JPH0386590A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To obtain high transfer density and high image quality and to improve the thermal fusion of an image receiving material and a dye donating material at the time of thermal transfer by constituting at least the outermost layer of an image receiving layer wherein a dye acceptive substance at least partially crosslinked is dispersed in a water-soluble binder. CONSTITUTION:In a thermal transfer image receiving material provided with at least one image receiving layer receiving a dye to form an image, at least the outermost layer thereof is composed of an image receiving layer wherein a dye acceptive substance at least partially crosslinked is dispersed in a water- soluble binder. The crosslinking agent crosslinking the dye acceptive substance is polyisocyanate and the water-soluble binder is one containing no primary or secondary amino group. The dye acceptive substance is composed of a dye acceptive polymer and/or a high b.p. org. solvent or a hot solvent and more pref. composed of a combination of the dye acceptive polymer and the hot solvent. As the especially pref. dye acceptive polymer, a polyester resin is designated. The crosslinking agent is used more pref. within a range of 1 - 20% by wt. of the dye acceptive polymer.

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 method using a heat-transferable dye. Thermal fusion of the image-receiving material and dye-donor material during thermal transfer is improved, the oil resistance of the image-receiving material after transfer is improved, the blurring of the transferred image over time and the adhesion color transfer are improved, and the image-receiving material is improved when stored in stacks. The present invention relates to a thermal transfer image-receiving material that has improved paper feeding and conveyance properties, as well as improved manufacturing suitability and cost.

(Prior 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.

(What the invention attempts to solve! IB) However, the thermal transfer image-receiving material used in this thermal transfer type thermal transfer recording method has the following problems.

When the thermal transfer dye-providing material and the thermal transfer image-receiving material are overlapped and the heat-transferable dye is transferred from the dye-providing material to the image-receiving material by applying heat, the two fuse together, and the dye-providing layer of the dye-providing material peels off, causing the image to be received. The material may adhere to the transfer surface of the material, or in severe cases, it may become impossible to transport the material, causing a malfunction that may cause the printer to stop. The above-mentioned failure occurs particularly when the applied voltage is increased and thermal transfer is performed at a high temperature in order to obtain a sufficient transfer density.

Usually, the polymer used in the image-receiving layer of the heat-transferable dye is soluble in organic solvents, so the coating solution for the image-receiving layer is organic solvent-based. JP-A-58-215398 describes that crosslinking a portion of the dye-receiving polymer in such a solvent coating system improves thermal fusion. However, the effect of improving heat fusion bonding by this method was not necessarily sufficient.

On the other hand, by changing the coating solution for the image-receiving layer from an aqueous solvent system to an aqueous dispersion system, that is, by dispersing the dye-receiving substance in a water-soluble binder and applying this dispersion to form the image-receiving layer. The improvement effect of heat fusion was obtained which was as good as that of JP-A-58-215398.

However, there has been a desire for an image receiving material with further improved thermal bonding.

In addition, the conventional image-receiving materials described in JP-A No. 58-215398 and others have problems such as blurring of transferred images over time and adhesive color transfer, and paper feeding problems such as multiple sheet feeding due to adhesive failure during stacking and storage. There is a problem with transportability.

That is, the term "blurring of transferred images over time" refers to a problem in which blurring of images tends to occur when the transferred image-receiving material is stored for a long period of time. Conventionally, in order to obtain high transfer density, the glass transition point (
It is known to use a dye-receiving polymer with a low Tg) or to add a plasticizer, but all of these methods worsen the blurring of transferred images over time. Therefore, it has been extremely difficult to improve the blurring of the transferred image over time and to obtain a high-density image.

Adhesive color transfer of transferred images is a problem in which when image-receiving materials after transfer are stacked, the transferred dye is re-transferred to the adhesive surface of another image-receiving material, causing stains.

In addition, the problem of paper feeding and conveyance is that during thermal transfer recording, image-receiving materials stacked in units of tens of sheets are fed and printed one by one, but slippage between the image-receiving materials occurs. If the performance is poor, multiple sheets will be fed. This is the i topic.

In addition, in conventional image receiving materials, the surface of the image receiving material after transfer has poor oil resistance, and when oil droplets adhere to the surface of the image receiving material, there is a problem that the image bleeds.

Furthermore, conventional image receiving materials have problems with manufacturability and cost. That is, since the polymer used in the image-receiving layer of the heat-transferable dye is usually soluble in organic solvents, the coating solution for the image-receiving layer is organic solvent-based.

Furthermore, it is necessary to clean the equipment, containers, etc. used for manufacturing with an organic solvent. Therefore, explosion-proof equipment is required for coating liquid preparation equipment, coating equipment, etc., and organic solvents are more expensive than water, which not only increases production costs, but also poses health problems for workers. There is also a problem. As described above, conventional organic solvent-based thermal transfer image-receiving materials have various problems in terms of manufacturing suitability.

Accordingly, the first object of the present invention is to provide a thermal transfer image-receiving material which has high transfer density and high image quality, and which has improved thermal fusion of an image-receiving material and a dye-donating material during thermal transfer.

A second object of the present invention is to provide a thermal transfer image-receiving material with improved oil resistance.

A third object of the present invention is to provide a thermal transfer image-receiving material in which transferred images are improved in blurring over time and adhesive color transfer.

A fourth object of the present invention is to provide a thermal transfer image-receiving material that has improved paper feeding and transport properties during stacking and storage.

A fifth object of the present invention is to provide a thermal transfer image-receiving material with improved manufacturability and cost. A thermal transfer image-receiving material comprising at least one image-receiving layer for receiving a dye transferred from a thermal transfer dye-providing material to form an image, wherein at least the outermost layer is at least partially crosslinked. The problem has been solved by a thermal transfer image-receiving material characterized by an image-receiving layer having a water-soluble binder dispersed in a water-soluble binder.

In particular, (1) in the thermal transfer image-receiving material of the present invention, the crosslinking agent that crosslinks the dye-receiving substance is a polyisocyanate;
A thermal transfer image-receiving material characterized in that the water-soluble binder is a water-soluble binder that does not contain a primary or secondary amino group. or a high boiling point organic solvent or a thermal solvent, more preferably, the dye-receiving substance is a combination of a dye-receiving polymer and a thermal solvent, and (3) the thermal transfer image-receiving material. A thermal transfer image-receiving material characterized in that the dye-receiving polymer is a polyester resin is preferred.

The present invention will be explained in more detail below.

The thermal transfer image-receiving material of the present invention is provided with a dye image-receiving layer. This image-receiving layer receives the heat-transferable dye that migrates from the thermal transfer dye-providing material during printing, and contains a dye-receiving substance in a water-soluble binder that has the function of dyeing the heat-transferable dye. It is dispersed and carried in the

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 resin obtained by condensation of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc.; polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, poly Polyacrylic ester resin or polymethacrylic ester resin such as butyl acrylate; Polycarbonate resin: Polyvinyl acetate resin;
Styrene acrylate resin; vinyltoluene acrylate resin, etc., specifically JP-A-59-101395,
No. 63-7971, No. 63-7972, No. 63-7
Examples include those described in No. 973 and No. 60-294862. In addition, commercially available products include Toyobo's Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130, and Kao's ATJI-2009.
TR-2010 etc. can be used.

(b) Those with urethane bonds 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 vR (e.g. fatty acid amides, sulfamide I [), as described in No. 9-178455, No. 59-178457, etc. , ethers, alcohols, paraffins, and silicone oils.

As a thermal solvent, ■ It must be compatible with the dye, ■ It is solid at room temperature, but it melts when heated by the thermal head during transfer (it can be mixed and melted with other components), ■ Thermal Compounds that have various properties such as not being decomposed by heating by the head are used.

Preference is given to compounds which exhibit a melting point of preferably 35 to 250°C, in particular 35 to 200°C, and have an (inorganic/organic) value <1.5.

Here, inorganicity and organicity are concepts for predicting the properties of compounds.
(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, 629348, 62-30247
No. 62-136646.

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

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

The above-mentioned high boiling point solvent and/or thermal solvent can be used in any proportion to the dye-receiving polymer, but it is preferably used in an amount of 0 to 100% by weight, particularly 250% by weight.

In the present invention, as the dye-receiving substance, the above-mentioned dye-receiving polymers, high-boiling organic solvents, and hot solvents can be used, but dye-receiving polymers are preferred, and dye-receiving polymers and hot solvents are more preferably used. It was used in combination. Furthermore, a particularly preferred dye-receiving polymer is a polyester resin.

In the present invention, crosslinking agents for dye-receptive substances such as dye-receptive polymers, high-boiling organic solvents, and thermal solvents include polyisocyanate compounds, polymethylol compounds, epoxy compounds, titanium coupling agents, silane coupling agents, aluminum chelating agents, zirconium-based chelating agents, etc. can be used, and polyisocyanate compounds are preferred.

The polyisocyanate compound is an isocyanate compound having two or more isocyanate groups, such as diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate, triisocyanates such as triphenylmethane triisocyanate, and those commercially available as polyisocyanates. can be used.

The crosslinking agent is 0.2 to 50% relative to the dye-receiving polymer.
It can be used in an amount of 1 to 20% by weight, preferably 0.5 to 25% by weight, more preferably 1 to 20% by weight.

Examples of the water-soluble binder used in the present invention include: (1) Vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and derivatives thereof (Japanese Patent Application Laid-open No. 60-145
No. 879, No. 60-220750, No. 61-1431
No. 77, No. 61-235182, No. 61-24518
No. 3, No. 61-237681, No. 61-261089
); ■Polyacrylamide, polydimethylacrylamide, polyacrylic acid or its salts, acrylic acid-
Polymers containing acrylic groups such as methacrylic acid copolymers or salts thereof, polymethacrylic acid or salts thereof, acrylic acid-vinyl alcohol copolymers or salts thereof (JP-A-6
0-168651, 62-9988) Starch, oxidized starch, starch acetate, carboxyl starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, 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
-262685, 61-143177, 61-
No. 181679, No. 61-193879, No. 61-2
(Refer to No. 87782); ■Synthetic polymers (specially Kaisho 61-32787, 61-2
37680, 61-277483); and (2) water-soluble polymers described in JP-A-56-58869.

Furthermore, various copolymers made water-soluble by monomer components containing 5QLe groups, coo' groups, Sow' groups, etc. can also be used.

When polyisocyanate is used as a crosslinking agent for a dye-receiving substance, it is preferable to use a water-soluble binder that does not contain -grade or secondary amino groups in terms of coating properties. Deactivated gelatin, such as phthalated gelatin, acetylated gelatin, and succinated gelatin, is preferred.

These water-soluble binders may be used alone or in combination of two or more.

The water-soluble binder and the dye-receptive substance are the acceptor'! /
The water-soluble binder is used in a ratio (weight ratio) of 1 to 100, preferably 2 to 30, particularly preferably 2.5 to 10.

As a method for dispersing the dye-receiving substance in a water-soluble binder, any known dispersion method for dispersing a hydrophobic substance in a water-soluble polymer can be used. Typically, the dye-receiving substance is dispersed in water. Examples include a method of emulsifying and dispersing food dissolved in an aqueous solvent immiscible with a water-soluble binder by mixing it with an aqueous solution of a water-soluble binder, and a method of mixing a latex of a dye-receiving polymer with an aqueous solution of a water-soluble binder.

The image-receiving layer may be one layer, or two or more layers may be provided. When the image-receiving layer is composed of two or more layers, a synthetic resin with a low glass transition point may be used for the image-receiving layer closer to the support. , using a high boiling point organic solvent or a hot solvent to improve the dyeing property of the dye, and using a synthetic resin with a higher glass transition point for the outermost layer, using a fluorine-containing compound, or using a high boiling point organic solvent. Minimize the amount of heat transfer and thermal solvent used, or avoid using them to avoid problems such as stickiness on the surface, adhesion to other materials, re-transfer of the dye to other materials after transfer, and blocking with the thermal transfer dye-providing material. It is desirable to have a structure that prevents this, and it is also desirable to use a mold release agent, which will be described later, in the outermost layer.

The total thickness of the image-receiving layer is 0.5 to 50 mm. m, especially 3-30
In the case of a two or more layer structure, the outermost layer is preferably in the range of o, i to 3-1, particularly 0.2 to 1.5.

There are no particular restrictions on the support used in the thermal transfer image-receiving material of the present invention, and any known support can be used.In the present invention, materials with high diffusivity for heat-transferable dyes can also be used as the support. .

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 (particularly 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 Japanese Society of Photographic Studies, "Fundamentals of Photographic Engineering W (1!l Salt Photography Edition)" (published by Corona Publishing, 1979), pages 223-24G. 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 resin, and - high-quality paper is used for boat fishing. 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 coating layer may be provided only on the surface of the support sheet on which the image-receiving layer is provided, but it may also be provided on both the front and back surfaces. Examples of polyolefins used include high-density polyethylene, low-density polyethylene, and polypropylene. Any of them 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 image-receiving layer is provided.

The thickness of the polyolefin coat is not particularly limited, but is usually preferably from 5 to 100 mm on one side. However, in order to obtain a higher transfer density, the thickness of the polyolefin coat on the image-receiving layer side is preferably thinner.

Pigments and fillers such as titanium oxide and ultramarine blue may be added to the polyolefin coat to increase whiteness, and the polyolefin coat may have a pigment of 0.05 to A thin gelatin layer of about 0.4 g/rrf may be provided.

The thermal transfer image-receiving material of the present invention may have an intermediate layer containing or not containing a water-soluble binder between the support and the image-receiving layer.

Depending on the material, the intermediate layer may be a kutsushiran layer, a porous layer, or a porous layer.
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 prevention layer is particularly suitable for heat-transferable dyes.
- It serves to prevent REM from changing. The binder constituting this diffusion prevention layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferred, and examples thereof include the water-soluble binders mentioned above as the binder 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.

When using a water-soluble polymer as a binder for a porous layer, there are two methods: 1. Dispersing porous particles in a water-soluble polymer and coating and drying. 2. Applying a water-soluble polymer liquid with air bubbles generated by mechanical stirring. Drying, ■ Foaming the water-soluble polymer solution with a foaming agent added before coating or foaming during the coating drying process, ■ Adding an organic solvent (preferably a solvent with a higher boiling point than water) to the water-soluble polymer solution. ) is emulsified and dispersed, and microvoids are formed in the process of coating and drying.

When using an organic solvent-soluble binder as the porous layer, use a liquid obtained by mechanically stirring a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate-butadiene to generate air bubbles as a support. ■ Coating a liquid mixture of the above synthetic resin emulsion or synthetic rubber latex with a foaming agent onto the support and drying it; ■ Synthesizing synthetic resins such as PVC plastisol, polyurethane, or styrene-butadiene systems, etc. A mixture of rubber and a foaming agent is applied onto a support and foamed by heating. ■ A solution of thermoplastic resin or synthetic rubber dissolved in an organic solvent and a solution that is less likely to evaporate than the organic solvent. A mixture of a non-solvent (including those whose main component is water) that is compatible with the thermoplastic resin or synthetic rubber and has no solubility is applied onto the support and dried to form a microporous layer. A method such as forming a substrate 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 50 mm, particularly preferably 1 to 20 mm.

The image receiving layer, the Silica layer, the porous layer, the anti-diffusion layer, the 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 rice powder such as synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. may be included.

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

Examples include K., Veenkataraman &amp;
lii'TheChemistry of 5ynth
etic Dyes” Volume 5 Chapter 8, Japanese Patent Publication No. 1983-14
Examples include compounds described in No. 3752 and the like. More specifically, stilbenzene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, birapurine compounds, carbostyril compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned.

Optical brighteners can be used in combination with antifade agents.

The thermal transfer dye-providing material is a thermal transfer dye-providing material having a thermal transfer layer containing a heat-transferable dye on a support,
Recording is performed by applying heat and transferring the dye in a pattern to the image-receiving layer of the thermal transfer image-receiving material.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. For example, polyethylene terephthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide. , polypropylene, polysulfone, cellophane, etc.

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 mm.
- An undercoat layer may be provided if necessary.Also, a dye diffusion prevention layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer.This will improve the transfer density. Improve further.

As the hydrophilic polymer, the water-soluble polymers described above can be used.

A slipping layer may also be provided to prevent the thermal herad from sticking to the dye-donor material; this slipping layer may contain lubricating substances, such as surfactants, solid or Consists of liquid lubricants or mixtures thereof.

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.

A thermal transfer dye-providing material using a thermally transferable dye basically has a thermal transfer 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 a suitable solvent, and then applying this coating solution to the thermal transfer dye-providing material. It is obtained by coating and drying to form a thermal transfer layer on one side of a support for the material, for example, in a coating amount resulting in a dry film thickness of about 0.2 to 5-1, preferably 0.4 to 2-2. .

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 112G-FS.

Miketon Polyester Yellow 3GSL, Kayasset Yellow 937, Sumikalon Left EFBL, Dianic Red ACE, Miketon Polyester Red FB
, Kayaset Red 126, ξ Ketone Fast Brilliant Blue 85 Kayaset Blue 136, etc. are preferably used. Other known heat-transferable dyes can also be used.

Also, JP-A No. 59-78895, No. 60-28451, No. 60-28453, No. 60-53564, No. 6
No. 1-148096, No. 60-239290, No. 60-
No. 31565, No. 60-30393, No. 60-535
No. 65, No. 60-27594, No. 61-262191
No. 60-152563, No. 61-244595, No. 62-196186, No. 63-142062, 6
No. 3-39380, No. 62-290583, No. 63-
No. 111094, No. 63-111095, No. 63-1
No. 22594, No. 63-71392, No. 63-746
Yellow pigments described in JP-A-60-223862, JP-A-60-28452, etc.
No. 60-31563, No. 59-78896, No. 60
-31564, 60-303391, 61-2
No. 27092, No. 61-227091, No. 60-30
No. 392, No. 60-30694, No. 60-13129
No. 3, No. 61-227093, No. 6G-159091
No. 61-262190, No. 62-33688,
No. 63-5992, No. 61-12392, No. 62-
No. 55194, No. 62-297593, No. 63-74
No. 685, No. 63-74688, No. 62-97886
Magenta dyes described in JP-A-59-78894, JP-A-59-78894, JP-A-60-31559, JP-A-60-53563, etc. No. 61-19396, No. 61-
No. 22993, No. 61-31467, No. 61-359
No. 94, No. 61-49893, No. 61-57651, No. 62-87393, No. 63-15790, No. 6
No. 3-15853, No. 63-57293, No. 63-7
No. 4685, No. 63-74688, No. 59-2274
No. 90, No. 59-227493, No. 59-22794
No. 8, No. 6G-131292, No. 60-131294
No. 60-151097, No. 60-151098, No. 6G-172591, No. 60-217266,
No. 60-239289, No. 60-239291, No. 60-239292, No. 61-148269, No. 6
No. 1-244594, No. 61-255897, No. 61
-284489, 61-368493, 62-
No. 132684, No. 62-138291, No. 62-1
No. 91191, No. 62-255187, No. 62-28
No. 8656, No. 62-311190, No. 63-144
Cyan dyes described in No. 089 and the like are also suitably 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. For example, polyamide resin, polyester resin,
Epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride resins (e.g. vinyl chloride-vinyl acetate copolymer) combination),
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 polyvinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, coumaron-indene resins, terpene resins, and polyolefin resins (for example, polyethylene and polypropylene) 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.

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.

As the mold release agent, conventional mold release agents such as solid or waxy substances such as polyethylene wax and adane wax; surfactants such as diphosphate esters; paraffin-based, fluorine-based and silicone-based oils or solid fine particles, etc. Although any agent can be used, silicone oil is particularly preferred.

As the silicone oil, in addition to unmodified silicone oils, modified silicone oils such as carboxy-modified, amino-modified, polyether-modified, alkyl-modified, and epoxy-modified silicone oils can be used. Examples include various modified silicone oils described on pages 6 to 18B of the "Modified Silicone Oil" technical data published by Shin-Etsu Silicone ■.

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. 58-215398 can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For curing water-soluble polymers, U.S. Pat.
No. 39, column 41, 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-based hardeners (formaldehyde, etc.), aziridine-based hardeners, ebony, etc.), vinylsulfone-based hardeners (N,N'-ethylene-bis(vinylsulfonylacetamodo)ethane) etc.), N-methylol hardeners (dimethylol urea, etc.), and polymer hardeners (compounds described in JP-A-62-234157, etc.).

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 spirointane 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. 3,352,681, etc.)
, benzophenone compounds (JP-A-56-2784, etc.), and other JP-A-54-48535, JP-A-62-13
There are compounds described in No. 6641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
same! 4,245.018 Chapter 3-36W, Volume 4, 2
54,195 No. 3 to 8 columns, JP-A-62-17474
No. 1, No. 61-88256, pages (27) to (29), and Japanese Patent Application No. 62-234103, No. 62-31096, No. 62-230596, 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.

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 in No. 1-88256 (page 29), JP-A-63-274944, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 63-274952.

Various surfactants can be used in the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material for purposes such as coating aids, improving releasability, improving slipperiness, and preventing static electricity.

For example, nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants, etc. can be used. Specific examples of these are disclosed in Japanese Patent Application Laid-Open No. 62-17346.
No. 3, No. 62-183457, etc.

In the present invention, a thermal transfer dye-providing material is superimposed on a thermal transfer image-receiving material, and thermal energy corresponding to image information is applied from either side, preferably from the back side of the thermal transfer dye-providing material, by a heating means such as a thermal helad. By applying this, the dye in the dye-donating layer can be transferred to the thermal transfer image-receiving material according to 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 , TV, CRTii 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.

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

Example 1 (Preparation of thermal transfer dye-providing material (A)) A 4.5-thick polyethylene terephthalate film provided with a heat-resistant slipping layer made of a thermosetting acrylic resin on one side (
Lumirror Nitoshi Co., Ltd.) was used as a support, and on the side opposite to the side on which the heat-resistant slipping layer was provided, a paint for forming a thermal transfer dye-donating layer having the following composition & [l acid compound (A)] was applied using a wire bar. The coating was applied so that the thickness after drying was 2-2, and polyvinyl butyral (Butvar 76: manufactured by Monsanto) 0.45 g/rd and poly(vinyl stearate) 0.3 g/rd were applied to the back side of the support. A slipping layer of M was coated from a tetrahydrofuran solution to obtain a thermal transfer dye-donor element (A).

Disperse dye (2,3-diphenoxyanthraquinone) Polyvinyl butyral resin (Denka Butyral 5000-A: @vaporized type) Methyl ethyl ketone toluene polyisocyanate (Takenate DIION F manufactured by Narita Pharmaceutical) g g 4 〇- 0d 0.2- (dye) Preparation of receptive polymer emulsion A) Straight-rolled gelatin aqueous solution (10% by weight) 100g Sodium dodecylbenzenesulfonate 5O- (5% by weight)
aqueous solution) water 5
0d, lL & old polyester resin (Byron 280: manufactured by Toyobo ■) 30g toluene
60g methyl ethyl keto 7
60g thermal solvent (1)”
After preparing 9 g of liquid ■, add liquid ■ into it while stirring liquid ■, and use a homogenizer to
A dye-receiving polymer emulsion A was prepared by emulsifying and dispersing at 15,000 rpm for 9 minutes.

In the above, diphenyl phthalate (DPP) was used as the thermal solvent as shown in Table 1.

(Preparation of dye-receptive polymer emulsion B) AuL water-soluble binder (1) 0 Sodium dodecylbenzenesulfonate (5% by weight aqueous solution) 00 g 50-Water 50-m polyester resin (Vylon 280: Toyobo) 30g toluene 60g methyl ethyl ketone 60g crosslinking agent (manufactured by
4.5g thermal solvent (1)”
4.5g epoxy modified silicone oil (KF-100T: manufactured by Shin-Etsu Silicone) 4.
5g In the above, as the water-soluble binder (1) 0, a 10% by weight aqueous solution of polyvinyl alcohol (PVA, degree of saponification 98%, degree of polymerization 2000) was used, and a crosslinking agent (l)
As shown in Table 1, polyisocyanate (KP-9O7 manufactured by Dainippon Ink ■) was used as the adhesive.

After sufficiently dissolving the liquid ■ and the liquid ■, add the liquid ■ into the liquid while stirring the liquid, and use a homogenizer to heat the mixture for 15,000 r.
A dye-receiving polymer emulsion B was prepared by emulsifying and dispersing the mixture at p- for 9 minutes.

(Preparation of coating solution for thermal transfer image-receiving material) 1st layer: Gelatin (10% by weight aqueous solution) 100g water 40
d Hardener (4% by weight aqueous solution) (1,2-bis(vinylsulfonylacetamido)ethane) 60m No. 21L Dye-receptive polymer emulsion A 100g water
50-Third layer (outermost layer): Dye-receptive polymer emulsion B 100g water
50. d
Surfactant (1)” 5% solution 6-(
Water/methanol-1/1 volume ratio) Surfactant (1)”: Jt CsF+tSOsN-(CHxCHzO)-r-(CH
tl "5O3Na (Preparation of thermal transfer image-receiving material) 180 g/r+ (thickness) paper is double-sided veneated with polyethylene in which titanium oxide is dispersed (pf! Thickness: 30-
), the first to third layers were applied to wet film thicknesses of 20.60 and 15 al/rrl, respectively,
After drying, thermal transfer image receiving materials 101 and 1 as shown in Table 1 are prepared.
02 was produced.

Furthermore, the following coating liquid compositions A and B were coated on the same support as the thermal transfer image-receiving materials 101 and 102 so that the dry thickness was 8IIm and 2-, respectively, and the mixture was heated at 80°C for 5 minutes and at 100°C. After drying for 30 minutes, thermal transfer image-receiving materials 103 and 104 as shown in Table 1 were prepared.

The thermal transfer image-receiving materials 102 and 104 are the thermal transfer image-receiving materials 101 and 103, respectively, with the crosslinking agent removed.

For the 1st layer Coating liquid & lllll containing polyester resin (Vylon 280: manufactured by Toyobo ■) 20g toluene 100jd Methyl ethyl ketone 10〇-For the 2nd layer Coating liquid m Acid B Polyester resin (Vylon 280: manufactured by Toyobo ■) 20g Toluene 10〇 -Methyl ethyl ketone 100-Epoxy modified silicone oil (KF-100↑: Shin-Etsu Silicone) 3
g Crosslinking agent (1)” 3
g 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, and using a thermal head from the support side of the thermal transfer dye-providing material, Output 0.25W/
Printing was carried out under the conditions of 31 ICs of 0.15 to 15 dots during pulse 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.

(Performance Evaluation) Zensha I: The extent to which the dye-donating layer of the dye-donating material peeled off and adhered (thermal fusion) to the surface of the obtained recorded thermal transfer image-receiving material was measured. The evaluation criteria for heat fusion are as follows.

O: No heat fusion.

Δ: Slight thermal adhesion is observed.

×: Heat fusion is observed on the entire surface.

XX: The thermal transfer image-receiving material and the dye-donating material were fused and the printer stopped.

还11-L对对UA: The reflection density of the saturated portion (Dmax) of the recorded thermal transfer image-receiving material was measured using a Status A filter.

The results are shown in Table 1.

No. 1 table Umbrella Compatible with Japanese Patent Application Publication No. 58-215398.

As is clear from the evaluation results in Table 1, JP-A-58-2
When a cross-linking agent is added to an organic solvent-based image-receiving layer according to No. 15398 (Comparative Image-Receiving Material 103), thermal adhesion is improved compared to that without a cross-linking agent (Comparative Image-Receiving Material 104), but it is still not sufficient. do not have.

Furthermore, by changing the image-receiving layer from an organic solvent system to an aqueous dispersion system (Comparative Image-Receiving Material 102), thermal fusion was further improved, but slight thermal fusion was observed.

On the other hand, as seen in the image-receiving material 101 of the present invention, when a crosslinking agent was added to the water-dispersed image-receiving layer, an extremely excellent image-receiving material with no thermal adhesion was obtained.

Example 2 Image-receiving materials 201 to 2 were prepared in the same manner as image-receiving material 101 of Example 1, except that the preparation of dye-receiving polymer emulsions A and B was changed as follows.
07 was produced.

(Preparation of dye-receptive polymer emulsion A) Sodium gelatin (10% by weight aqueous solution) 100g Sodium dodecylbenzenesulfonate 50d (5% by weight)
aqueous solution) water 5
0d Koto Red Cap Polyester Resin (1)” 30 g
Toluene 60g Methyl ethyl ketone 60g Heat solvent (1)
After preparing 12 g ■ liquid, ■
While stirring the liquid, add the liquid (2) into it, and use a homogenizer to emulsify and disperse at 15,000 rpm for 9 minutes.
Dye-receiving polymer emulsion A was prepared.

In the above, diphenyl phthalate (DPP) was used as the thermal solvent (1)'' as shown in Table 2.

Further, as the polyester resin, a polyester having the following composition was used.

Glycol component: nocutcu□0H (15 mol%) (35 mol%) (Preparation of dye-receptive polymer emulsion B) Upper and lower water-soluble binder (2)" 100g
Sodium dodecylbenzenesulfonate (5% by weight aqueous solution) 5011 Water 5
〇-E Five Class Precepts Polyester Resin (1)” 30 g
Toluene 60g Methyl ethyl ketone 60g Crosslinking agent (1
4.5g thermal solvent (1)”
4.5g epoxy modified silicone oil (KF-100T: manufactured by Shin-Etsu Silicone) 4.
5g In the above, the water-soluble binder (2)'' is polyvinyl alcohol (PVAi saponified [98%,
degree of polymerization 2000), hydroxyethylcellulose ()I
EC), gum arabic or carboxymethyl cellulose (CMC), and a crosslinking agent (
1) Polyisocyanate (KP-90: manufactured by Dainippon Ink ■) was used as shown in Table 2.

After sufficiently dissolving the liquid ■ and the liquid ■, add the liquid ■ into the liquid while stirring the liquid, and use a homogenizer to heat the mixture for 15,000 r.
A dye-receiving polymer emulsion B was prepared by emulsifying and dispersing the mixture at p- for 9 minutes.

The thermal transfer dye-providing material obtained in Example 1 and the thermal transfer image-receiving materials 201 to 207 obtained as described above are superimposed so that the dye-providing layer and the image-receiving layer are in contact with each other, and A thermal head is used, the output of the thermal head is 0.25W/dot, and the pulse width is 0.
15~15w5ec, dot density 6 dots/lIs
Printing was performed under the following conditions to dye the image-receiving layer of the thermal transfer image-receiving material with magenta dye in an imagewise manner.

(Performance Evaluation) School Apparatus: The extent to which the dye-donating layer of the dye-donating material was peeled off and adhered (thermal fusion) to the surface of the obtained recorded thermal transfer image-receiving material was measured. The evaluation criteria for heat fusion are as follows.

○: No heat fusion.

Δ: Slight thermal adhesion is observed.

×: Heat fusion is observed on the entire surface.

XX: The thermal transfer image-receiving material and the dye-donating material were fused and the printer stopped.

The reflection density of the saturated portion (Dmax) of the obtained recorded thermal transfer image-receiving material was measured using a Status A filter.

Furthermore, the obtained recorded thermal transfer image-receiving material was stored in an incubator at 60° C. for one month, and the blurring (bleeding) of the package was observed. The evaluation criteria for bleeding are as follows.

O: Almost no bleeding was observed, and the image quality was the same as that immediately after thermal transfer.

Δ: Slight bleeding was observed.

×: The degree of blurring was large and the image quality deteriorated.

Fifty sheets of the image-receiving material described above were stacked and automatically fed into a thermal transfer printer, and their paper feeding and conveying properties were examined.

Table 2 shows the number of times multiple sheet feeding occurred for each sample.

Aimoto Mori: After transfer, one drop of water was dropped on the surface of the image-receiving material, and after one minute, it was wiped off with a cloth, and bleeding and density reduction in that area were evaluated using the following criteria.

○: No bleeding or decrease in density.

Δ: There is some bleeding and/or a slight decrease in density.

×: People with stains and/or decreased concentration.

Thicket standing: In evaluating water resistance, one drop of ethanol was dropped instead of water, and the same evaluation was performed 10 seconds later.

Long [Eye 1 Hiiragi Kaichi] Place the transferred image-receiving material (black solid) and the untransferred image-receiving material (white solid) so that the image-receiving layer sides face each other, apply a load of 30 g/c + j, and store at 50°C for 3 days. After that, it was peeled off and the degree of retransfer from black betta to white betta was examined. The evaluation criteria are as follows.

O: Very little to no color transfer.

Δ: Slight color transfer (approximately 10% of black solid color) ×: Large color transfer (1/2 to 1/3 density of black solid color) The results are shown in Table 2.

(Left below) From the results in Table 2, it can be seen that the thermal transfer image-receiving material of the present invention, which has at least the outermost image-receiving layer containing a crosslinking agent such as polyisocyanate in a dye-receiving polymer and dispersed in a water-soluble binder, Paper feeding properties have been improved, there is no heat fusion, it is possible to obtain transferred images with high transfer density, and the image-receiving material after transfer has improved blurring over time, water resistance, oil resistance, adhesive color transfer, etc. It is clear that

Procedure Nail 11 XE Book October 1999 230 Commissioner of the Patent Office 1, I! Display of the matter 1999 Patent Office No. 221667 2, Name of the invention Thermal transfer image-receiving material 3゜Relationship with the case: Name of patent applicant (520) Fuji Photo Film Co., Ltd. 4, Agent 〒100 Address Tokyo Toranomon Mitsui Building 14th Floor 6, 3-8-1 Kasumigaseki, Chiyoda-ku, Tokyo, aI' will increase due to correction! Number of claims to be corrected (1) "201-207" on page 44, line 8 and page 47, line 8 of the specification are corrected to "201-206."

(2) Table 2 on page 51 of the same book has been corrected by 1111 as per the attached sheet.

Claims (1)

[Claims] A thermal transfer image-receiving material in which at least one image-receiving layer is provided on a support to form an image by receiving a dye that migrates from a thermal transfer dye-providing material when heated, and at least one of the outermost layers is formed on a support. 1. A thermal transfer image-receiving material, characterized in that the image-receiving layer has a crosslinked dye-receiving material dispersed in a water-soluble binder.