JPS61263935A - Diallylethene derivative - Google Patents

Abstract

NEW MATERIAL:A diallylethene derivative shown by the formula I (X and Y are 1-6C alkyl; A and B are group shown by the formula II, formula III or formula IV; R<1> and R<2> are 1-6C alkyl; R<3>, R<4> and R<5> are H, 1-6C alkyl, alkoxy or halogen). EXAMPLE:A compound shown by the formula V. USE:A novel dyestuff compound showing photochromism, useful as various recording materials, memorizing materials, reproducing material, printing sensitized materials, sensitized materials for laser, sensitized materials for photographic type setting, etc. Coloring in yellow with irradiation of ultraviolet rays, forming yellowing stably especially in the presence of oxygen, having thermal stability, showing no reduction in color concentration even under heating, fading and being restored to original cololess state by irradiation with visible light rays or laser beam, capable of repeating coloring-fading cycle. PREPARATION:A compound shown by the formula VI is reacted with a compound shown by the formula VII in the presence of zinc in a solvent by addition of titanium tetrachloride at -20-120 deg.C to give a compound shown by the formula I.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel diallylethene derivative, and more specifically to various recording/memory materials, copying materials, printing photoreceptors, laser photosensitive materials, and photosetting. The present invention relates to a novel compound having photochromic properties that can be used as a photosensitive material, an optical filter, a masking material, a photometer, a display material, etc.

(Prior Art) Conventionally, various compounds such as azobenzene-based, bioloken-based, spirobenzopyran-based, and spironaphthoxazine-based compounds have been proposed as compounds having photochromic properties. On the other hand, among other photochromic compounds, the polymer compound (a) shown below is known as being similar to the compound of the present invention.

(M, Ir1e +W, 5chnabel; Eur
, Polym, J., 18゜ (Problem to be solved by the invention) However, conventionally generally known photochromic properties such as the above-mentioned azobenzene type, viologen type, spirobenzopyran type, spironaphthoxazine type, etc. In addition to being thermally unstable in its colored state, the compound also has the problem that, when used as a recording material, for example, the stability of recording written by a photoreaction is poor. On the other hand, when the other photochromic compound (a) is irradiated with ultraviolet rays, it cyclizes, develops color, and converts into compound (b), as shown in the following reaction formula: This colored compound Φ) is extremely unstable, especially in the presence of oxygen, and has the problem that it changes into another type of irreversible compound (c) due to the oxidation effect of oxygen.

The present invention solves the above conventional problems and provides a reversible photochromic compound that stably produces a colored state even in the presence of oxygen, and the colored state is thermally stable. With the goal.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors discovered such a novel diallylethene derivative and completed the present invention. That is, the present invention relates to the general formula [I] B (wherein, X and y represent an alkyl group having 1 to 6 carbon atoms,
R3, R4, and R5 each represent a hydrogen atom, an alkyl group or alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom. ) The gist is diallylethene derivatives shown in

In the novel diallylethene derivative of the present invention, R3. Examples of the halogen atom represented by R4 and R5 include a chlorine atom, a bromine atom, and an iodine atom. Such a novel compound of the present invention can be produced, for example, as follows. That is, the following general formula l]A
-C-X ・・・・・・・・・ l] (In the formula, A,
has the same meaning as in the front leg general formula (1). )
The compound represented by the following general formula (1) % formula % (in the formula, B and Y have the same meanings as in the forefoot general formula [I]) is combined with under,
It can be produced by adding titanium tetrachloride and causing a reaction.

The reaction is usually carried out in an ether solvent such as ether, tetrahydrofuran, dioxane, etc., and the reaction temperature at that time is in the range of -40'C to 200'C, preferably in the range of -0 to 200'C.
Performs smoothly in the range of 120'C.

The diallylethene derivative of the present invention thus produced is
This is a novel dye compound exhibiting photochromism that solves the above conventional problems.

(Examples) 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 addition, "chi" means "weight section" unless otherwise specified.

Example 1 19.6f (03 mol) of zinc powder was charged into a three-bottle flask with a capacity of 1β, and 400rrJ of dioxane was added under a nitrogen atmosphere.
was added and stirred while maintaining the temperature at 15-20'C. To this, 28.5 r (o, 1 s mol) of titanium tetrachloride was added dropwise.
Next, 16.2 f (0.1 mol) of 1-acetyl-2,4,6-)limethylbenzene and 7100 m of dioxa were added.
Gradually drop the mixture with 13, and after the dropwise addition, 1 under reflux.
The mixture was stirred and reacted at 01°C for 8 hours. After cooling, a 10% potassium carbonate aqueous solution 171 was slowly added to the reaction solution. After that, the reaction product mixture was mixed with 200 m7 of ether! The ether layer was collected and dried, the solvent was distilled off, and the resulting reaction product mixture was purified by column chromatography (silica gel, solvent hexane) to obtain a compound represented by the following structural formula: (Theoretical yield: 65) The melting point of Motoichi was 150-153°C.

Using Motoichi 3v, this and thermoplastic polyester resin 10
A solution consisting of 7 (Vylon-200 manufactured by Toyobo Co., Ltd.) and a solvent methyl ethyl ketone 100f was applied to a polyester film (manufactured by Diafoil Co., Ltd., thickness 100 μm) using a bar coater flat plate 3, and dried at 85° C. for 10 minutes. The obtained sample is colorless under normal conditions, but when irradiated with ultraviolet light, it becomes yellow with high color density (λmax = 450
). This colored state was stably produced even in the presence of oxygen, and was also thermally stable, and no decrease in the color density of the colored state was observed even when heated.

Next, when irradiated with 488 μm argon laser light, the color disappeared and returned to its original colorless state.

Furthermore, the above coloring-decoloring cycle could be repeated.

Example 2 Zinc powder 19.6f (0,3
400 ml/l of tetrahydrofuran was added under a nitrogen atmosphere, and the mixture was kept at -10'C to -20C and stirred. To this, 28.4 M (0.15 mol) of titanium tetrachloride was added dropwise, followed by a mixed solution with 100 m71 of raw material 3-acetyl-2,5-dimethinofen 1s, 4y (o, t mol) trihydrofuran. was gradually added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 2 hours to react. After the reaction is complete,
A 10% aqueous potassium carbonate solution IE was slowly added to the reaction solution. After that, the reaction product mixture was diluted with 200 m7 of ether.
The ether layer was collected and dried, the solvent was distilled off, and the resulting reaction product mixture was purified by column chromatography (silica gel, solvent hexane) to give the following structural formula: % formula %) The indicated compound was obtained. (Theoretical yield: 40) The melting point of Motoichi was 75-77°C.

Using Motoichi 4F, this and thermoplastic polyester resin 10
A solution consisting of F (Vylon-200 manufactured by Toyobo Co., Ltd.) and 100 f of solvent methyl ethyl ketone was applied to a polyester film (thickness 100 μm manufactured by Diafoil Co., Ltd.) using Bar Coater Shop 3, and dried at 75° C. for 15 minutes. The obtained sample is colorless under normal conditions, but when irradiated with ultraviolet light, it becomes a deep yellow (λmax = 438 n
m) developed color. This colored state developed stably even in the presence of oxygen, and was also thermally stable, and no decrease in the color density of the colored state was observed even when heated to 80°C.

Next, when irradiated with 488 μm argon laser light, the color disappeared and returned to its original colorless state.

Furthermore, the above coloring-decoloring cycle could be repeated.

Example 3 Zinc powder 1962 (0.3 mol) was charged into a three-bottle flask with a capacity of 1 p, and tetrahydrofuran 4 was added under a nitrogen atmosphere.
001M was added and stirred while maintaining the temperature at -10°C to -20°C. 28.5ii' (0.15 mol) of titanium tetrachloride was added dropwise to this, and then 13.8% of the raw material 3-acetyl-2,5-dimethylfuran was added. A mixed solution of (0.1 mol) and 100 ml of tetrahydrofuran was gradually added dropwise, and after the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours to react. After the reaction was completed, 1000 m7i of a 10% hydrium carbonate aqueous solution was slowly added to the reaction solution. Thereafter, the reaction product mixture was dissolved in ether 1
Extracted 5 times with 50m7I, dried over sodium sulfate, distilled off the solvent, and purified the resulting reaction product mixture by column chromatography (silica gel, solvent n-hexane).
A compound represented by the following structural formula: was obtained. (Theoretical yield 35%) Crystal 4
1 and thermoplastic monopolyester resin 10f (
Toyobo Co., Ltd. Vylon-200) and solvent chloroform 1
A solution consisting of 007 was applied to a polyester film (manufactured by Diafoil Co., Ltd., thickness: 125 μm) using Bar Coater Uma 2, and dried at 75° C. for 30 minutes. The obtained sample was colorless under normal conditions, but when irradiated with ultraviolet light, it developed a yellow color with high color density (λmax) - 400 nm). This colored state was stably produced even in the presence of oxygen and thermally stable, and no decrease in the color density of the colored state was observed even when heated to 80°C. Next, 48
When irradiated with 8 nm argon laser light, the color disappeared and returned to its original colorless state.

(11) Furthermore, the above coloring-decoloring cycle could be repeated.

Example 4 Twenty types of difuryl edene derivatives of the present invention were further synthesized by a method similar to Examples 1 to 3, and each of the obtained derivatives had a structural formula similar to that of Examples 1 to 3. The color tone developed by UV irradiation and its λmax of each sample obtained by coating it on a polyester film are summarized in 1 and 2 of Table 1 below.

The colored states of each sample developed by ultraviolet irradiation are stable even in the presence of oxygen, are thermally stable, and no decrease in the color density of the colored state was observed even when heated. Ta.

Next, when irradiated with argon laser light of 488 nm, the color disappeared and it returned to its original colorless state. Moreover, such color development-
The decolorization cycle could be repeated in the same way for each sample.

(Effects of the Invention) As is clear from the above results, the diallylethene derivative of the present invention is a novel dye compound that exhibits photochromism, and develops a yellow color when irradiated with ultraviolet rays. It is stable even under low temperatures and thermally stable.There is no decrease in the density of the colored color even when heated, and when it is irradiated with visible light or laser light, it disappears and returns to its original colorless state. It is possible to return to the original state and repeat the cycle of coloring and decoloring, which is a remarkable effect of industrial value. Therefore, it is useful as various recording/memory materials, copying materials, printing photoreceptors, laser photosensitive materials, photosensitive materials for phototypesetting, optical filters, masking materials, photometers, display materials, etc.

Patent applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Tsunebe Ogawa Procedural amendment (voluntary) February 3, 1986

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] (wherein, X and Y represent an alkyl group having 1 to 6 carbon atoms,
A and B have ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
Represents a chemical formula, table, etc.▼ or ▲A mathematical formula, chemical formula, table, etc. exists▼, and R^
1, R^2 represents an alkyl group having 1 to 6 carbon atoms, R^2
3, R^4 and R^5 represent a hydrogen atom, an alkyl group or alkoxy group having 1 to 6 carbon atoms, or a halogen atom. ) diallylethene derivatives.