JPH0676558B2 - Indoaniline compounds and dyes for thermal transfer recording - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel indoaniline compound and a dye for heat-sensitive transfer recording using the same.

2. Description of the Related Art Conventionally, by using a transfer sheet in which an ink layer containing a sublimable dye is formed on a base film, the side opposite to the ink layer side of the transfer sheet is heated with a heat-sensitive head to form an ink layer. A sublimation-type thermal transfer recording system is known in which a dye is sublimated and transferred and recorded on a recording medium.

The sublimation-type thermal transfer recording method is considered to be suitable for full-color recording because the sublimation transfer amount of the dye can be adjusted by changing the energy applied to the thermal head. There is.

Usually, full-color recording is performed by using three color dyes, namely, a cyan color dye, a magenta color dye, and a yellow color dye, or, in some cases, four color dyes obtained by adding a black dye to the color dye. In order to obtain a good full-color recording of, each dye easily sublimes under the operating conditions of the thermal recording head, does not undergo thermal decomposition under the operating conditions of the thermal recording head, and has a preferable hue for color reproduction, It is necessary to satisfy the conditions such as a large molecular extinction coefficient, stability against light, moisture, chemicals, etc., easy synthesis, and excellent ink suitability.

However, none of the cyan dyes satisfies the above conditions.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention is capable of easily sublimating under the operating conditions of a thermal recording head, not thermally decomposing under the operating conditions of a thermal recording head, having a preferable hue for color reproduction, and It is an object of the present invention to provide a novel cyan color dye satisfying the conditions such as stability, easy synthesis, and ability to easily prepare a highly concentrated ink uniformly dissolved or dispersed.

Means for Solving the Problems The present invention has the general formula [I] (In the formula, -X represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an acetylamino group, a propionylamino group, a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and -Y represents a hydrogen atom or a methoxy group. , An ethoxy group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom or a methyl group, -A- represents -CO- or -COO-,
R represents a methyl group or a vinyl group which may be substituted with bromine, -R ¹ and -R ² are hydrogen atoms, as a substituent, an alkoxy group, a hydroxy group, a cyano group, an alkoxyalkoxy group, a chlorine atom, tetrahydrofuryl Group, an aryl group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an aryloxy group, an acryloyloxy group, an alkyl group which may have a methacryloyloxy group or an isocrotonoyl group, an allyl group, an aryl group, R ³ and -R ⁴ represents a hydrogen atom, an alkyl group which may be substituted by a fluorine atom, an alkoxy group, a halogen atom or a -NH-a-R. ) Is an indoaniline-based compound and a dye for heat-sensitive transfer recording.

The indoaniline-based compound of the present invention represented by the general formula [I] has the following general formula [II] ^{(Wherein, -A -, -. R 3} , -R 4 and -R are as defined above) and phenols represented by the following general formula [III] (In the formula, -X, -Y, -R ¹ and -R ² are the same as defined above.) And an aniline represented by the following formula:
It can be produced by heating.

The indoaniline compound of the present invention represented by the above general formula [I] can be used as a dye for thermal transfer recording. When the dye for thermal transfer recording of the present invention is applied to a sublimation type thermal transfer recording system, a dye is used. May be dissolved in a medium together with a concentrating agent, or dispersed in fine particles to prepare an ink, and the ink is applied onto a base film and dried to prepare a transfer sheet.

As the binder for ink preparation, cellulose-based, acrylic acid-based, starch-based and other water-soluble resins, acrylic resins, methacrylic resins, polystyrene, polycarbonate, polysulfone, polyether sulfone, soluble in organic solvents such as ethyl cellulose Resin etc. can be mentioned. When the resin is soluble in an organic solvent, it can be used not only as an organic solvent solution but also as an aqueous dispersion.

As a medium for ink preparation, in addition to water, alcohols such as methyl alcohol, isopropyl alcohol and isobutyl alcohol, methyl cellosolve, cellosolves such as ethyl cellosolve, aromatics such as toluene, xylene and chlorobenzene, ethyl acetate, Butyl acetate and other esters, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, methylene chloride, chloroform, trichlorethylene and other chlorine-based solvents, tetrahydrofuran, dioxane and other ethers, N, N-dimethylformamide, N- Organic solvents such as methylpyrrolidone may be mentioned.

As the base film to which the ink is applied for producing the transfer sheet, thin paper such as condenser paper and glassine paper, and plastic film having good heat resistance such as polyethylene, polyamide and polyimide are suitable. The thickness of the base film may be in the range of 3 to 50 μm.

The method for applying the ink to the base film can be carried out using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, etc., and the thickness of the ink coating layer is within the range of 0.1 to 5 μm after drying. (Yuki Harazaki, "Coating Method" (1979) Maki Shoten).

Functions and Effects of the Invention Since the dye represented by the above [I] of the present invention has a clear cyan color, it is suitable for obtaining a full-color record with good color reproducibility by combining with a suitable magenta color and yellow color. In addition, since sublimation is easy and the molecular extinction coefficient is large, it is possible to obtain high-speed recording with high color density without imposing a heavy burden on the thermal head. More heat,
Since it is stable against light, moisture, chemicals, etc., it is not thermally decomposed during transfer recording, and the preservability of the obtained record is excellent. Further, since the dye of the present invention has good solubility in an organic solvent and dispersibility in water, it is easy to prepare a highly concentrated ink that is uniformly dissolved or dispersed. Thus, it is possible to obtain a transfer sheet on which the dye is uniformly applied at a high concentration.
Therefore, by using these transfer sheets, it is possible to obtain a recording with good uniformity and color density.

EXAMPLES The present invention will be described in detail with reference to examples below, but the examples do not limit the present invention.

Example 1 (a) Production of compound 3.1 g of a phenol compound represented by 4.3 g of the compound represented by and added to 150 ml of ethanol,
After stirring at room temperature, an aqueous solution in which 3.4 g of silver nitrate was dissolved in 15 ml of water was added dropwise. Then add 15 ml of 28% ammonia water,
Further, an aqueous solution prepared by dissolving 10.5 g of silver nitrate in 10 ml of water was added dropwise, and the reaction was carried out at 30 to 40 ° C for 3 hours. After completion of the reaction, extract with chloroform, evaporate the solvent, and perform column purification with chloroform. A purified product of the indoaniline compound represented by

The maximum absorption wavelength (chloroform) of this product was 659 nm.

(B) Preparation of Ink Dye (Indoaniline Compound Obtained in (a) Above) 10
g Polysulfone resin ^* 10 g Chlorobenzene 80 g Total 100 g * Udel P-1700 (trade name) manufactured by Nissan Chemical Industries, Ltd. The mixture having the above composition was treated with a paint conditioner for 10 minutes to prepare an ink. The dye and resin were completely dissolved and a uniform solution ink could be produced.

(C) Preparation of transfer sheet The above ink was applied to a bar coater (RK Print Coat Instrume
No.1 manufactured by NTS Co., Ltd. is used for polyimide film (15μ
(m thickness), and then dried naturally to produce a transfer sheet.

(D) Transfer recording The ink-coated surface of the transfer sheet is superposed on the recording medium, and recording is performed by heating the surface of the transfer sheet opposite to the ink-coated surface under the following conditions using a thermal head to obtain a clear cyan color. It was possible to obtain a uniform and high color density record of 1.40.

Recording conditions Linear density in main scanning and sub-scanning: 4 dots / mm Recording power: 0.6 W / dot Heating time for head: 10 msec The recording medium is a water dispersion of 34 wt% saturated polyethethle (manufactured by Toyobo Co., Ltd.). , Bayronal MD-1200, trade name) 10g and silica (manufactured by Nippon Silica Industry Co., Ltd., Nip
Sil E220A, trade name) 1g was mixed and prepared on a fine paper (200μm thick) bar coater (RK Print Coat Instrum
No. 3) manufactured by ents Co., Ltd. was used for coating and then dried.

The color density was measured using a densitometer RD-514 type (manufactured by Macbeth, USA, filter: Rutten No. 25).

The light resistance test of the obtained record was carried out using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ± 2 ° C. However, almost no discoloration or fading occurred after irradiation for 40 hours.

Example 2 According to the method described in Example 1, indoaniline compounds shown in Table 1 below were produced. The maximum absorption wavelength (chloroform) of the obtained indoaniline compound is shown in Table 1.

Indium aniline compounds shown in Table 1 were used as dyes in place of the dyes used in Example 1, and ink was prepared, a transfer sheet was prepared, and transfer recording was carried out according to the method of Example 1, and the results were clear. It was possible to obtain a uniform recording with a uniform cyan color and a color density shown in Table 1.

Further, according to the method described in Example 1, a light fastness test of the obtained record was performed, and as a result, almost no discoloration or fading occurred.

Claims (4)

[Claims] 1. A general formula (In the formula, -X represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an acetylamino group, a propionylamino group, a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and -Y represents a hydrogen atom or a methoxy group. , An ethoxy group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom or a methyl group, -A- represents -CO- or -COO-,
R represents a methyl group or a vinyl group which may be substituted with bromine, and -R ¹ and -R ² are hydrogen atoms, as a substituent, an alkoxy group, a human viroxy group, a cyano group, an alkoxyalkoxy group, a chlorine atom, and tetrahydrofuryl. Group, an aryl group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an aryloxy group, an acryloyloxy group, an alkyl group which may have a methacryloyloxy group or an isocrotonoyl group, an allyl group, an aryl group, R ³ and −R ⁴ are hydrogen atoms,
It represents an alkyl group optionally substituted by a fluorine atom, an alkoxy group, a halogen atom or -N-H-A-R. ) An indoaniline-based compound represented by. 2. The indoaniline compound according to claim ^1, wherein -R represents a vinyl group, α-methylvinyl group or β-methylvinyl group, and -R ¹ and -R ² are hydrogen atoms. A compound representing a C _{1 to} C ₈ alkyl group, a C _{3 to} C ₈ alkoxyalkyl group, a C _{2 to} C ₄ hydroxyalkyl group, a β-cyanoethyl group, a β-chloroethyl group, an allyl group or a tetrahydrofurfuryl group. . 3. General formula (In the formula, -X represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an acetylamino group, a propionylamino group, a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and -Y represents a hydrogen atom or a methoxy group. , An ethoxy group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom or a methyl group, -A- represents -CO- or -COO-,
R represents a methyl group or a vinyl group which may be substituted with bromine, -R ¹ and -R ² are hydrogen atoms, as a substituent, an alkoxy group, a hydroxy group, a cyano group, an alkoxyalkoxy group, a chlorine atom, tetrahydrofuryl Group, an aryl group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an aryloxy group, an acryloyloxy group, an alkyl group which may have a methacryloyloxy group or an isocrotonoyl group, an allyl group, an aryl group, R ³ and -R ⁴ represents a hydrogen atom, an alkyl group which may be substituted by a fluorine atom, an alkoxy group, a halogen atom or a -NH-a-R. ) A dye for thermal transfer recording represented by. 4. The dye for thermal transfer recording according to claim 3, wherein -R is vinyl group, α-methylvinyl group,
represents a β-methylvinyl group, -R ¹ and -R ² are hydrogen atoms, C _{1 to} C ₈ alkyl group, C _{3 to} C ₈ alkoxyalkyl group, C _{2 to} C ₄ hydroxyalkyl group, β- A dye representing a cyanoethyl group, a β-chloroethyl group, an allyl group or a tetrahydrofurfuryl group.