JPH058561A - Dye for thermal sublimation transfer recording, thermal transfer ink composition and thermal transfer sheet - Google Patents

Abstract

PURPOSE:To enhance the sublimation speed at the time of transfer and image stability after transfer by using a compound represented by a specific general formula obtained by the oxidative bonding of substituted anilines and substituted phenols. CONSTITUTION:As a dye for thermal sublimation transfer recording used in color hard copy, a compound represented by general formula (1) (wherein R<1> is a hydrogen atom, a hydroxyl group, a substituted or non-substituted alkyl group or an alkoxy group, R<2>-R<4> are a hydrogen atom, a 1-4C alkyl group or a halogen atom. R<5>-R<8> are a hydrogen atom, a 1-4C alkyl group, an alkoxy group or an alkylcarbonylamino group and R<9> and R<10> are a hydrogen atom, a substituted or non-substituted alkyl group or an alkenyl group) is used. An ink composition for a thermal sublimation transfer sheet is obtained from said dye, a binder (resin) and an org. solvent and/or water.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art A thermal transfer recording system using a sublimation dye uses a transfer sheet in which a sublimation dye which is made into an ink is applied to a thin condenser paper or PET film having a thickness of several microns and which is selectively heated by a thermal head. This is one of the thermal transfer printing methods of transferring onto recording paper, and is currently used as a means for image recording (hard copy) of various image information. The sublimable dyes used here are characterized by abundant colors and excellent color mixing properties, and are required to have strong dyeing power and relatively high stability, but the amount of dyes that sublime depends on thermal energy and It has a great feature that other printing methods do not have in that the density afterward can be controlled in an analog manner. As a cyan dye for sublimation transfer, an indoaniline-based compound (Japanese Patent Application Laid-Open No. 61-61160) has attracted particular attention.
No. 22993, JP-A No. 61-31292), but very few have both a high sublimation rate and image stability after transfer, and it is expected that dyes satisfying optimum conditions as sublimable dyes will appear. It was

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sublimable dye, a thermal sublimation transfer ink composition and a thermal transfer sheet which have a high sublimation rate and image stability after transfer.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a specific compound can be an excellent dye for thermal sublimation transfer recording, and completed the present invention. That is, the present invention has the general formula (1)

[0005]

[Chemical 2]

[In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an alkenyl group or an aralkyl group, and R ^{2 to} R ⁴ are hydrogen. An atom, a C ₁ -C ₄ alkyl group,
Represents a halogen atom, R ^{5 to} R ⁸ are hydrogen atoms, C _{1 to} C ₄
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. ] A dye for thermal sublimation transfer recording represented by the following, an ink composition for a thermal sublimation transfer sheet containing the dye, and a thermal transfer sheet.

In the general formula (1), R ¹ is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy. , Tert
An alkoxy group such as -butoxy and n-hexyloxy, a cycloalkyl group such as cyclopentyl and cyclohexyl,
Phenyl, p-tolyl, m-tolyl, o-tolyl, p-
Shown are aryl groups such as chlorophenyl, m-chlorophenyl and o-chlorophenyl, alkenyl groups such as allyl, 2-butenyl, 3-butenyl and 3-methyl-2-butenyl, aralkyl groups such as benzyl and phenethyl, and alkyl groups here. Is methyl, ethyl, n-propyl, iso-
Propyl, n-butyl, iso-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-
An alkyl group such as octyl is shown, and the substituted alkyl group is
Alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-hexyloxy, methoxymethoxy, methoxyethoxy, ethoxyethoxy, methoxypropoxy, ethoxy. Alkoxyalkoxy groups such as propoxy, propoxypropoxy, phenoxy, p-methylphenoxy, m-methylphenoxy, o-methylphenoxy, p-chlorophenoxy, m-methylphenoxy, o-methylphenoxy and other aryloxy groups, thiophenoxy, Thioaryloxy groups such as p-methylthiophenoxy, m-methylthiophenoxy and o-methylthiophenoxy, methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, i o- propyl carbonylamino, n
-Alkylcarbonylamino group such as butylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, alkoxycarbonylamino group such as iso-propoxycarbonylamino, n-butoxycarbonylamino, formylamino group, methylcarbonyl, Alkylcarbonyl group such as ethylcarbonyl, n-propylcarbonyl, iso-propylcarbonyl and n-butylcarbonyl, alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl and n-butoxycarbonyl, methyl Carboxy, ethyl carboxy, n-propyl carboxy, is
Alkylcarboxy groups such as o-propylcarboxy and n-butylcarboxy, alkoxycarboxy groups such as methoxycarboxy, ethoxycarboxy, n-propoxycarboxy, iso-propoxycarboxy, n-butoxycarboxy, methoxycarbonylmethoxy, ethoxycarbonylmethoxy, n An alkoxycarbonylalkoxy group such as -propoxycarbonylmethoxy, iso-propoxycarbonylmethoxy and n-butoxycarbonylmethoxy; a halogen atom such as fluorine, chlorine and bromine; and an alkyl group substituted with a cyano group.

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.
A C ₁ -C ₄ alkyl group such as ert-butyl and a halogen atom such as fluorine, chlorine and bromine are shown.

In the general formula (1), R ^{5 to} R ⁸ are hydrogen atoms, C _{1 to} C ₄ alkyl groups, alkoxy groups, methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, iso- Alkylcarbonylamino groups such as propylcarbonylamino, n-butylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, is
Alkoxycarbonylamino group such as o-propoxycarbonylamino and n-butoxycarbonylamino, formylamino group, alkyl such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, iso-propylsulfonylamino and n-butylsulfonylamino. A sulfonylamino group and a halogen atom are shown. Alkyl C ₁ -C _4, alkoxy group, halogen atom has the same meaning as described above.

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. .

According to the research conducted by the present inventors, generally, in sublimation transfer type dyes, the sublimation rate at the time of transfer generally relates to the interaction between the dye molecules and the interaction between the dye molecules and the binder resin for ink. Knowledge was obtained. That is, it is preferable that the 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 ribbon production, and the best dye is the one. It became clear that there is.

The dye represented by the general formula (1) of the present invention is
Under the above conditions, a relatively good sublimation rate was obtained. 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 by 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. 5-50μ to improve heat transfer efficiency from the recording head to the dye
A thickness of about m is suitable. The dye carrying layer provided on the surface of the base material can be prepared 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, 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. 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 high-concentration ink that is uniformly dissolved or dispersed, and as a result, good color density recording is possible. Is a dye that 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 o-acetylaminophenol and 10 parts of 4-diethylamino-o-toluidine were dissolved in 120 parts of methanol, and 28 parts of 25% ammonia water was added dropwise, and then the liquid temperature was adjusted to 2
While maintaining at 0 ° C, 25 parts of ammonium persulfate was added in about 1 hour, and the reaction was carried out at room temperature for 2 hours. After reaction, separate,
The product was thoroughly washed with water and purified by column chromatography to obtain the target product (A).

Further, by using the compound of the following formula (A), an 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 640 nm.

[0023]

[Chemical 4]

(1) Method of Preparing Ink Dye of Formula (A) 3 Parts Polybutyral Resin 4.5 〃 Methyl Ethyl Ketone 46.25 〃 Toluene 46.25 〃 Using a glass bead, a dye conditioner having the above composition is used to prepare 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 (Vylon 103 Toyobo T
g = 47 ° C.) 0.8 part, EVA polymer plasticizer (Elvalloy 741p manufactured by Mitsui Polychemicals Tg = −37 ° C.) 0.2 part, amino-modified silicone (KF-857 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.04 part , Epoxy-modified silicone (KF-103, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.04 parts, methyl ethyl ketone / toluene / cyclohexane (weight ratio 4: 4: 2) 9.0 parts, the above components are mixed to prepare a coating liquid, which is then synthesized. Paper (made by Oji Yuka,
YUPO FPG # 150) with a bar coater (RK Prin)
Manufactured by 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 above-mentioned transfer sheet and the above-mentioned recording material are overlapped with their respective ink application surfaces and coating liquid application surfaces facing each other, and a thermal head applied voltage of 10 V and printing are performed from the back surface of the thermal 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 2.8 was obtained. The color density was measured using a densitometer RD-514 type (manufactured by Macbeth, USA) (filter: Ratten No. 58). 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 Also, 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 Tester 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 is 5 for the recorded image obtained.
After leaving it in an atmosphere of 0 ° C for 48 hours, it was judged by the sharpness of the image and the coloring when the surface was rubbed with a white paper. The sharpness of the image did not change, and the white paper was not colored. The fastness was good.

Example 2 Synthesis of the following formula compound (B) was carried out using p-diethylamino-o-
Toluidine (11 parts), 2-acetylethylcarbonylaminophenol (11.4 parts), methanol (63 parts) and water (38 parts)
Dissolved in a mixed solution of 25 parts, 31 parts of 25% ammonia water was added, the liquid temperature was maintained at 20 ° C., and 76.6 parts of 25% silver nitrate aqueous solution was added dropwise thereto in about 1 hour, and reacted at room temperature for 2 hours. It was After the reaction, the product was extracted with chloroform, washed well with water, and purified by column chromatography to obtain the desired product (B). The maximum absorption wavelength (λmax) in chloroform of the compound was 640 nm.

[0029]

[Chemical 5]

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 2.8. 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.

Examples 3 to 24 The cyan dyes shown in Table 1 were produced in the same manner as in Example 1, and ink was similarly prepared, a transfer sheet was prepared, a recording material was prepared, and transfer recording was carried out. Each record shown in Table 1 was 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 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.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

Claims (3)

[Claims] 1. The following general formula (1): [In the formula, R ¹ represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an alkenyl group or an aralkyl group, and R ² to
R ⁴ is a hydrogen atom, an alkyl group of C ₁ -C _4, a halogen atom, R ⁵ to R ⁸ is a hydrogen atom, an alkyl group of C ₁ -C _4, alkoxy group, alkylcarbonylamino group, alkoxycarbonyl An amino group, a formylamino group, an alkylsulfonylamino group, a halogen atom, R ⁹ , R
¹⁰ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aralkyl group, or an aryl group. ] A dye for thermal sublimation transfer recording represented by the following. 2. An ink composition for a heat-sensitive sublimation transfer sheet, which comprises the dye represented by the general formula (1) according to claim 1, a resin as a binder, an organic solvent and / or water. 3. A substrate sheet and a dye-carrying layer formed on one surface of the substrate sheet, and a dye contained in the dye-carrying layer is represented by the general formula (1) of claim 1. Thermal transfer sheet.