JPH07172074A - Transfer medium and thermal transfer recording method - Google Patents

Abstract

PURPOSE:To obtain a dye image having high optical density and improved light resistance even when a print sheet having an ink accepting layer containing no interlayer compound is thermally transferred by using a thermal transfer containing hydrophobic cation dye and to further improve light resistance of the image. CONSTITUTION:A transfer medium comprises a support 1, and an ink accepting layer 2 containing hydroxyl group-containing polymer or vinyl chloride polymer. A hydrophobic cation dye image is formed by thermal transfer recording the transfer medium by using thermal transfer containing hydrophobic cation dye a thermal transferable dye. In order to improve light resistance of the image, the transfer medium is heat-treated after the image is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a thermal transfer member such as an ink ribbon containing a hydrophobized cationic dye as a heat transferable dye in an ink layer to obtain a transferred image having high optical density and high light resistance. The present invention relates to an object to be transferred which is particularly suitable when performing thermal transfer recording.

[0002]

2. Description of the Related Art Conventionally, a thermal transfer member (for example, an ink ribbon) having an ink layer containing a disperse dye and an ink receiving layer comprising a binder resin such as polyester or cellulose ester having a good affinity for the disperse dye. Thermal transfer recording using a transfer body (for example, printing paper) is widely performed. In this thermal transfer recording, the ink layer of the ink ribbon and the ink receiving layer of the printing paper are superposed, and the ink layer is heated according to the image information so that the disperse dye therein is transferred to the ink receiving layer by thermal diffusion. , Forming a dye image.

However, the formed dye image is fixed only by a relatively weak interaction such as a van der Waals bond or a hydrogen bond between the binder resin of the ink receiving layer and the disperse dye, so that the ink is fixed. When a resin or solvent that has a higher affinity for the disperse dye than the binder resin of the receiving layer contacts the disperse dye, the disperse dye re-migrates from the ink receiving layer to the outside or elutes in the solvent, resulting in a blurred dye image. There was a problem such as. Further, when heat energy larger than the binding energy between the dye image and the binder resin is applied, there is a problem that the dye image is blurred.

In order to solve this problem, the heat transferable dye constituting the dye image is combined with the substance in the ink receiving layer by ionic bond showing relatively large binding energy,
It has been proposed to firmly fix the dye image on the ink receiving layer by this (Japanese Patent Laid-Open No. 4-2991).
83, Japanese Patent Application No. 4-217137 and Japanese Patent Application No. 4-217138). In these techniques, a hydrophobic cationic dye obtained by reacting a cationic dye with an organic anion is used as the heat transferable dye contained in the ink layer of the ink ribbon, while the ink for printing paper is used. The receiving layer contains an intercalation compound capable of incorporating a cation such as a cationic dye between the layers, for example, a clay mineral such as a montmorillonite group mineral. By carrying out the thermal transfer recording method using these ink ribbon and printing paper at the same time, a dye image having high optical density and excellent light resistance is formed on the printing paper.

[0005]

By the way, when performing thermal transfer recording with an ink ribbon containing a hydrophobic cationic dye,
Printing paper having an ink receiving layer containing an intercalation compound as described above is not always available, and a general printing paper having no ink containing such an intercalation compound and having an ink reception layer made of polyester, cellulose ester or the like is used. It is also conceivable to use photographic paper.

However, when a thermal transfer recording (for example, an ink ribbon) containing a hydrophobic cationic dye is carried out on a general printing paper having an ink receiving layer made of polyester, cellulose ester or the like, the ink receiving recording is carried out. Since the compatibility between the polyester or cellulose ester constituting the layer and the hydrophobized cationic dye is not sufficient, the dye image obtained has a low optical density and its light resistance is insufficient.

The present invention is intended to solve the problems of the prior art as described above, and a thermal transfer material containing a hydrophobized cationic dye was used to perform thermal transfer on a printing paper having an ink receiving layer containing no intercalation compound. Even in such a case, it is an object to obtain a dye image having high optical density and improved light fastness, and further improve the light fastness of the dye image.

[0008]

The present inventor has obtained a dye image having high optical density and improved light resistance by using a specific resin in the ink receiving layer of photographic paper.
Further, they have found that the light resistance of the dye image is further improved by heating the photographic printing paper on which the dye image is formed, and have completed the present invention.

That is, the present invention is characterized in that, in a transferred material comprising a support and an ink receiving layer formed thereon, the ink receiving layer contains a hydroxyl group-containing polymer or a vinyl chloride polymer. A transfer target is provided.

In the present invention, the ink layer of the thermal transfer member composed of the substrate and the ink layer formed thereon, and the ink of the transfer member composed of the support and the ink receiving layer formed thereon. In a thermal transfer recording method, which comprises transferring a heat transferable dye contained in the ink layer to the ink receiving layer by heating the ink layer in superposition with the receiving layer, according to image information. Provided is a thermal transfer recording method, characterized in that a hydrophobic cationic dye is used as the heat transferable dye, and the above-mentioned transferred material of the present invention is used as the transferred material.

The present invention will be described in detail below with reference to the drawings.

FIG. 1 shows a cross-sectional view of the transferred material of the present invention.
As shown in the figure, this transfer target is composed of a support 1 and an ink receiving layer 2 laminated on the support 1. Here, the ink receiving layer 2 contains a hydroxyl group-containing polymer or a vinyl chloride polymer as an essential component.

The hydroxyl group-containing polymer or vinyl chloride polymer as a constituent of the ink receiving layer 2 has a higher compatibility with the hydrophobizing cationic dye than polyesters and cellulose esters which are generally used as resins constituting the ink receiving layer. It is good. Therefore, the hydrophobicized cationic dye image can be held relatively firmly.

The hydroxyl group of such a hydroxyl group-containing polymer is derived from various hydroxyl group-containing monomer units, and as such a hydroxyl group-containing monomer unit, it is preferable to saponify polyvinyl acetate or the like. Examples thereof include vinyl alcohol units and hydroxylalkyl acrylate units. Here, as a specific example of the hydroxyl group-containing polymer having a hydroxylalkyl acrylate unit, S-REC EC
110, S-REC E-C130 (above, Sekisui Chemical Co., Ltd.), UCAR ^TR VYNC, UCAR ^TR VAG
F, UCAR ^TR VAGC, UCAR ^TR VROH, UCA
R ^TR VYES-4, UCAR ^TR VP-200 (above, Union Carbide make) etc. can be illustrated.

The hydroxyl group content in the hydroxyl group-containing polymer is 0.1 to 40% by weight, preferably 1 to 40% by weight.
It is 10% by weight. If the hydroxyl group content is less than 0.1% by weight, the receptivity of the hydrophobizing cationic dye will be insufficient, and if it exceeds 40% by weight, the water resistance of the ink receiving layer will be insufficient.

As the hydroxyl-containing polymer, a hydroxyl group-containing monomer homopolymer may be used, or a copolymer of the hydroxyl group-containing monomer and another monomer copolymerizable with the hydroxyl group-containing monomer may be used. Examples of such other monomer include vinyl chloride monomer, vinyl acetate monomer, vinylidene chloride monomer, vinyl ester monomer, styrene monomer, maleic anhydride monomer, and acrylic acid ester monomer. Among these, it is preferable to use a vinyl chloride monomer, and it is preferable to use the vinyl chloride monomer in an amount of 60% by weight or more of the hydroxyl group-containing polymer.

As the vinyl chloride polymer used in the ink receiving layer 2, polyvinyl chloride or polyvinylidene chloride can be used, but other vinyl monomers such as methacrylic acid ester and acrylic acid ester can be used. Copolymers can also be used. Among them, a copolymer of vinyl chloride and vinyl acetate can be preferably used. In this case, a copolymer obtained by saponifying a copolymer of vinyl chloride and vinyl acetate and introducing a hydroxyl group can be more preferably used. This saponified product is a vinyl chloride polymer and at the same time a hydroxyl group-containing polymer. Specific examples of the saponified product of the copolymer of vinyl chloride and vinyl acetate include Denka vinyl # 1000GK and Denka vinyl # 1000G.
KT, Denka Vinyl # 1000 GSK (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), S-REC A, S-REC AL
(Above, Sekisui Chemical Co., Ltd.), UCAR ^TM VAG
H, UCAR ^™ VAGD (above, manufactured by Union Carbide Co.) and the like can be exemplified.

The ink receiving layer 2 of the transferred material of the present invention comprises:
In addition to the above-mentioned hydroxyl group-containing polymer or vinyl chloride-based polymer, other synthetic resins may be blended as necessary. Such other synthetic resins include polyester resins, polyacrylic acid ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, vinyltoluene acrylate resins, cellulose ester resins, polyurethane resins, polyamide resins, urea resins, Caprolactone resin, styrene maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. can be illustrated, and these can also use an oligomer.

In the ink receiving layer 2 of the transferred material of the present invention, if necessary, a plasticizer, a solvent, a binder, a filler such as clay, a curing agent, an anti-fading agent, an ultraviolet absorber, an antioxidant. Agents, light stabilizers, optical brighteners, release agents, antistatic agents,
An antiblocking agent and the like can be included.

The support 1 for the transferred material of the present invention may have the same structure as that of the support conventionally used in this type of transferred material, for example, a polyolefin such as polypropylene or polystyrene. Synthetic paper,
Fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper,
Synthetic rubber latex-impregnated paper, synthetic resin internal paper, pulp-based paper such as paperboard, polyolefin, polyvinyl chloride,
Examples thereof include plastic films or sheets such as polycarbonate, and laminates thereof. In addition, it is preferable that the plastic film or sheet is subjected to white reflection treatment, if necessary.

The transferred material of the present invention described above can be used when thermal transfer recording is carried out using a thermal transfer material (for example, an ink ribbon) using an ordinary disperse dye as a heat transferable dye. In particular, it is particularly suitable for a thermal transfer recording method performed by using a thermal transfer member using a hydrophobic cationic dye as the heat transferable dye. By using a thermal transfer member using a hydrophobic cationic dye as the heat transferable dye and performing thermal transfer recording on the transferred material of the present invention, a hydrophobic cationic dye image having excellent light resistance and high optical density can be obtained. Obtainable.

In this thermal transfer recording method, it is preferable to further heat-treat the ink receiving layer after the hydrophobic cationic dye which is a heat transferable dye is transferred to the ink receiving layer of the transferred material. As described above, the light resistance of the dye image can be remarkably improved by the heat treatment.

Such heat treatment can be carried out by various means as long as the quality of the dye image is not deteriorated.
For example, between the laminator heated to a temperature of about 100 ℃, to pass the transferred material on which the dye image is formed within a few seconds, or to directly heat the transferred material by heating means such as a thermal head, It can be kept for several hours in a constant temperature bath at about 70 ° C.

In this thermal transfer recording method, the base material of the thermal transfer member, the binder resin of the ink layer, and the like may have the same structure as that used in the conventional ink ribbon. For example, as the substrate, it is possible to use a polyester film that has been subjected to heat-resistant lubricity treatment,
As the binder resin for the ink layer of the thermal transfer member, cellulose ester resin, polyvinyl butyral resin, or the like can be used. Further, as the means for selectively heating the ink layer, the same means as the conventional one can be used, and for example, a thermal head or a laser can be used.

Examples of the hydrophobized cationic dyes include azo dyes having amine salts or quaternary ammonium groups, triphenylmethane dyes, azomethine dyes, oxazine dyes,
Thiazine dyes such as C.I. I. Basic Yellow 1,2,11,13,14,19,21,25,28,
32, 33, 34, 35, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,2
2,23,24,27,29,32,38,39.4
0, C.I. I. Basic Violet 7, 10, 15,
21,25,26,27,28, C.I. I. Basic Blue 1,3,5,7,9,19,21,22,24,2
5,26,28,29,40,41,44,45,4
7, 54, 58, 59, 60, 64, 65, 66, 6
7,68,75, C.I. I. It is preferable to use a water-soluble dye such as Basic Black 2 or 8 which is made hydrophobic by substituting a counter ion of a water-soluble dye with a carboxylate anion, a sulfonate anion, a sulfate ester anion, or a phosphate ester anion. Specifically, Japanese Patent Application No. 4-217137
The hydrophobizing cationic dyes disclosed in the specification can be preferably used.

[0026]

In the thermal transfer material of the present invention, the ink receiving layer is composed of a hydroxyl group-containing polymer or a vinyl chloride-based polymer. Therefore, a hydrophobic cation dye is used to obtain a dye having a high optical density and sufficient light resistance. An image can be formed.

By subjecting the obtained dye image to heat treatment, its light resistance can be further improved.

[0028]

EXAMPLES The present invention will be described in detail below based on examples.

Examples 1 to 5 and Comparative Examples 1 to 3 (Preparation of transferred material) (Preparation of transferred material) Synthetic paper having a thickness of 150 μm (FPG-1)
50, manufactured by Oji Yuka Co., Ltd.) was coated with the resin composition for the ink receiving layer of Table 1 containing the resin for the ink receiving layer shown in Table 2 by a wire bar coating method to a dry thickness of 10 μm and dried. By doing so, the transferred material of the present invention was produced. The drying was carried out by holding in an oven at 100 ° C for 30 minutes.

[0030]

Table 1 Resin composition for ink receiving layer Component name Amount used (parts by weight) 1 Resin in Table 2 2 Polyisocyanate 1 (Takenate D-110N, manufactured by Takeda Pharmaceutical Co., Ltd.) 3 Modified silicone oil 0.8 ( SF8427, manufactured by Toray Dow Corning Co., Ltd.) 4 Toluene 40 5 Methyl ethyl ketone 40

[0031]

[Table 2] Resin for ink receiving layer Example 1 Denka vinyl # 1000GK (Denki Kagaku Kogyo Co., Ltd.) (saponified vinyl chloride-vinyl acetate copolymer) 2 UCAR ^TR VAGF (Union Carbide Co.) (vinyl chloride-acetic acid) Vinyl-hydroxyl alkyl acrylate copolymer) 3 S-REC E-C110 (Sekisui Chemical Co., Ltd.) (Vinyl chloride-hydroxyl alkyl acrylate copolymer) 4 Denka vinyl # 1000A (Denki Kagaku Co., Ltd.) (Vinyl chloride-vinyl acetate) Copolymer) 5 Denka Vinyl # 1000D (Denki Kagaku Kogyo Co., Ltd.) (Vinyl chloride-vinyl acetate copolymer) Comparative Example 1 Byron 200 (Toyobo Co., Ltd.) (Polyester) 2 Byron 290 (Toyobo Co., Ltd.) ( Polyester) 3 Stylak AS 769 (Asahi Kasei Co., Ltd.) (Acrylonitrile-styrene copolymer) (Preparation of thermal transfer material) On the surface of a polyethylene terephthalate film (Lumirror, manufactured by Toray Industries, Inc.) having a thickness of 6 μm and provided with a heat resistant slipping layer on the back surface, The composition for forming an ink layer in Table 3 was dried by a wire bar coating method so that the dry thickness was 1
A thermal transfer member was prepared by coating so as to have a thickness of μm.

[0032]

[Table 3] Ink layer forming composition Ingredient name Amount used (parts by weight) 1 Hydrophobizing cationic dye 2 (CI Basic Red 22 lauryl sulfate) 2 Polyvinyl butyral resin 2 (Denka Butyral 6000-CS, electrochemical Industrial Co., Ltd.) 3 Toluene 25 4 Methyl ethyl ketone 25 Using the transfer target and the thermal transfer member produced as described above, 12 gradation printing is performed by a video printer (CVP-G500, manufactured by Sony Corporation). It was

The maximum density portion (Dmax) of the transferred material on which the dye image was formed was measured with a Macbeth densitometer (TR924) having a status A filter. The results (immediately after printing) are shown in Table 4.

Further, in order to investigate the influence of the heat treatment on the light resistance, the transferred material on which the dye pixel is formed is divided into two groups (A group and B group), and the transferred material is peeled off in the A group. It is sandwiched by polyethylene terephthalate film, and it is heat laminator (Lamimark 32
0, made by Intercosmos Co., Ltd.) feed speed 0.4m
The heat treatment was carried out by passing once under the condition of / min. on the other hand,
The transfer target of Group B was not heat-treated.

Then, the transferred materials of both groups were exposed to xenon arc lamp light (irradiance: 340 W /
m ² ) was irradiated. Then, the dye image density (D
max) was measured in the same manner as described above, and the ratio (%) to Dmax (immediately after printing) when the xenon arc lamp was not irradiated was determined. The results are shown in Table 4.

[0036]

[Table 4] _{Transferred material} Dmax Light resistance test result (%) (immediately after printing) Group B (non-heated) Group A (heated) Example 1 2.08 43 89 2 1.92 36 79 3 1.94 37 83 4 1.61 34 67 5 1.39 26 59 Comparative Example 1 0.97 16 26 2 1.11 10 15 3 1.07 30 39 As is clear from Table 4, compared with the transferred material of the comparative example, the transferred material of the example A high optical density hydrophobized cationic dye image could be formed on the body (Dmax). Further, the light fastness of the image tended to be higher than that of the comparative example (Group B). In particular, when the transfer-receiving material of the example was heat-treated, the light resistance was remarkably improved (group A).

[0037]

INDUSTRIAL APPLICABILITY According to the present invention, a thermal transfer material containing a hydrophobized cationic dye has a high optical density and is improved even when the thermal transfer is carried out to a printing paper having an ink receiving layer containing no intercalation compound. A dye image having excellent light fastness is obtained. In addition, the light resistance can be further improved by heat-treating the transferred material on which the dye image is formed.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a transferred material of the present invention.

[Explanation of symbols]

 1 support 2 ink receiving layer

Claims (6)

[Claims] 1. A transferred material comprising a support and an ink receiving layer formed thereon, wherein the ink receiving layer contains a hydroxyl group-containing polymer or a vinyl chloride polymer. 2. The vinyl chloride polymer is vinyl chloride-
The transferred material according to claim 1, which is a vinyl acetate copolymer. 3. The transferred material according to claim 1, wherein the hydroxyl group-containing polymer or the vinyl chloride-based polymer is a saponified product of a vinyl chloride-vinyl acetate copolymer. 4. The transferred material according to claim 1, wherein the hydroxyl group-containing polymer or vinyl chloride polymer is a vinyl chloride-hydroxyl alkyl acrylate copolymer or a vinyl chloride-vinyl acetate-hydroxyl alkyl acrylate copolymer. 5. An ink layer of a thermal transfer member composed of a substrate and an ink layer formed thereon is superposed on the ink receiving layer of a transferred member composed of a support and an ink receiving layer formed thereon. In addition, in the thermal transfer recording method, which comprises transferring the heat transferable dye contained in the ink layer to the ink receiving layer by heating the ink layer according to image information, 5. A thermal transfer recording method, wherein a hydrophobic cationic dye is used as a dye, and the transferred material according to claim 1 is used as a transferred material. 6. The thermal transfer recording method according to claim 5, wherein after the heat transferable dye is transferred to the ink receiving layer of the transferred material, the ink receiving layer is further heat-treated.