JPH02300285A - Photochromic compound - Google Patents

Abstract

PURPOSE:To improve stability in a state of color development and cycle test durability by condensing an indoline compd. and an (un)substed. salicylaldehyde. CONSTITUTION:An indoline compd. of formula I [wherein R1-3 are each an alkyl, an alkoxy, an aralkyl or an aryl; R4-7 are each a 5-20C alkyl, H, an alkoxy, an aralkyl, an aryl, a halogen, an amino, (di)alkylamino or hydroxyl group and at least one of R4-7 is a 5-20C alkyl] and an (un)sabsted. salicylaldehyde of formula II [wherein R8-11 are each H, an alkyl, an alkoxy, an aralkyl, an aryl, a halogen, nitro, amino, (di)alkylamino, sulfon or hydroxyl group] are condensed to obtain a spiropyran photochromic compd. having a 5-20C alkyl group in the indoline moiety of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel photochromic compound, and more particularly to a spiropyran-based photochromic compound that has excellent stability in a coloring state.

[Conventional technology]

Spiropyran-based photochromic compounds are characterized by: (1) high absorbance in the colored form, (2) a large difference in the absorption wavelength between the colored and decolored forms (, (2) the absorption wavelength of the colored form can be arbitrarily changed by substituents, and (2) Since coloring and decoloring can be repeated, it is expected to be used as a rewritable optical recording material or a display material.

[Problems to be solved by the invention 5] However, conventional spiropyran-based photochromic compounds have poor thermal stability of colored bodies (and when applied as recording materials, there was a problem with storage stability of recordings.The cause of this is This is because the colored substance ring-opened by light returns to its original colorless substance due to a thermal reaction. Therefore, the present invention aims to provide a novel photochromic compound that solves this problem. .

[Means to solve the problem]

The photochromic compound of the present invention is a spiropyran photochromic compound represented by the following general formula, and is characterized by having an alkyl group having 5 to 20 carbon atoms in the indoline moiety.

(In the formula, R1, R2, R3 are alkyl groups, alkoxy groups, aralkyl groups, aryl groups, R4, R5, R6, R7
is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group,
However, at least one of R4, R5, R6, R7 is an alkyl group having 5 to 20 carbon atoms, R8, R9, RIOl
RII represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, a nitro group, an amino group, an alkylamino group, a dialkylamino group, a sulfone group, or a hydroxyl group. ) Since colored bodies of spiropyran-based photochromic compounds have a polar structure, this polarity can be reduced by introducing a substituent, that is, an alkyl group having 5 to 20 carbon atoms to the indoline moiety. stabilization will be achieved. The presence of an alkyl group having 5 to 20 carbon atoms is also an important factor when forming a film to use the photochromic compound of the present invention as a recording material or the like.

The photochromic compound of the present invention is obtained by condensing an indoline compound with substituted or unsubstituted salicylaldehyde. The compound of the above general formula can be synthesized according to the following reaction formula.

(In the formula, R1, R2, R3 are alkyl groups, alkoxy groups, aralkyl groups, aryl groups, R4, R5, R6, R7
is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group,
However, at least one of R4, R5, R6, and R7 is an alkyl group having 5 to 20 carbon atoms, R8, R9, R10, R
11 represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, a nitro group, an amino group, an alkylamino group, a dialkylamino group, a sulfone group, or a hydroxyl group. ) Among the above reaction formulas, the indoline compound is synthesized according to the following reaction formula using the corresponding aniline derivative as a starting material.

R・R7 R, R (wherein R1, R2, R3 are alkyl groups, alkoxy groups, aralkyl groups, aryl groups, R4, R5, R6, R7
is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group,
However, at least one of R4, R5, R6, and R7 represents an alkyl group having 5 to 20 carbon atoms. ) That is, a hydrazine derivative is obtained by diazotizing an aniline derivative with sodium nitrite and reducing it. This hydrazine derivative and 2-
Indolenine is obtained by heating and refluxing propanone under an acid catalyst.

This is treated with a halide having a substituent to be introduced into the N-position, and then desalted with sodium hydroxide to obtain the desired indoline compound.

Some specific examples of the photochromic compound of the present invention represented by the above general formula obtained by such a synthesis method are illustrated below.

Cl8H3? CH3 0CR, CH.

C, 8H3 The alkyl group in the specific examples illustrated may be branched or
Including unbranched ones.

The photochromic compound of the present invention can be used in various recording and storage materials, photoreceptors for printing, photoreceptors for holography, and the like. It can also be used as a material for optical filters, display materials, masking materials, light meters, decorations, etc.

The photochromic compound of the present invention includes alcohols such as methanol, ethanol, and isopropyl alcohol;
Ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethers such as ethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and n-butyl acetate; halogens such as benzene, toluene, xylene natono aromatic solvents, chloroform, and dichloromethane. It is dissolved in various solvents such as system solvents, n-hexane, cyclohexane, acetonitrile, dimethylformamide, dimethyl sulfoxide, and mixed solvents thereof.

In order to use the photochromic compound of the present invention as a photosensitive material, it can be dissolved in the above-mentioned solvent together with a polymeric substance, coated and dried on a support, directly mixed and dissolved in a polymeric substance to form a film, or It can be used by mixing with a molecular substance and then polymerizing and molding the low molecular substance. Further, it is also possible to form a film on a support by a vacuum evaporation method or a LB method.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

The photochromic compound of this example can be synthesized as follows.

p-Dodecylaniline was dissolved in acetic acid, and an aqueous sodium nitrite solution was added dropwise thereto over about 15 minutes to effect diazotization. A suspension of tin dichloride was added to the reaction solution and heated to 60° C. After 2 hours, hydrochloric acid was added and heating was continued for an additional 2 hours. Hydrochloric acid was added again to rapidly cool the reaction solution, and the precipitate that had separated out was suction-filtered to obtain p-dodecylphenylhydrazine hydrochloride.

(Yield 51.1%) The obtained p-dodecylphenylhydrazine hydrochloride was heated under reflux with isopropyl methyl ketone in ethanol under a sulfuric acid catalyst. After the reaction is complete, remove ethanol under reduced pressure,
After alkali treatment, extraction is performed with ethyl ether, 2.
3.3-trimethyl-5-dodecyl indolenine was obtained. (Yield 57.7%) Obtained 2, 3, 3. - trimethyl-5-dodecyl indolenine and octadecane iodide in n-butanol,
After heating under reflux for 4 hours, the solvent was removed under reduced pressure and treated with an alkali to give 1-octadecyl-3,3-dimethyl-5.
-dodecyl-2-methy.

Obtained Lenindoline. (Yield 17.9%) An ethanol solution of 1-octadecyl-3,3-dimethyl-5-dodecyl-2-methyleneindoline was added dropwise to an ethanol solution of 5-nitrosalicylaldehyde, and the reaction was carried out under reflux for 3 hours. Ta. After concentrating the reaction solution, it was separated by thin layer chromatography (developing solvent: ethyl acetate/n-hexane) to obtain the desired photochromic compound. (Yield 5.5
%) The attribution of the 'H-NMR spectrum of the compound of this example is shown below. For measurements, tetramethylsilane was used as an internal standard and deuterated chloroform was used as a solvent.

δ (ppm) 0.63-1.87 64Hm 1-ophtade'/JL
/ and the hydrogen bonded to the methylene group of 5-dodecyl, the hydrogen of the terminal methyl group of 1-ophtadecyl and 5-dobucyl, and the hydrogen of the 3,3-dimethyl group 2.55 2HtBound to the aromatic ring of 5-dodecyl Water in the methylene group 3.10 Hydrogen in the methylene group bonded to N of 2Htl-octadecyl 5.85 1Hd Hydrogen in the 3' position 6.40 to 8.
08 7Hm Aromatic hydrogen and hydrogen at the 4' position A 10% polyester solution containing 5% by weight of the photochromic compound thus obtained was coated on a quartz glass substrate using a spinner, and after vacuum drying at 60°C for 12 hours, a film with a thickness of 1 μm was formed. A sample was prepared.

In addition, a sample was prepared in which the obtained photochromink compound was deposited on a quartz glass substrate by a vacuum evaporation method.

Furthermore, since the photochromic compound of the present invention has an alkyl group having 5 to 20 carbon atoms in the indoline moiety,
It is possible to form a monolayer on the water surface. A Y-type LB film sample with 22 layers on both sides was produced on a quartz glass substrate at a mixing ratio of 1:3 with stearic acid using an LB film production apparatus.

To measure the photochromic properties, ultraviolet light around 35Qnm and visible light around 600nm were separated using an optical filter from a 500W xenon lamp, and these samples were alternately irradiated with each light. When irradiated with ultraviolet light, the sample turned dark blue, and the coloring was quite stable in the dark. When this dark blue sample was irradiated with visible light, the color disappeared, and when it was irradiated with ultraviolet light again, it developed a deep blue color. This cycle could be repeated.

Table 1 shows the photochromic properties of film samples prepared by dispersing the photochromic compounds of Examples in polyester. Stability refers to the absorbance of a colored material left in the dark after one hour as a value relative to the initial absorbance. Durability is expressed as a value of the absorbance of the colored body after alternately irradiating it with ultraviolet light and visible light 100 times relative to the initial absorbance.

(Example 2) A photochromic compound with the structural formula shown below.

CH.

When synthesizing indoline compounds from indolenine, iodized methane was used as an alkylation reagent, and 1
The reaction was carried out at 10°C. Other conditions were the same as in Example 1 to obtain the desired photochromic compound. (yield 7
．． 8%) A film sample was prepared in which the photochromic compound of this example was dispersed in polyester in the same manner as in Example 1, and the photochromic properties were measured. The results are shown in Table 1. .

In addition, a sample was also created in which the photochromic compound of this example was deposited on a quartz glass substrate by vacuum deposition.

Furthermore, the photochromic compound of this example was able to form a monomolecular film on the water surface, and an LB film sample was also created.

The above sample was alternately irradiated with ultraviolet light around 3600 m and visible light around 600 nm as in Example 1. When irradiated with ultraviolet light, the sample turned dark blue, and the coloring was quite stable in the dark. When this dark blue sample was irradiated with visible light, the color disappeared, and when it was irradiated with ultraviolet light again, it developed a deep blue color.

This cycle could be repeated.

(Comparative example) As a comparative example, the following photochromic compound was used in Example 1.
A membrane sample was prepared by dispersing it in polyester in the same manner as above. The photochromic properties of this compound are shown in Table 1.

Cl8H3 [Effects of the Invention] As stated above, in the photochromic compound of the present invention, the colored body is stabilized due to the alkyl group having 5 to 20 carbon atoms in the indoline moiety, and furthermore, the repeated durability is improved. We were able to.

Therefore, the present invention makes it possible to provide recording and display materials with good storage stability.

Procedural amendment June 27, 1999 Director General of the Japan Patent Office Yoshi 1) Takeshi Moon 1, Indication of the case 1999 Patent Application No. 120463 2, Name of the invention Photochromink compound 3, Person making the amendment Spacing Patent originator 5, date of amendment order, full text of amendment 1, title of the invention Photochromic compound 2, claim scope A photochromic compound characterized by being represented by the following general formula Among them, R1, R2, R3 are alkyl group, alkoxy group, ara, alkyl group, aryl group, R4, R5, R6, R
7 is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, or a hydroxyl group, provided that at least among R4, R5, R6, and R7; One is an alkyl group having 5 to 20 carbon atoms, R8, R9, RIOl
Rll represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, a nitro group, an amino group, an alkylamino group, a dialkylamino group, a sulfone group, or a hydroxyl group. 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel photochromic compound, and more particularly to a spiropyran-based photochromic compound that has excellent stability in a coloring state.

[Conventional technology]

Spiropyran-based photochromic compounds have: 1) high absorbance in the colored form, 2) a large difference in the absorption wavelength between the colored and decolored forms, 2) the absorption wavelength of the colored form can be changed arbitrarily by substituents, and 2) coloring and decoloring. Since it can repeat colors, it is expected to be used as a rewritable optical recording material or a display material.

[Problems to be solved by the invention 5] However, conventional spiropyran-based photochromic compounds have poor thermal stability of colored bodies (and when applied as recording materials, there was a problem with storage stability of recordings.The cause of this is This is because the colored substance ring-opened by light returns to its original colorless substance due to a thermal reaction. Therefore, the present invention aims to provide a novel photochromic compound that solves this problem. .

[Means to solve the problem]

The photochromic compound of the present invention is a spiropyran-based photochromic compound represented by the following general formula, and is characterized by having an alkyl group having 5 to 20 carbon atoms in the indoline moiety.

(In the formula, R1, R2, R3 are alkyl groups, alkoxy groups, aralkyl groups, aryl groups, R4, R5, R6, R7
is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group,
However, at least one of R4, R5, R6, R7 is an alkyl group having 5 to 20 carbon atoms, R8, R9, RIOlR
ll represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, a nitro group, an amino group, an alkylamino group, a dialkylamino group, a sulfone group, or a hydroxyl group. ) Colored bodies of spiropyran-based photochromic compounds have a polar structure, so by introducing a substituent that reduces this polarity, that is, introducing an alkyl group having 5 to 20 carbon atoms to the indoline moiety, the colored body can be improved. Stabilization will be achieved. The presence of an alkyl group having 5 to 20 carbon atoms is also an important factor when forming a film to use the photochromic compound of the present invention as a recording material or the like.

The photochromic compound of the present invention is obtained by condensing an indoline compound with substituted or unsubstituted salicylaldehyde. The compound of the above general formula can be synthesized according to the following reaction formula.

R,,R,.

(In the formula, R1, R2, R3 are alkyl groups, alkoxy groups, aralkyl groups, aryl groups, R4, R5, R6, R7
is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group,
However, at least one of R4, R5, R6, and R7 is an alkyl group having 5 to 20 carbon atoms, R8, R9, RIOlR
ll represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, an /S rogene atom, a nitro group, an amino group, an alkylamino group, a dialkylamino group, a sulfone group, or a hydroxyl group. ) Among the above reaction formulas, the indoline compound is synthesized according to the following reaction formula using the corresponding aniline derivative as a starting material.

R1 R4R? Re　　　R? R, Rfu kLl　　　　R.

(In the formula, R1, R2, R3 are alkyl groups, alkoxy groups, aralkyl groups, aryl groups, R4, R5, R6, R7
is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group,
However, five or fewer of R4, R5, R6, and R7 (one of which represents an alkyl group having 5 to 20 carbon atoms) is used.That is, by diazotizing an aniline derivative with sodium nitrite and reducing it, a hydrazine derivative can be obtained. obtain. This hydrazine derivative and 2-
Indolenine is obtained by heating and refluxing propanone under an acid catalyst.

This is treated with a halide having a substituent to be introduced into the N-position, and then desalted with sodium hydroxide to obtain the desired indoline compound.

Some specific examples of the photochromic compound of the present invention represented by the above general formula obtained by such a synthesis method are illustrated below.

CH3 NO2 NO2 The alkyl groups in the specific examples illustrated may be branched or
Including unbranched ones.

The photochromic compound of the present invention can be used in various recording and storage materials, photoreceptors for printing, photoreceptors for holography, and the like. It can also be used as a material for optical filters, display materials, masking materials, light meters, decorations, etc.

The photochromic compound of the present invention includes alcohols such as methanol, ethanol, and inopropyl alcohol;
Ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethers such as ethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and n-butyl acetate; aromatic solvents such as benzene, toluene, and xylene nato; halogens such as chloroform and dichloromethane nato; It is dissolved in various solvents such as system solvents, n-hexane, cyclohexane, acetonitrile, dimethylformamide, dimethyl sulfoxide, and mixed solvents thereof.

In order to use the photochromic compound of the present invention as a photosensitive material, it can be dissolved in the above-mentioned solvent together with a polymeric substance, coated and dried on a support, directly mixed and dissolved in a polymeric substance to form a film, or It can be used by mixing with a molecular substance and then polymerizing and molding the low molecular substance. Further, it is also possible to form a film on a support by a vacuum evaporation method or a LB method.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

(Example 1) The photochromic compound of this example can be synthesized as follows.

p-Dodenylaniline was dissolved in acetic acid, and an aqueous sodium nitrite solution was added dropwise thereto over about 15 minutes to effect diazotization. A suspension of tin chloride was added to the reaction solution, heated to 60°C, and after 2 hours, acid was added, and heating was continued for an additional 2 hours. Hydrochloric acid was added again to rapidly cool the reaction solution, and the precipitate that had separated out was suction-filtered to obtain p-dodecylphenylhydrazine hydrochloride.

(Yield 51.1%) The obtained p-dodecylphenylhydrazine hydrochloride was heated under reflux with inpropyl methyl ketone in ethanol under a sulfuric acid catalyst. After the reaction is complete, remove ethanol under reduced pressure,
After alkali treatment, extraction is performed with ethyl ether, 2.
3.3-) Dimethyl-5-dodecyl indolenine was obtained. (Yield 57.7%) Obtained 2, 3, 3. -trimethyl-5-dodecylindolenine and octadecane iodide in n-butanol
After heating under reflux for an hour, the solvent was removed under reduced pressure, and 1-octadecyl-3,3-dimethyl-5-
Dodecyl-2-methyleneindoline was obtained. (Yield 17
．． An ethanol solution of 1-octadecyl-3,3-dimethyl-5-dodecyl-2-methyleneindoline was added dropwise to an ethanol solution of 5-nitrosalicylaldehyde (9%), and the reaction was carried out under reflux for 3 hours. After concentrating the reaction solution, it was separated by thin layer chromatography (developing solvent: ethyl acetate/n-hexane) to obtain the desired photochromic compound. (Yield 5.5%) The assignment of the 'H-NMR spectrum of the compound of this example is shown below. In the measurement, tetramethylsilane was used as an internal standard and deuterated chloroform was used as a solvent.

δ (ppm) 0.63-1.87 64Hm Hydrogen bonded to the methylene group of 1-octadecyl and 5-dodecyl, hydrogen of the terminal methyl group of 1-octadecyl and 5-dodecyl, and hydrogen bonded to the 3,3-dimethyl group Hydrogen 2.55 2Ht Hydrogen of the methylene group bonded to the aromatic ring of 5-dodecyl 3.10 2Ht Hydrogen of the methylene group bonded to N of 1-octadecyl 5.85 1Hd Hydrogen of the 3' position 6.40 ~8.08 7Hm A 10% by weight solution of polyester containing 5% by weight of the photochromic compound thus obtained and aromatic hydrogen and hydrogen at the 4' position was coated on a quartz glass substrate, and after vacuum drying at 60°C for 12 hours, the film thickness was determined. 1μm
A sample was prepared.

In addition, a sample was prepared in which the obtained photochromic compound was deposited on a quartz glass substrate by vacuum deposition.

Furthermore, since the photochromic compound of the present invention has an alkyl group having 5 to 20 carbon atoms in the intone part,
It is possible to form a monolayer on the water surface. A Y-type LB film sample with 22 layers on both sides was prepared on a quartz glass substrate using a LB film forming apparatus at a mixing ratio of 1:3 with stair and phosphoric acid.

To measure the photochromic properties, the samples were alternately irradiated with ultraviolet light around 360 nm and visible light around 5QQ nm, which were obtained by separating light from a 500 W xenon lamp using an optical filter. When exposed to ultraviolet light, the sample turned dark blue, and the color remained fairly stable in the dark. When this dark blue sample was irradiated with visible light, the color disappeared, and when it was irradiated with ultraviolet light again, it developed a deep blue color. This cycle could be repeated.

Table 1 shows the photochromic properties of film samples prepared by dispersing the photochromic compounds of Examples in polyester. Stability refers to the absorbance of a colored material left in the dark one hour later relative to its initial absorbance. Durability is expressed as a value of the absorbance of the colored body after alternately irradiating it with ultraviolet light and visible light 100 times relative to the initial absorbance.

(Example 2) A photochromic compound with the structural formula shown below.

When synthesizing indoline compounds from indolenine, methane was used as an alkylation reagent, and 1
The reaction was carried out at 10°C. Other conditions were the same as in Example 1 to obtain the desired photochromic compound. (yield 7
．． 8%) A film sample was prepared in which the photochromic compound of this example was dispersed in polyester in the same manner as in Example 1, and the photochromic properties were measured. The results are shown in Table 1.

In addition, a sample was also created in which the photochromic compound of this example was deposited on a quartz glass substrate by vacuum deposition.

Furthermore, the photochromic compound of this example was able to form a monomolecular film on the water surface, and an LB film sample was also created.

The above sample was alternately irradiated with ultraviolet light around 36 Q nm and visible light around 5 Q Q nm as in Example 1. When irradiated with ultraviolet light, the sample turned dark blue, and the coloring was quite stable in the dark. When this dark blue sample was irradiated with visible light, the color disappeared, and when it was irradiated with ultraviolet light again, it developed a deep blue color. This cycle could be repeated.

(Comparative Example) As a comparative example, the following 7 otochromic compounds were used in Example 1.
A membrane sample was prepared by dispersing it in polyester in the same manner as above. The photochromic properties of this compound are shown in Table 1.

〔Effect of the invention〕

As described above, in the photochromic compound of the present invention, the colored body was stabilized due to the alkyl group having 5 to 20 carbon atoms in the indoline moiety, and the durability was also improved. .

Therefore, the present invention makes it possible to provide recording and display materials with good storage stability.

Claims (1)

[Claims] A photochromic compound characterized by being represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1, R2, R3 are alkyl groups, alkoxy groups, aralkyl groups, aryl groups, R4, R5, R6, R7
is an alkyl group having 5 to 20 carbon atoms, a hydrogen atom, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group,
However, at least one of R4, R5, R6, R7 is an alkyl group having 5 to 20 carbon atoms, R8, R9, R10, R
11 represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, a halogen atom, a nitro group, an amino group, an alkylamino group, a dialkylamino group, a sulfone group, or a hydroxyl group. )