group, chloro group and bromo group; cyano group; carboxy group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl group; 2 to 2 carbon atoms such as acetyl group and benzoyl group
10 acyl groups; a nitro group and the like.

Further, when R ¹ is a cycloalkyl group, an aralkyl group or an aryl group, specific examples of the substituent contained in the cycloalkyl group, the aryl part of the aralkyl group and the substituent derivative of the aryl group include a hydroxy group. Organic substituted amino groups such as methylamino group and diethylamino group; alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, tert-butoxy group; aralkoxy groups having 7 to 15 carbon atoms such as benzyloxy group; phenoxy group An aryloxy group having 6 to 14 carbon atoms such as 1-naphthoxy group; a lower alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group and tert-butyl group; fluoro group, chloro group,
Halo group such as bromo group; cyano group; carboxy group;
Alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl group; Acyl group having 2 to 10 carbon atoms such as acetyl group and benzoyl group; Halogen-substituted alkyl group having 1 or 2 carbon atoms such as trifluoromethyl group; Nitro group And so on. Further, these substituents may be included not only as a mono-substituted product but also as a poly-substituted product having a plurality of 2- or more-substituted substituents. Moreover,
There is no problem even if the substituents in the multi-substituted product are the same or different. The position of the substituent should be changed depending on the purpose or use.

Next, R ² , R ³ , R in the general formula (A)
^{Although 4} and R ⁵ are as described above, they may be the same or different.

The compound of the formula (A) is different in that the conventionally known spirooxazine compound has an indoline ring as a constituent, whereas it has a benz (g) indoline ring as a constituent. That is, since the number of benzene rings is increased by one as compared with the conventional spirooxazine compound, the colored species are less likely to undergo the matrix effect due to the three-dimensional structure.
For example, it has a great feature that there is almost no difference in the color tone of the coloring species in a polar solvent such as methanol and a non-polar solvent such as toluene.

Typical examples of the compound represented by the formula (A) include spiro [benz (g) indoline-2,3 '-[3H] -naphtho [2,1-b] (1,
4) Oxazine] 's 1,3,3-trimethyl derivative, 1
-Hexyl-3,3-dimethyl-5-chloro derivative, 1
-(3-Promooctdecyl) -3,3-dimethyl-5-
Trifluoromethyl derivative, 1- (10-phenyleicosyl) -3,3-dimethyl-5-methoxy derivative, 1
-Isopropyl-3,3,5-trimethyl derivative, 1-
tert-Butyl-3,3-dimethyl-5'-carboxy derivative, 1- (4-chlorocyclohexyl) -3,3-dimethyl-8'-nitro derivative, 1- (3-aminocyclooctyl) -3,3 -Dimethyl-8'-bromo derivative,
1-benzyl-3,3-dimethyl-9'-fluoro derivative, 1- (3-methylbenzyl) -3,3-dimethyl-
7'-ethoxy derivative, 1- (4-acetylbenzyl)
-3,3-Dimethyl-5-ethoxy-8'-butyl derivative, 1- (3,5-bistrifluoromethylbenzyl)
-3,3-Dimethyl-5-chloro derivative, 1- (2
3,4,5,6-pentafluorobenzyl) -3,3-
Dimethyl-5-trifluoromethyl derivative, 1- (2-
Naphthyl) methyl-3,3-dimethyl-5-methoxy derivative, 1- (3-methoxy-2-naphthyl) methyl-
3,3,5-Trimethyl derivative, 1- (5-tert-butyl-1-naphthyl) ethyl-3,3-dimethyl-5'-
Carboxy derivative 1- (9-anthracyl) methyl-
3,3-Dimethyl-8'-nitro derivative, 1- (9-phenanthryl) methyl-3,3-dimethyl-8'-bromo derivative, 1-phenyl-3,3-dimethyl-9'-fluoro derivative, 1 -(4-Nitrophenyl) -3,3-
Dimethyl-7'-ethoxy derivative, 1- (2,4,6-
Trimethylphenyl) 3,3-dimethyl-5-ethoxy-8'-butyl derivative, 1- (1-naphthyl) -3,3
-Dimethyl-5-chloro derivative, 1- (4-bromo-2
-Naphthyl) -3,3-dimethyl-5-trifluoromethyl derivative, 1- (9-cyano-1-anthracyl)-
3,3 dimethyl-5-methoxy derivative and the like can be mentioned.

The novel spirooxazine compound of the present invention represented by the formula (A) is a photochromic compound which is excellent in fatigue resistance against color development and erasure by light, and whose absorption wavelength of the color-developing species is hardly influenced by the matrix.

The compound of the formula (A) of the present invention is produced, for example, according to the following production method.

General formula (I)

[Chemical 3] A 2-methylenebenz (g) indoline compound represented by the formula (II)

[Chemical 4] A compound of formula (A) is produced by reacting a nitrosonnaphthol compound represented by

As another example of the method for producing the compound of the formula (A) of the present invention, the general formula (IV)

[Chemical 5] And a trimethylbenz (g) indolenine compound represented by the formula (I), a quaternizing agent R ¹ -X (X is an anionic leaving group), a base and a compound of the general formula (II) are added in any order and reacted. be able to.

Preferred examples of the purification method in the production stage include recrystallization with various solvents, column chromatographic separation with silica rum, or treatment with activated carbon.

The photochromic material of the present invention is an optically transparent resin such as diethylene glycol bisallyl carbonate polymer, polymethacrylate and copolymers thereof, celluloses, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyester resin, polycarbonate, Polystyrene and its copolymer, epoxy resin, (halogenated) bisphenol A di (meth) acrylate polymer and its copolymer,
(Halogenated) bisphenol A urethane-modified di (meth) acrylate polymers and copolymers thereof, nylon resins, polyurethanes and the like are preferably blended and used. The blended resins can be used as an optical element having a color change property by light. Suitable examples of the optical element include sunglasses lenses, ski goggles, protective glasses lenses, curtains, clothes, toys, and the like.

Various methods such as a dyeing method, a casting method, and a coating method of a blended polymer solution can be applied as a method of blending the photochromic material of the present invention with a resin.

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, it is 0.01 to 20% by weight.
Is preferable.

[0020]

【Example】

Example 1 1,3,3-Trimethylspiro [benz (g) indoline-2,3 ′-[3H] -naphtho [2,1-b]
Synthesis of (1,4) oxazine] 1,3,3-trimethyl-2-methylenebenz (g) indoline 5 g and 1-nitroso-2-naphthol 5 g
Is dissolved in 100 ml of ethanol and refluxed in a nitrogen stream for 2 hours. After the reaction, cooling causes crystals to precipitate. A small amount of ethanol is added to this, and it is collected by filtration. A solution of the obtained crude crystal in ethanol is heated to 50-60 ° C., 10 g of activated carbon is added, and the mixture is sufficiently stirred. After that, the mixture was filtered, and the pale yellow solid obtained by concentrating the filtrate was recrystallized from ethanol to give 1,3,3-trimethylspiro [benz (g) indoline-2,3 ′-[3H] -naphtho [2,2].
1-b] (1,4) oxazine] was obtained as pale yellow crystals.

Analysis result (melting point) 218 ° C. Application Example The compound of this example was dissolved in methyl alcohol at a concentration of 0.1% by weight. The solution was irradiated with ultraviolet rays using a chemical lamp, and the solution immediately turned light blue (light blue). In addition, this product immediately returned to the original colorless state when the light irradiation was removed. Even when the color development and color erasing tests were repeated 50 times, the same photochromic properties as those of the first time were exhibited and the fatigue resistance was excellent.

Next, when the solvent was changed from methyl alcohol to toluene, the same phenomenon was observed, and it was found that there was almost no effect of the matrix.

[0023]

INDUSTRIAL APPLICABILITY The photochromic material of the present invention is colorless in a general state regardless of the type of solvent and matrix polymer, but immediately upon being irradiated with ultraviolet rays, it changes to a material having an absorption wavelength in the visible light region. However, when the irradiation of ultraviolet rays is stopped, it immediately returns to the original colorless state.

The photochromic material of the present invention has the characteristics that the coloring speed is high, the decoloring speed is high, the absorption wavelength of the coloring species is not easily influenced by the matrix, and the fatigue resistance is good. It is a material. Further, the photochromic material of the present invention has excellent acid resistance and can be easily added to an organopolysiloxane system.

Claims (1)

[Claims] 1. A photochromic material comprising a spirooxazine compound represented by the general formula (A). [Chemical 1] (In the formula, R ² , R ³ , R ⁴ , and R ⁵ are an alkyl group having 1 to 40 carbon atoms, a halogen-substituted alkyl group having 1 or 2 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, a nitro group. Represents a substituent selected from, n is an integer of 0 to 2, m
And t is an integer of 0 to 4, q is an integer of 0 to 2, R ² , R
³ , R ⁴ and R ⁵ may be the same or different. R ¹ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, and an unsubstituted or substituted aralkyl group having 6 to 14 carbon atoms. It represents a substituent selected from a substituted or substituted aryl group. )