JPH07228584A - Spironaphthoxazine compound and photosensitive material produced by using the compound - Google Patents

Abstract

PURPOSE:To obtain a spironaphthoxazine compound expressed by a specific formula, having excellent fatigue resistance, developing red color by sunlight or ultraviolet irradiation, returning to the original state e.g. by shielding the light and useful for plastic article, etc. CONSTITUTION:N This spironaphthoxazine compound is expressed by formula I [R1 is a (substituted)alkyl, a (substituted)alkoxyalkyl, a (substituted)alkenyl, a (substituted)cycloalkyl or a (substituted)aryl; R2 and R3 areeach an alkyl, an alkoxyalkyl; R2 and R3 may together form a ring; R4 and R5 each H, a (substituted)alkyl; R4 and R5 may together form a nitrogen-containing heterocyclic group; R6 is H or an alkyl; R7 is cyano, nitro, a perfluoroalkyl, F, Cl or Br; the substitution site of R7 is 1', 3' or 4' excluding 2'], e.g. the compound of formula II. The compound can be produced e.g. by reacting an indolenine compound with an amine compound and a nitrosonaphthol compound in a reaction solvent such as benzene at 0-200 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has photochromic properties. The present invention relates to a spironaphthoxazine compound, more specifically, a plastic product, an optical filter, a recording material, a textile product, which changes color by irradiation with light.
It is used for decorative materials and toys.

[0002]

2. Description of the Related Art Conventionally, as a photochromic compound,
Spironaphthoxazine compounds are known. For example, JP-B-45-28892 and JP-B-49-4863.
No. 1, JP-A-55-36284, JP-A-61.
-501145, JP-A-1-163184, JP-A-1-129869, and JP-A-3-227.
Compounds having the following structures are known in Japanese Patent Application Laid-Open No. 988, Japanese Patent Application Laid-Open No. 4-136085, and the like.

[0003]

[Chemical 3]

[0004]

[Chemical 4]

[0005]

[Chemical 5]

[0006]

[Chemical 6]

[0007]

However, the conventionally known spironaphthoxazine compounds are known to have good light resistance, but when they are developed, the color tone is red purple to blue green, and the hue is abundant. Was lacking. In particular, a photochromic light-sensitive material having a maximum absorption wavelength at the time of color development of 500 to 560 nm, excellent fatigue resistance against repeated color-erasing and coloration, and excellent as a magenta of three primary colors having sufficient color density has been desired. .

[0008]

As a result of various studies to solve these problems, the present inventors have found that in the general formula (1) below, a chlorine atom, a bromine atom, or a fluorine atom is conventionally located at the 2'position. , A cyano group and a nitro group are substituted, a spironaphthoxazine compound is known, but the present inventors are surprised only when these substituents are substituted at the 1 ', 3'or 4'positions. In particular, it was found that when the color was developed, the hue was significantly shifted and the color was red, and the present invention was completed.

[0009]

[Chemical 7]

(In the general formula, R ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and R ₂ and R ₃ independently represents an alkyl group or an alkoxyalkyl group, or R ₂ and R ₃ are bonded to each other and may be cyclized, and R ₄ and R ₅ are independent of each other, a hydrogen atom or an alkoxy group. A group or an alkyl group which may be substituted with a hydroxy group, or R ₄ and R ₅ may be bonded to each other or cyclized to form a nitrogen-containing heterocycle, wherein R ₆ is hydrogen or an alkyl group. R ₇ is a cyano group, a nitro group,
It represents a perfluoroalkyl group, a fluorine atom, a chlorine atom, or a bromine atom, and the substitution position of R ₇ is 1 ′ except 2 ′,
3'or 4 ') and a light-sensitive material containing the compound.

In the formula, R ₁ is an alkyl group: an methoxyethyl group, an ethoxyethyl group or another alkoxyalkyl group: a methoxyethoxyethyl group, an n-butoxyethoxyethyl group or another alkoxyalkoxyalkyl group: a methoxyethoxyethoxyethyl group, Alkoxyalkoxyalkoxyalkyl groups such as ethoxyethoxyethoxyethyl, phenyloxyethyl group, naphthyloxyethyl group, optionally substituted aryloxyalkyl groups such as P-chlorophenyloxyethyl group: benzyl group, phenethyl group, P-chloro Phenylalkyl group which may be substituted such as benzyl group and P-nitrobenzyl group: cyclohexylmethyl group, cyclohexylethyl group, cycloalkylalkyl group such as cyclopentylmethyl group: allyloxyethyl group, -Alkenyloxyalkyl group which may be substituted such as bromoallyloxyethyl group: cyanoalkyl group such as cyanoethyl group, cyanomethyl group: hydroxyethyl group, hydroxyalkyl group such as hydroxymethyl group, tetrahydrofurfuryl group, tetrahydrofuryl group Tetrahydrofurylalkyl group such as ethyl group: a substituted or unsubstituted alkyl group such as a cenylethyl group, a cenylalkyl group such as a cenylmethyl group, an allyl group, a substituted or unsubstituted alkenyl group such as a 2-chloroallyl group, a phenyl group, Substituted or unsubstituted aryl groups such as P-methylphenyl group, naphthyl group and m-methoxyphenyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, and those substituted with these cycloalkyl groups Can be mentioned . Of these, R ₁ is preferably an alkyl group having 1 to 6 carbon atoms, an allyl group, a phenyl group or the like.

R ₂ and R ₃ represent an alkyl group: an alkoxyalkyl group such as a methoxyethyl group and an ethoxyethyl group. R ₂ and R ₃ are particularly lower groups such as a methyl group, an ethyl group, a propyl group and a butyl group. An alkyl group or R ₂ ,
A cyclohexyl group in which R ₃ is cyclized is preferable.

Specific examples of the amino group substituted with the substituents R ₄ and R ₅ include the followings. Amino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, t-propylamino group, t-butylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, A di-n-butylamino group,

Ethylmethylamino group, n-propylmethylamino group, n-butylethylamino group, n-propyl (n-butyl) amino group, hydroxyethylamino group,
A methoxypropylamino group, a di-hydroxyethylamino group, a methoxyethoxyethylamine, and R ₄ and R ₅ are combined to form a nitrogen-containing double ring as an example.

[0015]

[Chemical 8]

[0016]

[Chemical 9]

[0017]

[Chemical 10]

[0018]

[Chemical 11]

[0019]

[Chemical 12]

[0020]

[Chemical 13]

[0021]

[Chemical 14]

[0022]

[Chemical 15]

[0023]

[Chemical 16]

[0024]

[Chemical 17]

[0025]

[Chemical 18]

[0026]

[Chemical 19]

[0027]

[Chemical 20]

[0028]

[Chemical 21]

[0029]

[Chemical formula 22]

[0030]

[Chemical formula 23]

[0031]

[Chemical formula 24]

R ₆ is preferably a hydrogen atom or an electron donating group such as an alkyl group.

Further, the substituent R ₁ of the general formula (1) is an alkylene group, an alkylene (polyoxy) alkylene group or an alkylenearylalkylene group [in the general formula (2), -A
The dimer of the following general formula (2) obtained in place of [indicated as-] was a photochromic compound having red color development, excellent fatigue resistance against repeated red color development, and having sufficient color density. .

[0034]

[Chemical 25] (In the formula, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are as defined in the general formula (1))

The spironaphthoxazine compound of the present invention can be synthesized by various methods. For example, it can be obtained by reacting an indolenine compound with an amine compound and a nitrosonaphthol compound. The spironaphthoxazine compound of the present invention can be synthesized by a known method. As the reaction solvent, benzene, toluene, xylene, nitrobenzene, methanol, propanol, butanol, acetone, methyl ethyl ketone, dichloromethane, dichloroethane, trichloroethane, etc. can be used. Reaction temperature is 0-200
℃.

As the light-sensitive material of the present invention, the spironaphthoxazine compound of the present invention is dissolved in a solvent and coated on a support, or the compound is microencapsulated with gelatin or the like and mechanically attached to the support. Or
Those adhered with a binder resin, kneaded with the binder resin, or uniformly dispersed by a method such as solvent dispersion, or a resin composition obtained by adding the compound at the time of resin synthesis by a known method. Created. When producing the light-sensitive material, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a stabilizer such as a metal salt of naphthenic acid, and the like may be added. As the support, one that does not interfere with the color development and decolorization of the compound. Specifically, paper, pallita paper, synthetic paper, fiber, synthetic resin, film, metal plate, glass and the like can be used. As the binder resin, those which do not interfere with the color development and decolorization of the compound are preferable. The addition ratio of the compound is 0.01 to 50%, preferably 0.1 to 30% with respect to the resin. Synthetic resin film,
As the binder resin, for example, polyethylene glycol resin, polystyrene resin, polyvinyl butyral resin, polyvinyl chloride resin, polyvinyl butyral resin,
Polymethylmethacrylate polyvinyl chloride resin, vinyl acetate copolymer resin, polycarbonate resin, styrene-butadiene copolymer resin, acrylic resin, epoxy resin, silicone resin, acetyl cellulose resin, polyester resin, polyurethane resin, etc. Resin can be used. Examples of the organic solvent used include benzene, toluene, xylene, tetrahydrofuran, acetone, methyl ethyl ketone cyclohexane,
Acrylonitrile, methanol, ethanol, methyl cellosolve, ethyl cellosolve, ethyl acetate, dioxane and the like can be mentioned. Furthermore, these mixed solvents can also be used conveniently. A known method can be applied as a method for forming the photosensitive layer in a film shape on the support. The film thickness is 0.5μ depending on the purpose of use as a photosensitive material.
m to 1.0 mm is preferable, and particularly 5 μm to 0.5 m
m is preferred.

[0037]

【Example】

The present invention is described in detail below with reference to specific synthesis examples and examples of use as photosensitive materials, but the present invention is not limited to these examples.

Example 1 Synthesis of compound (1)

8 g of 1-nitroso-2-naphthol was dissolved in 300 ml of benzene, 3 g of piperidine was added thereto, and the mixture was stirred overnight at room temperature. Next, 4 g of a mixture (1: 1) of 1,3,3-trimethyl-2-methylene-6-trifluoromethylindolenine and 1,3,3-trimethyl-2-methylene-4-trifluoromethylindolenine (1: 1) was added. In addition, the mixture was stirred at room temperature overnight. After completion of the reaction, the solvent was distilled off with an evaporator, the reaction product was separated and purified by silica gel column chromatography (solvent: benzene), and 0.2 g of a light brown crystal having a melting point of 213 to 215 ° C. represented by the following structural formula. Got

[0041]

[Chemical formula 26]

The elemental analysis values of the compound (1) were as follows: Elemental theoretical value Measured value C 70.13% 70.22% H 5.89% 5.93% F 11.88% 11.80% N 8 0.76% 8.80%

Example 2

10 mg of the compound (1) obtained in Example 1 was mixed with a thermoplastic polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd .:
It was dissolved in 3.3 g of NV = 30%, MEK / toluene = 2/8, and a bar coder (winding wire diameter 0.3
mm), and dried at 70 ° C. for 30 minutes to obtain a coating film. The surface of this photosensitive coating was irradiated with 9 W of black light from a height of 3 cm for 30 seconds at room temperature, and immediately after that, the maximum absorption wavelength was measured with a color eye (manufactured by Macbeth Co.) to give a red color of 556 nm. Then, by blocking the ultraviolet rays and leaving it for several hours or irradiating it with visible light, the original colorless state was restored, and this change could be repeated.

Example 3

Compound (1) is added to urethane resin at 0.3%
It was added to make a film. Then from a height of 3 cm 9
Irradiate W black light for 30 seconds, and immediately after that,
When the maximum absorption wavelength was measured with a color eye (manufactured by Macbeth Co.), a red color of 557 nm was developed. Next, when ultraviolet rays were blocked and left for several hours, or when visible light was irradiated, the original colorless state was restored, and this change could be repeated.

Example 4

Compound (1) was added to polystyrene resin
0.1% was added to form a film, which was irradiated with an 80 W high-pressure mercury lamp at an irradiation distance of 10 cm for 2 seconds, and immediately after that, the maximum absorption wavelength was measured with a color eye (manufactured by Macbeth Co.).
The color developed was red at 55 nm. Next, when ultraviolet rays were blocked and left for several hours, or when visible light was irradiated, the original colorless state was restored, and this change could be repeated.

Example 5

Compound (1) was added to acrylic resin in an amount of 0.
1% was added to form a film, which was irradiated with an 80 W high pressure mercury lamp at an irradiation distance of 10 cm for 2 seconds, and immediately after that, the maximum absorption wavelength was measured with a color eye (manufactured by Macbeth Co.).
The color developed was red at 53 nm. Next, when ultraviolet rays were blocked and left for several hours, or when visible light was irradiated, the original colorless state was restored, and this change could be repeated.

Example 6

1.4 g of the compound (1) was added to oil (KMC1
13 (manufactured by Kureha Chemical Co., Ltd.)) at 94 ° C., and after cooling to room temperature, 5% Scripset # 520 70 g
Was added and emulsified with a homomixer for 15 minutes to obtain an emulsion. Next, a mixture of 6 g of melamine, 17 g of formalin and 37 g of water was adjusted to pH 9 with 5% NaOH water, and the mixture was adjusted to 3 at 60 ° C.
After stirring for 0 minutes, the total amount of emulsion is added to this reaction solution,
Furthermore, it stirred at 80 degreeC for 90 minutes. After the reaction solution was cooled to room temperature, it was adjusted to PH9 again with 5% NaOH aqueous solution. The resulting particle microcapsule slurry liquid is filtered, washed with water, and dried to obtain a compound (1) -containing 2 to 10 μm.
The melamine resin film microcapsules of When this microcapsule was taken out of the room and exposed to sunlight, it turned red. When it was returned to the room, it turned white.

Example 7

Dioctyl phthalate was used in place of KMC113 in Example 6 to obtain microcapsules of 2 to 10 μm. When this microcapsule was taken out of the room and exposed to sunlight, it turned red. After returning to the room,
It turned white.

Example 8

A 3% chloroform solution of the compound (1) was added to
After coating on the surface of the glass substrate treated with trimethylchlorosilane, it is carried out at 250 rpm for 60 seconds and at 1000 rpm for 15 seconds.
Each spin was added for 0 seconds and dried. This substrate was initially colorless, but was irradiated with 9 W of black light from a height of 3 cm for 30 seconds, and immediately after that, the maximum absorption wavelength was measured with a color eye (manufactured by Macbeth Co.) to give a red color of 555 nm. . Next, it was allowed to stand for several hours after being blocked from ultraviolet rays, or when it was irradiated with visible light, the original colorless state was obtained, and this change could be repeated.

Various spironaphthoxazine compounds were synthesized in the same manner as in the synthesis example of the compound (1). A photoreceptive film coating was formed on the art paper by using the obtained compound by the method according to Example 2, and the maximum absorption wavelength (λmax) was measured by irradiating with ultraviolet light by a black light.
The results are shown in Tables 1 and 2. R _{1 to} R in Tables 1 and 2
₇ and A represent each substituent of the above general formulas (1) and (2).

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

INDUSTRIAL APPLICABILITY The present invention relates to a spironaphthoxazine compound having excellent fatigue resistance and a sufficient red color density. That is, this compound develops a red color by irradiation with sunlight or ultraviolet rays, and when it blocks light or is irradiated with visible light, it returns to its original state, and this change can be repeated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location G03C 1/73 503 9413-2H (72) Inventor Nobuo Suzuki 3-7 Kamiyacho, Kita-ku, Tokyo No. 6 Hodogaya Chemical Co., Ltd. Tokyo factory

Claims (3)

[Claims] 1. A spironaphthoxazine compound represented by the general formula (1): In the formula, R ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group,
R ₂ and R ₃ each independently represent an alkyl group or an alkoxyalkyl group, or R ₂ and R ₃ are bonded to each other and may be cyclized, and R ₄ and R ₅ are independently hydrogen atoms, An alkoxy group or an alkyl group which may be substituted with a hydroxy group, or R ₄
R ₅ and R ₅ may bond to each other or cyclize to form a nitrogen-containing heterocycle. R ₆ represents a hydrogen atom or an alkyl group. R ₇
Represents a cyano group, a nitro group, a perfluoroalkyl group, a fluorine atom, a chlorine atom or a bromine atom, and the substitution position of R ₇ is 1 ′, 3 ′ or 4 ′ except 2 ′. 2. A spironaphthoxazine compound represented by the general formula (2): In the formula, A represents an alkylene group, an alkylene (polyoxy) alkylene group, or an alkylenearylalkylene group, and R ₂ and R ₃ independently of each other represent an alkyl group or an alkoxyalkyl group, or R ₂ and R
₃ is bonded to each other and may be cyclized, and R ₄ and R ₅ each independently represent a hydrogen atom, an alkoxy group or an alkyl group which may be substituted with a hydroxy group, or R ₄ and R 5 ₅ may be bonded to each other or cyclized to form a nitrogen-containing heterocycle. R ₆ represents hydrogen or an alkyl group. R ₇ represents a cyano group, a nitro group, a perfluoroalkyl group, a fluorine atom, a chlorine atom or a bromine atom, and the substitution position of R ₇ is 1 ′, 3 ′ or 4 ′ except 2 ′. 3. A photosensitive material containing the spironaphthoxazine compound represented by claim 1 or 2.