JPH05125061A - Pendant type triazole compound - Google Patents

Abstract

PURPOSE:To obtain a new thermostable compound useful as a photochromic material, especially an optical-optical memory material, etc. CONSTITUTION:A compound expressed by formula I [R1 to R3 may be same or different and at least one thereof is group containing C, H or X (X is F, Cl, Br or I)], e.g. (3'-amino-1',2',4'-triazole)azo-1,2,4-triazole. The compound expressed by formula I is obtained by reacting (4'-amino-2',3',5'-triazole)azo-2,3,5- triazole expressed by formula II with polymethacryloyl chloride expressed by formula III in a solvent (e.g. 1,4-dioxane) at ambient temperature to 70 deg.C. The compound expressed by formula I irreversibly initiates a structural change by irradiation with light. In an optical-optical memory material, etc., recorded information can stably be held for a long period even in high-temperature rooms.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pendant triazole compound. More specifically, the present invention relates to a pendant polymer having a so-called triazole compound having a so-called photochromic property in a side chain, which undergoes a reversible structural change upon light irradiation, and a material using the pendant polymer.

[0002]

2. Description of the Related Art Photochromic materials undergo reversible structural changes upon irradiation with light, and can be used in various applications such as memory materials and printing utilizing changes in the hydrophilicity of the surface. However, the photochromic materials that have been studied so far have one of their isomers that is thermally unstable, and is easily converted into a stable isomer. The storage range and stability were not reliable for a certain period of time, and it was difficult to apply the photochromic substance alone to other substances even in actual use.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel pendant type triazole compound which has photochromic properties, is stable in any isomer, and can be used practically.

[0004]

The pendant type triazole compound of the present invention has the chemical formula 1 and the chemical formula 2.

[0005]

[Chemical 3]

(Wherein the substituents R ₁ , R ₂ and R ₃ are
They may be the same or different and at least one represents a carbon-containing group, -H, or -X (X = F, Cl, B.
r, I)), preferably R ₁ ,
R ₂ and R ₃ are the same. Further, the more desirable pendant triazole compounds of the present invention, wherein the substituent is -CH ₃ or -H.

[0007]

[Chemical 4]

(Wherein the substituents R ₄ , R ₅ and R ₆ are
They may be the same or different, and at least one represents a carbon-containing group, —H, or —X (X═F, Cl, B
r, I)), preferably R ₄ ,
R ₅ and R ₆ are the same. Further, the more desirable pendant triazole compounds of the present invention, wherein the substituent is -CH ₃ or -H.

[0009]

According to the structure of the present invention, by irradiating the substances of the structures A and C with the light of the specific wavelengths (λ ₁ ) and (λ ₃ ) as shown in the chemical formulas 3 and 4, , And the structure is changed to structure B and structure D.
When another specific wavelengths (λ ₂ ) and (λ ₄ ) are applied to the structures B and D, the substances of the original structures A and C are restored. During this time, structures A and B, and structures C and D
In, the molecular weight does not change, but the structure changes and the absorption wavelength changes.

[0010]

[Chemical 5]

[0011]

[Chemical 6]

(Each isomer of Chemical Formula 3 and Chemical Formula 4 and mixtures thereof are included in the present invention.) These compounds are structurally stable and thermally stable in each state.

[0013]

EXAMPLES The compounds represented by the chemical formulas 1 and 2 according to the present invention can be produced by synthesizing a photochromic compound and adding it as a side chain of a polymer. As one of them, (3′-amino-1 ′, 2
′, 4′-Triazole) azo-1,2,4-triazole is bound to polymethacrylic acid chloride (PMAC) by an acid amide bond (hereinafter referred to as PTAM) in the production procedure of Chemical Formula 5 and (5 ′ -Mercapto-1 ',
2 ′, 4′-triazole) azo-1,2,4-triazole is bound to polymethacrylic acid chloride (PMAC) by an acid amide bond (hereinafter referred to as PMTM). Show the method.

[0014]

[Chemical 7]

[0015]

[Chemical 8]

[Production Example] Production method of (3'-amino-1 ', 2', 4'-triazole) azo-1,2,4-triazole 3,5-diamino-1,2,4-triazole 1. 98
g (0.02 mol), concentrated hydrochloric acid 4 ml (4.8 mol)
And 10 ml of water are mixed to make a solution, and ice is mixed to bring the temperature to about 0.
℃. Sodium nitrite 1.38g (0.02mo
l) was dissolved in 5 ml of water and slowly added dropwise to the reaction solution while stirring at 5 ° C. Next, 1.38 g (0.02 mol) of 1,2,4-triazole was dissolved in 10 ml of water and slowly added dropwise to the reaction solution while stirring at 5 ° C.
Subsequently, the reaction solution was stirred at room temperature for several hours. This reaction solution was separated and purified to obtain (4'-amino-2 ', 3', 5'-
Triazole) azo-2,3,5-triazole 0.5
23 g (yield 14.6%) was obtained.

Method for producing PTAM (4'-amino-2 ', 3', 5'-triazole) azo-2,3,5-triazole 1.0 g (0.0056)
(mol) was dissolved in 20 ml of ethyl acetate, 0.56 g of triethylamine was added, and the mixture was stirred. 0.29 g of polymethacrylic acid chloride (PMAC) was slowly added dropwise to 10 ml of 1.4-dioxane solution at room temperature. After stirring for several hours, the mixture was stirred at 70 ° C. for 1 hour. The reaction solution was separated and purified to obtain 0.18 g of PTAM (yield 2
6.0%).

Next, the photoisomerization reaction formula of PTAM is shown in chemical formula 7, and FIG. 1 shows the absorption spectrum in each structure.

[0019]

[Chemical 9]

Further, the measurement results of the thermal stability of PTAM structure F at 40 ° C. are shown in FIG.

Method for producing (4'-amino-2 ', 3', 5'-triazole) azo-4-mercapto-2,3,5-triazole 3,5-diamino-1,2,4-triazole 1 .98
g (0.02 mol), concentrated hydrochloric acid 4 ml (4.8 mol)
And 10 ml of water are mixed to make a solution, and ice is mixed to bring the temperature to about 0.
℃. Sodium nitrite 1.38g (0.02mo
l) was dissolved in 5 ml of water and slowly added dropwise to the reaction solution while stirring at 5 ° C. Then 5-mercapto-1,
2,4-triazole 2.02 g (0.02 mol)
Was dissolved in 10 ml of water and slowly added dropwise to the reaction solution while stirring at 5 ° C. Subsequently, the reaction solution was stirred at room temperature for several hours. The reaction solution was separated and purified to give 0.54 g of (4'-amino-2 ', 3', 5'-triazole) azo-4-mercapto-2,3,5-triazole (yield 1
4.6%) was obtained.

Method for producing PMTM (4'-amino-2 ', 3', 5'-triazole) azo-4-mercapto-2,3,5-triazole 1.1
g (0.0056 mol) was dissolved in 20 ml of ethyl acetate, 0.56 g of triethylamine was added, and the mixture was stirred.
There, polymethacrylic acid chloride (PMAC) 0.29
10 g of 1.4-dioxane solution was slowly added dropwise at room temperature. After stirring for several hours, the mixture was stirred at 70 ° C. for 1 hour. This reaction solution is separated and purified to obtain 0.2 PMTM.
3 g was obtained (yield 26.0%).

Next, the photoisomerization reaction formula of PMTM is shown in Chemical Formula 8, and FIG. 3 shows the absorption spectrum in each structure.

[0024]

[Chemical 10]

Furthermore, the measurement results of the thermal stability of PMTM structure F at 40 ° C. are shown in FIG.

[0026]

As described above, the triazole compound having the photochromic property according to the present invention is thermally stable, and can record information stably for a long time even in a high temperature room when using a photo-optical memory material or the like. Has the effect.

[Brief description of drawings]

FIG. 1 is an absorption spectrum diagram of structures E and F of chemical formula 7 in an example of the present invention.

FIG. 2 is a diagram in which the abscissa represents time and the ordinate represents the ratio of absorption wavelength for the structure F of the chemical formula 7 in the example of the present invention (measurement wavelength was 360 nm).

FIG. 3 is an absorption spectrum diagram in the structures G and H of the chemical formula 8 in the example of the present invention.

FIG. 4 is a diagram in which the abscissa represents time and the ordinate represents the ratio of absorption wavelength for the structure H of the chemical formula 8 in the example of the present invention (measurement wavelength was 360 nm).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isao Mizuma 3-3-5 Yamato, Suwa City, Nagano Seiko Epson Corporation

Claims (10)

[Claims] 1. A pendant type triazole compound represented by Chemical Formula 1. [Chemical 1] (In the formula, the substituents R ₁ , R ₂ , and R ₃ may be the same or different, and at least one of them contains a carbon group,
Represents H, -SH ₂ , or -X (X = F, Cl, B
r, I)) 2. The pendant triazole compound according to claim 1, wherein the substituents are the same. 3. The pendant type triazole compound according to claim 2, wherein the substituent is —CH ₃ . 4. The pendant triazole compound according to claim 2, wherein the substituent is —H. 5. A pendant type triazole compound, which partially comprises the structure according to claim 1, 2 or 3 or 4. 6. A pendant type triazole compound represented by Chemical Formula 2. [Chemical 2] (In the formula, the substituents R ₄ , R ₅ and R ₆ may be the same or different, and at least one of them contains a carbon group,
Represents H, -SH ₂ or -X (X = F, Cl, Br,
I)) 7. The pendant type triazole compound according to claim 6, wherein the substituents are the same. 8. The pendant triazole compound according to claim 7, wherein the substituent is —CH ₃ . 9. The pendant type triazole compound according to claim 7, wherein the substituent is —H. 10. A pendant type triazole compound, which partially comprises the structure according to claim 6, 7 or 8 or 9.