JPH085896B2 - Photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a light-sensitive material using a novel spirooxazine compound.

More specifically, it relates to a light-controlling material such as light-controlling glass for automobiles and building materials, an optical filter, a masking material, or a photosensitive material using a novel spirooxazine-based compound having photochromic properties that can be used as a photometer. .

[Conventional technology]

It is known that spirooxazine compounds have a photochromic property of developing or decoloring upon irradiation with light, and various photochromic photosensitive materials using the same have been proposed.

For example, Japanese Examined Patent Publication (Kokoku) No. 45-28892 proposes a photochromic material containing a spironaphthoxazine compound represented by the following formula.

(In the formula, R ^a represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group.) Further, Japanese Patent Publication No. 49-48631 discloses a spironaphthoxazine having the following formula. A photochromic photosensitive material in which a base compound is dispersed in a polymer has been proposed.

(In the formula, R ^b is CH _{2 n} COOH, CH _{2 n} CN or CH _{2 n} C.
OOR (R is an alkyl group of 1 to 5 carbon atoms): R ^c and R ^d is an alkyl group having 1 to 5 carbon atoms: R ^e is a hydrogen atom, 1 to carbon atoms
5 alkyl groups, halogen atoms, nitro groups, cyano groups, alkoxycarbonyl groups having 2 to 6 carbon atoms or alkoxy groups having 1 to 5 carbon atoms are shown. Further, Japanese Patent Laid-Open No. 55-36284 proposes a photochromic compound represented by the following formula.

(In the formula, one of R ^f and R ^g is a halogen atom or a lower alkoxy group and the other is a hydrogen atom, and R ^h and R ⁱ are a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. Further, USP 4,342,668 proposes a photochromic compound represented by the following formula.

(In the formula, one of R ^j and R ^k is a halogen atom or a lower alkoxy group, the other is a hydrogen atom, and R ^l and R ^m are a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. represents an atomic, R ⁿ represents an alkyl group having from 2 to 10 carbon atoms.) typically, the photochromic photosensitive material, those of spironaphthoxazine compound into the polymer compound dissolved or dispersed as described above into a film Used by forming a film.

[Problems to be Solved by the Invention]

However, in the case of the conventional spirooxazine compound, since the compatibility with the polymer compound is poor, the color density and the fastness of the colored state are not always sufficient.

Therefore, a robust photochromic light-sensitive material having good contrast and showing a large color density cannot be obtained.

[Means for solving the problem]

The present invention provides a photosensitive material between two transparent substrates, at least one of which is represented by the following general formula [I]. (In the formula, m represents 0 to 3, and n represents an integer of 0 to 6.
However, m and n do not represent 0 at the same time. R ¹ represents a hydrogen atom and a C _{1 to} C ₃ alkyl group, R ² , R ³ represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, or R ² , R ³ May be bonded to each other and may be cyclized. A represents an alkylene group,
B represents a heteromonocycle, and rings X and Y represent a hydrocarbon aromatic ring or a heteroaromatic ring which may be substituted with an alkyl group or an alkoxy group. ) A photosensitive material comprising a substrate and a photosensitive layer containing a spirooxazine-based compound represented by

 Hereinafter, the present invention will be described in detail.

The spirooxazine compound used in the present invention is represented by the above general formula [I].

In the formula, R ¹ represents a hydrogen atom or a C ₁ to C ₃ alkyl group of a methyl group, an ethyl group, a linear or branched propyl group, and R 1
^2, R ³ is an alkyl group such as an alkyl group of C ₁ ~ _23: methoxyethyl group, an alkoxyalkyl group such as an ethoxyethyl group: cyclohexyl group, cycloalkyl groups such as cyclopentyl group: phenyl, p- methylphenyl group, A substituted or unsubstituted aryl group such as naphthyl group and m-methoxyphenyl group is shown. Or R ² and R ³ are linked to each other to form a ring,
A cyclohexyl group, a cyclopentyl group, a cycloheptyl group, etc. may be formed. As R ² and R ³ , a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a phenyl group, or a cyclohexyl group in which R ² and R ³ are bonded to each other is preferable.

Examples of the alkylene group of A include the following.

Examples of the hydrocarbon aromatic ring or heteroaromatic ring which may be substituted with an alkyl group or an alkoxy group of the rings X and Y include a benzene ring, a naphthalene ring, a quinoline ring and a phenanthrene ring, and these rings are C ₁ It may be substituted with an alkyl group such as _-6 alkyl group or an alkoxy group such as C _1-6 alkoxy group. Can be given.

In the spirooxazine-based compound of the present invention, in particular,
A compound in which the ring X is a benzene ring and the ring Y is a naphthalene ring, a quinoline ring or a phenanthrene ring is preferable.

Examples of the heteromonocycle of B include furan ring, thiophene ring,
Examples thereof include a pyrrole ring, a pyrrolidine ring, a pyridine ring, a morpholine ring, a dioxane ring, a piperazine ring and a piperidine ring.

The compound used in the present invention can be produced, for example, as follows. That is, the following general formula [II] (In the formula, R ² , R ³ and ring X are the same as defined above.) The indolenine derivative represented by the following general formula [III] (In the formula, A, B, n, m and R ¹ are the same as defined above.) Alkylation with a p-toluenesulfonic acid ester, and then the following general formula [IV] (In the formula, ring Y is the same as the above definition.), And it can be produced by reacting with a nitroso-hydroxy derivative.

The alkylation reaction with p-toluenesulfonic acid ester is carried out without a solvent or in a nonpolar solvent such as an aromatic solvent such as chlorobenzene or dichlorobenzene at a reaction temperature of 80 to 200 ° C. 130-150 ℃ preferably without solvent
Can be implemented smoothly.

Then, the reaction with the nitroso-hydroxy derivative, piperidine, piperazine, triethylamine, in the presence of a basic catalyst such as morpholine, methanol, ethanol, propanol, alcohol solvents such as butanol, acetone, ketone solvents such as methyl ethyl ketone, dichloromethane, It is carried out in the presence of a polar or non-polar solvent such as a halogenated hydrocarbon solvent such as trichloroethane. The reaction temperature is in the range of 0 to 200 ° C. Preferably, in ethanol, methyl ethyl ketone, acetone,
It can be smoothly carried out at 40 ° C to 120 ° C in the presence of a piperidine catalyst.

The compound used in the present invention may be produced by another method, for example,
It can also be manufactured as follows. That is, the following general formula [V] (Wherein R ¹ , R ² , R ³ , A, B, m, n and ring X are the same as defined above) and the following general formula [IV] (In the formula, ring Y is the same as the above definition.), And it can be produced by reacting with a nitroso-hydroxy derivative.

The reaction is usually performed in the presence of a polar or non-polar solvent such as an alcoholic solvent such as methanol, ethanol, propanol and butanol, a ketone solvent such as acetone and methyl ethyl ketone, and a halogenated hydrocarbon solvent such as dichloromethane and trichloroethane. You. The reaction temperature is 0 ° C to 200 ° C, and preferably 4 ° C.
It can be carried out smoothly at 0 ° C to 120 ° C.

The compound used in the present invention is a novel dye and is a compound exhibiting photochromism. That is, this compound develops a color upon irradiation with ultraviolet rays and then returns to its original state when irradiated with visible light or heated to 80 ° C. or higher, and this change can be repeated.

The light-sensitive material of the present invention has a light-sensitive layer containing the spirooxazine compound described above between at least one transparent substrate and can be obtained according to a known method.

The substrate in the present invention may be either transparent or opaque, but in order to expose it to light, the substrate on at least one side of the photosensitive layer needs to be transparent.
As a material of the substrate, a support such as glass, plastic, paper, a plate-like or foil-like metal, or a composite thereof is used. Glass and plastic are preferable from various points. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polycarbonate resin, and polysulfone resin.

In the light-sensitive material of the present invention, the light-sensitive layer may contain a resin that dissolves or disperses this compound, in addition to the above-mentioned spirooxazine-based compound. Examples of the resin include polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, and the like. Examples thereof include carbon chloride, benzene, cyclohexane, methyl ethyl ketone, tetrachloroethane, toluene, ethanol and ethyl cellosolve.

The use ratio of the compound of the present invention is 0.1 with respect to the resin.
-50%, preferably 5-20%.

Further, the light-sensitive material of the present invention may contain additives such as a light resistance improver, a triplet quencher and an antioxidant, if necessary.

As a method for forming the photosensitive layer, a commonly used coating method such as a doctor blade method, a casting method, a spinner method or a dipping method is used.

The thickness of the photosensitive layer is 0.5μ to 10mm, preferably 5μ to 100μ
Is.

〔Example〕

Next, the present invention will be described more specifically by way of examples, but the following examples do not limit the present invention in any way.

Example 1 The following structural formula 2,3,3,5-tetramethylindolenine represented by 17.3 g
And the following structural formula P-toluenesulfonic acid ester derivative 2 represented by
5.6 g of the mixture was reacted at 110 ° C for 4 hours, cooled to room temperature, 200 ml of ethanol was added, and the following structural formula was added. 17.3 g of 1-nitroso-2-naphthol and 10.1 g of triethylamine were added, and the mixture was reacted under reflux for 2 hours in a nitrogen atmosphere. After cooling, chloroform was extracted, dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (solvent: toluene).
Colorless crystals (3.0 g, relative yield 7%) were obtained. The obtained compound is represented by the following structural formula and has the physical properties shown below.

The melting point was 169 to 169.5 ℃, and the mass spectrum was M ⁺ 412, which was in agreement with the molecular weight. In addition, the figure of infrared absorption spectrum
It is shown in FIG.

Polyvinyl butyral resin containing 1g of this compound and a plasticizer
9g, solvent (ethanol: toluene: n-butanol = 50: 4)
5: 5) A 90 ml solution was applied to a glass substrate using a bar coater, dried at 70 ° C. for 10 minutes, and a glass plate was further stacked on this photosensitive layer and vacuum-pressed. The obtained sample was colorless under normal conditions, but when it was irradiated with ultraviolet rays, it developed a highly concentrated blue color (λ _max = 620 mm).

Next, when the ultraviolet irradiation was stopped, the original colorless state was restored.
This change could be repeated. Fig. 3 shows a diagram of the absorption spectrum during color development.

Example 2 The following structural formula 15.9 g of 2,3,3-trimethylindolenine represented by and the following structural formula P-toluenesulfonic acid ester derivative 2 represented by
6.8 g of the mixture was reacted for 4 hours at 110 ° C.
The following compounds were synthesized in the same manner as in.

The melting point of this compound is 130-131 ° C and the mass spectrum is
Consistent with molecular weight at M ⁺ 424. Figure 2 shows the infrared absorption spectrum.

Using this compound, a photosensitive sample was prepared in the same manner as in Example 1 and was irradiated with ultraviolet rays to give a highly concentrated blue color (λ _max : 620 m
m) developed.

Next, when the ultraviolet irradiation was stopped, the original colorless state was restored.
This change could be repeated.

Example 3 By the method according to Examples 1 and 2, the compounds shown in Table 1 below were synthesized. When they were laminated between two glass substrates in the same manner as in Example 1 and irradiated with ultraviolet rays, they each developed a color tone and λ _max shown in Table 1. Next, when the irradiation was stopped, the original colorless state was restored. This change could be repeated.

[Effects of the Invention] As described above, according to the present invention, the spirooxazine-based compound represented by the general formula [I] has good compatibility with a polymer compound, and by using this compound, It is possible to obtain a photochromic photosensitive material having a good contrast and a large color density.

[Brief description of drawings]

1 and 2 show infrared absorption spectra of the spirooxazine-based compounds prepared in Example 1 and Example 2, respectively. FIG. 3 shows the absorption spectrum of the photochromic photosensitive material of Example 1 at the time of color development.

Claims (1)

[Claims] 1. Between two substrates, at least one of which is transparent,
As a photosensitive substance, the following general formula [I] (In the formula, m represents 0 to 3, and n represents an integer of 0 to 6.
However, m and n do not represent 0 at the same time. R ¹ represents a hydrogen atom and a C _{1 to} C ₃ alkyl group, R ² , R ³ represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, or R ² , R ³ May be bonded to each other and may be cyclized. A represents an alkylene group,
B represents a heteromonocycle, and rings X and Y represent a hydrocarbon aromatic ring or a heteroaromatic ring which may be substituted with an alkyl group or an alkoxy group. ) A photosensitive material provided with a photosensitive layer containing a spirooxazine compound represented by the formula (1).