JPH02225486A - Spiroxazine-based compound and photosensitive material using the same compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [n is 0-4; R<1> represents (substituted)alkyl, (substituted)alkenyl, (substituted)cycloalkyl or (substituted)aryl; R<2> and R<3> represent alkyl or alkoxyalkyl, provided that R<2> and R<3> may be linked with each other to form a ring; A represents alkylene; R<4> represents -NRR' (R and R' represents H, alkoxy, etc.); R<5> to R<8> represent H, cyano, alkyl, alkoxy, nitro, etc.]. EXAMPLE:A compound expressed by formula II. USE:A photosensitive material, having photochromism and usable as a fiber product, plastic product, dimming material, optical filter, masking material or actinometer changing color by light irradiation. 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 nitrohydroxy-quinoline derivative expressed by formula V and an ammonia or amines expressed by 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 irradiated with light, and a photosensitive material using the compound. It is.

[Conventional technology]

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

For example, Japanese Patent Publication No. 61501) No. 45 proposes a spironaphthoxazine compound represented by the following formula.

(wherein the residues R1 to R9 have the following meanings: R', R
h and Rc are the series - H, CN, SCN, NOx, X.

CHzX, CXz (X-halogen), -O
R'-3Rゝ -COR'-COOR'
(Rh = H alkyl with up to 18 C atoms,
aryl, heteroaryl), >, Ar (cyclic aromatic or heteroaromatic ring system), R', R'', R',, R9: series -H,R 'CHAR' NH2, NHR
L NR' 2 , OR'5RI(R'
= a substituent consisting of an alkyl residue (aryl or heteroaryl residue) having up to 8 C atoms, with the proviso that R,
(When '=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. 4.5-28892 describes A photochromic material containing a spironaphthoxazine compound as shown in the following formula has been proposed.

(In the formula, Rc represents a hydrogen atom, a halogen atom, a cyan group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group.) In addition, Japanese Patent Publication No. 49-48631 describes spironaphthoxazine systems such as the following formula. Photochromic light-sensitive materials have been proposed in which compounds are dispersed in polymeric substances.

Rd is an alkyl group having 1 to 5 carbon atoms; Re is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group,
It represents a cyano 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.

l(1' (wherein Rh is +CHz-)-, 1COOH.

-(-CH, +-5CN or +CH□±-n C00
R (R4i alkyl group having 1 to 5 carbon atoms): R' and (
In the formula, one of Rf and R9 is a halogen atom or a lower alkoxy group, and the other is a hydrogen atom, and Rh and Rc are a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. ) Furthermore, USP 4,342.668 proposes a photochromic compound as shown in the following formula.

R'' (in the formula, one of Rj and R'' is a halogen atom or a lower alkoxy group, the other is a hydrogen atom, and R1 and R''
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and Rfi represents an alkyl group having 2 to 10 carbon atoms), and these photochromic compounds are dissolved or dispersed in a polymer compound to form a film. Photochromic photosensitive materials have been proposed in which the photosensitive layer is coated on a substrate, or a photosensitive layer is formed by stacking another substrate on top of the photosensitive layer.

[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 polymeric compounds, resulting in poor color density and color fastness. It wasn't always enough.

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

[Means for Solving the Problems] The present invention relates to the general formula (1) [wherein n represents an integer of O to 4, R' is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted Alternatively, it represents an unsubstituted cycloalkyl group or a substituted or unsubstituted aryl group.

R1 and R3 represent an alkyl group or an alkoxyalkyl group, or RZ and R2 may be bonded to each other and cyclized. A represents a linear or branched alkylene group, R4 represents -NRR' (R, R' represents an alkyl group optionally substituted with a hydrogen atom, an alkoxy group, an alkoxyalkoxy group, or a hydroxy group, R,R
' may be bonded to each other or cyclized to form a nitrogen-containing heterocycle. ), and R5, R6, R7, and R1' are hydrogen atoms and cyan groups.

Alkyl group, alkoxy group, nitro group, alkoxycarbonyl group, alkylcarbonyl group, trifluoromethyl group, halogen atom, hydroxy group.

Indicates 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 (1)
It is expressed as

In the formula, R1 is an alkyl group such as a C+, ZS alkyl group; 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; methoxy Alkoxyalkoxyalkoxyalkyl groups such as ethoxyethoxyethyl group and ethoxyethoxyethoxyethyl group; optionally substituted aryloxyalkyl groups such as phenyloxyethyl group, naphthyloxyethyl group, p-chlorophenyloxyethyl group; Hensyl group, phenethyl group group, p-chlorobenzyl group, p-
Optionally substituted phenylalkyl groups such as nitrobenzyl group; cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, cyclopentylmethyl group; substituted phenylalkyl groups such as allyloxyethyl group, 3-bromoallyloxyethyl group, etc. optional alkenyloxyalkyl groups; cyanoalkyl groups such as dianoethyl group and cyanomethyl group; hydroxyalkyl groups such as hydroxyethyl group and hydroxymethyl group; tetrahydrofuryl alkyl groups such as tetrahydrofurfuryl group and tetrahydrofurylethyl group; thienylethyl group , substituted or unsubstituted alkyl groups such as thienylalkyl groups such as thienylmethyl groups, substituted or unsubstituted alkenyl groups such as allyl groups and 2-chloroallyl groups, phenyl groups, p-methylphenyl groups, naphthyl groups, m Substituted or unsubstituted aryl groups such as -MeI xyphenyl group, or cycloalkyl groups such as cyclohexyl group and cyclopentyl group;
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 are alkyl groups such as C+-te alkyl groups:
It represents an alkoxyalkyl group such as a methoxyethyl group or an ethoxyethyl group, and R2 and R3 may be bonded to each other and cyclized to form a cycloalkyl group such as a cyclohexyl group, a cyclopentyl group, or a cyclohebutyl group. R1
, R3 is particularly preferably a lower alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a cyclohexyl group obtained by cyclizing R2 and R3.

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

CHz CH, -fCHz→-r, -CHCH2
CR3CH:1-CH.

C1]- -CHCHI zHs zHs CH.

-(-CH, →-ding.

+CHz→-“.

1+CH2→-“cH, CHzCH CH3C)Hl(n) -CH,CH CaHq(n+ -NHC! Oh.

-NHC.

OCH,tA is preferably a linear alkylene group having 1 to 6 carbon atoms. It is preferable that n represents 1.

Examples of R4 include the following.

NHz, NHCH3, NHCzHs.

NHCH2C82CH2, -NH(CHI)3CHff
.

N HCH(CH:l ) t OCR, and an example of a compound in which R and R' are bonded and cyclized to form a nitrogen-containing heterocycle is -NHGHz CH(CHz )! .

N (CH3) z, N (Ct
Hs)z.

N (Cal H?.+)z, N (C
As R4, a piperidinyl group, a morpholinyl group, a dimethylamino group, and a diethylamino group are particularly preferable.

More preferred are a piperidinyl group and a morpholinyl group.

R', Rh, R', and R' are hydrogen atoms, diano groups, alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, and propyl groups, and 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy groups; Alkoxy group of 6: nitro group; alkoxycarbonyl group having an alkoxy group having 1 to 6 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group: carbon number such as ethylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, etc. Alkylcarbonyl group having 1 to 6 alkyl groups Nitrifluoromethyl group: Halogen atom such as chlorine atom, bromine atom, iodine atom:
Indicates hydroxy group, dicarboxyl group, etc. This Φ-like R5
, Rh, R'l, and R8 are preferably a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a hydroxy group.

The compound of the present invention can be produced, for example, as follows. That is, the following general formula (II) (wherein RZ
, R3, R5, and R6 are the same as defined above. ) is represented by the following general formula (III) (wherein A, % n and R' are the same as defined above).
The compound is alkylated with I)-4 luenesulfonic acid ester represented by the following general formula (IV) (wherein, R7 and R1) are the same as defined above. ) and N HRR'
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-toluenesulfonic acid ester is carried out without a solvent or in a nonpolar solvent such as an aromatic solvent such as chlorohenzene or dichlorobenzene.
It is carried out at a reaction temperature of 0°C.

Preferably, it can be carried out smoothly at 100 to 150°C without a solvent. After this reaction, add alkali such as Naz CO3 and NaOH and water, stir at 60°C, and separate the oil layer.
Distill 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, or trichloroethylene. Reaction temperature is 0-200℃
It will be carried out within the scope of. Preferably, in ethanol, methyl ethyl ketone, acetone, trichloroethylene, 4
It can be carried out smoothly at 0°C to 120°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.

Examples of the resin for dissolving or dispersing the compound of the present invention include polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy resin, phenol resin, polyacetal resin, etc. Examples of solvents used include carbon tetrachloride, Hensen,
Examples include cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, tetrachloroethane, toluene, ethanol, and ethyl cellosolve. The proportion of the compound of the present invention used is 3 to 50%, preferably 5 to 20%, based on the resin.

When using the spirooxazine compound of the present invention in microcapsule form, the method is described in the literature [written by Tamotsu Kondo,
Examples include the commonly known method described in "Latest Microencapsulation Technology" (published by Sogo Gijutsu Center). That is, chemical methods such as interfacial polymerization method and 1 nsitu polymerization method,
Examples include physicochemical methods such as phase separation methods (simple coacervation method, complex coacervation method), interfacial precipitation method, and physical/mechanical methods such as spray drying method and air suspension coating method.

Preferred microencapsulation methods include phase separation of gelatin-based membrane agents (e.g., gelatin-gum arabic membrane agents, gelatin-carboxymethylcellulose-based membrane agents), and in-5-itu method using melamine-formaldehyde resin.
Examples include polymerization methods.

Methods for forming a photosensitive layer on a film as a substrate include the doctor blade method, casting method, spinner method,
A commonly used coating method such as a dipping method is used.

The thickness of the film is between 0.5 μm and 1.0 I*m, preferably between 5 μm and 100 μm. The photosensitive 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-)luenesulfonic acid ester derivative 1 represented by the following structural formula
1) 3.0 g of the mixture was reacted at 0° C. for 4 hours, and after cooling to room temperature, 5.8 g of Na and coal were added and stirred. Next, 8 Qml 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.

Add this to 150m7 of trichlorethylene! Among them, 5-nitroso-6-hydroxyquinoline 8 represented by the following structural formula
．． 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.

(Physical property values) (1) Melting point 70°C (2) Mass spectrum (measurement conditions near 0 eV 150°C) m/e 47 0 (M4) 455 (M” CH:l) 425 (M
"-3CH,) (3+1R spectrum data is shown in Figure-1.

Using 0.2 g of this compound, thermoplastic polyester resin 1
．． 0 g (manufactured by Toyobo Co., Ltd., trade name: Vylon-200), a solution consisting of 100 g of notyl ethyl ketone as a carrier) was transferred to a polyester film (manufactured by Diafoil Co., Ltd., thickness 100 μm).
It was coated using Bar Coater 3 and dried at 75° C. for 10 minutes. The obtained sample is colorless under normal conditions, but
When irradiated with ultraviolet rays, a highly concentrated purple color (λ□, = 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.

This product showed good contrast between the color density before and after UV irradiation, showed a large color density, and had excellent light resistance.

Example 2 Using 14.8 g of p-toluenesulfonic acid methoxyethyl ester instead of 13.0 g of p-toluenesulfonic acid methoxyethyl ester in Example I,
In the same manner as in Example 1, a spirooxazine compound of the present invention represented by the following structural formula was obtained.

CJ＜OCz! LOCH: + When this compound was applied to a polyester film in the same manner as in Example 1, it turned dark purple (
λ, , = 575 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 12.3 g of the compound represented by the following structural formula was dissolved in 200 ml of trichlorethylene, and 9.0 g of the compound represented by the following structural formula and 9.0 g of morpholine were dissolved.
g was added thereto, 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 the spirooxazine compound of the present invention represented by the following structural formula.

When irradiated with ultraviolet rays, the color tones shown in Table 1, λamx
The color developed. 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.

When this compound was applied to a polyester film in the same manner as in Example 1, it was exposed to deep purple color (λ) by ultraviolet irradiation.
, 1X = 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 coated on a polyester film by a method similar to Example 1, and in addition to the spirooxazine compounds listed in Table 1 as examples, the compounds listed in Table 2 below were However, the present invention is not limited thereto.

〔Effect 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.In particular, it has excellent compatibility with polymer compounds, so it has a deep color and good light resistance. - It is possible to obtain a composition with good stability against repeated decolorization.

It is also possible to microencapsulate the present compound.

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

[Brief explanation of the drawing]

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-').

Claims (2)

[Claims] (1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, n represents an integer from 0 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. R^2 and R^3 represent an alkyl group or an alkoxyalkyl group, or R^2 and R^3 may be bonded to each other and cyclized. A represents a linear or branched alkylene group, and R^4 represents -NRR' (R and R' represent a hydrogen atom, an alkyl group optionally substituted with an alkoxy group, an alkoxyalkoxy group, or a hydroxy group); Indicates R, R'
may be bonded to each other or cyclized to form a nitrogen-containing heterocycle. ), R^5, R^6, R^7, R^8 are hydrogen atoms, cyano groups, alkyl groups, alkoxy groups, nitro groups, alkoxycarbonyl groups, alkylcarbonyl groups,
Trifluoromethyl group, halogen atom, hydroxy group,
Indicates a 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: