JPH06143836A - Dye and ink composition for thermal transfer recording and transfer sheet - Google Patents

Abstract

PURPOSE:To obtain an ink compsn. containing a sublimable dye having both of a high sublimation speed and image stability after transfer by using a compd. having a specific structure as a dye for thermal transfer recording. CONSTITUTION:An ink compsn. for thermal transfer recording contains a dye for thermal transfer recording represented by formula I, a binder resin and an org. solvent and/or water. In the formula I, R<1> is an alkyl group, an alkoxy group, a cycloalkyl group or an aryl group, R<2>-R<4> are 11, a 1-4C alkyl group or halogen, R<5>-R<8> are H, a 1-4C alkyl group, an alkoxy group, an alkylcarbonylamino group, an alkoxycarbonylamino group, a formylamino group, an alkylsulfonylamino group or halogen and R<9> and R<10> are H, an alkyl group, an alkenyl group, an aralkyl group or an aryl group. By using this dye, recording having good color density can be obtained at a high sublimation speed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye for thermal transfer recording (hereinafter abbreviated as sublimation dye), a thermal transfer recording ink composition, and a transfer sheet which are used for color hard copy by a sublimation thermal transfer recording system. Regarding

[0002]

2. Description of the Related Art In a thermal transfer recording system using a sublimation dye, an ink-formed sublimation dye is applied to a thin condenser paper or PET film having a thickness of several microns, and this is selectively heated by a thermal head and transferred to a recording paper. This is one of the thermal transfer printing methods, and is currently used as a means for recording various types of image information (hard copy). The sublimation dye used here is rich in color and excellent in color mixing property, has strong dyeing power, and is required to have relatively high stability, but in the above recording method, the amount of dye sublimated depends on thermal energy,
Since the density after dyeing can be controlled in an analog manner, it has a great feature not found in other printing methods. As cyan dye sublimation dyes, indoaniline compounds (Japanese Patent Application Laid-Open No. 61-22993 and Japanese Patent Application Laid-Open No. 6-29693) have been particularly attracting attention.
No. 1-31292), but very few have both a high sublimation rate and image stability after transfer, and it has been expected that dyes satisfying optimum conditions as sublimation dyes will appear.

[0003]

The object of the present invention is to provide a sublimation dye having a high sublimation rate and image stability after transfer,
An object of the present invention is to provide an ink composition containing the dye and a transfer sheet.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have generally found that in sublimation transfer dyes, the sublimation rate at the time of transfer is the interaction between the dye molecules. It was found that they are related to the interaction between the dye molecule and the binder resin for ink. That is, it is preferable that the dye has good solubility in the ink solvent and 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 ribbon production. It became clear that there is. As a result of further examination based on the above findings, the following general formula (1)
The present invention has been completed by discovering that the compound represented by the formula (3) satisfies the above conditions and can be an excellent dye for thermal transfer recording. That is, the present invention is represented by the general formula (1)

[0005]

[Chemical 2]

[In the formula, R ¹ represents a substituted or unsubstituted alkyl group, an alkoxy group, a cycloalkyl group or an aryl group, R ^{2 to} R ⁴ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, A halogen atom, R ^{5 to} R ⁸ are hydrogen atoms,
Represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkylcarbonylamino group, an alkoxycarbonylamino group, a formylamino group, an alkylsulfonylamino group or a halogen atom, and R ⁹ and R ¹⁰ are hydrogen atoms, substituted or unsubstituted Represents an alkyl group, an alkenyl group, an aralkyl group, or an aryl group. ] It is a dye for thermal transfer recording represented by. Further, the present invention comprises a heat-sensitive transfer recording ink composition by containing a heat-sensitive transfer recording dye represented by the general formula (1), a binder resin and an organic solvent and / or water. Further, the present invention is 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 present invention will be described in detail below. In the compound of the general formula (1) in the present invention, R ¹ is a substituted or unsubstituted alkyl group, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso.
-Butoxy, sec-butoxy, tert-butoxy,
Alkoxy groups such as n-hexyloxy, cycloalkyl groups such as cyclopentyl and cyclohexyl, phenyl,
An aryl group such as p-tolyl, m-tolyl, o-tolyl, p-chlorophenyl, m-chlorophenyl and o-chlorophenyl is shown.

Here, the alkyl group is methyl, ethyl, n
-Propyl, iso-propyl, n-butyl, iso-
It is an alkyl group such as butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the substituted alkyl group is methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso
-Butoxy, sec-butoxy, tert-butoxy,
Alkoxy group such as n-hexyloxy, alkoxyalkoxy group such as methoxymethoxy, methoxyethoxy, ethoxyethoxy, methoxypropoxy, ethoxypropoxy, propoxypropoxy, phenoxy, p-methylphenoxy, m-methylphenoxy, o-methylphenoxy, p -Chlorophenoxy, m-methylphenoxy,
Aryloxy group such as o-methylphenoxy, thiophenoxy, p-methylthiophenoxy, m-methylthiophenoxy, thioaryloxy group such as o-methylthiophenoxy, methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, iso- Alkylcarbonylamino groups such as propylcarbonylamino, n-butylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, iso-propoxycarbonylamino,
Alkoxycarbonylamino group such as n-butoxycarbonylamino, formylamino group, alkylcarbonyl group such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, iso-propylcarbonyl, n-butylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n- Alkoxycarbonyl groups such as propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, methylcarboxy, ethylcarboxy, n-
Propylcarboxy, iso-propylcarboxy, n
-Alkylcarboxy groups such as butylcarboxy, methoxycarboxy, ethoxycarboxy, n-propoxycarboxy, iso-propoxycarboxy, alkoxycarboxy groups such as n-butoxycarboxy, methoxycarbonylmethoxy, ethoxycarbonylmethoxy, n-
Alkoxycarbonylalkoxy groups such as propoxycarbonylmethoxy, iso-propoxycarbonylmethoxy, n-butoxycarbonylmethoxy, fluorine, chlorine,
An alkyl group substituted with a halogen atom such as bromine or a cyano group is shown.

In the general formula (1), R ^{2 to} R ⁴ are hydrogen atom, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t.
It represents an alkyl group having 1 to 4 carbon atoms such as ert-butyl and a halogen atom such as fluorine, chlorine and bromine.

In the general formula (1), R ^{5 to} R ⁸ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, iso- Alkylcarbonylamino groups such as propylcarbonylamino, n-butylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino,
Alkoxycarbonylamino group such as iso-propoxycarbonylamino, n-butoxycarbonylamino, formylamino group, methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, iso
-Propylsulfonylamino, n-butylsulfonylamino, and other alkylsulfonylamino groups, and halogen atoms are shown. The alkyl group having 1 to 4 carbon atoms, the alkoxy group and the halogen atom have the same meanings as described above.

Further, in the general formula (1), R ⁹ and R ¹⁰ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aralkyl group or an aryl group, which have the same meanings as described above. Have.

The dye represented by the general formula (1) of the present invention can be obtained by an oxidative bond between a substituted aniline and a substituted phenol according to the following reaction formula (Chemical Formula 3) according to a conventional method.

[0013]

[Chemical 3]

As a method for producing a thermal transfer recording ink using the dye of the present invention, the dye may be mixed with an appropriate resin, solvent or the like to prepare the recording ink. In this case, the amount of the dye in the thermal transfer recording ink is usually 2 to 5% by weight. Further, as the thermal transfer method, the transfer sheet is prepared by applying the ink obtained by the above method onto a suitable substrate,
A method in which the sheet is superposed on a recording medium and then heated and pressed from the back surface of the sheet with a thermal recording head can be mentioned, whereby the dye on the sheet is transferred onto the recording medium.

The resin for preparing the above-mentioned ink may be one used in ordinary printing inks, such as rosin-based, phenol-based, xylene-based, petroleum-based, vinyl-based, polyamide-based, alkyd-based, nitrocellulose. Oil-based resins such as resins and alkyl celluloses, 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, and dimethylformamide can be used. When an aqueous resin is used, water or water and a mixture of 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 of about μm is suitable.

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, Polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins,
Copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, cellulosic resins such as ionomers, cellulose diacetate and cellulose triacetate, fibers made of polycarbonate, polysulfone, polyimide, woven cloth, film, sheet, molding Things etc. are mentioned. 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 the processed paper, good recording with excellent image stability under high temperature and high humidity can be performed. Further, films of various resins or synthetic paper made from them can also be used. Furthermore, after transfer recording, a polyester film, for example, is hot-pressed and laminated on the transfer recording surface, whereby the coloring of the dye can be improved and the storage stability of the recording can be achieved.

[0020]

The cyan dye represented by the general formula (1) of the present invention can control the sublimation transfer amount of the dye by changing the energy applied to the thermal head at the time of thermal transfer. 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. Moreover, since the dye of the present invention has good solubility in an organic solvent and dispersibility in water, it is easy to prepare a high-concentration ink that is uniformly dissolved or dispersed. As a result, a dye having a high sublimation rate and a good color density can be obtained, and the dye is practically valuable.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples. Parts in the examples indicate parts by weight. % Means% by weight. Example 1 10 parts of 2-acetylaminocarbonylphenol and 4
-Dissolve 10 parts of diethylamino-2-toluidine in 120 parts of methanol, add 28 parts of 25% ammonia water dropwise, and then add 1 part of sodium persulfate while maintaining the liquid temperature at 20 ° C.
3.4 parts were added in about 1 hour, and it was made to react at room temperature for 2 hours.
After the reaction, the product was separated, washed well with water, and purified by column chromatography to obtain the desired product (A) (chemical formula 4). Further, by using the compound of the following formula (A) (Formula 4), ink was prepared, a transfer sheet and a recording material were prepared and transfer recording was carried out. The maximum absorption wavelength (λmax) in chloroform of the compound was 630 nm.

[0022]

[Chemical 4]

(1) Method for Preparing Ink Dye of Formula (A) 3 Parts Polybutyral Resin 4.5 Parts Methyl Ethyl Ketone 46.25 Parts Toluene 46.25 Parts A dye mixture of the above composition is used in a glass conditioner and a paint conditioner. The ink was prepared by mixing for about 30 minutes.

(2) Method for producing 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 part (bylon 103 Toyobo Tg = 47 ° C.) EVA polymer plasticizer 0.2 part (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) The above is mixed to prepare a coating liquid, and synthetic paper (manufactured by Oji Yuka,
Epo FPG # 150) with a bar coater (RK Prin)
No. t Coat Instruments, No.
1) 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 transfer sheet and the recording material are overlaid with the ink application surface and the coating liquid application surface facing each other, and the thermal head applied voltage of 10 V from the back surface of the thermal transfer sheet for printing. Recording was carried out under the condition of a time of 4.0 milliseconds, and a cyan recording having a color density of 2.70 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

The light fastness test of the obtained recording was carried out at a black panel temperature of 63 ± 2 ° C. using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.). The image stability under high temperature and high humidity was also excellent. Further, 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 coloring when the surface was rubbed with a white paper, and the sharpness of the image did not change. Also, the white paper was not colored and the fastness of the recorded image was good.

Example 2 11 parts of 4-diethylamino-2-toluidine and 14.1 parts of 2-benzoylaminocarbonylaminophenol were dissolved in a mixed solution of 63 parts of methanol and 38 parts of water,
31 parts of 25% ammonia water was added, the liquid temperature was kept at 20 ° C., 14.8 parts of sodium persulfate was added thereto in about 1 hour, and the reaction was carried out at room temperature for 2 hours. After the reaction, the product was extracted with chloroform, washed well with water, and purified by column chromatography to obtain the desired product (B) (Chemical Formula 5). The maximum absorption wavelength (λmax) of the compound in chloroform was 625 nm.

[0029]

[Chemical 5]

Ink preparation, transfer sheet, recording material preparation and transfer recording were carried out in the same manner as in Example 1 to obtain a color density of 2.65.
A cyan record was obtained. When a light resistance test was conducted on all of these recordings by the same method as in Example 1,
The recording 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 20 The cyan dyes shown in Table 1 (Tables 1 to 3) were produced in the same manner as in Example 1, and inks, transfer sheets and recording materials were prepared in the same manner. Production and transfer recording were performed to obtain each recording shown in Table 1 (Tables 1 to 3). 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 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. In Table 1 (Table 1), those having good judgment results of light fastness and fastness are shown by “◯”.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

Comparative Examples 1 to 5 In the same manner as in Example 1, using cyan dyes shown in Table 2 (Table 4), ink preparation, transfer sheet preparation, recording material preparation, and transfer were performed. A record was made. Also,
A light resistance test and a fastness test were performed in the same manner as in Example 1. As a result, as shown in Table 2 (Table 4), none satisfying the conditions of maximum transfer density, light resistance and fastness at the same time was not obtained, the image became unclear, and the white paper was markedly colored and defective. . In Table 2 (Table 4), those having good judgment results of light resistance and fastness are shown as “◯”, and those having poor judgment are shown as “x”.

[0036]

[Table 4]

Claims (3)

[Claims] 1. The following general formula (1) (chemical formula 1): [In the formula, R ¹ represents a substituted or unsubstituted alkyl group, an alkoxy group, a cycloalkyl group or an aryl group, and R 1
^{2 to} R ⁴ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and R ^{5 to} R ⁸ represent a hydrogen atom and 1 to 4 carbon atoms.
Represents an alkyl group, an alkoxy group, an alkylcarbonylamino group, an alkoxycarbonylamino group, a formylamino group, an alkylsulfonylamino group, a halogen atom, and R ⁹ and R ^{10 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an alkenyl. A group, an aralkyl group and an aryl group are shown. ] The dye for thermal transfer recording represented by the following. 2. A thermal transfer recording ink comprising at least a thermal transfer recording dye represented by the general formula (1) according to claim 1, a binder resin, an organic solvent and / or water. Composition. 3. 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 a sensation represented by the general formula (1) according to claim 1. A transfer sheet characterized by being a dye for thermal transfer recording.