JPS6314786A - Spironaphthoxazine based compound and photosensitive material using said compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X<1>, X<2>, Y<1> and Y<2> represent alkyl, alkoxyalkyl, cycloalkyl or aryl, or X<1> and X<2> as well as Y<1> and Y<2> may be linked with each other to form a ring; Z represents optionally substituted alkylene which may be linked through other group or atom, or (substituted) arylene; R<1>-R<8> represent H, halogen atom, alkyl, alkoxy (carbonyl), alkoxysulfonyl or alkylsulfonyl]. EXAMPLE:A compound expressed by formula II. USE:A coloring matter for a photosensitive material having photochromic property. PREPARATION:For example, a 2,3,3-trimethylinodolenine derivative expressed by formulae III and IV is reacted with a dihalide expressed by the formula A-Z-A (A represents halogen atom) and further reacted with a 1-nitroso-2- naphthol derivative expressed by formulae V and VI.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a photosensitive layer on a substrate containing a novel spironaphthoxazine compound having photochromic properties and a resin in which the compound is dissolved or dispersed. It is related to photosensitive amulets.

It is known that it has a photochromic property that develops or discolors when irradiated with light, and a number of photochromic photosensitive materials using this property have been proposed.

For example, in Japanese Patent Publication No. Bj-2 and D, a photochromic material containing a spironaphthoxazine compound as shown in the following formula is proposed.

(In the formula, 1 (1 is a hydrogen atom, a halogen atom, a cyan group,
Indicates an alkyl group or alkoxy group having 7 to ♂ carbon atoms.

) Furthermore, in Japanese Patent Publication No. 419-41/3/, a fu-1 chromic photosensitive paulownia material = 3- was proposed in which a spironaphthoxazine compound as shown in the following formula was dispersed in a polymeric substance. Tebru.

b (wherein, Rbc(:0H2fncQOJ (-On, +
nON -1 Talo i% OH79000R (R is an alkyl group with carbon number/~!), RO and Hd have carbon number/~
! alkyl group; C is a hydrogen atom, an alkyl group having 7 to 1 carbon atoms, a halogen atom, a nitro group, a cyan group, a carbon number -
~g(alkoxycarbonyl group or carbon number of II/~
Indicates J' alkoxy groups. ) Also, Tokukai Akio Δ-
--3 Otsu λ♂g issue proposes a photochromic compound as shown in the following formula.

OH8 (in the formula, one of R' and LHR" is a halogen atom or a lower alkoxy group, the other is a water bulk atom, and Hh and R1
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. ) Also, UEIP, 3, 6
Sixth, photochromic compounds as shown in the following formula have been proposed.

Rn (in the formula, one of Hj and P is a halogen atom or a lower alkoxy group, the other is a hydrogen atom, and R1 and aff
i represents a bulky water atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and Rn represents an alkyl group having 2 to /θ carbon atoms. ) Usually, the photochromic photosensitive I material is used in the form of a film in which a spironaphthoxazine compound is dissolved or dispersed in a polymer compound as described above.

In the case of products, the color density and the fastness of the colored state were not necessarily sufficient. Therefore, it has not been possible to obtain a photochromic light-sensitive material that exhibits a good contrast between coloring and decoloring and a high degree of coloring.

(Problems to be Solved by the Invention) The present invention provides spironaphthoxazine, which has great color development performance, excellent fastness in the normal color state, and photochromic properties with good cycling stability for color development and decolorization. The object of the present invention is to provide a photosensitive material comprising a compound based on the compound and a photosensitive material containing the compound.

(Means for Solving the Problems) That is, the present invention provides a general formula [I]
, 7 k represents a koxyalkyl group, a cycloalkyl group, or an aryl group, and XI and X2, and y+ and Y2 may be bonded to each other and cyclized. 2 may be substituted through another group or atom, or even if it is substituted, alkylene,
&, indicates an arylene group which may be kl, and R1,
R, R1,)j4, Rco, R6,8, and R11 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxysulfonyl group, and an alkylsulfonyl group. ) and a photosensitive material using the same.

In the spironaphthoxazine compound represented by the general formula [1] of the present invention, xl, x2, Yl, and Y2 are 0. ~78, preferably, an alkyl group such as an alkyl group of number 01~; an alkoxyalkyl group such as a methoxyethyl group or an ethoxyethyl group; a cycloalkyl group such as a cyclohexyl group or a pentyl group; a phenyl group, p-methylphenyl Xl and X2, Yl and yt are mutually cyclized to form a cycloalkyl group such as a cyclohexyl group, a cyclopentyl group, a cyclohebutyl group, etc. te b moyokomi.

As xl, x2, Y8, Y2, methyl group, ethyl group, globyl group, butyl group, phenyl group, agglomerated cyclohexyl group, etc. are preferable.

For z, -〇H! -1 (OH2+, moan2-),
+ang-),,÷0H2-),,+OH*+6,(O
H1 Juku SoOH, 9, LIMsOH3 OH.

-OH, 00) L, -1-〇, H400, H, -1 occupancy H
Alternatively, an arylene group which may be substituted through a 3 or atom or substituted with f11 is added.

R1,1(!, R3,1(4, RII, H”, R7
, ” means hydrogen atom; chlorine atom, Ugurashi atom,
A halogen atom such as a halogen atom + an alkyl group such as a C1-6 alkyl group; C4~. an alkoxy group such as an alkoxy group, or an alkoxycarbonyl group such as an alkoxycarbonyl group of CI to 6, an alkoxysulfonyl group such as a methoxysulfonyl group or an ethoxysulfonyl group, or an alkylsulfonyl group such as a methylsulfonyl group or an ethylsulfonyl group. Can be mentioned.

The compound of the present invention can be produced, for example, as follows. That is, the following general formula % formula % [111) (wherein, Xl, X2, Yl, Y2, R1, R2, R5,
R6 is the same as defined above. ), Ru1, 3.3-trimethylindolenine derivative has the following general formula [IV] A-Z-A...
...[■] (In the formula, human represents a halogen atom, and 2
is the same as the above definition. ) is reacted with a dihalide represented by the following general formula [■] and [v1] N.

(In the formula, R3, 1i, 4, R7 and R1 are the same as defined above.) It can be produced by reacting a /-nitrone-11 naphthol interferomer represented by the following formula.

The alkylation reaction using a dihalide is carried out in a hot solvent or a nonpolar solvent such as an aromatic solvent such as chlorobenzene or dichlorobenzene at a reaction temperature of 0 to 200°C. Preferably, it can be carried out smoothly at 73θ to /J-0°C without a solvent.

Next, the reaction with the /-nitrone-naphthol derivative is carried out using methanol, ethanol, glopanol,
The reaction is carried out in a polar or non-polar solvent such as an alcohol solvent such as butanol, a ketone solvent such as acetone or methyl ethyl ketone, or a halogenated hydrocarbon IA solvent such as dichloromethane or trichloroethane. The reaction temperature was 0-. It is carried out at a temperature of 200°C. Preferably ethanol, methyl ethyl ketone. It can be carried out smoothly in acetone at 41°C to 2θ°C in the presence of a piperidine catalyst.

The compound of the present invention can also be produced, for example, as follows. That is, the following general formula [■] -12 ~ ■ 2 ... Song [■]] Dragon (in the formula, xl,) i't, Yl, Y! ,Z, R1,R
”, )jff, R11 is the same as the above definition) and the compound represented by the general formula [v], [■]O (wherein, R4, R7, and R8 are the same as the above definition) JR can be produced by reacting with a /-nitroso-2-naphthol derivative a).

The reaction is usually carried out using methanol, ethanol, propatool,
It is carried out in polar or non-polar solvents such as alcoholic solvents such as butanol, ketonic solvents such as acetone, methyl ethyl ketone, and halogenated hydrocarbon solvents such as dichloromethane and trichloroethane. The reaction temperature is 0
It is carried out in the range of ~200°C, preferably 4t.

It can be carried out smoothly at ~/2θ℃.

The compound of the present invention is a compound that exhibits photochromism, such as a novel coloration. That is, this compound develops a color when irradiated with ultraviolet rays, and then irradiated with visible light.
When heated above ℃, it returns to its original colorless state, and this change can be repeated.

A photosensitive material having a photosensitive layer on a substrate containing a resin in which the novel compound of the present invention is dissolved or dispersed can be obtained according to a known method.

Examples of the resin for dissolving or dispersing the compound of the present invention include polyester resin, polystyrene resin, polyvinyl butyl resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, etc. Examples of solvents that can be used include carbon tetrachloride, benzene, cyclohexane, methyl ethyl ketone, tetrachloroethane, toluene, ethanol, and ethyl celluloph.

The ratio of the compound of the present invention to be used is 3~!
θchi, preferably! 〜−θchi.

Other additives other than the compound and resin of the present invention include transition metal chelate compounds (such as acetylacetonate chelate, bisphenyldithiol , salicylaldehyde oxime, bisdithiol-α-
diketone, etc.) may be included.

As a method for forming the film, commonly used coating methods such as a doctor grade method, a casting method, a spinner method, and a dipping method are used.

The thickness of the film is θ,jllIP~/,0IIIJ,,
Desirable 15 = <Ha! ~/θOμ.

The substrate in the present invention may be transparent or opaque, but when the substrates are provided on both sides of the photosensitive layer, at least one side must be transparent in order to be exposed to light. As the material of the substrate, supports such as glass, plastic, paper, plate-shaped or foil-shaped metal, and composites thereof are used, but glass and plastic are preferable from various points of view. Examples of the plastic include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, polyethylene resin, polyethylene resin, polycarbonate resin, and polysulfone resin.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example/ Represented by the following structural formula. 2. ! ,! -) Limethylindolenine /j, ri9 and dibromobutane lθ, /I represented by the following structural formula % formula % A mixture of 11
The reaction was carried out at 0°C for several hours, and after cooling to room temperature, ethanol aθ
0〆 and further represented by the following structural formula /-nitroso-2-naphthol/7. j # and triethylamine/θ,/Ii were added, and the mixture was allowed to react under reflux under a nitrogen atmosphere for 2 hours. After cooling, it was extracted with chloroform, dried over sodium sulfate, the solvent was distilled off, and separated and purified by chromatography (solvent: benzene) to obtain spironaphthate, which has a melting point of 2, t-, 227°C and is represented by the following structural formula. Colorless crystals of an oxazine compound were obtained.

The physical property values (mass spectrum) are as follows. (Measurement conditions near 0BV, 210℃) m/e t/co
(M+) Otsuj7 (M”-/yo) /70 (base peak) Using this compound ay b1 Thermoplastic polyester resin/θI
(Vylon-200, manufactured by Toyobo Co., Ltd.), a solution consisting of the solvent methyl ethyl ketone/θθl was applied using a bar coater plate 3 on a polyester film (manufactured by Diafoil Co., Ltd., thickness 10θμ), and dried for 70 minutes. The sample was colorless under normal conditions, but when irradiated with ultraviolet light, it developed a highly concentrated blue color (λ la, X m and θ inm).

Next, it returned to its original colorless state by irradiating it with visible light or heating it to temperatures above θ°C.This change could be reversed.

Dibromobutane in Example/Example/ Dibromobutane instead of 0Jji? The following compound was obtained in the same manner as in Example, except that the following compounds were used.

=19= The physical property values (mass spectrum) are as follows. (Measurement conditions near θeV, 27θ℃) m/θ tsy (M”
) 639 (M"-#) /7θ (ba, se peak) When this compound was applied to a polyester film in the same manner as in Example, it turned to a deep blue color (λ
ma, x- to O to nm). Next, some prisoners will be exposed to visible light! When heated above θ°C, it returned to its original colorless state. This change could be repeated.

Example 3 A compound represented by the following structural formula, θ! l z, -methyl ethyl ketone/θθθ pass] Then, a compound j ¥, A // represented by the following Hti structural formula was added, and the mixture was reacted under reflux for 3 hours. Cool in Murokashi, distill off the solvent, separate using column chromatography (using benzene as the solvent),
A spironaphthoxazine compound represented by formula #4 was obtained.

OH80H.

The physical property values (mass spectrum) are as follows. (Measurement conditions near 0θv, 3θ0”C) m/θ 7.30
(M+) 7/j (M"-/j) /70 (base peak) When this compound was applied to a polyester film in the same manner as in Example, it turned out to be a light brownish blue (
λIflaX! , g□jnm). Next, should we irradiate visible light? When heated above θ°C, it returned to its original colorless state.

This change could be repeated.

Examples Various spironaphthoxazine compounds represented by the general formula m and listed in Table 1 below were synthesized by methods similar to those described in Examples/--3. When the obtained compound was coated on a polyester film and irradiated with ultraviolet rays, each color was developed to the color tone and λmax shown in Table 1. Next, irradiate visible light or? When heated above θ°C, it returned to its original colorless state. This change could be repeated.

No. 1 / Application (Effects of the Application) The spironaphthoxazine compound of the present invention has photochromic properties and is excellent in color fastness and color fastness, so it is resistant to color loss and is resistant to color development and decolorization. Good stability over time. This photosensitive paulownia material, which has a photosensitive layer on a substrate made of a resin in which spironaphthoxazine compounds are dissolved or dispersed, can be used for various recording/memory materials, copying materials,
It can be used as a printed photoreceptor, a dimming I material, a photosensitive material for lasers, a photosensitive I material for photosetting, an optical filter, a masking material, a photometer, and a display material.

Patent Applicant Nissan Motor Co., Ltd. 01 or 7) Agent Patent Attorney Hase - (and 7 others) (Voluntary) Procedural Amendment dated July 77, 1988 F2 Invention Name Subironamethoxazine Compound and photosensitive material using said compound 3 Person making the amendment Applicant (39ri) Nissan Motor Co., Ltd. (and 1 other person) 4 Agent 10 () 2-5-2 Marunouchi, Chiyo III-ku, Tokyo (and 1 other person)
5. Subject of amendment Contents of amendment in column 6 of "Detailed Description of the Invention" of the specification (1) "Film formation" at the end of page 6 of the specification is corrected to "film formation."

"alkyl such as an alkyl group; Jirct~, an alkyl group such as an alkyl group;" is corrected.

(3) Table 1 Example Person 3 of Specification Cloth Tube 3 Rishin? Correct the compound as (Cl42)t.

(4) The following examples are added after Example V3 in Table 1, page 4t1 of the specification.

Claims (3)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼‥‥‥‥‥[I] (In the formula, X^1, It represents an alkyl group, a cycloalkyl group, or an aryl group, and X^1 and X^2, Y^1 and Y^2 may be bonded to each other and cyclized. Z may be connected through another group or atom. It often represents an optionally substituted alkylene group or an optionally substituted arylene group, and R^1
, R^2, R^3, R^4, R^5, R^6, R^7,
R^8 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxysulfonyl group, or an alkylsulfonyl group. ) A spironaphthoxazine compound represented by (2) X^1, X^2, Y^1 in general formula [I]
, Y^2 is a methyl group, the spironaphthoxazine compound according to claim (1). (3) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼‥‥‥‥‥[I] (In the formula, X^1, X^2, Y^1, Y^2 are alkyl groups, It represents an alkyl group, a cycloalkyl group, or an aryl group, and X^1 and X^2, Y^1 and Y^2 may be bonded to each other and may be cyclized.Is Z connected to another group or atom? or an optionally substituted alkylene group, an optionally substituted arylene group, R^1,
R^2, R^3, R^4, R^5, R^6, R^7, R
^8 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxysulfonyl group, or an alkylsulfonyl group. ) A photosensitive material having, on a substrate, a photosensitive layer containing a resin in which a spironaphthoxazine compound represented by the following formula is dissolved or dispersed.