JP3009161B2 - Cyan heat-sensitive sublimation transfer sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a cyan color thermosensitive sublimation transfer sheet for a thermosensitive sublimation transfer system.

More specifically, in a method of sublimation transfer by heating with a thermal head or the like to obtain a color copy with good gradation, a color copy having good dyeing properties and coloring properties and excellent fastness is obtained. Transfer sheet to be used.

[Conventional technology]

In the thermal sublimation transfer system, when a thermal transfer film coated with an ink containing a dye for sublimation thermal transfer is overlaid on an image receiving paper and heat-pressed with a thermal head, the dye sublimates and transfers to the image receiving paper to obtain a full-color copy with good gradation. It is a method.

The feature of the thermal sublimation recording system is that a thermal head is mainly used as a hardware device, and it is compact and has excellent maintainability and reliability. Secondly, a mixed color image at a molecular level can be obtained, so that recording close to silver halide color photography with excellent gradation and reproducibility is possible.

Furthermore, this system has been applied to a wide variety of full-color recording systems such as CG (computer graphics), plate making systems, video movies and still video systems, and prepaid cards, and has recently received particular attention.

More specifically, a method in which a transfer sheet coated with a sublimable dye is heated by a thermal head controlled by a color signal of a still image, and the transfer sheet is
Usually, three primary colors of yellow, magenta and cyan are used. Furthermore, in order to provide light and dark, four primary colors may be used by adding black to the above three primary colors.

[Problems to be solved by the invention]

The following conditions are required as the quality required for the cyan-based heat-sensitive sublimation transfer sheet.

Good compatibility or solubility with the solvent and binder resin in the ink used when applying to the transfer sheet.

The energy required for sublimation dyeing from the transfer sheet to the image receiving paper is as low as possible, and an image with color value is transferred on the image receiving paper.

The transferred image is greenish cyan, which is a so-called three primary color, and has little turbidity.

The dye does not recrystallize in the transfer sheet even when heated or humidified.

The transferred image has good light fastness and storage stability.

Among the above-mentioned conditions, what is particularly required is that the ink has high solubility in a solvent and good compatibility with a binder resin.

That is, in the thermal sublimation transfer system, the dye must be completely dissolved in the binder resin on the transfer sheet in order to sublime at the molecular level.

If the dye is transferred in a state of being insoluble in the binder resin on the transfer sheet, a uniform image cannot be obtained, the image density is low, and the commercial value is extremely poor.

Further, with respect to cyan, it is strongly desired that green cyan is preferred and that turbidity is small.

At present, there is no transfer sheet that satisfies all the necessary conditions for the above-mentioned transfer sheet.

[Means for solving the problem]

The present inventors have conducted intensive studies in order to solve the above problems, developed a transfer sheet that satisfies all of the above conditions, and completed the present invention.

That is, in the present invention, general formula (I) (In the formula, R ₁ represents a hydrogen atom, an optionally substituted alkyl group, an alkoxy group, an alkenyl group, an aralkyl group, an optionally substituted aryl group, a cycloalkyl group, a heterocyclic group, and R ₂ represents Represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and R ₃ and R ₄ are a hydrogen atom, an alkyl group, an alkoxy group, an alkenyloxy group, an aralkyloxy group, an aryloxy group, an alkylcarbonylamino group, or an alkylsulfonylamino group. Represents an alkoxycarbonylamino group, a formylamino group, a halogen atom,
R ₅ and R ₆ each represent an alkyl group which may be substituted, and may form a ring with each other. And the general formula (II) Wherein R ₇ and R ₉ represent a hydrogen atom, an alkyl group, or an aryl group, and R ₈ represents a halogen atom, a cyano group, a formyl group,
OR ₁₀ and CONHR ₁₀ are shown, wherein R ₁₀ represents an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or optionally substituted aryl group. ]
It has been surprisingly found that a transfer sheet satisfying all of the above-mentioned conditions can be obtained by blending at least two or more kinds of dyes each carried one or more from the group of cyan sublimable dyes.

More specifically, the dye represented by the general formula (I) alone has good solubility in the solvent and the resin in the ink and has a high color value and is a clear greenish cyan. Not perfect in terms. That is,
Although the above conditions are satisfied, there is a problem in that they are satisfactory.

On the other hand, the dye represented by the general formula (II) has good solubility in the solvent and resin in the ink when used alone, has no recrystallization in the binder resin in the transfer sheet, and has good ribbon storage stability. In addition, the transferred image receiving paper has good light fastness and storage stability, and is a clear cyan, but is not perfect in terms of color value.

In other words, the above conditions and the conditions up to are satisfied, but there is a problem in that they are satisfied.

As described above, each of the dyes of the general formulas (I) and (II) alone has a problem, but as a result of intensive studies,
It has been found that a transfer sheet that satisfies all of the above conditions can be obtained by blending at least two or more dyes selected from one or more of the dye groups of the general formulas (I) and (II). Completed the invention.

The mixing ratio is an arbitrary ratio determined by adjusting the color to greenish cyan. Further, a third component may be added in addition to the above combination.

Specifically, the compound of the general formula (I) is such that R ₁ is a hydrogen atom,
Methyl, ethyl, n-propyl, iso-propyl, n-
Butyl, iso-butyl, sec-butyl, t-butyl, β-
Substituted or unsubstituted alkyl groups such as chloroethyl, β-cyanoethyl, methoxyethyl, ethoxyethyl, methylcarbonylmethyl, methoxycarbonylmethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec -Butoxy, t
-Alkoxy groups such as butoxy, allyl, alkenyl groups such as 1-butenyl, aralkyl groups such as benzyl and phenethyl, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-methoxyphenyl, m-
Methoxyphenyl, an optionally substituted aryl group such as p-methoxyphenyl, cyclopentyl, a cycloalkyl group such as a cyclohexyl group, a heterocyclic group shown below, R ₂ is a hydrogen atom, methyl, ethyl, n-propyl, iso
-Propyl, n-butyl, iso-butyl, sec-butyl,
alkyl groups such as t-butyl, methoxy, ethoxy, n-
Propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, alkoxy groups such as t-butoxy, fluorine, chlorine, represents a halogen atom such as bromine, R ₃ ,
R ₄ is a hydrogen atom, methyl, ethyl, n-propoxy, iso
-Alkyl groups such as propoxy, n-butyl, iso-butyl, sec-butyl, t-butyl, methoxy, ethoxy,
alkoxy groups such as n-propoxy, iso-propoxy, n-butoxy, allyloxy, 1-butenyloxy, 2
Alkenyloxy such as -methyl-1-butenyloxy,
Benzyloxy, an aralkyloxy group such as phenethyloxy, phenoxy, p-methylphenyloxy, m-methylphenyloxy, an aryloxy group such as o-methylphenyloxy, methylcarbonylamino, an alkylcarbonylamino group such as ethylcarbonylamino, Methylsulfonylamino, an alkylsulfonylamino group such as ethylsulfonylamino, methoxycarbonylamino, an alkoxycarbonylamino group such as ethoxycarbonylamino, a formylamino group, fluorine, chlorine, a halogen atom such as bromine, and R ₅ and R ₆ are Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-
Butyl, t-butyl, β-chloroethyl, β-cyanoethyl, methoxyethyl, ethoxyethyl, methylcarbonylmethyl, methoxycarbonylmethyl, unsubstituted or substituted alkyl groups such as ethylcarbonylaminoethyl. A ring may be formed.

As a specific example of the general formula (II), R ₇ and R ₉ are the same or independently of each other, a hydrogen atom, an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, phenyl, p-
Methylphenyl, m-methylphenyl, o-methylphenyl, p-methoxyphenyl, m-methoxyphenyl,
R ₈ represents a halogen atom such as fluorine, chlorine, bromine, a cyano group, a formyl group, or COOR ₁₀ , CONHR ₁₀
Wherein R ₁₀ is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-
Butyl, β-chloroethyl, β-cyanoethyl, methoxyethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylcarbonylmethyl, unsubstituted or substituted alkyl groups such as methoxycarbonylmethyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, allyl, 2-methyl-1-propenyl, 1-butenyl, 2-
An alkenyl group such as methyl-1-butenyl; an aralkyl group such as benzyl and phenethyl; and an aryl group such as phenyl, p-methylphenyl, m-methylphenyl and o-methylphenyl are shown.

The dye represented by the general formula (I) can be obtained by oxidizing a substituted aniline and a substituted phenol in an alcohol solvent at room temperature by a known method.

The dye represented by the general formula (II) can be produced by a known method such as 1-amino-4-bromoanthraquinone-2-carboxylic acid, 1-amino-2,4-dibromoanthraquinone,
Using any of 1-amino-4-nitroanthraquinone-2-carboxylic acid, quinizarin and the like as a starting material, for example, it can be synthesized by the following reaction route.

As a method of manufacturing a transfer sheet, a thermal transfer recording ink composed of a dye, a binder resin, and a solvent is applied on a transfer sheet base material to prepare a transfer sheet. In this case, the amount of the dye in the thermal transfer recording ink is usually 2 to 5
% By weight.

As the resin for adjusting the thermal transfer recording ink, those used in ordinary printing inks may be used, such as rosin, phenol, xylene, petroleum, vinyl, polyamide, nitrocellulose, and alkyl celluloses. Oil-based resins or aqueous resins such as maleic acid-based, acrylic acid-based, casein, shellac and glue can be used.

Examples of the solvent for ink preparation include alcohols such as methanol, ethanol, propanol and butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as benzene, toluene and xylene, ethyl acetate and butyl acetate. And ketones such as acetone, methyl ethyl ketone and cyclohexane, and hydrocarbons such as ligroin, cyclohexane and kerosene.

As the base material of the transfer sheet to which the ink is applied, thin paper such as condenser paper and glassine paper, and a plastic film having good heat resistance such as polyester, polyamide and polyimide are suitable, but these base materials are obtained from a thermal head. In order to improve the efficiency of heat transfer to the dye, a thickness of about 2 to 20 μm is appropriate.

Examples of the recording material include polyethylene, polyolefin resins such as polypropylene, halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, vinyl polymers such as polyvinyl alcohol, polyvinyl acetate, and polyacrylester, polyethylene terephthalate, and poly (ethylene terephthalate). Polyester resins such as butylene terephthalate, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, ionomers, cellulose diacetate, cellulose resins, polycarbonate, polysulfone, polyimide, etc. Fiber, woven fabric, film, sheet, molded product and the like. Particularly preferred is a sheet or film made of polyethylene terephthalate.

Further, in the present invention, a resin obtained by adding acidic fine particles such as silica gel to the resin is coated on plain paper, impregnated, laminated with a resin film, or specially processed paper subjected to acetylation treatment. By doing so, good recording excellent in image stability under high temperature and high humidity can be performed. Also, films of various resins or synthetic papers made therefrom can be used.

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

[Action and effect]

The cyan sublimation transfer sheet of the present invention containing at least two or more dyes each selected from one or more of the dye groups of the general formulas (I) and (II) has a solubility in a solvent and a binder resin in the ink. Is good, the storage stability in the binder resin on the sheet is good.

Further, the transfer sheet of the present invention has a good sublimation speed by heating with a thermal head, and the hue transferred to the image receiving paper is a green cyan color of three primary colors of printing, less turbid, and has color value.

Further, the transferred image-receiving paper has very good light fastness and storage stability, and is a practically useful cyan sublimation transfer sheet.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to Examples.

 In the examples, "parts" represents weight.

Example 1 (I) Method for adjusting ink Polybutyral resin 4.5 parts Methyl ethyl ketone 46.25 parts Toluene 46.25 parts The ink was prepared by mixing the dye mixture having the above composition with glass beads for about 30 minutes using a paint conditioner.

(2) Transfer Sheet Preparation Method The above ink was subjected to heat treatment on the back surface thereof using a gravure proofing machine (plate depth 30 μm). As 3.5μ thick polyethylene terephthalate film dry weight is 1.0 g / m ^2,
The coating was dried.

(3) Recording material preparation method Polyester resin 0.8 part (Vylon 103 Toyobo Tg = 47 ° C) EVA polymer plasticizer (Elvaloy 741p Mitsui / Dupont Polychemical Tg =-
0.2 parts Amino-modified silicone 0.04 parts (KF-857 Shin-Etsu Chemical Co., Ltd.) Epoxy-modified silicone (KF-103 Shin-Etsu Chemical Co., Ltd.) 0.04 parts Methyl ethyl ketone / toluene / cyclohexane 9.0 parts (weight ratio 4: 4: 2) , A coating liquid was prepared, and a bar coater (RK.Print Coat Inatru) was applied to synthetic paper (Yoji FPG # 150 manufactured by Oji Yuka).
It was prepared by applying at a rate of 4.5 g / m ² when dried using No. 1) manufactured by ments Co., Ltd. and drying at 100 ° C. for 15 minutes.

(4) Transfer recording The transfer sheet and the recording material are overlapped with their respective ink-coated surfaces and coating liquid-coated surfaces facing each other.
Recording was performed under the conditions of 4.0 milliseconds, and a greenish cyan color having a color density of 2.2 was obtained.

The color density was measured by a densitometer RD-918 manufactured by Macbeth, USA.
It measured using. A xenon fedometer (manufactured by Suga Test Instruments Co., Ltd.) was used as a light fastness tester for the obtained recording at a black panel temperature of 63 ± 2 ° C.
The color hardly changed after irradiation for 40 hours, and the image stability under high temperature and high humidity was excellent.

Also, the fastness of the obtained recorded image was left in an atmosphere of 50 ° C. for 48 hours, and then the sharpness of the image was determined by the sharpness of the image and the coloring when the surface was rubbed with white paper. The white paper was not colored, and the fastness of the recorded image was good.

Examples 2 to 8 Using the dyes shown in Table 1 manufactured by a conventional method in place of the dyes used in Example 1, adjusting the ink in the same manner as in Example 1 to prepare a transfer sheet and record. When the material was prepared and transfer-recorded, a green cyan color, which is the three primary colors of printing, having the densities shown in Table 1 was obtained, and the fastness was excellent as in Example 1.

────────────────────────────────────────────────── ─── Continued on the front page (72) Keisuke Takuma, Inventor 300, Hiraharacho, Omuta-shi, Fukuoka Examiner Isao Fujii (56) References JP-A-61-235190 (JP, A) JP-A-62-255189 (JP) , A) Japanese Patent Application Laid-Open No. Hei 2-214692 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40 CAS (STN)

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) (In the formula, R ₁ represents a hydrogen atom, an optionally substituted alkyl group, an alkoxy group, an alkenyl group, an aralkyl group, an optionally substituted aryl group, a cycloalkyl group, a heterocyclic group, and R ₂ represents Represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and R ₃ and R ₄ are a hydrogen atom, an alkyl group, an alkoxy group, an alkenyloxy group, an aralkyloxy group, an aryloxy group, an alkylcarbonylamino group, or an alkylsulfonylamino group. Represents an alkoxycarbonylamino group, a formylamino group, a halogen atom,
R ₅ and R ₆ each represent an alkyl group which may be substituted, and may form a ring with each other. And the general formula (II) (In the formula, R ₇ and R ₉ are the same or independently, each represents a hydrogen atom, an alkyl group, an aryl group, R ₈ represents a halogen atom, a cyano group, a formyl group, COOR ₁₀ , CONHR ₁₀ ,
Here, R ₁₀ represents an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group. ] A cyan-based heat-sensitive sublimation transfer sheet comprising at least two or more dyes selected from the cyan sublimable dye group.