JPH06191167A - Indoaniline compound and its use - Google Patents

Abstract

PURPOSE:To prepare a heat sensitive transfer recording ink composition which possesses high sublimating rate and stability of an image after transfer, by mixing up a specific indoaniline compound and binder resin into an organic solvent and/or water. CONSTITUTION:A heat sensitive transfer recording ink composition is prepared by compounding. agitating and mixing up an indoaniline compound and binder resin represented by a formula I (R1 represents H, a halogen atom and a C1-C4 alkyl group, R3 and R3 represent H and a C1-C4 alkoxy group, R4 and R5 represent H and a C1-C4 alkyl group and R6 and R7 represent an alkyl group and alkenyl group) into an organic solvent and/or water. This ink composition is applied onto a base such as a plastic film and dried, to which a coloring matter carrying layer is laminated and a transfer sheet is obtained. Oily resin such as phenol and aqueous resin such as casein are available as an exemplification of resin and aromatics such as benzene and toluene are available as the exemplification of the solvent to prepare the ink composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an indoaniline compound and a heat-sensitive transfer recording dye, a heat-sensitive transfer recording ink composition and a transfer sheet, which are used for color hard copy by a sublimation heat transfer recording system, which is an application of the compound.

[0002]

2. Description of the Related Art A thermal transfer recording system using a sublimation dye is applied to a recording paper by coating a thin condenser paper or PET film having a thickness of several microns with an ink-forming sublimation dye and selectively heating it with a thermal head. This is one of the thermal transfer printing methods for transferring and is currently used as a means for recording various kinds of image information (hard copy).

The sublimation dye used here is characterized by abundant colors and excellent color mixing properties, strong dyeing power and relatively high stability. In the sublimation thermal transfer recording system, the amount of dye sublimated is thermal energy. It has a great feature not found in other printing methods in that the density after dyeing can be controlled in an analog manner.

Indoaniline compounds (JP-A-61-22933 and JP-A-61-31292) are particularly attracting attention as cyan dyes for sublimation transfer, but have a high sublimation rate. There are very few that also have image stability after transfer, and it has been expected that dyes satisfying the optimum conditions as sublimable dyes will appear.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an indoaniline compound and a dye for thermal transfer recording and an ink composition for thermal transfer recording which have a high sublimation rate as an application of the compound and image stability after transfer. To provide an object and a transfer sheet.

[0006]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have generally found that in dyes for thermal transfer recording, the sublimation rate at the time of transfer is different from each other between dye molecules. It was found that it is related to the action and the interaction between the dye molecule and the binder resin for the ink. That is, it is preferable that the sublimation dye has good solubility in the ink solvent and also has a low melting point, and that the interaction with the binder resin for the ink is small enough not to impair the storage stability after the transfer sheet is manufactured. It became clear that the dye was a dye, and it was found that the indoaniline compound represented by the general formula (1) or (Chemical Formula 2) described below can be an excellent cyan-based dye for thermal transfer recording, and the present invention was completed. . That is, the present invention provides the following general formula (1)

[0007]

[Chemical 2]

[Wherein R ₁ is a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group,
It represents an alkoxycarbonyl group or an alkylaminocarbonyl group, and R ₂ and R ₃ are hydrogen atoms, halogen atoms, C _{1 to} C ₄
Represents an alkyl group of C _{1 to} C ₄ alkoxy group, R ₄ ,
R ₅ represents a hydrogen atom, a halogen atom, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, and R ₆ and R ₇ Represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, an aralkyl group, a substituted or unsubstituted aryl group, a halogenoalkyl group, a cyanoalkyl group, a hydroxyalkyl group or an alkylcarboxyalkyl group. ] An indoaniline compound represented by the following, the use of the same compound as a dye for thermal transfer recording using the same compound, an ink composition for thermal transfer recording containing the dye, a binder resin and an organic solvent and / or water, and The present invention relates to a transfer sheet comprising a base material sheet and a dye carrying layer formed on one surface of the base material sheet, and the dye contained in the dye carrying layer is the above dye.

The indoaniline compound represented by the general formula (1) (Chemical formula 2) of the present invention satisfies the above-mentioned conditions and can obtain a relatively good sublimation rate.

The present invention will be described in detail below. In the general formula (1), R ₁ is a hydrogen atom, a halogen atom such as fluorine, chlorine or bromine, methyl, ethyl, n-propyl or iso.
-Propyl, n-butyl, iso-butyl, tert-
Alkyl C ₁ -C ₄ a butyl, methoxy, ethoxy, n- propoxy, iso- propoxy, n- butoxy, an alkoxy group having C ₁ -C _4, such as tert- butoxy,
Methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl, n-
Butoxycarbonyl, iso-butoxycarbonyl, t
Alkoxycarbonyl groups such as ert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, iso-propylaminocarbonyl, n-butylamino. Carbonyl, i
so-butylaminocarbonyl, tert-butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, di-n-propylaminocarbonyl, di-iso-propylaminocarbonyl , Di-n-
An alkylaminocarbonyl group such as butylaminocarbonyl and di-iso-butylaminocarbonyl is shown,
R ₂ and R ₃ are hydrogen atoms, halogen atoms such as fluorine, chlorine and bromine, C _{1 to} C ₄ alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl and iso-butyl, Examples thereof include C _{1 to} C ₄ alkoxy groups such as methoxy, ethoxy, n-propoxy, and n-butoxy, R ₄ ,
R ₅ is a hydrogen atom, a halogen atom such as fluorine, chlorine or bromine, a C ₁ -C ₄ alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl or iso-butyl, methoxy or ethoxy. , n- propoxy, n- alkoxy C ₁ -C ₄ butoxy, etc., methylcarbonylamino, ethylcarbonylamino, n- propyl carbonylamino, iso- propyl carbonylamino, n- butylcarbonyl alkylcarbonylamino group of the amino or the like , Alkoxycarbonylamino groups such as methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, iso-propoxycarbonylamino, n-butoxycarbonylamino, methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, is - propylsulfonyl amino, n
- include an alkylsulfonylamino group of butyl sulfonylamino or the like, R _6, R ₇ is a hydrogen atom, methyl, ethyl, n- propyl, iso- propyl, n- butyl, i
Alkyl groups such as so-butyl, n-pentyl, n-heptyl, n-octyl, alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxyethyl, n-propoxyethyl, n-butoxyethyl, allyl, 2-butenyl, Alkenyl groups such as 3-butenyl, aralkyl groups such as benzyl and phenethyl, phenyl, o-tolyl, m
-Tolyl, p-tolyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, etc., substituted or unsubstituted aryl groups, chloromethyl, 2-chloroethyl, 2
-Halogenoalkyl groups such as chloropropyl and 3-chloropropyl, cyanoalkyl groups such as cyanomethyl and cyanoethyl, hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl and hydroxypropyl, methylcarboxyethyl, ethylcarboxyethyl and n-propylcarboxyethyl. , Iso-propylcarboxyethyl,
Examples thereof include alkyl carboxyalkyl groups such as n-butyl carboxyethyl, iso-butyl carboxyethyl, tert-butyl carboxyethyl, n-pentyl carboxyethyl, and n-hexyl carboxyethyl.

The compound represented by the general formula (1) (Chemical formula 2) of the present invention is obtained by an oxidative bond between a substituted phenol and a substituted aniline as shown by the following chemical formula (Chemical formula 3) by a conventional method. .

[0012]

[Chemical 3]

[X is a leaving group such as H or halogen. As a method for producing a heat-sensitive transfer recording ink using the dye of the present invention, the above-mentioned indoaniline compound may be mixed with an appropriate resin, solvent or the like to prepare the recording ink. In this case, the amount of the indoaniline compound in the thermal transfer recording ink is usually 2 to 5% by weight.

As the thermal transfer method, the ink obtained by the above method is applied onto a suitable substrate to prepare a transfer sheet, the transfer sheet is superposed on the recording medium, and then the thermal recording head is used from the back side of the sheet. A method of heating and pressurizing can be mentioned, and by doing so, the indoaniline compound on the sheet is transferred onto the recording medium.

The resin for preparing the above-mentioned ink may be any resin used in ordinary printing inks, such as rosin type, phenol type, xylene type, petroleum type, vinyl type, polyamide type, alkyd type, nitrocellulose. Oil-based resins such as resins and alkylcelluloses, or aqueous resins such as maleic acid-based, acrylic acid-based, casein, shellac, and glue can be used.

Further, as a solvent for preparing the ink,
Alcohols such as methanol, ethanol, propanol and butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone and cyclohexanone Hydrocarbons such as ketones, ligroin, cyclohexane, kerosene, dimethylformamide, etc. can be used, but when an aqueous resin is used, water or a mixture of water and the above solvents can also be used. .

Suitable substrates for applying ink include thin paper such as condenser paper and glassine paper, and films of plastics having good heat resistance such as polyester, polyamide and polyimide. These substrates are heat-sensitive. 5 to 50 in order to improve heat transfer efficiency from the recording head to the dye
A thickness on the order of micrometers is suitable. The dye carrying layer provided on the surface of the base material can be produced by applying the above-mentioned ink to the base material.

Examples of the recording medium include polyolefin resins such as polyethylene and polypropylene, halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, vinyl polymers such as polyvinyl alcohol, polyvinyl acetate and polyacrylic ester, and polyethylene. Polyester resins such as terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene and propylene with other vinyl monomers, cellulosic resins such as ionomers, cellulose diacetate and cellulose triacetate. Examples include fibers, woven fabrics, films, sheets, and molded products made of polycarbonate, polysulfone, polyimide, and the like. Particularly preferred is a woven fabric, sheet or film made of polyethylene terephthalate.

Further, in the present invention, plain paper coated or impregnated with a resin to which acidic fine particles such as silica gel have been added, resin film laminated, or special acetylated special resin is used. By using a processed paper or the like, good recording with excellent image stability under high temperature and high humidity can be performed. Also, films of various resins or synthetic papers made from them can be used.

Furthermore, after transfer recording, a polyester film, for example, is hot pressed and laminated on the transfer recording surface to improve the coloring of the dye and to improve the storage stability of the recording.

[0021]

EXAMPLES The present invention will be described in detail below with reference to examples.
In the examples, "part" indicates part by weight and "%" indicates% by weight. Example 1 A compound of the following formula (A) (Chemical Formula 4) was produced by the following method to prepare an ink, a transfer sheet and a recording medium,
Transfer recording was performed and its evaluation was performed.

[0022]

[Chemical 4]

10 parts of 4-N, N-diethylamino-2-toluidine and 4-iso-propoxycarbonyl-N-
16 parts of (2-hydroxyphenyl) phthalimide are dispersed in a mixed solution of 63 parts of methanol and 38 parts of water, and 30 parts of 25% ammonia water is added thereto, while maintaining the liquid temperature at 20 ° C., 10 parts of sodium persulfate. Was added over about 1 hour, and the mixture was reacted at room temperature for 2 hours. After the reaction, the precipitate was separated and purified by column chromatography to obtain the target compound (A) (Chemical Formula 4). The maximum absorption wavelength (λmax) of the compound in toluene was 640 nm. The melting point was 170.1 to 172.8 ° C, and the elemental analysis values were as follows. Elemental analysis value (C ₂₉ H ₂₉ N ₃ O ₅ ) C H N calculated value (%) 69.72 5.85 8.41 Measured value (%) 69.60 5.78 8.49

(1) Method for Preparing Ink Dye of Formula (A) (Chemical Formula 4) 3 parts Polybutyral resin 4.5 parts Methyl ethyl ketone 46.25 parts Toluene 46.25 parts Glass dye is used for the dye mixture having the above composition. Then, the ink was prepared by mixing with a paint conditioner for about 30 minutes.

(2) Method for preparing transfer sheet Using a gravure proofing machine (plate depth: 30 μm), a dry coating amount of 1.0 g / m ² was applied to a polyethylene terephthalate film having a thickness of 9 μm, the back surface of which was heat-treated. Was applied and dried.

(3) Preparation of Recording Material Polyester Resin 0.8 Parts (bylon 103 Toyobo Tg = 47 ° C.) EVA Polymer Plasticizer 0.2 parts (Elvalloy 741p Mitsui Polychemical Tg = 37 ° C.) Amino Modified silicone 0.04 part (KF-857 manufactured by Shin-Etsu Chemical Co., Ltd.) Epoxy-modified silicone 0.04 part (KF-103 manufactured by Shin-Etsu Chemical Co., Ltd.) Methyl ethyl ketone / toluene / cyclohexane 9.0 parts (weight ratio 4: 4: 2) or more To prepare a coating solution, which was then coated on a synthetic paper (Oji Yuka, YUPO FPG # 150) with a bar coater (RK Pr).
Manufactured by int Coat Instruments, N
o1) was applied at a rate of 4.5 g / m ² when dried, and dried at 100 ° C. for 15 minutes.

(4) Transfer recording The above-mentioned transfer sheet and the above-mentioned recording medium are superposed on each other with the ink application surface and the coating liquid application surface facing each other, and a thermal head applied voltage of 10 V and printing are performed from the back surface of the transfer sheet. Recording was carried out under the condition of a time of 4.0 milliseconds, and a cyan recording having a color density of 2.40 was obtained. The color density was measured using a densitometer RD-514 type (filter: Ratten No. 58) manufactured by Macbeth Co., USA. The color density was calculated by the following formula. Color Density = log ₁₀ (Io / I) Io = Intensity of Light Reflected from Standard White Reflector I = Intensity of Light Reflected from Test Object In addition, a light resistance test of the obtained record was performed using a xenon fade meter (suga). It was carried out at a black panel temperature of 63 ± 2 ° C. by using a tester (manufactured by Testing Machine Co., Ltd.), but it was not discolored by irradiation for 40 hours, and the stability of the image under high temperature and high humidity was excellent. In addition, the fastness was determined by leaving the obtained recorded image in an atmosphere of 50 ° C. for 48 hours, and then determining the sharpness of the image and the coloring on the white paper when the surface was rubbed with a white paper. There was no change and the white paper was not colored, and the fastness of the recorded image was good.

Example 2 A compound represented by the following formula (B) (formula 5) was produced by the following method.

[0029]

[Chemical 5]

10 parts of 4-N, N-diethylamino-2-toluidine and 4-di-n-butylaminocarbonyl-N
20 parts of-(2-hydroxyphenyl) phthalimide was dispersed in a mixed solution of 63 parts of methanol and 38 parts of water, and 30 parts of 25% ammonia water was added to the mixture solution, while maintaining the liquid temperature at 20 ° C. Parts were added over about 1 hour and reacted at room temperature for 2 hours. After the reaction, the precipitate was separated and purified by column chromatography to obtain the target compound (B) (Chemical Formula 5). The maximum absorption wavelength (λmax) of the compound in toluene was 640 nm. The melting point was 163.5 to 165.9 ° C, and the elemental analysis values were as follows. Elemental analysis _{(C 34 H 40 N 4 O} 4) C H N calc (%) 71.81 7.09 9.85 Found (%) 71.69 6.90 9.93

Using this dye (B), an ink was prepared, a transfer sheet and a recording material were prepared, and transfer recording was carried out in the same manner as in Example 1 to obtain a cyan recording having a color density of 2.38. When a light fastness test was conducted on all the recordings by the same method as in Example 1, the recordings hardly changed, and the stability of the image under high temperature and high humidity was excellent. Further, a fastness test was conducted in the same manner as in Example 1, but the sharpness of the image did not change, the white paper was not colored, and the fastness of the recorded image was good.

Examples 3 to 17 Table 1 (Tables 1 to 4) was prepared in the same manner as in Example 1.
In the same manner, the cyan dye shown in is prepared, and the ink is prepared, the transfer sheet is prepared, the recording material is prepared, and transfer recording is performed.
The respective records shown in Table 1 (Tables 1 to 4) were obtained. When a light resistance test was conducted on all of these recordings by the same method as in Example 1, the recordings showed almost no change and the stability of images under high temperature and high humidity was excellent. Further, a fastness test was conducted in the same manner as in Example 1, but the sharpness of the image did not change, the white paper was not colored, and the fastness of the recorded image was good. In Table 1 (Tables 1 to 4), the light resistance and the fastness were judged to be good, and the result was marked with a circle.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

Comparative Examples 1 to 4 In the same manner as in Example 1, the compounds shown in Table 2 (Table 5) were subjected to ink preparation, transfer sheet preparation, recording medium preparation, and transfer recording. Further, a light resistance test and a fastness test were performed in the same manner as in Example 1. The results are shown together in Table 2 (Table 5). In Table 2 (Table 5), those having good judgments of light resistance and fastness are indicated by ◯, and those having poor results are indicated by x.

[0038]

[Table 5]

[0039]

INDUSTRIAL APPLICABILITY Since the indoaniline compound represented by the general formula (1) or (Chemical Formula 2) of the present invention can control the dye sublimation transfer amount by changing the energy applied to the thermal head during thermal transfer, Gradation recording is easy and suitable for full color recording. Further, since it is stable against heat, light, moisture, chemicals, etc., it is not thermally decomposed during transfer recording, and the preservability of the obtained record is excellent. Also,
Since the indoaniline compound of the present invention has good solubility in an organic solvent and dispersibility in water, it is easy to prepare a uniform solvent or a high-concentration ink dispersed therein, and as a result, recording with good color density is possible. You can get
It is a dye that is practically valuable.

Claims (4)

[Claims] 1. The following general formula (1) (chemical formula 1): [In the formula, R ₁ represents a hydrogen atom, a halogen atom, a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, an alkoxycarbonyl group, or an alkylaminocarbonyl group, and R ₂ ,
R ₃ represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, and R ₄ and R ₅ represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group. , C _{1 to} C ₄
Represents an alkoxy group, an alkylcarbonylamino group, an alkoxycarbonylamino group, and an alkylsulfonylamino group, and R ₆ and R ₇ are a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkenyl group, an aralkyl group, or a substituted or unsubstituted aryl group. Group, halogenoalkyl group, cyanoalkyl group, hydroxyalkyl group, alkylcarboxyalkyl group. ] The indoaniline compound represented by these. 2. The general formula (1) (formula 1) according to claim 1.
A dye for thermal transfer recording having a structure represented by: 3. The general formula (1) (formula 1) according to claim 1.
An ink composition for thermal transfer recording containing an indoaniline compound represented by the following, a binder resin, an organic solvent and / or water. 4. A transfer comprising a base sheet and a dye-supporting layer formed on one surface of the base sheet, wherein the dye contained in the dye-supporting layer is the indoaniline compound according to claim 1. Sheet.