JPH03227989A - Spirooxazine-based compound and photosensitive material using the same compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I {n is 1-4; R<1> is (substituted) alkyl, (substituted) alkenyl, (substituted) aryl, etc., provided that R<1> is not (substituted) 1-5C alkyl when n is 1; R<2> and R<3> are alkyl, alkoxyalkyl, etc.; A is alkylene; R<4> is -NRR' [R and R' are H, (substituted) alkyl, etc.]; R<5> to R<9> are H, cyano, alkyl, nitro, halogen, OH, carboxyl, etc.}. EXAMPLE:A compound expressed by formula II. USE:Useful as textile products, plastic products, dimming materials, optical filters, masking materials and actinometers capable of changing color by irradiation with light. PREPARATION:An indolenine derivative expressed by formula III is alkylated with a p-toluenesulfonic acid ester expressed by formula IV and then reacted with a nitrosohydroxyquinoline derivative expressed by formula V and ammonia or amines expressed by the formula NHRR'.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel spirooxazine compound and a photosensitive material using the compound.

Specifically, it relates to a novel compound with photochromic properties that can be used as a textile product, plastic product, light control material, optical filter, masking material, or light meter that changes color when exposed to light, and a photosensitive material using the compound. be.

[Conventional technology]

It is known that spirooxazine compounds have photochromic properties that cause them to develop or discolor when irradiated with light.

For example, spironaphthoxazine compounds of the following formula are proposed in Japanese Patent Publication No. 1983-501145.

Rd (wherein the residues R'' to R9 have the following meanings: Ra, R
b and R' are the series -H, -CN, -3CN, -No□, -X1CH,
X, -CX3 0 (-halogen 7), -OR'SRh,
one or more of -COR''', -COORh (alkyl, aryl, heteroaryl with up to R''-H2S C atoms), >Ar (cyclic aromatic or heteroaromatic ring system) substituents, R″, R′! , Rf,, R9: series -H, -R'-CH2R" -NH2, NH
R', -NRヱ2, -OR'-3R'(R' -
a substituent consisting of an alkyl residue (aryl or heteroaryl residue) having up to 8 C atoms, with the proviso that R'
=H, at least one of the residues R', R', or Rf is not a methyl group.) On the other hand, as a photochromic light-sensitive material, for example, Japanese Patent Publication No. 45-28892 discloses spironaphthods as shown in the following formula. Photochromic materials containing oxazine compounds have been proposed.

(In the formula, R'' represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group.) In addition, in Japanese Patent Publication No. 49-48631, spironaphthoxazines such as the following formula are described. Photochromic light-sensitive materials have been proposed in which a type compound is dispersed in a polymeric substance.

b (In the formula, Rb is +CH2→TCOOH.

+CH2-)-7CN or +CH2-+TC00R(
R is an alkyl group having 1 to 5 carbon atoms): Rc and Rd are alkyl groups having 1 to 5 carbon atoms; Re is a hydrogen atom;
It represents five alkyl groups, a halogen atom, a nitro group, a cyan group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. ) Furthermore, JP-A-55-36284 proposes a photochromic compound as shown in the following formula.

(In the formula, one of Rr and R9 is a halogen atom or a lower alkoxy group, and the other is a hydrogen atom, and R1- and R' represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. ) Furthermore, US Pat. No. 4,342,668 proposes a photochromic compound as shown in the following formula.

RIN (wherein, one of R' and Rk is a halogen atom or a lower alkoxy group, the other is a hydrogen atom, and R1 and RIN
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and R9 represents an alkyl group having 2 to 10 carbon atoms. ) Then, a photochromic compound is dissolved or dispersed in a polymer compound to form a film, or coated on a substrate to form a photosensitive layer, or another substrate is layered on top of these to form a photochromic photosensitive material. is proposed.

[Problem to be solved by the invention]

However, conventional spirooxazine compounds have poor solubility in organic solvents, making it difficult to form a photosensitive layer by coating, and poor compatibility with polymer compounds, resulting in poor color density and color fastness. was not always sufficient.

Therefore, a robust photochromic light-sensitive material exhibiting good contrast and high color density could not be obtained.

[Means to solve the problem]

The present invention relates to general formula (I) [wherein n represents an integer of 1 to 4, R1 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted cycloalkyl group] Indicates an unsubstituted aryl group. However, when n represents 1, R' does not represent a substituted or unsubstituted C,-CS alkyl group.

R2 and R3 may each independently represent an alkyl group or an alkoxyalkyl group, or R2 and R3 may be bonded to each other and cyclized. A represents a linear or branched alkylene group, and R4 represents -NRR' (R and R'
independently represent a hydrogen atom, an alkoxy group, or an alkyl group optionally substituted with an alkoxyalkoxy group or a hydroxy group, or R and R' are bonded to each other and cyclized to form a nitrogen-containing heterocycle. You can. ), R5, R6, R'? , R11 and R9 each independently represent a hydrogen atom, a cyano group, an alkyl group, an alkoxy group, a nitro group, an alkoxycarbonyl group, an alkylcarbonyl group, a trifluoromethyl group, a halogen atom, a hydroxy group or a carboxyl group. ] The gist is a photosensitive material provided with a spirooxazine compound represented by the following and a photosensitive layer containing the compound.

The present invention will be explained in detail below.

The spirooxazine compound of the present invention has the general formula [■
].

In the formula, R1 is an alkyl group such as an alkyl group of Cl-211; an alkoxyalkyl group such as a methoxyethyl group or an ethoxyethyl group; an alkoxyalkoxyalkyl group such as a methoxyethoxyethyl group or an n-butoxyethoxyethyl group; methoxyethoxy Alkoxyalkoxyalkoxyalkyl groups such as ethoxyethyl group and ethoxyethoxyethoxyethyl group:
phenyloxyethyl group, naphthyloxyethyl group, p
-Optionally substituted aryloxyalkyl group such as chlorophenyloxyethyl group; optionally substituted phenylalkyl group such as Hensyl group, phenethyl group, p-chlorobenzyl group, p-nitrobenzyl group; cyclohexylmethyl group , cycloalkylalkyl groups such as cyclohexylethyl group and cyclopentylmethyl group; optionally substituted alkenyloxyalkyl groups such as allyloxyethyl group and 3-bromoallyloxyethyl group; cyanoalkyl groups such as cyanoethyl group and cyanomethyl group Groups; hydroxyalkyl groups such as hydroxyethyl groups and hydroxymethyl groups; tetrahydrofuryl alkyl groups such as tetrahydrofurfuryl groups and tetrahydrofurylethyl groups; substituted or unsubstituted thienyl alkyl groups such as thienylethyl groups and thienylmethyl groups; Alkyl group, allyl group,
Substituted or unsubstituted alkenyl groups such as 2-chloroallyl group, substituted or unsubstituted aryl groups such as phenyl group, p-methylphenyl group, naphthyl group, m-methoxyphenyl group, or cyclohexyl group, cyclopentyl group, etc. Furthermore, the cycloalkyl group of
These cycloalkyl groups are halogen atoms, alkyl groups,
Examples include those substituted with an alkoxy group or the like. Among these, R1 preferably represents a group having 1 to 6 carbon atoms, such as an alkyl group, an allyl group, or a phenyl group.

R2 and R3 represent an alkyl group such as an alkyl group of Cl-2fi: an alkoxyalkyl group such as a methoxyethyl group or an ethoxyethyl group, and R2 and R3 are bonded to each other and cyclized to form a cyclohexyl group, a cyclopentyl group, or a cycloheptyl group. may form a cycloalkyl group such as a group. R
z and R3 are particularly lower alkyl groups such as methyl group, ethyl group, propyl group, butyl group, or R2 and R3.
A cyclohexyl group in which 3 is cyclized is preferable.

Examples of the linear or branched alkylene group of A include the following.

2 +CHz→ko -(-CH2→1- CH2 CH(-CH2→-r CH.

-(-CH2→-rCHCHz CR3 3 -(-CH2→□rCH CR3 CH2 CH 3 H7+II) CH2CH C4Hq+n) A is preferably a linear alkylene group having 1 to 6 carbon atoms.

Examples of R4 include the following.

NH2-NHCH3, -NHC2H5゜-NHCH2C
H2CH3, -NH(CH2)3CH3N HCH(C
R3) 2 NHCH2CH(CH3)z N (CH3)2 , N ('C2R5)Z
.

N (C3H7+,,))2,-N (C4Hq
+, l, )2.

4 HC2 H4 Oh.

HC3 6 CH3 CH3 In addition, as examples of R1 R' which form a nitrogen-containing heterocycle by bond cyclization, 5 6 R4 is particularly preferably a piperidinyl group, a morpholinyl group, a dimethylamino group, or a diethylamino group.

More preferred are a piperidinyl group and a morpholinyl group.

R5, R6, R7, R8, R9 are hydrogen atoms and diano groups:
Alkyl groups with 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, alkoxy groups with 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group: Nitro group: methoxycarbonyl group, ethoxy 7 carbonyl group, 1 or more carbon atoms such as propoxycarbonyl group
Alkoxycarbonyl group having 6 alkoxy groups: Alkylcarbonyl group having an alkyl group having 1 to 6 carbon atoms such as methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, trifluoromethyl group: chlorine atom, bromine atom, iodine atom Halogen atoms such as: hydroxy group,
Indicates carboxyl group, etc. Such R5, R6, R7,
Preferred groups for R8 and R9 are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, and a hydroxy group.

The compound of the present invention can be produced, for example, as follows. That is, the following general formula C11) (wherein, R
Z, R3, R5, R6, and R9 are the same as defined above. ) is alkylated with a p-)luenesulfonic acid ester represented by the following general formula (III) (wherein A, n, and R' are the same as defined above),
Next, a nitrosohydroxyquinoline derivative represented by the following general formula (IV) O (wherein R7 and RI' are the same as defined above) and NHRR'
It can be produced by reacting with ammonia or amines represented by (R, R' are the same as defined above).

The alkylation reaction using p-) luenesulfonic acid ester is carried out without a solvent or in a non-polar solvent such as an aromatic solvent such as chlorobenzene or dichloromenzene.
It is carried out at a reaction temperature of 'C.

9 Preferably, it can be carried out smoothly at 100 to 150°C without a solvent. After this reaction, an alkali such as Naz co3 or NaOH and water are added, followed by stirring at 60°C, separating the oil layer, and distilling it under reduced pressure.

Next, the reaction with the nitrosohydroxyquinoline derivative and ammonia or amines is carried out using an alcoholic solvent such as methanol, ethanol, propatool, butanol,
It is carried out in the presence of a polar or non-polar solvent such as a ketone solvent such as acetone or methyl ethyl ketone, or a halogenated hydrocarbon solvent such as dichloromethane, trichloroethane, trichloroethylene, or chlorobenzene. The reaction temperature is carried out in the range of 0 to 200°C. Preferably,
40°C to 120° in ethanol, methyl ethyl ketone, acetone, trichloroethylene, chlorobenzene
It can be implemented smoothly with C.

The compound of the present invention is a novel dye and a compound exhibiting photochromism. That is, this compound develops color when exposed to ultraviolet rays, and then the ultraviolet rays are blocked and left for several hours, or
Alternatively, when exposed to visible light, it returns to its original state, and this change can be repeated.

The photosensitive material of the present invention has a photosensitive layer on a substrate containing the above-mentioned compound or a microcapsule of the compound dissolved or dispersed in a resin, and can be obtained according to a known method. can.

The substrate in the present invention may be either 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, and 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, polypropylene resin, polycarbonate resin, polysulfone resin, and the like.

Resins that dissolve or disperse the compound of the present invention include 1 polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, polyacetal resin Examples of the solvent used include carbon tetrachloride, benzene, cyclohexane, methyl ethyl ketone, methyl isobutylene, tetrachloroethane, toluene, ethanol, and ethyl cellosolve. The usage ratio of the compound of the present invention is 3 to 3 to
50%, preferably 5-20%.

When using the spirooxazine compound of the present invention in microcapsules, the commonly known method described in the literature ["Latest Microencapsulation Technology" by Tamotsu Kondo (published by Sogo Gijutsu Center Publishing)] can be mentioned. . Namely, chemical methods such as interfacial polymerization method and in 5 in situ polymerization method, physicochemical methods such as phase separation method (simple coacervation method, complex coacervation method), interfacial precipitation method, etc.
Examples include physical and mechanical methods such as spray drying and air suspension coating.

Preferred microencapsulation methods include a phase separation method using a gelatin-based membrane agent (e.g., gelatin-gum arabic membrane agent, gelatin-carboxymethylcellulose membrane agent), and an in-5it method using a melamine-formaldehyde resin.
Examples include the u-polymerization method.

As a method for forming a photosensitive layer on a film as a substrate, commonly used coating methods such as a doctor blade method, a casting method, a spinner method, and a dipping method are used.

The thickness of the film is 0.5 μm to 1.0 mm, preferably 5 μm-1001I. The light-sensitive material of the present invention may contain various additives, if necessary.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 8.6 g of 2,3,3.5-tetramethylindolenine represented by the following structural formula and p-toluenesulfonic acid ester derivative 1 represented by the following structural formula
3.7 g of the mixture was reacted at 110° C. for 4 hours, and after cooling to room temperature, 5.8 g of Na2CO+ was added and stirred. Next, 80 ml of water was added, and after stirring at 60°C for 2 hours, the oil layer was separated and distilled under reduced pressure to obtain an indoline derivative represented by the following structural formula %.

Furthermore, this was added to 5-nitroso-6-hydroxyquinoline 8 represented by the following structural formula in 150 mj2 of trichlorethylene.
．． 6 g and 8.5 g of piperidine under reflux for 3 hours. After cooling, trichlorethylene was removed, and the reaction product was separated and purified by silica gel column chromatography (solvent: toluene) to obtain 0.2 g of brown powder. The obtained compound is represented by the following structural formula and has the physical properties shown below.

5 (C3+tlteN403) (Physical property values) (1) Melting point 70°C (2) Mass spectrum (measurement conditions: 10eV 150°C
) m/e 514 (M") 499 (M" CH3) 469 (M" -3C) I3) (3) IR spectrum data is shown in Figure-1.

Using 0.2 g of this compound, thermoplastic polyester resin 1
．． A solution consisting of 0 g (manufactured by Toyobo Co., Ltd., trade name: Vylon-200) solvent methyl ethyl ketone] was applied to a polyester film (manufactured by Diafoil Co., Ltd., thickness 100 μm) using bar coater No. 3, and dried at 675°C for 110 minutes. . The obtained sample was colorless under normal conditions, but when irradiated with ultraviolet light, it developed a highly concentrated purple color (λmax -575 nm).

Next, they were left in their original colorless state by blocking ultraviolet rays and leaving them for several hours, or by irradiating them with visible light. This change could be repeated.

The main island had good color density contrast before and after UV irradiation, showed high color density, and had excellent light resistance.

Example 2 14.4 g of p-toluenesulfonic acid ethoxyethoxyethyl ester was used instead of 13.7 g of p-)luenesulfonic acid methoxyethoxyethyl ester in Example 1.
A spirooxazine compound of the present invention represented by the following structural formula was obtained in the same manner as in Example 1.

7 When this compound was applied to a polyester film in the same manner as in Example 1, it turned dark purple (
A color was developed at λ1IaX=s 75 nm).

The material was then left in its original colorless state by blocking ultraviolet rays and leaving it for several hours, or by irradiating it with visible light.

This change could be repeated.

Example 3 15.1 g of the compound represented by the following structural formula was dissolved in 200 mj2 of trichlorethylene, 9.0 g of the compound represented by the following structural formula and 9°Og of morpholine were added, and the mixture was reacted under reflux for 4 hours. Next, the mixture was cooled to room temperature, the solvent was distilled off, and the mixture was separated and purified by column chromatography (solvent used: toluene) to obtain a spirooxazine compound of the present invention represented by the following structural formula.

9 When this compound was applied to a polyester film in the same manner as in Example 1, it turned dark purple (λ
max = 573 nm). The material was then left in its original colorless state by blocking ultraviolet rays and leaving it for several hours, or by irradiating it with visible light.

This change could be repeated.

Example 4 Spirooxazine compounds of the present invention shown in Table 1 below were synthesized by a method similar to Examples 1 to 3. The obtained compound was applied onto a polyester film in the same manner as in Example 1, and when irradiated with ultraviolet rays, the color developed to the color tones λA and X shown in Table 1, respectively. The material was then left in its original colorless state by blocking ultraviolet rays and leaving it for several hours, or by irradiating it with visible light. This change could be repeated.

0 3 34 35 In addition to the spirooxazine compounds listed in Table 1 as Examples, the compounds listed in Table 2 below can be used, but the present invention is not limited thereto.

6 7 [Effects of the Invention] The photochromic compound of the present invention has excellent solubility in organic solvents, so it is easy to form a film by coating, and in particular, it has excellent compatibility with polymer compounds, so it has a dark color. Moreover, it is possible to obtain a composition that has good light resistance and good stability over repeated color development and decolorization.

It is also possible to microencapsulate books (:, :b).

Such compounds of the present invention are used as textile products, plastic products, light control materials, optical filters, masking materials, photometers, and display materials that change color upon irradiation with various types of light.

[Brief explanation of drawings]

FIG. 1 shows the IR spectrum of the spirooxazine compound of Example 1 of the present invention, where the vertical axis represents transmittance (%T) and the horizontal axis represents wave number (cm-'). 8

Claims (2)

[Claims] (1) The following general formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼... [I] [In the formula, n represents an integer from 1 to 4, R^1 is a substituted or unsubstituted alkyl group, It represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group. However, when n represents 1, R^1 does not represent a substituted or unsubstituted C_1-C_5 alkyl group. R^2 and R^3 each independently represent an alkyl group or an alkoxyalkyl group, or R^2 and R^3 may be bonded to each other to form a cyclization. A represents a linear or branched alkylene group, and R^4 is -NRR' (even if R and R' are independently substituted with a hydrogen atom, an alkoxy group, an alkoxyalkoxy group, or a hydroxy group) indicates a good alkyl group, or R and R
' may be bonded to each other or cyclized to form a nitrogen-containing heterocycle. ), R^5, R^6, R^7, R^8 and R^9 are each independently a hydrogen atom, a cyano group, an alkyl group, an alkoxy group, a nitro group, an alkoxycarbonyl group, an alkylcarbonyl group. , trifluoromethyl group, halogen atom, hydroxy group or carboxyl group. ] A spirooxazine compound represented by (2) General formula [I] in claim (1) on the substrate
A photosensitive material comprising a photosensitive layer containing a spirooxazine compound represented by: