JPH03295686A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To ensure that a thermal transfer image receiving material, obtained has high transfer density, superior transferred image preservation and improved manufacturing aptness by providing an image receiving layer consisting of a composition of a color-receptive material dispersed in a water-soluble binder and also of at least, one layer of image-receiving surface constituent layers of an image receiving material which contains natural polymer polysaccharide originating from red algae. CONSTITUTION:A color image receiving layer is provided in a thermal transfer image receiving material and a color receptive material which acts as a promoter for fixing of a thermally migrating color dispersed and carried in a water-soluble binder. A natural polymer polysacoharide originating from red algae is allowed to be added to at least, one of the image receiving constituent layers, preferably at least, one of the image receiving layers and more preferably, the entire image receiving constituent layer. Of natural polysaccharide originating from red algae, agaragar, copper cargeenan, lamda carageenan, oita cargeenan and farceleran are used.

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. , relates to a thermal transfer image-receiving material with improved image storage stability.

(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.

(Problems to be Solved by the Invention) However, the thermal transfer image receiving material used in this thermal transfer type thermal transfer recording method has the following problems.

(2) Generally, the polymer used in the image-receiving layer of heat-transferable dyes is soluble in organic solvents, so 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.

Furthermore, there is a desire to reduce the coating and drying load, and in particular, if the coating and drying speed can be increased to easily and quickly produce a thermal transfer image-receiving material, it would be advantageous in terms of shortening the manufacturing process and lowering the manufacturing cost.

(2) On the other hand, in the conventional thermal transfer type thermal transfer recording method, various methods have been used to obtain high transfer density and high sensitivity, but each method has the following problems.

(1) As a binder for the image-receiving layer, a polymer that softens or becomes rubbery during thermal transfer is used, or a plasticizer is used.

However, when such means are used, unevenness occurs on the transfer surface at the highest density portion, and gloss is also lost. Furthermore, there is a problem in that when the thermal transfer image-receiving material after transfer is stored for a long period of time, image blurring tends to occur.

(2) Lowering the glass transition point (Tg) of the dye-receiving polymer.

In this method, in order to obtain sufficient density, lowering the glass transition point below room temperature may cause the transferred image to blur, or if the transferred image-receiving materials are stacked, the transferred dye may be re-transferred to the adhesive surface. There is a problem called (so-called adhesive color transfer).

(3) A plasticizer such as oil that is soluble in dyes is contained in the image-receiving layer.

Similar to (2) above, this method has the problem of blurring of the transferred image over time and re-transfer. Furthermore, if raw image-receiving materials produced by this method are stored in piles, blocking failures are likely to occur.

(4) A porous layer containing porous particles is provided as a low thermal conductivity layer in order to prevent thermal diffusion during thermal transfer and increase the temperature of the transfer surface.

This method has the problem of reducing the glossiness of the surface of the image-receiving material.

(5) Synthetic paper with voids is used as the support.

This method is prone to curling after thermal transfer and has high material costs.

(6) Increasing the dye concentration of the dye-donating layer of the dye-donating material.

In this method, if the dye-providing material is stored for a long period of time, the dye may migrate to the back side of the support or precipitate on the surface, resulting in a decrease in density and the occurrence of unevenness.

(7) Adjust the voltage applied to the thermal head.

This method has problems in that it shortens the life of the thermal head and tends to cause thermal fusion of the image-receiving material and the dye-donating material.

As mentioned above, there are various problems when trying to obtain high transfer density and high sensitivity, but in particular, with conventional organic solvent-based thermal transfer image-receiving materials, when the transfer density is high, the transferred image tends to blur over time. Therefore, it has been extremely difficult to satisfy both high transfer density and image storage stability at the same time.

Therefore, there has been a strong desire to develop a thermal transfer image-receiving material that has high transfer density, excellent storage stability of transferred images, and improved manufacturing suitability.

(Means for Solving the Problems) The above-mentioned problems are solved by providing at least one image-receiving layer on the support for receiving the dye that migrates from the thermal transfer dye-providing material when heated to form an image. In the provided thermal transfer image-receiving material, the image-receiving layer is made of a composition in which a dye-receiving substance is dispersed in a water-soluble binder, and at least one of the layers constituting the image-receiving surface of the image-receiving material is a natural pigment derived from red algae. The problem was solved by a thermal transfer image-receiving material characterized by containing a high-molecular polysaccharide.

In the present invention, the dye-receiving substance is not applied using an organic solvent as in the past, but is dispersed in a water-soluble binder. It is non-hazardous, significantly reduces manufacturing costs, and has very low negative effects on worker health.
It is completely unexpected that a layer containing at least a dye-receiving substance dispersed and supported in a water-soluble binder as in the present invention can sufficiently accept heat-transferable dyes and produce images with particularly high transfer density. That's true. Furthermore, images obtained using the thermal transfer image-receiving material of the present invention exhibit extremely little blurring even when stored for a long period of time, and have excellent image storage stability. Furthermore, it has been found that re-transfer (adhesive color transfer failure) is extremely unlikely to occur when transferred image-receiving materials are stacked and stored.

In addition, when the dye-receiving layer has a multilayer structure of two or more layers, the coating and drying steps had to be repeated many times with conventional organic solvent coating solutions, but the dye-receiving material coating solution of the present invention has a water-based coating solution. Since it is a binder solution, simultaneous multilayer coating is possible, and by containing natural polymer molecules derived from red algae, the centrifugal properties of the coating solution are improved, shortening the manufacturing process and reducing manufacturing costs. and furthermore,
It is now possible to apply with a curtain coat.

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

In the present invention, at least one of the layers constituting the image-receiving surface, preferably at least one layer of the image-receiving layer, and more preferably all the layers constituting the image-receiving surface are derived from red algae. It is characterized by containing the following.

The natural polymeric polysaccharides derived from red algae used in the present invention include "Food Industry" Vol. 31 (1988) No. 21
Natural polymeric polysaccharides obtained by extraction and purification from red algae listed in Table 1 on page 1 can be mentioned. Natural high-molecular polysaccharides obtained by extraction and purification from red algae are often a mixture of various types. In the present invention, this mixture can be used as it is, or it can be used alone with even higher purity.

Among the natural high-molecular polysaccharides derived from red algae used in the present invention, those particularly suitable for the present invention include agar, cumber carrageenan, lambda carrageenan, iota carrageenan, farcellan, and the like. These substances are also available commercially. For example, kappa-carrageenan is available as Tight-gelling agent NK-4 manufactured by Taito Co., Ltd., and a mixture of lambda carrageenan and a trace amount of kappa-carrageenan is available as Tight-gelling agent MV manufactured by Hakuto Co., Ltd.

Natural polymer multi-I derived from red algae of the present invention! The amount used can be set arbitrarily, but it is 0.005 per 1nf of support.
~10g, particularly about 0.02~4g is appropriate. In addition, 1 water-soluble binder (including natural polymer polyimide I!)
When set to 00, natural polymer multi-I! The class is 0.5-50,
In particular, it is preferable to use a ratio of 1 to 30.

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 acid ester resin or polymethacrylic acid ester resin such as butyl acrylate; Polycarbonate resin; Polyvinyl acetate resin;
Styrene acrylate resin; vinyltoluene acrylate resin, etc. Specifically, Japanese Patent Publication No. 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 2801 Byron 300, Byron 103, Byron GK-140, Byron GK-130, Kao's ATR-2009, ^T
R-2010, Pluscoat Z-466 manufactured by Gooh Kagaku,
Z-448, Z-455, Z-461, Z-767, Z
-771, Takamatsu oil type Bess Resin A-1243, A-
2141, A-2151, Dainippon Ink Finetex ES-611, ES-650, ES-670, E
S-675, ES-850, 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.

In the thermal transfer image-receiving material, particularly in the image-receiving layer, it is preferable to 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), as described in No. 9-178455, No. 59-178457, etc. Examples include compounds such as ethers, alcohols, paraffins, and silicone oils.

As a thermal solvent, 1) it must be compatible with the dye, 2) it is solid at room temperature, but melts when heated by the thermal head during transfer (it can also be mixed and melted with other components); Compounds that have various properties such as not being decomposed by heating with a mulhead are used.

Preference is given to compounds which exhibit a melting point of preferably 35 to 250" C1, in particular 35 to 200 DEG 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, 62-9348, 62-3024
No. 7 and No. 62-136646.

Although the high-boiling organic solvent and/or thermal solvent can be used alone in the form of micro-dissolved or dispersed particles in the image-receiving layer, it is more preferable to use them 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 has a structure in which a dye-receiving substance is dispersed and supported in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of crosslinking with a hardening agent is preferred.

Examples of water-soluble polymers used in the present invention include vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridinium, cationic modified polyvinyl alcohol, and derivatives thereof (Japanese Patent Laid-Open No. 60-1458
No. 79, No. 60-220750, No. 61-14317
No. 7, No. 61-235182, No. 61-245183
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 (see JP-A-60-168651 and JP-A-62-9988); starch, oxidized starch, acetic acid starch, amine starch, carboxyl starch,
Natural polymers or their derivatives such as dialdehyde starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose (JP-A-59-1
No. 74382, No. 60-262685, No. 61-14
No. 3177, No. 61-181679, No. 61-193
No. 879, No. 61-287782); polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, maleic acid-vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer, maleic acid-alkyl vinyl ether copolymer, Synthetic polymers such as polyethyleneimine (see JP-A Nos. 61-32787, 61-237680, and 61-277483)
; and water-soluble polymers described in JP-A No. 56-58869.

Various copolymers which are made water-solubilized by a heptamer component containing ester, 8036 group, caae group, SOt6 group, etc. can also be used.

It is preferable to use gelatin as the water-soluble binder,
Specifically, gelatin and its derivatives such as lime-treated gelatin, decalcified lime-treated gelatin, acid-treated gelatin, phthalated gelatin, acetylated gelatin, and succinated gelatin, Bull, Soc, Phot
, Japan, No. 16. p30 (1966)
Examples include enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in .

The use of gelatin as a water-soluble binder is usually preferable because it allows set drying, but by incorporating the natural polymer molecule am derived from red algae according to the present invention, set drying is possible even when using a water-soluble binder other than gelatin. This has made it possible to significantly reduce the drying load. Additionally, drying can now be done at room temperature.

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

The water-soluble binder (including cases containing natural polymeric polysaccharides derived from red algae) and the dye-receptive substance have a receptor substance/water-soluble binder ratio (weight ratio) of 1 to 20,
It is preferably used in a range of 2 to 10, particularly preferably 2.5 to 7.

As a method for dispersing a dye-receiving substance in a water-soluble binder (including cases containing the natural polymeric polysaccharide derived from red algae), a known dispersion method for dispersing a hydrophobic substance in a water-soluble polymer can be used. Either method 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, and mixing a latex of a dye-receiving polymer with an aqueous solution of a water-soluble binder. There are methods of mixing.

Particularly preferred is a method in which a solution obtained by dissolving a dye-receiving substance and a thermal solvent in an organic solvent immiscible with water is emulsified and dispersed in an aqueous solution of a water-soluble binder.

In the present invention, the coating solution temperature can be set at 30 to 50°C, preferably around 40°C, and the drying temperature can be set to room temperature.

The image receiving layer may be one layer, or two or more layers may be provided. When two or more layers are provided, it is preferable that at least one of them, especially all of the image-receiving layers, contains the natural polymer N derived from the red algae.

Further, the polysaccharide can also be contained in a layer other than the image-receiving layer, for example, an intermediate layer.

When the image-receiving layer is composed of two or more layers, a synthetic resin with a low glass transition point is used for the image-receiving layer closer to the support, or
The structure uses a high boiling point organic solvent or a hot solvent to improve the dyeing property of the dye, and the outermost layer is made of a synthetic resin with a higher glass transition point, a fluorine-containing compound, or a high boiling point organic solvent or a hot solvent. Minimize the amount of thermal solvent used or do not use it at all 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 configuration that prevents this. It is also desirable to use a mold release agent, which will be described later, in the outermost layer.

The overall thickness of the image-receiving layer is preferably in the range of 1 to 30-1, especially 2 to low.Compared to conventional solvent-based systems, it is possible to use a hot solvent with high solubility for the dye without deteriorating other properties. Since it can be used as a receptive substance, it has become possible to make the layer thinner.

In the case of a structure with two or more layers, the outermost layer is 0.1 to 3-1, especially 0.
．． It is preferably in the range of 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 coated 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 "Fundamentals of Photographic Engineering (Silver Salt Photography Edition)" edited by the Photographic Society of Japan (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 -
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 the polyolefins used include high-density polyethylene, low-density polyethylene,
Examples include polypropylene, but any material 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 it is usually preferred to have a thickness of 5 to 100 mm on one side. However, in order to obtain higher transfer density, it is preferable that the polyolefin coat on the image-receiving layer side be thinner.

Pigments and fillers such as titanium oxide and ultramarine blue may be added to the polyolefin coat to increase whiteness. Further, the polyolefin coated paper may have a thin gelatin layer of about 0.05 to 0.4 g/nf on its surface (the side on which the image receiving layer is provided and/or its back surface).

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.

The intermediate layer can be a cushion layer, a porous layer, or a
Either one of the dye diffusion prevention layers has 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.
Although solvent-soluble binders may be used, water-soluble binders are preferred, and examples thereof 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.

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 the above synthetic resin emulsion or synthetic rubber latex mixed 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 m, particularly preferably 1 to 20 m.

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, VeenkataralIlan
W rThe Chemistry 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, pyrazoline 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. Examples include polyethylene terephthalate, polyamide, polycarbonate, glassine, condenser paper, cellulose ester, fluorine polymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, cellophane, and the like.

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 mm.
It is m. An undercoat layer may be provided if necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer. This further improves 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-donating material. This slipping layer is composed of lubricating substances, such as surfactants, solid or liquid lubricants or mixtures thereof, with or without polymeric binders.

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. Good too. For example, when printing each color repeatedly according to color separation signals to form an image such as a color photograph, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing the dye to be provided 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. .

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 82G-FS.

Miketon Polyester Yellow 3GSL, Kayasset Yellow 937, Sumikalon Red EFBL, Dianic Red ACE, Miketon Polyester Red FB.

Kayaset Red 126, Miketon Fast Brilliant Blue B, 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. 63142062, 63
-39380, 62-290583, 6311
No. 1094, No. 63-111095, No. 63-122
No. 594, No. 63-71392, No. 63-74685
No. 63-74688, Japanese Patent Application No. 63-51285 (describing the dye represented by the following general formula).

2 In the formula, R3 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, R2 represents a hydrogen atom, an alkyl group, or an aryl group, and R3 represents an aryl group or a heteryl group. represents, R4 and R5 may be the same or different,
Each represents a hydrogen atom or an alkyl group. The above substituents may be further substituted. ), etc., JP-A-60-223862, JP-A-60-28452,
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. 61227093, No. 60-159091, No. 61-262190, No. 62-33688, No. 63-5992, No. 61-12392, No. 6255
No. 194, No. 62-297593, No. 63-7468
No. 5, No. 6374688, No. 62-97886, No. 62-132685, No. 61-163895, No. 6
No. 2-211190, No. 62-99195, Patent Application No. 1983
No. 2-220793 (describing the dye represented by the following general formula).

I X = Y In the formula, R2 and R2 are each a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, alkoxy group,
group, aryloxy group, aralkyl group, cyano group, acylamino group, sulfonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group,
represents an acyl group or an amino group, R8 and R4 each represent
Represents an alkyl group, cycloalkyl group, aralkyl group or aryl group. R3 and R4 may be bonded to each other to form a ring, or R2 and R8, R, and R4 may be bonded to each other to form a ring. n represents an integer of 0 to 3. X, Y, alkyl group, cycloalkyl group, aralkyl group,
(represents an aryl group, an alkoxy group, an aryloxy group or an amino group). Also, X and Y are in a certain issue, 61-19
No. 396, No. 61-22993, No. 61-31467
No. 61-35994, No. 61-49893, No. 61-57651, No. 62-87393, No. 63-
No. 15790, No. 63-15853, No. 63-572
No. 93, No. 63-74685, No. 63-74688, No. 59-227490, No. 59-227493,
No. 59-227948, No. 60-131292, No. 60-131294, No. 60-151097, No. 6
No. 0-151098, No. 60-172591, No. 60
-217266, 60-239289, 60-
No. 239291, No. 60-239292, No. 61-1
No. 48269, No. 61-244594, No. 61-25
No. 5897, No. 61-284489, No. 61-368
No. 493, No. 62-132684, No. 62-1382
No. 91, No. 62-191191, No. 62-25518
No. 7, No. 62-288656, No. 62-311190
No. 63-144089, patent application No. 62-17662
No. 5 (Describes the dye represented by the general formula below.

It may also form an unsaturated carbocyclic ring. The above substituents may be further substituted. ), etc. In the formulas, Ql contains at least one nitrogen atom, and together with the bonded carbon atom, a 5-membered ring or more Represents an atomic group necessary to form a nitrogen-containing heterocycle, R1 represents an acyl group or a sulfonyl group, R2 represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, R1 represents a hydrogen atom, a halogen atom, It represents an alkoxy group or an aliphatic group having 1 to 6 carbon atoms, P represents a halogen atom, an alkoxy group, or an aliphatic group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. R
3 may be combined with L, R2, or R4 to form a ring. R6 and R5 represent a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, or an aromatic group. R3 and R6 may be combined with each other to form a ring. Also R3 and/or R1
may be combined with R4 to form a ring. ) 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. things are selected. 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 mold release agents, conventionally known mold release agents such as solid or waxy substances such as polyethylene wax and amide wax; surfactants such as phosphate esters; paraffin, fluorine and silicone 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. 5B-215398 can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For curing water-soluble polymers, U.S. Pat.
39 No. 4111, JP-A-59-116655, JP-A No. 6
The hardeners described in Nos. 2-245261 and 61-18942 are suitable for use.

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

Antifading agents may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Antifading agents include, for example, 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. 3,352,681, 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.

Examples of metal complexes include U.S. Pat. No. 4.24LL55, U.S. Pat.
254.195 No. 3-811. Japanese Patent Publication No. 62-1747
No. 41, No. 61-88256, pages (27)-(29),
Patent application No. 62-234103, No. 62-31096,
There are compounds described in 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. It's okay.

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 No. 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 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 for creating prints from , TV screens, CRT 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 polyethylene terephthalate film with a thickness of 4.5* 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 a coating composition (A) for forming a thermal transfer dye-donating 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. Coat and form so that the thickness after drying is 2-, and slipping polyvinyl butyral (Butvar 76: manufactured by Monosanto) 0.45 g/rd, poly(vinyl stearate) o, 3 g/rrT on the back side of the support. A layer was coated from a tetrahydrofuran solution to obtain a thermal transfer dye-donor element (A).

Disperse dye (2,3-gefnoxiant 4g laquinone) Polyvinyl butyral resin (Denka 4g butyral 5000-^: vaporized type) Methyl ethyl ketone
40d toluene
40+d polyisocyanate (takenate 0.2dD
IION: Sokoen Yakuhin Co., Ltd.) (Preparation of dye-receptive polymer emulsion A), l! IL-gelatin (10% by weight aqueous solution) 100g K-carrageenan (1% by weight aqueous solution) 50g Sodium dodecylbenzenesulfonate 50aC (5% by weight aqueous solution) 30g Toerne 60g Methyl ethyl ketone 60g Heat Solvent (diphenyl phthalate) 12g Prepare solution (2). Add solution (2) into solution I while stirring, and emulsify and disperse at 15,000 rpm for 9 minutes using a homogenizer to obtain dye-receiving polymer emulsion A. Prepared.

In the above, Elythyl 3500 (manufactured by Unitika) was used as the dye-receiving polymer (1).

(Preparation of dye-receptive polymer emulsion B) Tsuchikyu Gelatin (10% by weight aqueous solution) 100g K-carrageenan (1% by weight aqueous solution) 50g Sodium dodecylbenzenesulfonate 50- (5% by weight aqueous solution) ■Sputum composition pigment Receptive polymer (2)” 30 g Toluene 60 g Methyl ethyl ketone 60 g Thermal solvent (diphenyl phthalate) 3 g Thermal solvent (dicyclohexyl 3 g phthalate) Epoxy-modified silicone oil 3 g (KF-1
00T: Manufactured by Shin-Etsu Silicone) ■Liquid, ■After thoroughly dissolving liquid,
Solution (2) was added to solution (2) while stirring, and emulsified and dispersed using a homogenizer at 15,000 rpm for 9 minutes to prepare a dye-receiving polymer emulsion B.

In the above, as the dye-receiving polymer (2)'', the following were used, mixed in equal amounts.

Kemit R-188 (manufactured by Toshi) Kemit ni-1294 (manufactured by Toshi) Polyester RP-200 (Japanese synthetic type) Elythyl X
A-8153 (manufactured by Unitika) S-LEC BLS (manufactured by Block Chemical) (Preparation of coating solution for thermal transfer image-receiving material) 1st layer: Gelatin (10% by weight aqueous solution) 100g water
40M1 hardener (4% by weight aqueous solution) 60d [1,2-
Bis(vinylsulfonylacetamido)ethane] Second layer: Dye-receptive polymer emulsion A 100g water
50d third layer (
Outermost layer): Dye-receptive polymer emulsion B 100g water
50d Surfactant (1) 15% solution 6m (water/methanol - 1/1 volume ratio) Surfactant (1) 1 C,H.

CsH++ SOJ 云CHzC)lzoya-CHzh-
SOJa (Preparation of thermal transfer image-receiving material) The above-mentioned first to third layers were each laminated to a wet film thickness of 20.60 on a support made of paper with a thickness of 180 g/nr laminated on both sides with polyethylene in which titanium oxide was dispersed. and 15
d/rW and dried to form a thermal transfer image receiving material 101.
was created.

Thermal transfer image-receiving material 101 was prepared in exactly the same manner except that the same amount of water was used instead of K-carrageenan.
02 was produced.

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 a thermal head is used from the support side of the thermal transfer dye-providing material, and the output of the thermal head is 0.25w/dot, pulse width 0.15-15-sec, dot density 6
Printing was carried out under the conditions of dot/-1 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 (Dmax) of the recorded thermal transfer image-receiving material was measured using a Status A filter.

D+max of image-receiving material 101 was 2.28, while On+ax of image-receiving material 102 was 2.03.

Further, the obtained recorded thermal transfer image-receiving material was stored in an 80° C. incubator for two weeks, and bleeding of the color image was observed.

Although some bleeding of the color image was observed in the image-receiving material 1020, there was no bleeding of the color image in the image-receiving material 101 of the present invention.

Furthermore, stack the transferred image receiving sheets facing each other 100c.
It was stored at 60°C for 3 days under a load of 1 kg per ti, and then peeled off to examine the degree of retransfer (adhesion color transfer failure).

It was confirmed that image-receiving material 101 was significantly improved in terms of adhesive color transfer failure compared to image-receiving material 102.

(Effects of the Invention) According to the present invention, it is possible to obtain a transfer image-receiving material that has a high transfer density, excellent storage stability of transferred images, and improved manufacturing suitability.

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, the image-receiving layer comprising a dye-receiving material. A thermal transfer image-receiving material comprising a composition in which the image-receiving material is dispersed in a water-soluble binder, and at least one of the layers constituting the image-receiving surface of the image-receiving material contains a natural polymeric polysaccharide derived from red algae. .