JPS62280264A - Dithienyldicyanoethene derivative and recording material obtained by using same - Google Patents

Abstract

NEW MATERIAL:Compds. of formula I, wherein R<1> and R<2>, R<3>, R<4>, R<5> and R<6> are each an alkyl. EXAMPLE:A compd. of formula II. USE:The title derivatives which are photochlromic dyes which reversibly form red color by ultraviolet radiation and turn original light yellow when irradiated with visible light and are useful as recording materials, memory materials, copying materials, dimming materials, sensitized materials for printing, etc. PREPARATION:A 4-cyanomethyl-2,3,5-trialkylthiophene of formula III is condensed with a compd. of formula IV in a solvent consisting of water and an org. solvent (e.g., CCl4) and in the presence of a phase transfer catalyst (e.g., triethylbenzylammonium chloride) at an alkaline pH and a temp. of room temp. to 100 deg.C.

Description

[Detailed description of the invention] 3. Detailed description of the invention [Industrial application field].

The present invention relates to a novel 1,2-di(2,3,5-trialkylchenyl)-1,2-dicyanoethene conductor and an optical recording material using the same. For more information,
The present invention is useful as various recording/memory materials, copying materials, light control materials, printed photoreceptors, laser photosensitive materials, photosensitive materials for photosetting, optical filters, masking materials, light meters, and display materials. The present invention relates to a novel compound having photochromic properties and an optical recording material using the same.

[Prior Art] Various compounds having photochromic properties that develop or discolor when irradiated with light are known, and photochromic materials using these compounds have been proposed.

For example, JP-A-55-149812 proposes a photochromic light-sensitive material in which a spiropyran compound of the following formula is dispersed in a nitrocellulose resin.

(In the formula, Ra represents a hydrogen atom or a halogen atom, and Rb
represents an alkyl group, and Ro represents a hydrogen atom or an alkoxy group. ) Furthermore, JP-A-50-28824 proposes a photochromic light-sensitive material in which a spiropyran compound of the following formula is dispersed in a polymeric compound having an alcoholic hydroxyl group.

(In the formula, Rd and Re represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.)
No. 28892 proposes a photochromic material containing a spironaphthoxazine compound as shown in the following formula.

H3 (In the formula, Rf represents a hydrogen atom, a halogen atom, a cyan group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group.) Incidentally, in recent years, attempts have been made to use such photochromic compounds as reversible optical recording materials. There is a lot of research being done on this, but in this case it is required that the following conditions are met.

■ Semiconductor laser sensitivity ■ Non-destructive readout ■ Thermal stability of recording ■ Fast response speed ■ Repeat durability [Problems to be solved by the invention When cophotochromic compounds are used as optical recording materials, particularly important problems are: Among the above requirements, the thermal stability of the recording is insufficient, and the recording written by a photochemical reaction is unstable. That is, in the case of conventional photochromic compounds, the colored state is generally thermally unstable and returns to its original state within several hours at room temperature.
It has the disadvantage of poor recording thermal stability.

On the other hand, those with good thermal stability generally have a problem of poor repeat durability, and none of the conventional photochromic compounds can be said to have sufficiently satisfactory characteristics as optical recording materials.

[Means and effects for solving the problems] As a result of intensive studies to obtain a photochromic compound suitable for use as an optical recording material, which does not have the above-mentioned conventional problems, the present invention has developed a new photochromic compound that exhibits good photochromism. It was completed by the discovery of a compound.

That is, the present invention provides a dithenyldicyanonithene derivative represented by the general formula [Eco (wherein RI, R2, R3, R4, R5, and R6 represent an alkyl group) and a recording layer containing the same. The gist is an optical recording material that has

The present invention will be explained in detail below.

The dithenyldicyanonithene derivative of the present invention is represented by the general formula [II, where RI, R2,
The alkyl groups represented by R3, R4, R5, and RQ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, 5ec-butyl group, n-pentyl group. group, n-heptyl group, n-hexyl group,
CI=a, preferably C+ to C4, cententhate or branched alkyl groups such as n-octyl group, 2-ethylhexyl group, n-stearyl group, and the like.

The compound of the present invention can be produced, for example, as follows. That is, the following general formula [II], [III
] (In the formula, RI, R2, R3, 4, R5, Rfl are the same as the above definitions.) 4-cyanomethyl-2,3,5-)-realkylthiophene represented by: in water-organic solvent, It can be produced by condensation in an alkaline environment in the presence of a phase transfer catalyst.

The organic solvent used in the condensation reaction is preferably a halogen solvent such as dichloromethane, chloroform, carbon tetrachloride, or tetrachloroethane. Furthermore, examples of the phase transfer catalyst include tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium chloride, and the like. Furthermore, the alkaline agents used include sodium hydroxide,
Examples include potassium hydroxide.

The condensation reaction temperature is preferably from room temperature to 100'C, particularly preferably from 40 to 50C.

The dithenyldicyanoedene derivative of the present invention is, for example,
When irradiated with light of 200 to 420 nm, a structural change occurs as shown in the following formula, resulting in a pale yellow to red compound [I
V]. Moreover, this red colored state can be reversibly restored by photoreaction. That is, for example,
When irradiated with light of 420 to 600 nm, it can be returned to its original state as shown in the following formula.

[II [ff] The colored state of the dithenyldicyanoethene derivative of the present invention has extremely high thermal stability, and even when heated at high temperature for a long time, the colored state does not change and is well maintained. Ru.

Therefore, the ditininyl dicyanoethene derivative of the present invention is
It can be advantageously used in reversible optical information recording materials.

The optical recording material of the present invention having a recording layer containing such a novel compound of the present invention can be easily obtained according to a known method.

For example, (1) the dithenyldicyanoethene derivative of the present invention may be added to polyester resin, polystyrene resin, polyvinyl butyral resin, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, cellulose acetate, epoxy It is dispersed or dissolved in a solvent such as carbon tetrachloride, benzene, cyclohexane, methyl ethyl ketone, tetrachloroethane, etc. together with a binder such as a resin or phenol resin, and then applied onto a suitable substrate.

(2) The dithenyldicyanoedene derivative of the present invention is vapor-deposited on a suitable substrate by a known vapor deposition method or a co-evaporation method with other compounds.

(2) The dichenyldicyanoedene rust conductor of the present invention is dissolved in the above-mentioned solvent and sealed in a glass cell or the like.

The optical recording material of the present invention can be manufactured by forming a recording layer by the method described above.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 (1) Preparation of dithenyl dicyanoethene derivative 50% sodium hydroxide solution (T! 120 ml) and triethylbenzylammonium chloride 0.25 g (0,001 mol) were stirred at 40°C. A mixed solution of 15.3 g (0.09 mol) of 4-cyanomethyl-2,3,5-trimethylthiophene represented by the following structural formula and 15.3 g (0.1 mol) of carbon tetrachloride was added to the solution for 30 minutes. The mixture was added dropwise at 45° C. and reacted with stirring for 1 hour and 30 minutes.

The reaction mixture was poured into 300 ml of water, stirred well, and extracted three times with 100 ml of ether, followed by 1 ml of chloroform.
Extracted twice with 00 mfL. The organic layers were combined, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a dark red oily product.

This product was separated and purified by silica gel column chromatography, and crystallized from ether-hexitine to give a yellow powder of 6.0. z (yield 47%) was obtained. The melting point of this product is 16
The temperature was 2-164°C.

From the measurement results of physical properties in (2), this substance was identified as 1,2-di(2,3,5-trimethylchenyl), -1,2-dicyanoethene shown by the following structural formula. .

(i) p, m, r (CDCJ23) δ=2.13 S
3H2,30S 3H 2,47S 3H (ii) MS (m/e) 325(M
+)311 (M''-GH3) (iii) I R (liquid paraffin) 2220c
z-'1440cm "" (3) Photochromic property (reversible memory property) Above (1)
) was dissolved in benzene at a concentration of 10-4 mol/°C.
It was sealed in a glass cell of cm x 4 cm, and 404.
When irradiated with 5 nm monochromatic light for 2 minutes, it was colored red, and its absorption spectrum was as shown by the solid line in Figure 1.
It changed to what is shown by the dotted line. That is, upon irradiation with light at 404.5 nm, a - change in the following formula occurred, resulting in red coloring.

[B] This colored state is very thermally stable, with a temperature of 12°C at 8°C.
As shown in FIG. 2, no decrease in the absorption of the colored state was observed even after heating for more than an hour.

Next, 546.1 nm was applied to the red colored glass cell.
When irradiated with monochromatic light for 5 minutes, the color immediately disappeared and changed to its original color.

This change could be repeated reversibly.

Example 2 The following structure was prepared in the same manner as in Example 1 except that 19.2 g of the compound represented by the groove below was used instead of 4-cyanmethyl-2゜3.5-trimethylthiophene. 1,2-di(2,3,5-)-linitylchenyl)-1,2-dicyanoedene was obtained.

In the same manner as in Example 1, a benzene solution of the obtained compound was sealed in a glass cell, and 404.5n was added to the glass cell.
When irradiated with m monochromatic light for 2 minutes, it was colored red.

This colored state was thermally very stable. Next, 54
When irradiated with 6.1 nm monochromatic light for 5 minutes, the color immediately disappeared. This change could be repeated reversibly.

Example 3 A compound in which R I in the general formula [I, R [I] is an alkyl group shown in Table 1 was synthesized by a method similar to Example 1, and a benzene solution of the obtained compound was added to When an ultraviolet irradiation test was conducted in the same manner as in Example 1, the colors developed were as shown in Table 1.

Moreover, each colored state was very thermally stable. Next, when this colored product was irradiated with visible light, it was able to fade back to its original pale yellow state. This change could be repeated reversibly.

Table 1 [Effects of the Invention] As detailed above, the 1,2-di(2°3.5-
Trialkyl'chenyl)-1,2-dicyanoethene derivatives are novel dyes and compounds that exhibit good photochromism. That is, the compound of the present invention is colored red when irradiated with ultraviolet rays, and this colored state is extremely stable thermally, but when irradiated with visible light, it returns to its original pale yellow state. This change can thus be repeated reversibly.

Because of its extremely excellent photochromism, the compound of the present invention can be used in various recording/memory materials, copying materials, light control materials, printed photoreceptors, laser photosensitive materials, photosensitive materials for phototypesetting, and optical filters. It is extremely useful as a masking material, light meter, and display material.

Therefore, the optical recording material of the present invention having a recording layer containing such a compound of the present invention satisfies requirements such as semiconductor laser sensitivity, nondestructive readout, thermal stability of recording, fast response speed, and repetition durability. All of them are fully satisfactory and have extremely excellent properties.

[Brief explanation of drawings]

FIG. 1 is a diagram showing optical changes in the absorption spectrum of the compound of the present invention in the optical recording material prepared in Example 1, where the horizontal axis shows wavelength (mm) and the vertical axis shows absorbance. FIG. 2 is a diagram showing the thermal stability of the colored state of the compound of the present invention in the optical recording material prepared in Example 1, in which the horizontal axis represents time (hr) and the vertical axis represents absorbance.

Claims (4)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1, R^2, R^3, R^4, R^5, R
^6 represents an alkyl group. ) A dithienyldicyanoethene derivative represented by (2) In the general formula [I], R^1, R^2, R
The derivative according to claim 1, wherein ^3, R^4, R^5, and R^6 represent a linear or branched alkyl group having 1 to 20 carbon atoms. (3) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R^1, R^2, R^3, R^4, R^5, R
^6 represents an alkyl group. ) An optical recording material comprising a recording layer containing a dithienyldicyanoethene derivative represented by: (4) In the general formula [I], R^1, R^2, R
3. The optical recording material according to claim 3, wherein ^3, R^4, R^5, and R^6 represent a linear or branched alkyl group having 1 to 20 carbon atoms.