JPH05262055A - Thermal transfer recording material - Google Patents

Abstract

PURPOSE:To prevent the color shift transfer caused by the slip between a dye donating layer and a dye receiving layer by combining a thermal transfer dye donating material compounded with a matting agent and a thermal transfer image receiving material with at least one constitutional layer. CONSTITUTION:A dye thermally sublimed or becoming movable by heat and a binder resin are dissolved or dispersed in a proper solvent and org. and/or inorg. fine particles are compounded with said solvent to prepare a coating solution which is, in turn, applied to one surface of a support to be dried to produce a thermal transfer dye donating material having a dye donating layer. A dispersion prepared by compounding a substance receiving a thermal transfer dye such as a polyester resin or a polyacrylic ester resin with orgt. and/or inorg. fine particles along with a water-soluble binder is applied to a support to be dried to produce a thermal transfer image receiving material having a dye receiving layer. As org. fine particles, starch or cellulose ester is used and, as inorg. fine particles, silicon dioxide or titanium oxide is used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermal transfer recording material comprising a thermal transfer dye-donating material and a thermal transfer dye-image receiving material.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the respective information processing systems have also been developed and adopted. As one of such recording methods, the thermal transfer recording method has been widely used recently because the apparatus used is light and compact, noise-free, excellent in operability and maintainability, and easy to colorize. . This thermal transfer recording method is roughly classified into two types, a heat melting type and a heat transfer type. In the latter method, a thermal transfer dye-donor material having a dye-donor layer containing a binder and a heat transferable dye on a support is superposed with a thermal transfer dye-image receiving material, and heat is applied from the support side of the dye-donor material, and heat is applied. It is a method of obtaining a transferred image by transferring a heat transferable dye in a pattern to a recording medium (heat transfer dye image receiving material). Here, the heat transferable dye means a dye which can be transferred from the thermal transfer dye-donor material to the thermal transfer dye image-receiving material by sublimation or diffusion in a medium. In such a thermal transfer recording method, color image information is yellow,
It is converted into magenta and cyan electric signals, transmitted to the thermal printer device, and recorded.

Next, when these signals are applied by heat, a binder and a yellow, magenta, or cyan dye-donor layer are sequentially coated on the support and the surface on the dye-donor layer side of the thermal transfer dye-donor material. The surface of the thermal transfer dye image receiving material having the dye receiving layer containing the dye receiving material provided on the support is superposed on the surface of the dye receiving layer side and placed between the thermal head and the platen roller. Heat is applied from the back side of the. At this time, the thermal transfer dye-providing material is used in a roll form. And, the thermal head has a large number of heating elements for sequentially aligning the transfer start position with the heat application of the yellow, magenta, or cyan dye-donor layer in response to the yellow, magenta, and cyan electric signals. The transport of the dye-donor layer and the dye-receiving layer is repeated,
A color hard copy corresponding to the original color image is obtained. When the transfer of the yellow, magenta, and cyan dye-donor layers and dye-receiving layers for transfer initiation alignment during the application of such heat is carried out, the dye-donor layer of the thermal transfer dye-donor material and the dye of the thermal transfer dye-image-receiving material are usually used. It is performed by the frictional force with the receiving layer.

[0004]

However, the thermal transfer image receiving material used in this thermal transfer type thermal transfer recording method has the following problems. Generally, in the thermal transfer recording method, the dye-donating layer and the dye-receiving layer are easily heat-sealed when heat is applied. To prevent this, a modified and / or unmodified silicone oil and / or a fluorine-based releasing agent is used as a dye. Although it is effective to include it in the donor material and / or the dye receiving material,
As a result, the frictional force between the dye-donor layer of the thermal transfer dye-donor material and the dye-receiving layer of the thermal transfer dye image-receiving material is reduced, so that slippage occurs between the two and the transfer start position of the dye-donor layer and the dye-receiver layer. A gap will occur. Then, the transfer start position comes to the dye-donor layer of a different hue, which is located in front of the dye-donor layer to be originally transferred, and heat is applied thereto by the thermal head, so that "color shift transfer" occurs.

Therefore, an object of the present invention is to provide a dye-donor layer of a thermal transfer dye-donor material even if various releasing agents are contained in order to improve the problems such as heat fusion between the dye-donor layer and the dye-receiving layer. It is an object of the present invention to provide a thermal transfer recording material in which slippage does not occur between the thermal transfer dye image receiving material and the dye receiving layer of the thermal transfer dye image receiving material, that is, an image defect such as "color shift transfer" does not occur.

[0006]

The above problems are caused by a thermal transfer dye-donating material having a dye-donating layer comprising at least a heat-transferable dye and a binder resin on a support, and a dye-receiving material containing a dye-receiving substance on the support. Consisting of a thermal transfer dye image-receiving material provided with a layer, contacting the dye-donor layer and the dye-receiving layer,
In a thermal transfer recording material in which a dye is transferred from a dye-donor layer to a dye-receiving layer by heating according to an image signal to record, at least one of the layers constituting the thermal transfer dye-donating material and the side provided with the dye-donating layer A thermal transfer recording material is characterized in that at least one layer constituting the thermal transfer image receiving material on the side where the dye image receiving layer is provided contains organic and / or inorganic fine particles. The contents of the thermal transfer recording material used in the present invention will be specifically described below. Organic and / or inorganic fine particles (hereinafter abbreviated as matting agent) used in the present invention are well known in the photographic art, and are organic and / or inorganic dispersible in a new aqueous organic colloid binder. It can be defined as a discontinuous solid particle of material.

Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.) and alkaline earth metal salts (eg, sulfates and carbonates, specifically, barium sulfate). , Calcium carbonate, magnesium sulfate, calcium carbonate, etc., silver halide grains that do not form an image (such as silver chloride and silver bromide, to which an iodine atom may be added as a halogen component, though slightly), and glass. Of these, silicon dioxide is preferable.

Examples of organic matting agents include starch, cellulose ester (eg, cellulose acetate propionate, etc.), cellulose ether (eg, ethyl cellulose), synthetic resin and the like. Examples of synthetic resins are water-insoluble or sparingly soluble synthetic polymers such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg vinyl acetate), acrylonitrile. , Olefins (eg ethylene, propylene) and styrene, alone or in combination, or with them, acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfone A polymer having a monomer component of a combination of acids and the like can be used. Of these, polymethylmethacrylate and polyethylene are preferable.

[0009]

[Chemical 1]

Benzoguanamine resin can also be preferably used.

[0011]

[Chemical 2]

The average particle size of these matting agents is suitably about 0.1 to 10 μm, preferably 0.2 to 5 μm, and more preferably 0.5 to 3 μm when used in a thermal transfer dye-providing material. .. When used in a thermal transfer dye image receiving material, the average particle size is preferably 0.2 times to 5 times the film thickness of the thermal transfer dye image receiving material, and more preferably a matting agent having an average particle size of 0.5 times to 3 times. .. The coating amount of the matting agent when used in the thermal transfer dye providing material 0.001 to 0.1 g / m ² of the appropriate, preferably 0.002~0.1g / m ^2, more preferably 0 .00
It is 5 to 0.07 g / m ² . When used in the thermal transfer dye image-receiving material 0.05~8g / m ^2-position appropriate, preferably 0.1-5 g / m ^2, more preferably 0.3 to 3 g /
m ² .

In the present invention, in order to improve the releasability between the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably the surfaces of both materials contacting each other. It is preferable to add a release agent to the outermost layer corresponding to the above. As the release agent, solid or wax-like substances such as polyethylene wax, amide wax and Teflon powder, surfactants such as fluorine-based and phosphoric acid ester-based, paraffin-based, silicone-based and fluorine-based oils, etc. Any of the release agents can be used, but especially silicone oil and fluorine-based surfactants,
Fluorine-based oil (or grease) and fluorine-based solid fine particles are preferable.

As the silicone oil, in addition to non-modified silicone oil, modified silicone oil such as carboxy-modified, amino-modified, epoxy-modified, polyether-modified or alkyl-modified can be used. Examples thereof include various modified silicone oils described on pages 6 to 18B of "Modified Silicone Oil" technical data published by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with an isocyanate) is preferable, and emulsified and dispersed in a water-soluble binder for use. In this case, carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name X)
-22-3710) is preferable. Examples of the modified silicone oil include those having the following skeleton structure and compounds thereof. (1) Epoxy-modified silicone oil

[0015]

[Chemical 3]

(2) Alkyl-modified silicone oil

[0017]

[Chemical 4]

(3) Polyether-modified silicone oil

[0019]

[Chemical 5]

(4) Alcohol-modified silicone oil

[0021]

[Chemical 6]

(5) Amino-modified silicone oil

[0023]

[Chemical 7]

(6) Carboxyl-modified silicone oil

[0025]

[Chemical 8]

(7) Fluorine-modified silicone oil

[0027]

[Chemical 9]

(8) Higher fatty acid-modified silicone oil

[0029]

[Chemical 10]

(9) Epoxy / polyether modified silicone oil

[0031]

[Chemical 11]

(10) Alkyl / polyether modified silicone oil

[0033]

[Chemical 12]

The silicone oil used in the present invention can be used in combination of two or more kinds. The amount of the modified and / or unmodified silicone oil used in the present invention is 0.1 to 50% by weight, preferably 1% by weight based on the total weight of the dye-receptive polymer and the water-soluble binder in the layer to which the silicone compound is added. -40% by weight, particularly preferably 2-30% by weight.

The modified and / or unmodified silicone oil used in the present invention is added to the coating solution as follows. [1] When the coating liquid is an organic solvent system Silicone oil is added as it is to the coating liquid in the required amount, and the mixture is stirred and homogenized. [2] When the coating liquid is water-based (a) Silicone oil is added as it is or diluted with an organic solvent incompatible with water, emulsified and dispersed in water or a hydrophilic polymer aqueous solution. (B) When an organic solvent solution of the dye-receptive polymer is emulsified and dispersed in the hydrophilic polymer, it is dissolved in the dye-receptive polymer solution and emulsified and dispersed. (C) When the silicone oil is soluble in water or an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.), it is dissolved in the solvent and added, or added directly to the coating solution.

The fluorine-containing compound used in the present invention may be a low molecular weight compound or a high molecular weight compound. As examples of these compounds, those having a low molecular weight are described in US Pat. Nos. 3,775,126 and 35899.
No. 06, No. 3798265, No. 3779768, No. 4407937, West German Patent No. 1293189, British Patent No. 1259398, JP-A-48-87826,
49-10722, 49-46733, 50
─16525, 50―113221, 50-1
61236, 50-99525, 50-160
034, 51-43131, 51-10641
No. 9, No. 51-7917, No. 51-32322, No. 51-151125, No. 51-151126, No. 5
1-151127, 51-129229, 52
─127974, 522-50023, 53-8
No. 4712, No. 53-146622, No. 54-142
No. 24, No. 54-48520, No. 55-7762,
56-55942, 56-114944, 5
6-114945, Japanese Patent Publication No. 57-8456, 57
-12130, 57-12135, 58-94
Compounds described in No. 08 and the like can be mentioned. Further, as a polymer, US Pat. Nos. 4,175,969 and 408 are used.
7394, 4016125, and 3676123.
No. 3,679,411, No. 4,304,852, JP-A Nos. 52-129520, 54-158222, 5
5-57842, 57-11342, 57-1
9735, 57-179837, "Chemical Review N
o. 27, New Fluorine Chemistry ", edited by The Chemical Society of Japan, 198
0 years), "functional fluorine-containing polymer" (edited by Nikkan Kogyo Shimbun, 1982) and the like. These fluorine-containing compounds can be produced by the method described in the above-mentioned related documents, and more generally,
It can be synthesized by fluorinating the corresponding hydrocarbons. For fluorination of hydrocarbons, see “New Experimental Chemistry Course”, Vol. 14 [I] (Maruzen, 1977), 308
-See page 331 for detailed information.

Preferred examples of the fluorine-containing compound used in the present invention are shown below. [1] Fluorine-based surfactant

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

Besides, Megafac F-171 to 173, F-141 to 144 and F17 manufactured by Dainippon Ink and Chemicals, Inc.
0-173, F-180-184, F-192-19
5, F-522; Surflon S-11 manufactured by Asahi Glass Co., Ltd.
1-113, S-131-133, S-141, S-1
01, S-105, S-381, S-382; Futegent 400S manufactured by Neos Co., Ltd., and the like. Among these, betaine-based surfactants are preferably used.

[2] Fluorine-based oil (or grease)

[0046]

[Chemical 19]

[3] Fluorine-based solid fine particles These fine particles include tetrafluoroethylene resin, tetrafluoroethylene telomer, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, trifluorochlorochloride. Examples of the fine particles include ethylene resin.

These are commercially available as fine powders, organic solvent dispersions or aqueous dispersions. For example, Teflon (R) 6-J (fine powder) 60-J (fine powder) from Mitsui DuPont Fluorochemical Co., Ltd. ) 62-J (fine powder) 30-J (aqueous dispersion) 120-J (aqueous dispersion) From DuPont Vydax (R) 1000 (organic solvent dispersion) AR (organic solvent dispersion) WD (aqueous dispersion) ) From Daikin Industries, Ltd. Polyflon (R) TFE (organic solvent dispersion) NEOFLON (R) FEP (organic solvent dispersion) VDF (fine powder) CTFE (organic solvent dispersion) Lubron (R) L-5 ( Powder) L-2 (powder) LD-1 (organic solvent dispersion liquid) and the like.

The solid fine particles of the fluorine-containing compound used in the present invention are fine powders of the above-mentioned fluorine-containing compound, and the particle diameter of the fluorine solid fine particles is preferably 0.01 to 30 μm.
m, and more preferably 0.1 to 10 μm.

The fluorine-containing compound used in the present invention is added to the coating solution as follows. [1] Fluorine-based surfactant (a) It is dissolved in water or an organic solvent compatible with water or a mixed solvent thereof and added to the coating solution. (B) It is dissolved in an organic solvent incompatible with water, emulsified and dispersed in water or an aqueous solution of a hydrophilic polymer, and added to the coating liquid. (C) The organic solvent solution of the dye-receptive polymer is dissolved and contained in the dye-receptive polymer solution when emulsified and dispersed in the hydrophilic polymer. [2] Fluorine-based oil (a) Fluorine-based oil is added as it is or diluted with an organic solvent incompatible with water, emulsified and dispersed in water or a hydrophilic polymer aqueous solution. (B) Add in the same manner as in (c) of [1]. [3] In the case of fluorine-based solid fine particles (a) A surfactant (in particular, a fluorine-based surfactant is preferred) is dispersed in water or a hydrophilic polymer using a disperser such as a homogenizer. (B) First, it is dispersed in an organic solvent (in particular, a fluorine-based solvent is preferable), and then a surfactant (in particular, a fluorine-based surfactant is preferable) is emulsified and dispersed in water or a hydrophilic polymer aqueous solution as a dispersion aid. And add.

In the present invention, the fluorine-containing solid fine particles are preferably 0.001 to 5 g / m ² , more preferably 0.
002 to 1 g / m ² , and particularly preferably 0.005 to 0.
Used in the range of 5 g / m ² . The fluorine-containing solid fine particles may be present in any constituent layer of the dye-donor material and / or the image-receiving material including at least the outermost layer, but the outermost layer is preferable. It is preferable to use at least a fluorinated surfactant as the fluorinated compound, and to use it in combination with fluorinated oil and / or fluorinated solid fine particles. Further, the effects of the present invention are further exerted by using various release agents such as silicone oils described later.

As the support for the thermal transfer dye-providing material, any of those conventionally known can be used. Examples thereof include polyethylene terephthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-providing material is generally 2 to
It is 30 μm. An undercoat layer may be provided if necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye donating layer.

The thermal transfer dye-providing material using the heat transferable dye basically has a dye-providing layer containing a dye and a binder which are movable by heat on a support. This thermal transfer dye-providing material is prepared by dissolving or dispersing a dye and a binder resin, which are conventionally known to be sublimated or become mobile by heat, in a suitable solvent to prepare a coating solution,
This is applied to one side of the support of a conventionally known thermal transfer dye-donor element, for example, about 0.2 to 5 μm, preferably 0.4 to 2
It can be obtained by forming a dye-donor layer by coating and drying at a coating amount that results in a dry film thickness of μm. The dye-donor layer may be formed of one layer, but may be formed of two or more layers for use in a method in which the dye-donor layer is repeatedly used many times. In this case, the dye content and dye / binder ratio in each layer may be different.

As the dye useful for forming such a dye-donating layer, any of the dyes conventionally used in thermal transfer dye-donating materials can be used, but the particularly preferred dye in the present invention is about 150 to 800. It has a small molecular weight and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility and the like. Specific examples thereof include disperse dyes, basic dyes, oil-soluble dyes, and the like. Among them, Sumikaron Yellow E4GL, Dianex Yellow H2G-FS, Miketone Polyester Yellow 3GSL, Kayaset Yellow 937, Sumikaron Red, among others. EFBL, Dianix Red ACE, Mitoken Polyester Red FB, Kayaset Red 126, Miketone Fast Brilliant Blue B, Kayaset Blue 136 and the like are preferably used.

Further, it is preferable to use a yellow dye represented by the following general formula (Y). General formula (Y)

[0056]

[Chemical 20]

(Wherein D ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group or a carbamoyl group, and D ² represents a hydrogen atom,
It represents an alkyl group or an aryl group, D ³ represents an aryl group or a heteryl group, and D ⁴ and D ⁵ represent a hydrogen atom or an alkyl group. The above groups may be further substituted. ) Specific examples of compounds are shown below.

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

As the magenta dye, the dye of the following general formula (M) is preferable. General formula (M)

[0061]

[Chemical formula 23]

(Wherein D ^{6 to} D ¹⁰ are hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group,
It represents an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group or an amino group, and D ¹¹ and D ¹² represent a hydrogen atom, an alkyl group or an aryl group. D ¹¹ and D ¹²
May be bonded to each other to form a ring, or D ⁸ and D ¹¹ or / and D ² and D ¹² may be bonded to form a ring. X, Y and Z are = C (D ¹³⁾ - or a nitrogen atom (D ¹³ represents a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxy group, an aryloxy group, and an amino group).
When X and Y are = C (D ¹³ )-, or Y and Z are
When = C (D ¹³ )-, two D ^13's may combine with each other to form a saturated or unsaturated carbocycle. Further, the above groups may be further substituted. Specific compound examples are shown below.

[0063]

[Chemical formula 24]

[0064]

[Chemical 25]

As the cyan dye, the following general formula (C) is used.
Are preferred. General formula (C)

[0066]

[Chemical formula 26]

(In the formula, D ^{14 to} D ²¹ are synonymous with D ^{6 to} D ¹⁰ , and D ²² and D ²³ are synonymous with D ¹¹ and D ^12. ) Specific examples of compounds are shown below.

[0068]

[Chemical 27]

[0069]

[Chemical 28]

It is preferable to introduce the anti-fading group described in Japanese Patent Application No. 1-271078 into the compounds of the above-mentioned general formulas (Y), (M) and (C) since the light fastness is improved.

As the binder resin used with the dye of the present invention, any of the binder resins known in the art for such purpose can be used, and the binder resin usually has high heat resistance and, when heated, can be used as a binder resin. Those that do not prevent migration are selected. For example, polyamide resin, polyester resin, epoxy resin, polyurethane resin, polyacrylic resin (for example, polymethylmethacrylate, polyacrylamide, polystyrene-acrylonitrile), vinyl resin such as polyvinylpyrrolidone, polyvinyl chloride resin ( For example, vinyl chloride-vinyl acetate polymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, Cellulose triacetate), polyvinyl alcohol resins (eg polyvinyl alcohol, polyvinyl butyral) Partially saponified polyvinyl alcohol) of petroleum resins, rosin derivatives, coumarone over indene resin, terpene resin, polyolefin resin (e.g. polyethylene, polypropylene) or the like is used. Such a binder resin is preferably used in a ratio of about 50 to 200 parts by weight, for example, per 100 parts by weight of the dye. In the present invention, a conventionally known ink solvent can be freely used as an ink solvent for dissolving or dispersing the dye and the binder resin.

The dye-donor layer is formed by selecting a hue so that a desired hue can be transferred when printed, and arranging two or more dye-donor layers having different hues side by side in one thermal transfer dye-donor material. May be. For example, when an image such as a color photograph is formed by repeating printing of each color according to the color separation signal, it is desirable that the hue when printing is cyan, magenta, and yellow, and such a hue is provided. Line up the three dye-donor layers containing the dye. Alternatively, in addition to cyan, magenta, and yellow, a dye-donor layer containing a dye that imparts a black hue may be added. It is preferable to provide a mark for position detection at the same time when any one of the dye-donor layers is formed at the time of forming these dye-donor layers, because an ink or a printing step different from the dye-donor layer formation is not required.

In the present invention, the support used in the thermal transfer dye image-receiving material is capable of withstanding the transfer temperature and is required to have smoothness, whiteness, slipperiness, friction, antistatic properties, dents after transfer and the like. Anything that is satisfactory can be used. For example, synthetic paper (polyolefin-based, polystyrene-based, etc.), 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 Paper support such as coated paper, paperboard, cellulose fiber paper, polyolefin coated paper (paper coated on both sides with polyethylene), polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate,
It is also possible to use various plastic films or sheets of polycarbonate or the like, films or sheets treated to give white plasticity or porosity to the plastic, or a laminate of any combination of the above.

The thermal transfer dye image receiving material is provided with an image receiving layer. This image-receiving layer receives the heat-transferable dye that migrates from the heat-transfer dye-providing material during printing, and the substance capable of receiving the heat-transferable dye that has the function of dyeing the heat-transferable dye is used alone. Or a film having a thickness of about 0.5 to 50 μm, which is included together with the binder substance. The following resins are examples of polymers that are typical examples of substances that can receive a heat transferable dye.

(A) Those having an ester bond. Dicarboxylic acid components such as terephthalic acid, isophthalic acid and succinic acid (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.), ethylene glycol, diethylene glycol, propylene glycol,
Polyester resin obtained by condensation of neopentyl glycol, bisphenol A, etc., polyacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate, etc. or polymethacrylic acid ester resin, polycarbonate resin, polyvinyl acetate Resin, styrene acrylate resin, vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395 and 63-7971.
No. 63-7972, 63-7793, 60
The compounds described in No. 294862 can be mentioned.
As commercially available products, Toyon Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-13.
0, ATR-2009, ATR-2010 made by Kao, Elitel UE3500, UE3210, X made by Unitika
A-8153, Polyester TP-2 manufactured by Nippon Synthetic Chemical Industry
20, R-188 and the like can be used.

(B) Those having a urethane bond. Polyurethane resin, etc. (C) Those having an amide bond. Polyamide resin, etc. (D) Those having a urea bond. Urea resin etc. (E) Those having a sulfone bond. Polysulfone resin, etc. (F) Others having a highly polar bond. Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the synthetic resin as described above, a mixture or copolymer of these may be used.

The thermal transfer dye image-receiving material, particularly the image-receiving layer, may contain a high-boiling organic solvent or a thermal solvent as a substance capable of receiving the heat transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent are JP-A-62-174754 and JP-A-64-254525.
No. 3, No. 61-209444, No. 61-2005538
No. 62-8145, No. 62-9348, No. 62
The compounds described in Nos. -30247 and 62-136646 can be mentioned.

In the present invention, the image receiving layer of the thermal transfer dye image receiving material may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but water-soluble polymers having a group capable of undergoing a crosslinking reaction by a hardening agent are preferable, and gelatins are particularly preferable.

The image receiving layer may be composed of two or more layers.
In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a dye having a high boiling point organic solvent or a heat solvent is used to enhance the dyeing property, and the outermost layer has a glass transition point. Use a synthetic resin with a higher point, reduce the amount of high boiling organic solvent or thermal solvent to the required minimum amount or do not use it, and make the surface sticky, adhere to other substances, re-transfer to other substances after transfer. It is desirable to have a structure that prevents troubles such as transfer and blocking with a thermal transfer dye-providing material. The total thickness of the image receiving layer is 0.5 to 50 μm, especially 3 to 30 μm.
Is preferred. In the case of a two-layer structure, the outermost layer is 0.1-2
It is preferably in the range of 0.2 μm, particularly 0.2 to 1 μm.

As the method for dispersing the receptive substance in the water-soluble binder, any known dispersion method for dispersing the hydrophobic substance in the water-soluble polymer can be used. Typically, a method in which a liquid obtained by dissolving a receptive substance in an organic solvent immiscible with water is mixed with an aqueous solution of a water-soluble binder and emulsified and dispersed, and a latex of a receptive substance (polymer) is aqueous solution of a water-soluble binder. There is a method of mixing with.

In the present invention, the thermal transfer image receiving material may have an intermediate layer between the support and the image receiving layer. The intermediate layer is one of a cushion layer, a porous layer, a dye diffusion preventing layer, or a layer having two or more functions depending on the constituent material, and also serves as an adhesive in some cases.
The dye diffusion-preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable,
As an example thereof, the above-mentioned binder of the image receiving layer, particularly gelatin is preferable. The porous layer is a layer which prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support and effectively utilizes the applied heat.

In the present invention, in addition to the object of the present invention, an image receiving layer, a cushion layer, a porous layer, which constitutes a thermal transfer image receiving material,
For the diffusion preventing layer of the dye, the adhesive layer, etc., silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate,
Barium sulfate, aluminum silicate, synthetic zeolite,
Fine powders of zinc oxide, lithobon, titanium oxide, alumina, etc. may be contained.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. As an example, K. Veenkatarama
n edition "The Chemistry of Synth
"tic Dyes" Vol. 5, Chapter 8, JP-A-61-1
The compounds described in No. 43752 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material used in the present invention may be cured with a hardener. In the case of curing an organic solvent-based polymer, JP-A Nos. 61-199997 and 58-21539.
The hardeners described in No. 8 and the like can be used. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
55, 62-245261 and 61-18942.
The hardeners described in No. etc. are suitable for use. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-6-61
2-234157 etc. are mentioned.

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind. Examples of the antioxidant include chroman compounds, coumarans compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
The compounds described in JP-A-61-159644 are also effective.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4
-Thiazolidone compounds (U.S. Pat. No. 3,352,681
No., etc.), benzophenone compounds (JP-A-56-278)
No. 4, etc.) and other JP-A Nos. 54-48535 and 62.
There are compounds described in Nos. -136641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,24.
No. 5,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A Nos. 62-174741 and 61-8.
8256, pages (27) to (29), JP-A-1-75
There are compounds described in JP-A No. 568 and JP-A No. 63-199248.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272, pages 125-137. An anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be contained in the image-receiving material in advance, or may be supplied to the image-receiving material from the outside by a method such as transferring from the dye-providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. Nonionic surfactants, anionic surfactants, amphoteric surfactants and cationic surfactants can be used. Specific examples of these are disclosed in JP-A-62-1734.
63, 62-183457 and the like.

When a substance capable of accepting a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, an optical brightening agent and other hydrophobic compounds are dispersed in a water-soluble binder, the dispersion It is preferable to use a surfactant as an auxiliary agent.
For this purpose, in addition to the above-mentioned surfactants, the surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

As mentioned above, the dye-donor element of the invention comprises
Used to form transfer images. Such a process
As described above, the dye-donor material is image-wise heated by using a thermal head or a laser, and the dye image is transferred to the image-receiving material to form a transferred image.

The dye-donor elements of the invention are used in sheet form or in continuous rolls or ribbons. If a continuous roll or ribbon is used, it may have areas of different dyes, such as cyan and / or magenta and / or yellow and / or black and other dyes that have only one type of dye or are heat transferable. Have separately. That is, one-color, two-color, three-color, or four-color materials (or even multi-color materials) are included within the scope of the present invention.

In a preferred embodiment of the invention, the dye-donor element comprises a polyethylene terephthalate support coated in successive repeating areas of a cyan dye, a magenta dye and a yellow dye, the steps being carried out sequentially for each color to give a three-part dye. Form a color transfer image. Of course, when this process is performed in a single color, a monochrome transfer image is obtained. Lasers used to thermally transfer dyes from dye-donor elements to image-receiving elements include ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, solid state lasers such as ruby and YAG, or A laser such as a semiconductor laser such as gallium-arsenic emitting in the infrared region of 750 to 870 nm can be used. However, practically, the semiconductor laser is effective in terms of small size, low cost, stability, reliability, durability and ease of modulation.

[0093]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following specific examples as long as the gist of the invention is not exceeded.

Example 1 Preparation of Thermal Transfer Dye-donor Material of the Present Invention A polyester film having a thickness of 6 μm and a width of 95 mm provided with a heat-resistant slip layer made of a thermosetting acrylic resin on one side was used as a support. On the surface opposite to the side provided with the heat resistant slipping layer, a detection mark having a length of 20 mm with a gravure ink for black plate and an ink composition for forming a dye-donor layer having the following composition were used, and inorganic and / or organic fine particles As shown in Table-2, silicone oil as a mold is changed variously,
Length 17 so that the coating amount after drying is 1.2 g / m ^2.
Dye-donor elements 1 to 8 were prepared by coating the dye-providing materials at 0 mm sequentially.

(Ink Composition for Coating Thermal Transfer Dye Donor Layer) Yellow Dye Transfer Layer Yellow Dye (Dye Y-1) 3 g Inorganic and / or Organic Fine Particles [Table 1] Ag Polyvinyl Butyral Resin 3 g (Denka Butyral manufactured by Electrochemical Co., Ltd.) 5000-A) Silicone oil (KF-96 manufactured by Shin-Etsu Chemical) Xml Toluene 50 ml Methyl ethyl ketone 50 ml Polyisocyanate 0.05 ml (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) Magenta dye transfer layer Magenta dye (the dye M-2) 3 g Inorganic and / or organic [Table 1] Ag polyvinyl butyral resin 3 g (Denka Butyral 5000-A manufactured by Electrochemical) Silicone oil (KF-96 manufactured by Shin-Etsu Chemical) Xml Toluene 60 ml Methyl ethyl ketone 60 ml Polyisocyanate 0.05 ml (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) Cyan dye transfer layer Cyan dye (the dye C-2) 3 g Inorganic and / or organic fine particles [Table 1] Ag polyvinyl butyral resin 3 g (Denka Butyral 5000-A manufactured by Electrochemical) Silicone oil ( Shin-Etsu Chemical KF-96) Xml Toluene 50 ml Methyl ethyl ketone 50 ml Polyisocyanate 0.05 ml (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.)

[0096]

[Table 1]

[Preparation of thermal transfer dye image-receiving material of the present invention]:
In the dye image-receiving layer coating liquid composition having the following composition on the support shown in Table 2, the type and amount of the inorganic and / or organic fine particles and the releasing agent were changed as shown in Table 3 to perform wire bar coating. To obtain a thermal transfer dye image-receiving material 1 to 12 by coating so that the thickness after drying would be 8 μm. The sample size was cut into 100 mm × 140 mm.

[0098]

[Table 2]

(Composition for coating thermal transfer dye image receiving material) Polyester resin (Vylon 200 manufactured by Toyobo) 25 g Inorganic and / or organic fine particles [Table 3] Bg Curing agent (Polyisocyanate KP-90 manufactured by Dainippon Ink and Chemicals) 4 g Separated Molding agent (Shin-Etsu Silicone silicone oil KF-857) Yg Methyl ethyl ketone 85g Toluene 85g

[0100]

[Table 3]

Dye-donor element 1 obtained as described above
~ 8 and the dye image receiving materials 1 to 13 in the combinations shown in Table 4,
Overlap each so that the dye-donor layer and the image-receiving layer are in contact,
The yellow and magenta static coefficient of friction between them was measured. Furthermore, a gray image was printed with a video printer using the combination of the above materials. However, the order of transferring each dye-donor layer was yellow, magenta, and cyan. At this time, if slippage occurs between the dye-donor material and the dye-image-receiving material, the trailing edge of the printed image is displaced at the transfer start position between the dye-donor layer and the dye-image receiving layer, depending on the degree of slippage. Since the transfer start position comes on the dye-donor layer in front of the dye-donor layer to be transferred, and the heat is applied thereto by the thermal head, an image defect such as "color shift transfer" occurs. These evaluations, along with the presence or absence of release agents,
⊚ (no image defect mentioned above), ○ (the above-mentioned image defect did not occur, but it was barely reached), Δ (the above-mentioned image defect occurred slightly), and × (the above-mentioned image defect occurred). Table 4 together with static friction.

[0102]

[Table 4]

When a matting agent is contained in the dye-donor layer and the dye-image receiving layer as described above, the coefficient of static friction is increased, slippage does not occur between the dye-donor layer and the dye image-receiving layer, and no defective portion is generated in the image. I understand.

[0104]

INDUSTRIAL APPLICABILITY According to the present invention, by using a thermal transfer recording material characterized by containing organic and / or inorganic fine particles in the dye-donor layer and the dye-image receiving layer, thermal fusion, paper feeding property and It is possible to obtain a print that does not cause slippage between the dye-donor material and the dye-image-receiving material even if a release agent is used to improve transportability, that is, does not cause image defects such as “color shift transfer”. it can.

Claims (3)

[Claims] 1. A thermal transfer dye-receiving material having a dye-donor layer comprising at least a heat transferable dye and a binder resin on a support and a dye-receiving layer containing a dye-receiving substance on the support. A thermal transfer recording material comprising a material, a dye-donor layer and a dye-receiving layer are brought into contact with each other, and the dye is transferred from the dye-donating layer to the dye-receiving layer by heating according to an image signal for recording. Thermal transfer characterized by containing organic and / or inorganic fine particles in at least one layer on the side provided with a dye-donor layer and at least one layer on the side provided with a dye-image receiving layer in the layer constituting the thermal transfer image-receiving material. Recording material. 2. A thermal transfer dye-donating material having a dye-donating layer comprising at least a heat-transferable dye and a binder resin on a support, and a dye-receiving layer containing a dye-receiving substance on the support. A thermal transfer recording material comprising a material, a dye-donor layer and a dye-receiving layer being brought into contact with each other, and the dye being transferred from the dye-donor layer to the dye-receiving layer by heating according to an image signal for recording. The dye transfer material contains a modified and / or unmodified silicone oil and / or a fluorine-based releasing agent, and at least one layer constituting the heat transfer dye donating material is provided with a dye donating layer and the thermal transfer image receiving layer. A thermal transfer recording material, characterized in that at least one layer constituting the material on the side where the dye image-receiving layer is provided contains organic and / or inorganic fine particles. 3. A thermal transfer dye-donating material having a dye-donating layer comprising at least a heat transferable dye and a binder resin on a support, and a dye-receiving layer containing a dye-receiving substance on the support. A thermal transfer recording material comprising a material, a dye-donor layer and a dye-receptive layer being brought into contact with each other, and the dye being transferred from the dye-donor layer to the dye-receiving layer by heating according to an image signal for recording. The material contains a modified and / or unmodified silicone oil and / or a fluorine-based releasing agent, and at least one layer of the layers constituting the thermal transfer dye-donating material is provided with a dye-donating layer and the thermal transfer image-receiving material. A material for thermal transfer recording, characterized in that at least one of the constituent layers on the side where the dye image-receiving layer is provided contains organic and / or inorganic fine particles.