JPS62155283A - Photochromic composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a spirooxazine based compound and a phenolic compound as active ingredients, capable of giving a colored state stable even at high temperatures, having good contrast and providing a high coloring density and useful for recording memorizing material, etc. CONSTITUTION:A composition containing a spirooxazine based compound expressed by formula I (R<1> and R<2> are alkyl, allyl, aryl or aralkyl; ring A and ring B are benzene ring, naphthalene ring or heterocyclic ring which may be substituted; X is O or S), preferably a compound expressed by formula II (n is 1-4; R<2> and R<3> are alkyl; R<4>, R<5>, R<6> and R<7> are H, halogen, alkyl, etc.; Y is CH or N) and a phenolic compound, preferably a compound expressed by formula III or IV (Z is O, S, etc.; m is 0 or 1; X<1>-X<8> are H, halogen, etc.; Y<1>-Y<5> are hydrocarbon group, halogen, etc.) as active ingredients. The amount of the phenolic compound to be added is preferably within the range of 3-50wt% based on the dyestuff.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel photochromic composition.

In detail, each building has photochromic properties that can be used as recording/memory materials, copying materials, printing photoreceptors, laser photosensitive materials, photosensitive materials for photosetting, optical filters, masking materials, light meters, and display materials. The present invention relates to a novel photochromic composition having the following properties.

[Conventional technology]

It is known that spirooxazine compounds have photochromic properties that develop or discolor when irradiated with light.
Various photochromic light-sensitive materials using this material have been proposed.

For example, Tokuko Showa 4'! -Izag9U publication proposes a photochromic material containing a spironaphthoxazine compound as shown in the following formula.

(In the formula, Ra represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having carbon number/-1, or an alkoxy group.) -4cgA3/ publication proposes a photochromink light-sensitive material in which a spironaphthoxazine compound represented by the following formula is dispersed in a polymeric substance.

(In the formula, R is +all0OOH, +(E, nayuON
or +OH, Sun000R (R is an alkyl group with carbon number/~S), Ro and Rd are alkyl group with carbon number/-, 1, and Ro is a hydrogen atom, an alkyl group with 7 to 5 carbon atoms. , a halogen atom, a nitro group, a cyan group, an alkoxycarbonyl group having up to 6 carbon atoms, or a carbon number l-
5 alkoxy groups) Also, JP-A-Sho, 1tj-3
6λ Zahiro publication proposes a photochromic compound as shown in the following formula (in the formula, one of R and Rg is a halogen atom or lower alkoxy, the other one is hydrogen, and Rh
and R1 represents hydrogen, lower alkyl, lower alkoxy, or a halogen atom) Photochromic light-sensitive materials are usually produced by forming a film in which a 2-pyronaphthoxazine compound is dispersed in a polymer compound as described above. used.

However, conventional photochromic light-sensitive materials containing spirooxazine compounds have insufficient color development properties and are unable to provide good contrast and large color density. Furthermore, there was a problem in that the coloring properties at high temperatures were poor.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a photochromic composition that exhibits good coloring properties at high temperatures.

[Means for solving problems]

That is, the present invention relates to the general formula [l] (wherein R1 and R'' represent an alkyl group, an allyl group, an aryl group, or an aralkyl group, and rings A and B are optionally substituted benzene rings, naphthalene rings, etc.). A photochromic composition is characterized in that it contains a spirooxazine compound represented by a ring or a heterocycle, and X represents 0- or S, and a phenolic compound.

The above photochromic composition of the present invention
The spirooxazine compound represented by the formula cI) preferably has the general formula [1l) (C crystal 0) nR'' (in the formula, n represents an integer of l-da, and Ro and R represent an alkyl group). R4, R@, R@ and R9 represent a hydrogen atom, halogen atom, alkyl group, alkoxy group or alkoxycarbonyl group, Y represents OH or N)
Examples include compounds represented by:

On the other hand, the phenolic compound preferably has the general formula [l) or I:1V)Xl XI
I xt Y'Y exclamation or /, X'SX'SX', Xl, Za, Z
a, X7 and Xl represent a hydrogen atom, a halogen atom, a hydrocarbon group;
Examples include compounds represented by a halogen atom, an alkoxy group, a phenoxy group, or a hydroxy group.

Furthermore, among the phenolic compounds, bisphenol compounds represented by the above general formula [1] are particularly preferred, and specific examples are as follows.

The amount of the phenolic compound added is 0.0% by weight based on the pigment. /~/! It is used in the range of Oq6, preferably in the range of J-70.

The photochromic composition of the present invention can be prepared by dispersing or dissolving the spirooxazine compound and phenolic compound in a suitable binder.

Examples of the binder include polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, etc., and preferably polyester resin. resin,
Examples include polyvinyl butyral resin and polyvinylidene chloride resin.

The novel compositions of the present invention exhibit photochromism. That is, the photochromic composition of the present invention develops a color when irradiated with ultraviolet rays, and returns to its original colorless state when it is irradiated with visible light or heated, and this change can be reversed.

〔Effect of the invention〕

The composition of the present invention improves the stability of the color development state, so that a high contrast and high color density can be obtained, and the color development stability at high temperatures is also good.

Such compositions can be used in various recording/memory materials, copying materials,
Printed photoreceptors, photosensitive materials for lasers, photosensitive materials for phototypesetting or optical filters, masking materials, light meters,
Used as display material.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example/Spironaphthoxazine compound represented by the following structural formula %Formula % 11 The following structural formula/e11. A solution consisting of 100 g of a mixed solvent (toluene:tetrahydrofuran:cyclohexanone=-2:u:/) was applied to a polyester film (manufactured by Diafoil Co., Ltd., thickness 100μ) using a bar coater &J, and heated at 75°C. Dry for 10 minutes. The obtained sample was colorless under normal conditions, but when irradiated with ultraviolet light, it developed a high-density blue color (λmax = 6/g nm). The color development stability was also good, and the color development at high temperatures was also good.

Then, when exposed to visible light, it returned to its original colorless state.

This change was able to be repeated. Example Bisphenol Ao in Example/up.

Instead, bisphenol BO,1Ili represented by the following structural formula was used and applied to a polyester film in the same manner as in Example 1. When irradiated with ultraviolet rays, it turned dark blue (λmax
= 4/7 nm). Then, when exposed to visible light, it returned to its original colorless state.

This change was repeatable.

Examples 3-/S Using the method according to Example/and λ, using the photochromic dye and phenolic compound shown in Table 1,
When coated on a polyester film and irradiated with ultraviolet light, each color developed to the color tone λmax shown in Table 1. Then, when exposed to visible light, it returned to its original colorless state. This change was repeatable.

Comparative Example/A sample was obtained by coating on a polyester film in the same manner as in Example 1, except that a predetermined amount of the spironaphthoxazine compound shown in Table 1 was used. This sample was irradiated with ultraviolet rays, and the color density of the sample that developed color is shown in Table 1.

Similarly, Table 2 also shows the color density when bisphenol S was added to the spironaphthoxazine compounds of Examples and Examples.

The color density of Example 11 of the present invention is as shown in the table above, when the color density of Comparative Example is 100, and it develops a deep color when irradiated with ultraviolet rays. A film was obtained.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (1 other person)

Claims (3)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1 and R^2 represent an alkyl group, an allyl group, an aryl group, or an aralkyl group, Ring A and Ring B represent an optionally substituted benzene ring, naphthalene ring, or heterocycle, and X represents 0 or S) and is characterized by containing a spirooxazine compound and a phenolic compound. Photochromic composition. (2) In the photochromic composition according to claim 1, the spirooxazine compound has the general formula [I
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (In the formula, n represents an integer from 1 to 4, R^1 and R^3
represents an alkyl group, R^4, R^5, R^6 and R^
7 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkoxycarbonyl group, and Y represents OH or N). (3) In the photochromic composition described in claim 1, the phenolic compound has the general formula [III] or [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [III] ▲ Numerical formulas, chemical formulas, There are tables etc.▼... [IV] (In the formula, Z represents O, S, sulfonyl, carbonyl, alkylene or alkenylene, m represents 0 or 1, X^1, X^2, X^3 , X^4, X^5, X^6,
X^7 and X^8 represent a hydrogen atom, a halogen atom or a hydrocarbon group, and Y^1, Y^2, Y^3, Y^4 and Y
^5 represents a hydrocarbon group, halogen atom, alkoxy group, phenoxy group or hydroxy group).