JPH03110196A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To improve the density of an image by a method wherein an intermediate layer is provided between image receiving layers or an image receiving layer and a base material and contains a substance which generates heat by heating during thermal transfer. CONSTITUTION:A substance which is caused by heating to enter into exothermic decomposition has a structure that a molecular shown by the formula I bonds to carbon atoms, and a concrete example is a compound A having a structure shown by the formula II. The compound A decomposes and generates heat when heated up to 125 deg.C. When the exothermic substance is contained in a dye image receiving layer or an intermediate layer provided between the image receiving layer and a base material, the exothermic substance decomposes and generates heat by heating by a thermal head during thermal transfer. The average temperature inside the dye image receiving layer increases during thermal transfer, and the high temperature period lasts for a long time after heating so that a high density of an image is obtainable. The content of the exothermic substance is preferably in a range of 0.5g/m<2>-10g/m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermal transfer image-receiving material used in a thermal transfer recording method, and particularly to a thermal transfer image-receiving material capable of obtaining high-density images.

(Background Art) In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices suitable for each information processing system have also been developed and adopted. The thermal transfer recording method is one of these recording methods.The equipment used is lightweight, compact, noiseless, easy to operate,
It has excellent maintainability and can be easily colored, so it has been widely used recently. This thermal transfer recording method can be roughly divided into two types: a thermal melting type and a thermal transfer type. In the latter method, a thermal transfer dye-providing material having a dye-providing layer containing a binder and a heat-transferable dye on a support is superimposed on a thermal transfer image-receiving material, and heat is applied from the support side of the dye-providing material to create a pattern formed by the thermal application. This is a method of obtaining a transferred image by transferring a heat-transferable dye onto a recording medium (thermal transfer image-receiving material).

Note that the term "thermally transferable dye" as used herein refers to a dye that can be transferred from a thermal transfer dye-providing material to a thermal transfer image-receiving material by sublimation or diffusion in a medium.

(Problems to be Solved by the Invention) However, conventional thermal transfer image-receiving materials have a problem in that the obtained images do not have sufficient density. Furthermore, if the energy applied to the thermal head during thermal transfer is increased in order to improve the density of the image on the thermal transfer image-receiving material where the transferred image density is insufficient, there is a problem that the durability of the thermal head deteriorates.

(Means for Solving the Problems) The above-mentioned problems can be solved in thermal transfer image-receiving materials having an image-receiving layer capable of receiving a dye on a support. In the present invention, the heat-generating material contained in the dye image-receiving layer and the intermediate layer contains a substance that generates heat when heated during thermal transfer. It is a substance that causes exothermic decomposition or exothermic reaction when heated.

Examples of substances that cause exothermic decomposition upon heating include substances having a structure in which the following partial structure (1) is bonded to a carbon atom.

Specific examples of substances that cause exothermic decomposition upon heating include compounds with the following structures.

<Compound A> Compound A decomposes and generates heat when heated to 125°C. The calorific value is 1g when determined by calorimeter measurement.
Approximately 10 cal per serving. Therefore, when this exothermic substance is contained in the dye image-receiving layer or the intermediate layer provided between the image-receiving layer and the support, the exothermic substance decomposes and generates heat due to the heat from the thermal head during thermal transfer. As a result, compared to a thermal transfer image-receiving material that does not contain a pyrogenic substance, the average temperature within the dye image-receiving layer during thermal transfer increases, and the high temperature retention time after heat application becomes longer. , high image density can be obtained.

The content of the pyrogen is preferably 0.5 g/rd to 10 g/pp; if the content is less than 0.5 g/rrf, no improvement in image density due to the effect of heat generation is observed;
g/nf or higher, unevenness occurs on the surface of the dye image-receiving layer due to aggregation of exothermic substances.

The pyrogen can be added by dissolving the pyrogen in an organic solvent and then coating it, or by dispersing the pyrogen in a resin dissolved in an organic solvent or in gelatin dissolved in water. be.

Examples of exothermic substances other than Compound A having the partial structure (2) include the following, but the exothermic substances of the present invention are not limited thereto.

(2) An example of an exothermic reaction caused by heating is a polymerization reaction initiated by an initiator that melts at a high temperature.

Examples of the polymerization initiator include azo compounds that decompose at high temperatures. Specific examples include 2.2' azobisisobutyronitrile (mP=10.6°C), 1.1'-azobis(cyclohexane-1-carnide), and examples of monomers that can be polymerized include vinyl acetate, methyl acrylate, and acrylonitrile. , methyl methacrylate, monosubstituted ethylene with styrene, or 1,1-disubstituted ethylene.

Other exothermic reactions include the reaction of oxidized metals with peroxides and alkalis.

These are, respectively, the temperature at which exothermic decomposition begins or
The amount of heat generated during exothermic decomposition is different. Therefore, by containing a combination of several types of these compounds, desirable gradation characteristics can be obtained, such as improving only the high-density portions of the image or improving only the intermediate-density portions.

The support used in the thermal transfer image-receiving material of the present invention is not particularly limited, and any known support can be used.

General specific examples of supports are listed below.

■Synthetic paper (polyolefin-based, polystyrene-based, etc. synthetic paper), ■High-quality paper, art paper, coated paper, cast coat paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin interior Paper supports such as paperboard, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene);
Various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc., and films or sheets processed to give white reflective properties to these plastics.

Moreover, a laminate formed by any combination of the above items (1) to (2) can also be used.

Among these, polyolefin coated paper is preferred because it has features such as not causing concave deformation due to heating during thermal transfer, excellent whiteness, and little curling.

Polyolefin-coated paper is described, for example, in the book edited by the Photographic Society of Japan [Fundamentals of Photographic Engineering (Silver Salt Photography M) J (published by Corona Publishing, 1979), pages 223-240. This polyolefin coated paper basically consists of a support sheet and a polyolefin layer coated on the surface of the support sheet. The support sheet is made of something other than synthetic resin, and for example -a, high-quality paper is used. The polyolefin coat may be applied by any method as long as the polyolefin layer is in close contact with the surface of the support sheet, but it is usually applied by an extrusion method. The polyolefin coat layer may be provided only on the surface of the support sheet on which the receptor layer is provided, but
It may be provided on both the front and back sides.

Polyolefins used include high-density polyethylene, low-density polyethylene, and polypropylene.
Any of these may be used; however, considering the heat insulation effect during transfer, it is preferable to use low-density polyethylene, which has lower thermal conductivity, on the side where the receiving layer is provided.

The thickness of the polyolefin coat is not particularly limited, but is usually preferably 5 to 100 μm on one side. However, in order to obtain a higher transfer density, it is preferable that the polyolefin coating on the receiving layer side be thinner.

Pigments and fillers such as titanium oxide and ultramarine may be added to the polyolefin coat to increase whiteness, and the polyolefin coated paper has a pigment of 0.05 to A thin gelatin layer of about 9.4 g/s'' may be provided.

The thermal transfer image-receiving material is provided with a dye image-receiving layer.

This image-receiving layer receives the heat-transferable dye transferred from the thermal transfer dye-providing material during printing, and contains a dye-receiving substance that functions to dye the heat-transferable dye alone or Thickness 0.5 including with other binder substances
It is preferable that the film has a thickness of about 50 μm.

Examples of dye-receiving polymers that are representative examples of dye-receiving substances include the following resins.

(a) Dicarboxylic acid components having ester bonds such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components contain sulfonic groups,
Polyester resins obtained by condensation of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc. with carboxyl groups (which may be substituted with carboxyl groups, etc.): polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl Polyacrylic acid ester resin or polymethacrylic acid ester resin such as acrylate: Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395, JP-A-63-7971 No. 63-7972, No. 63-79
Examples include those described in No. 73 and No. 60-294862. In addition, commercially available products include Toyobo's Byron 2901, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130, Kao's ATR-2009, AT
R-2010 etc. can be used.

Mouth) Those with urethane bond polyurethane resin, etc.

(c) Those with an amide bond polyamide resin, etc.

(d) Those with urea bonds urea resin etc.

(e) Those with a sulfone bond.

polysulfone resin, etc.

(f) Others having highly polar bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resins mentioned above, mixtures or copolymers thereof can also be used.

The thermal transfer image-receiving material, particularly the image-receiving layer, may contain a high-boiling organic solvent or a thermal solvent as a dye-receiving substance or as a dye diffusion aid.

Examples of high boiling point organic solvents include JP-A-59-83154;
No. 59-178451, No. 59-178452, No. 59-178453, No. 59-178454, No. 5
Esters (e.g. phthalate esters, phosphate esters, fatty acid esters), amides (e.g. fatty acid amides, sulfamides), ethers as described in No. 9-178455, No. 59-178457, etc. Examples include compounds such as alcohols, paraffins, and silicone oils.

As a thermal solvent, it must be: - compatible with the dye but incompatible with the water-soluble binder; - solid at room temperature, but melts when heated by the thermal head during transfer (i.e., does not mix with other components). Compounds are used that have the following properties: (1) they do not decompose when heated with a thermal head; Preferably 35~
Preference is given to compounds which exhibit a melting point of 250 DEG C., especially 35 DEG to 200 DEG C., and have an (inorganic/organic) ratio of 1.5.

Here, inorganic and organic are concepts used to predict the properties of compounds, and details can be found in, for example, "Chemistry Domain 111719".
(1957).

Specific examples of high boiling point organic solvents and thermal solvents include JP-A-62-174754, JP-A-62-245253, and JP-A-62-245253.
No. 1-209444, No. 61-200538, No. 62
-8145, 62-9348, 62-3024
No. 7 and No. 62-136646.

The high-boiling organic solvent and/or thermal solvent can be used alone in microdispersed form in the image-receiving layer, or can be used in combination with the dye-receiving polymer.

Further, the above-mentioned high boiling point organic solvent may be used for the purpose of improving slipperiness, peelability, curl balance, etc.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which the dye-receiving substance is dispersed and supported in a water-soluble binder. In this case, various known water-soluble polymers may be used as the water-soluble binder. However, a water-soluble polymer having a group that can undergo a crosslinking reaction with a hardening agent is preferred.

The water-soluble polymers used in the present invention include polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridinium, cation-modified polyvinyl alcohol silkworm polymer and its derivatives (Japanese Patent Application Laid-Open No. 60-14587
No. 9, No. 60-220750, No. 61-14317
No. 7, No. 61-235182, No. 61-245183
No. 61-237681, No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid-methacrylic acid copolymer or its salt, polymethacrylic acid or a salt thereof, a polymer containing an acrylic group such as an acrylic acid-vinyl alcohol copolymer or a salt thereof (JP-A No. 60-168651, No. 62-9)
988), starch, oxidized starch, starch acetate, amine starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxy Natural polymers such as ethyl cellulose and hydroxypropyl cellulose or their derivatives (JP-A-59-174382, JP-A-60-2)
No. 62685, No. 61-143177, No. 61-18
No. 1679, No. 61-193879, No. 61-287
(See No. 782).

polyethylene glycol, polypropylene glycol,
Polyvinyl methyl ether, maleic acid-vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer,
Synthetic polymers such as maleic acid-alkyl vinyl ether copolymer and polyethyleneimine (JP-A-61-327
No. 87, No. 61-237680, No. 61-27748
3) and the water-soluble polymers described in JP-A No. 56-58869.

Furthermore, various copolymers made water-solubilized by monomer components containing SO, - groups, COO- groups, Sow- groups, etc. can also be used.

It is particularly preferable to use gelatin as a water-soluble binder because it can be dried as a set, so the drying load is much lower.Specifically, gelatin is used as a water-soluble binder. gelatin and its derivatives such as gelatin, succinated gelatin, Bull, Soc, Phot,
Japan, No. 16. Enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in P2O (1966) can be mentioned.

Only one type of these water-soluble polymers may be used,
Two or more types may be used in combination.

The water-soluble binder and the dye-receiving substance have a weight ratio of dye-receiving substance/water-soluble binder=1 to 20, preferably 2.
-10, particularly preferably 2.5-7.

As a method for dispersing the dye-receiving substance in the water-soluble binder, any known dispersion method for dispersing a hydrophobic substance in a water-soluble polymer can be used. Typical methods include emulsifying and dispersing a dye-receiving substance dissolved in an organic solvent that is immiscible with water and mixing it with an aqueous solution of a water-soluble binder; There are methods such as mixing with an aqueous solution of

The image receiving layer may be one layer or may be composed of two or more layers. When two or more layers are provided, a synthetic resin with a low glass transition point is used for the layer closer to the support, or a high boiling point organic solvent or a hot solvent is used to improve the dyeability of the dye.
For the outermost layer, use a synthetic resin with a higher glass transition point, minimize the amount of high-boiling point organic solvents and hot solvents, or avoid using them to prevent surface stickiness, adhesion with other substances, and post-transfer. It is desirable to have a structure that prevents failures such as re-transfer of the dye to other substances and blocking with the thermal transfer dye-providing material.

The total thickness of the image-receiving layer is 0.5 to 50 μm, particularly 3 to 30 μm.
#m, in the case of a two-layer configuration, the outermost layer is 0. 1~20μm1
In particular, it is preferably in the range of 0.2 to 10 μm.

The thermal transfer image-receiving material of the present invention may have an intermediate layer between the support and the image-receiving layer.

The intermediate layer can be a cushion layer, a porous layer, or a
This layer has one of the functions of a dye diffusion prevention layer or a layer having two or more of these functions, and in some cases also serves as an adhesive.

The dye diffusion-preventing layer plays a role, in particular, in preventing the heat-transferable dye from diffusing into the support. The binder constituting this diffusion prevention layer may be water-soluble or organic solvent-soluble, but preferably a water-soluble binder.
Preferred examples include the water-soluble binders mentioned above as binders for the image-receiving layer, particularly gelatin.

The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the image-receiving layer to the support and effectively utilizes the applied heat.

3) A water-soluble polymer solution containing a foaming agent is foamed before application or foamed during the coating and drying process; 4) A water-soluble polymer solution containing bubbles is applied and dried. Microvoids can be formed by emulsifying and dispersing an organic solvent (preferably a solvent with a boiling point higher than water) in a polymer solution, and forming microvoids during the coating and drying process.

When using an organic solvent-soluble binder as the porous layer, 1) a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate-butadiene system is mechanically stirred to support a liquid in which air bubbles are generated; 2) Apply the above synthetic resin emulsion or synthetic rubber latex mixed with a foaming agent onto the support and dry it. 3) Synthetic resin such as PVC plastisol, polyurethane, or styrene-butadiene type. 4) A solution of thermoplastic resin or synthetic rubber mixed with a foaming agent is applied onto a support and foamed by heating. A mixture of a non-solvent (including those whose main component is water) that is compatible with organic solvents and insoluble in thermoplastic resins or synthetic rubbers is applied onto a support and dried. A method such as forming a microporous layer can be used.

If the image-receiving layer is on both sides of the support, the intermediate layer may be provided on both sides, or may be provided on only one side.

The thickness of the intermediate layer is preferably 0.5 to 50μ, particularly preferably 1 to 20μ.

The image receiving layer, cushion layer, porous layer, diffusion prevention layer, adhesive layer, etc. constituting the thermal transfer image receiving material of the present invention include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, Fine powders of synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. may also be included.

A fluorescent brightener may be used in the thermal transfer image-receiving material.

Examples include K, VeenkataramaJJi
rThe Chemis-try of 5ynthe
tic DyesJ Volume 8 Chapter 8, JP-A-61-143
Examples include compounds described in No. 752 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. It will be done.

Optical brighteners can be used in combination with antifade agents.

The thermal transfer dye-providing material used in the present invention is a thermal transfer dye-providing material having a dye-providing layer containing a heat-transferable dye on a support, in which the dye is transferred in a pattern by applying heat to the image-receiving material of the thermal transfer image-receiving material. A thermal transfer dye-providing material having a heat-melting ink layer (dye-donating layer) on a support and a thermal transfer image-receiving material in which the ink is melted in a pattern by applying heat. This includes two types that are recorded by being transferred to a computer.

The dye-donor layer is formed by selecting a dye so that the desired hue can be transferred when printed, and if necessary, arranging two or more dye-donating layers with different dyes on one thermal transfer dye-donating material. For example, when forming an image such as a color photograph by repeatedly printing each color according to the color separation signal, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing dyes that provide a unique hue are arranged.

Alternatively, a dye-donating layer containing a dye that gives a black hue in addition to cyan, magenta, and yellow may be added; however, when forming these dye-donating layers, the formation of any one of the dye-donating layers and It is preferable to provide a mark for position detection at the same time, since no ink or printing process separate from the formation of the dye-donating layer is required.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. Examples include polyethylene terephthalate; polyamide; polycarbonate; krasin oxide; condenser oxide; cellulose ester; fluorine polymer: polyether; polyacetal; polyolefin; polyimide; polyphenylene sulfide; polypropylene; polysulfone; cellophane.

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 mm.
μ. If necessary, an undercoat layer may be provided, and a dye diffusion prevention layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer, thereby further improving the transfer density. As the hydrophilic polymer, the water-soluble polymers described above can be used.

A slipping layer may also be provided to prevent the thermal head from sticking to the dye-donor material; this slipping layer may contain a lubricating material, such as a surfactant, solid or liquid, with or without a polymeric binder. Consists of lubricants or mixtures thereof.

A thermal transfer dye-providing material using a heat-transferable dye basically has a dye-providing layer on a support containing a dye that sublimes or becomes mobile by heat and a binder. This thermal transfer dye-providing material is prepared by preparing a coating solution by dissolving or dispersing a dye that sublimes or becomes mobile by heat and a binder resin in an appropriate solvent, and applying this to one side of a support. The thermal transfer layer can be obtained by coating and drying the coating amount to give a dry film thickness of, for example, about 0.2 to 5 μm, preferably 0.4 to 2 μm to form a thermal transfer layer.

Dyes useful for forming such a thermal transfer layer include:
Although any dye conventionally used in thermal transfer dye-providing materials can be used, particularly preferred in the present invention are dyes of about 15
It has a small molecular weight of about 0 to 800, and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility, etc.

Specifically, for example, disperse dyes, basic dyes, oil-soluble dyes, etc. can be mentioned, but in particular, Sumikaron Yellow E
4GL, Dianix Yellow H2G-FS, Miketon Bolier Tell Yellow 36SL, Kayasset Yellow 937, Sumikalon Red EFBL, Dianix Red ACE, Miketon Bolier Tell Red FB, Kayasse Tread 126, Miketon Fast Brilliant Plue B, Kayasset Blue 136 or the like is preferably used.

Other known heat-transferable dyes can also be used.

Furthermore, as the binder resin used with the above dye, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not hinder the transfer of the dye when heated. things are selected. For example, polyamide resin, polyester resin,
Epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride resins (e.g. vinyl chloride-vinyl acetate) copolymers), polycarbonate resins, polystyrene, polyphenylene oxide, cellulose resins (e.g. methylcellulose, ethylcellulose, carboxymethylcellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate), polyvinyl Alcohol resins (for example, partially saponified polyvinyl alcohols such as povinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, coumaron-indene resins, terpene resins, polyolefin resins (for example, polyethylene and polypropylene), etc. are used.

Such a binder resin is preferably used in a proportion of, for example, about 80 to 600 parts by weight per 100 parts by weight of the dye.

In the present invention, any conventionally known ink solvent can be freely used as the ink solvent for dissolving or dispersing the above pigment and binder resin.

A second embodiment of the thermal transfer dye-providing material is an embodiment in which the thermal transfer layer is a thermal melt transfer layer composed of an ink for forming a thermal transfer layer consisting of a wax containing a coloring agent such as a dye or a pigment. This ink is made by distributing and dispersing colorants such as carbon black and various dyes and pigments using waxes with appropriate melting points, such as paraffin wax, microcrystalline wax, carnauba wax, and urethane wax, as a binder. It is what it is. The ratio of the colorant and wax used is preferably such that the colorant accounts for about 10 to 65% by weight in the heat-melting transfer layer to be formed, and the thickness of the layer to be formed is about 1.5 to 6 Oa- Preparation of the ink and application onto the support can be carried out according to known techniques.

In order to prevent sticking due to the heat of the thermal head and improve slippage when printing from the back side of the dye-donating material, it is preferable to apply an anti-sticking treatment to the side of the support on which the dye-donating layer is not provided.

For example, as a polyvinyl butyral resin, it is preferable to provide a heat-resistant slip layer mainly consisting of ■ a reaction product of polyvinyl butyral resin and an isocyanate, ■ an alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, and ■ a filler. It is preferable to have a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110"C, and a vinyl butyral moiety of 15 to 40% by weight from the viewpoint of having many reaction sites with isocyanate. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Toho Chemical's Gafac RD720 or the like is used, and it is preferably used in an amount of about 1 to 50% by weight, preferably about 10 to 40% by weight based on the polyvinyl butyral resin. .

It is desirable that the heat-resistant slip layer has heat resistance as the lower layer.
A combination of a synthetic resin that can be cured by heating and its curing agent,
For example, a combination of polyvinyl butyral and polyvalent incyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and a titanium chelating agent, or polyester and organic titanium compound may be provided by coating.

The dye-donor element may also be provided with a hydrophilic barrier layer to prevent diffusion of the dye towards the support. Hydrophilic dye barrier layers contain hydrophilic materials useful for their intended purpose. Generally excellent results are obtained with gelatin, poly(acrylamide), poly(isopropylacrylamide),
Butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly(vinyl alcohol), poly(ethyleneimine), poly(acrylic acid), mixture of poly(vinyl alcohol) and poly(vinyl acetate) , by using a mixture of poly(vinyl alcohol) and poly(acrylic acid) or a mixture of cellulose monoacetate and poly(acrylic acid). Particularly preferred is poly(
acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has the desired effect. Preferred specific examples include (acrylonitrile-vinylidene chloride-acrylic acid) copolymer ( Weight ratio 14:80:6
), (butyl acrylate-2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear/saturated polyesters such as Bostik 7650 (Emhart, Bostick) stick chemical group) or chlorinated high density poly(ethylene-trichloroethylene) resins. There is no particular limit to the amount of the undercoat layer applied, but it is usually used in an amount of 0.1 to 2.0 g/m''.

In the present invention, in order to improve the releasability of the thermal transfer dye-providing material and the thermal transfer image-receiving material, the dye-providing material and/or
Alternatively, it is preferable to include a release agent in the layers constituting the image-receiving material, particularly preferably in the outermost layer corresponding to the surface where both materials come into contact.

Examples of mold release agents include solid or waxy substances such as polyethylene wax, amide wax, and Teflon powder; surfactants such as fluorine-based and phosphate esters; and conventionally known oils such as paraffin-based, silicone-based, and fluorine-based oils. Although any of the above mold release agents can be used, silicone oil is particularly preferred.

As the silicone oil, in addition to unmodified silicone oil, modified silicone oils such as carboxy-modified, amino-modified, and epoxy-modified silicone oils can be used.

Examples include various modified silicone oils described in pages 6 to 18B of "Modified Silicone Oil J Technical Data" published by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, this binder When an amino-modified silicone oil having a group that can react with a crosslinking agent (for example, a group that can react with isocyanate) is emulsified and dispersed in a water-soluble binder, carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd.) (manufactured by product name: X-22-3710) is valid.

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be hardened with a hardening agent.

When curing organic solvent-based polymers, JP-A-61
Hardeners described in Japanese Patent No. 199997 and No. 5B-215398 can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For curing water-soluble polymers, U.S. Patent No. 4.678.7
39 No. 416, JP-A-59-116655, JP-A No. 62
Hardeners described in Japanese Patent Nos. 245261 and 61-18942 are suitable for use.

More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners (bis(vinylsulfonylacetamide)ethane, etc.),
N-methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A No. 62-234157, etc.) may be used.

Antifading agents may be used in thermal transfer dye-providing materials and thermal transfer image-receiving materials, such as antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

Benzotriazole compounds (
U.S. Patent No. 3.533.794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3.352681, etc.),
Benzophenone compounds (JP-A-56-2784, etc.), other JP-A-54-48535, JP-A-62-136
There are compounds described in No. 641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, U.S. Patent No. 4.241.155,
No. 4.245.018, columns 3 to 36, No. 4.25 of the same
4.195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), Japanese Patent Application No. 1982-234103, JP-A No. 62-31096, JP-A-62 There are compounds described in No.-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

The anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be included in the image-receiving material in advance, or it may be supplied to the image-receiving material from the outside by a method such as transfer from a dye-donating material. You can.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, accelerating development, and the like.

Nonionic surfactants, anionic surfactants.

Amphoteric surfactants and cationic surfactants can be used. Specific examples of these are JP-A-62-173463,
It is described in No. 62-183457 and the like.

In addition, when dispersing substances that can accept heat-transferable dyes, M-type agents, anti-fading agents, ultraviolet absorbers, optical brighteners, and other hydrophobic compounds in a water-soluble binder, the interface is used as a dispersion aid. It is preferable to use surfactants; for this purpose, in addition to the above-mentioned surfactants, JP-A-59-15763
The surfactants described on pages 37-38 of No. 6 are particularly preferably used.

The constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static electricity, improving releasability, etc. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57 -9053 No. 8 to 17 columns,
Fluorine surfactants described in JP-A-61-20944 and JP-A-62-135826, oily fluorine compounds such as fluorine oil, solid fluorine compound resins such as tetrafluoroethylene resin, etc. Examples include hydrophobic fluorine compounds.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc.
In addition to the compounds described on page 29 of No. 1-88256, Japanese Patent Application No. 110064/1988, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 62-110065.

In the present invention, a thermal transfer dye-providing material is superimposed on a thermal transfer image-receiving material, and thermal energy is applied according to image information from either side, preferably from the back side of the thermal transfer dye-providing material, using a heating means such as a thermal head. Thereby, the dye in the dye-donating layer can be transferred to the thermal transfer image-receiving material depending on the magnitude of heating energy, and a color image with excellent clarity and resolution and gradation can be obtained.

The heating means is not limited to a thermal head, and known means such as a laser beam (for example, a semiconductor laser), an infrared flash, a thermal pen, etc. can be used.

In the present invention, by combining the thermal transfer dye-providing material with the thermal transfer image-receiving material, images can be printed by printing using various thermal printing printers, by facsimile, or by magnetic recording, magneto-optical recording, optical recording, etc. It can be used to create prints from , television, CR7 screens, etc.

For details on the thermal transfer recording method, see Japanese Patent Application Laid-Open No. 60-348.
You can refer to the description in No. 95.

EXAMPLES The present invention will be explained in more detail by showing examples below.

Example 1 (Preparation of thermal transfer dye-providing material) A 5.5 μm thick polyethylene terephthalate film (manufactured by Lumirror Nitoshi Co., Ltd.) having a heat-resistant slipping layer made of a thermosetting acrylic resin on one side was used as a support. A coating composition for forming a thermal transfer dye-providing layer having the following composition was coated with a wire bar on the side opposite to the side on which the heat-resistant slipping layer was provided, so that the thickness after drying was 2. A thermal transfer dye-providing material was obtained by coating and forming the dye in such a manner that the color was 100 nm.

Disperse dye (1,4-diamino-2,3-diphenoxyanthraquinone) 4g polyvinyl butyral resin (Denka Butyral 5000-A: Denkaji type) 4g methyl ethyl ketone 40M1 toluene 4 (ld polyisocyanate) 0.2111 (Takene) DIION: manufactured by Shikinichi Yakuhin) (Preparation of thermal transfer image receiving material 1) As a support, synthetic paper with a thickness of 150 μm (manufactured by Tamago Yuka: Y
A thermal transfer image-receiving material 1 was prepared by applying a coating composition for an image-receiving layer having the following composition to the surface of UPO-FPG-150) by wire bar coating so that the dry thickness was 15 μm.

Drying was performed for 30 minutes in an oven at a temperature of 100° C. after temporary drying with a hair dryer.

Compound A was used as the pyrogen. After the following coating composition was prepared, it was stirred for 10 minutes with high-speed stirring II (15,000 rpm) to disperse the pyrogen.

Polyester resin a 20g Compound A 5g Amino-modified silicone oil 1g (KF-8
57: Shin-Etsu Silicone) Polyisocyanate 3g (k
P-90: manufactured by Dainippon Ink) The composition of methyl ethyl ketone toluene polyester resin a is shown below.

is mol%) 5m 5M1 (units) = <<- o+1cLl- ←- silkworms (Preparation of thermal transfer image-receiving material 2) Apply a paint for the lower layer of the image-receiving layer to the following composition on the surface of a support having the same contents as the image-receiving material. The composition was applied by wire bar coating to a dry thickness of lOμ. The drying method was the same as that for image-receiving material 1. The following coating composition was prepared in the same manner as image-receiving material 1, and then mixed with a high-speed stirrer (15
00 rpm) for 10 minutes to disperse the pyrogen.

Polyester resin 8 20g Compound A 10g Amino-modified silicone oil 1g (KF-857:
(manufactured by Shin-Etsu Silicone) Polyisocyanate 3g (K
P-90: manufactured by Dainippon Ink) Methyl ethyl ketone 85ad Toluene 85W1 On the lower image-receiving layer above, a coating composition for the upper layer of the image-receiving layer having the following composition was applied by wire bar coating to a dry thickness of 5μ, and thermal transfer was performed. Image receiving material 2 was produced.

Polyester resin a 20g Amino modified silicone oil 1g (kF-8
5'l: Shin-Etsu Silicone) Polyisocyanate
3g (h, r'-9o: manufactured by Dainippon Ink) Methyl ethyl ketone 85jd Toluene 85d (Preparation of thermal transfer image-receiving material 3) A coating composition for the lower image-receiving layer of image-receiving material 2 was applied to the surface of a support having the same contents as image-receiving material 1. A composition having the same content as above is applied to a dry thickness of 10 μm, and on top of this, a composition having the same content as the image-receiving layer coating composition of Image-receiving material 1 is applied to a dry thickness of 5 μm. Apply the heat transfer image-receiving material 3 as shown below.
was created.

(Preparation of thermal transfer image-receiving material 4) Prepare a resin coat by laminating polyethylene to a thickness of 15 μm and 25 μm on both sides of a 200 μm paper, and coat the image-receiving material 2 on the laminated surface with a thickness of 15 μm as a paint for the lower layer of the image-receiving layer. A composition in which polyester resin a in the composition was replaced with Toyobo Vylon 280 had a dry thickness of 1.
0μ, and then apply image-receiving material 1 on top of it.
A composition obtained by replacing polyester resin a in the image-receiving layer coating composition with Toyobo Vylon 280 has a dry thickness of 5.
A thermal transfer image-receiving material 4 was prepared by coating the film so as to have a thickness of μ.

(Preparation of thermal transfer image-receiving material 5) A coating composition for an image-receiving layer having the following composition was coated on the surface of the same support as in Example 1 by wire bar coating so that the dry thickness was 10 μm to prepare a thermal transfer image-receiving material. 5 was produced. The drying method was the same as in Example 1.

Polyester resin 8 20g Vinyl acetate 20g 2.2'-Azobisisobutyronitrile 0.2g Amino-modified silicone oil 1g (KF-857: manufactured by Shin-Etsu Silicone) Polyisocyanate) 3g (
KP-90: manufactured by Dainippon Ink) Methyl ethyl ketone 85mToluene 85W1 (Preparation of thermal transfer image-receiving material 6) A composition having the same contents as the image-receiving layer coating composition of Example 2 was applied on the surface of the support having the same contents as in Example 1. The thickness when dry is 15μ
A thermal transfer image-receiving material 6 was prepared by coating the film in an amount of m.

(Preparation of thermal transfer image-receiving material 7) A composition obtained by replacing the polyester resin a of the image-receiving layer coating composition of Example 1 with Toyobo Vylon 280 was applied to the surface of the same support as in Example 4. Thermal transfer image-receiving material 7 was prepared by coating to a thickness of 15 μm.

The thermal transfer dye-providing material and the thermal transfer image-receiving material obtained as described above are superimposed so that the dye-providing layer and the image-receiving layer are in contact with each other. Output 0.25W/
Printing was carried out under the conditions of a dot pulse width of 0.15 to 15 ssec and a dot density of 6 dots/- to dye the image-receiving layer of the thermal transfer image-receiving material with magenta dye in an imagewise manner.

The reflection density of the saturated portion (DIlax) of the recorded thermal transfer image-receiving material was measured using a status filter, and the results are shown in Table 1.

Claims (1)

[Claims] In a thermal transfer image-receiving material having an image-receiving layer capable of receiving a dye on a support, the image-receiving layer or an intermediate layer provided between the image-receiving layer and the support contains a substance that generates heat when heated during thermal transfer. A thermal transfer image-receiving material characterized by: