JPH04173189A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To prevent the precipitation of a dye even when a transfer image is preserved for a long period of time by adding an aqueous polyester resin and an amphoteric surfactant to an image receiving layer. CONSTITUTION:An image receiving layer receiving the dye transferred from a thermal transfer dye donating material at the time of heating to form an image is provided on a support and this image receiving layer contains an aqueous polyester resin and an amphoteric surfactant. The aqueous polyester resin is a polyester resin dissolved or dispersed in water and may be mixed with and dispersed in a water-soluble binder to be supported. The amphoteric surfactant pref. contains at least one 1-4C saturated or unsaturated hydrocarbon group in one molecule thereof and a fluorine type amphoteric surfactant containing a fluorine atom in its molecule is especially pref.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a thermal transfer image-receiving material for thermal transfer recording, and particularly to a thermal transfer image-receiving material that has excellent manufacturing suitability and improved storage stability of images. be.

(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 Present Invention) Organic solvent-soluble polymers are usually used in thermal transfer image-receiving materials used in this thermal transfer type thermal transfer recording method. However, the use of organic solvents increases manufacturing costs and is also undesirable from the viewpoint of health care of workers who handle organic solvents. For this reason, attempts have been made to use water-based polymers as image-receiving materials, but the fixation of the transfer dye in the image-receiving layer is insufficient, and the transferred image may not be left for a long period of time or exposed to high-humidity, high-temperature conditions. When this happens, the dye bleeds out onto the surface of the image-receiving material, staining clothes and hands, or causing significant discoloration of the image.

In order to improve the fixing properties of the transferred dye in the image-receiving material, it is possible to use a modified polyester resin or a copolymer containing vinyl chloride as the image-receiving material (Japanese Patent Application Laid-open No. 2-34392, Japanese Patent Application Laid-open No. 1-160681). Method of heat treatment (JP-A-63-69690, JP-A-63-31738)
6, Japanese Unexamined Patent Publication No. 64-5887), etc. have been proposed. However, in the former case, the resin used is water-insoluble, and it is necessary to use an organic solvent such as toluene or methyl ethyl ketone that is undesirable for the human body. The latter method requires the preparation of processing equipment for heating and also requires additional costs such as electricity.

The purpose of the present invention is to reduce the use of organic solvents in the production of thermal transfer image-receiving materials, thereby solving production costs and safety problems, and preventing dye precipitation even after long-term storage of transferred images. The object of the present invention is to provide a thermal transfer image-receiving material that is free from heat transfer.

(Means for Solving the Problems) An object of the present invention is to provide at least an image-receiving layer on a support for receiving the dye transferred from the thermal transfer dye-providing material when heated to form an image. In a thermal transfer image-receiving material provided with one layer, the image-receiving layer was achieved by a thermal transfer image-receiving material containing an aqueous polyester resin and an amphoteric surfactant.

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 contains water-based polyester resin as a dye-receiving polymer that has the function of receiving heat-transferable dyes transferred from the thermal transfer dye-providing material during printing and dyeing the heat-transferable dyes. use. The aqueous polyester resin that can be used in the present invention refers to a polyester resin dissolved or dispersed in water.

Specifically, U.S. Patent No. 4,252,885;
, No. 241, 169, No. 4. 394. No. 442,
Water-based polyesters described in European Patent No. 29,620, European Patent No. 78°559, JP-A-54-43017, Research Disclosure 18928 (January 1982 issue) and the like can be mentioned.

More specifically, one or more acids or acid anhydrides or lower alkyl esters of acids shown below in [I] are used as glycols under the reaction conditions for producing glycols, polyesters, or copolyesters shown below in (IF). Refers to an aqueous polyester prepared by condensation of one or more suitable acting substances by conventional methods and dissolved or dispersed in the condensate.

Acids [I] that can be used in the synthesis of aqueous polyesters in the present invention include ester-forming aromatic carboxylic acids; terephthalic acid, isophthalic acid, phthalic acid, 2,5
-dimethyltylphthalic acid, naphthalene dicarboxylic acids,
Biphenyldicarboxylic acid, benzophenonetetracarboxylic acid, trimellidic acid, pyromellitic acid, trimesic acid, etc., and ester-forming aromatic sulfonic acids: sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4- Sulfonaphthalene-2゜7-dicarboxylic acid, etc., and saturated linear aliphatic dicarboxylic acids having 4 to 8 methylene groups; acids such as adipic acid, pimelic acid, speric acid, azelaic acid, and sebacic acid. At least one organic acid or an ester-forming derivative of such an acid, ie an anhydride or a lower alkyl ester (10 or less carbon atoms in the alkyl group).

Among these, trimellidic anhydride; sulfoisophthalic acid, isophthalic acid, terephthalic acid, or ester-forming derivatives thereof are particularly preferred.

In addition, the glycols [I[) that can be used when synthesizing the aqueous polyester in the present invention include ethyl glycol, 1, 2-propanediol, 1,3-propanediol, 1, 3-butanediol, 1, 4
-butanediol, l, 5-pentanediol, ■, 6-hexanediol, 1,8-octanediol, 1. These include 4-cyclohexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, styrene oxide, bisphenol A1 phenyl glycidyl ether, and the like. Among these, diethylene glycol, ethylene glycol, l, 2
-Propanediol, diethylene glycol, neopentyl glycol, bisphenol A, etc. are preferred.

Also, if desired, ethylene glycol monobutyl ether, tridecanol, butoxyethoxypropanol,
One or more monohydric alcohols such as benzyl alcohol, cyclohexanol, and hexadecanol, preferably benzyl alcohol or cyclohexanol, are added to the polyester or copolyester structure in the reaction mixture from which the polyester or copolyester is prepared. It is possible to modify the acid number of the polyester or copolyester by including a sufficient amount to react with a selected number of pendant carboxyl groups.

Other properties of the polyester or copolyester, such as hardness, tack, flexibility, solubility, hydrolysis resistance and glass transition temperature, can be modified, if desired, by difunctional acids, carboxyglycols, polyfunctional alcohols, amines and Modifications can be made by adding one or more modifiers, such as amino alcohols, to the reaction mixture from which the polyester or copolyester is produced. Suitable modifiers include isophthalic acid, terephthalic acid, phthalic anhydride, formic acid, maleic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, succinic acid, dimethylolpropanoic acid, glycerin, ethanolamine , ethylene diamine and hexamethylene diamine, with isophthalic acid, terephthalic acid, phthalic anhydride, chlorendic anhydride, maleic anhydride and ethanolamine being preferred.

The molecular weight of the polyester or copolyester may be between 500 and 50,000.

Products commercially available as water-based polyesters include, for example, Toyobo's Pyronal MD-1200° Reaction Chemical Theory PluscohZ-466, Z-448, Z-455, Z-
461, Z-767, Z-771, RZ-105, Peslesin A manufactured by Takamatsu Yushi, -1243, A-2141, A
-2151, 5H-2101, Dainippon Ink Finetex ES-611, ES-650, ES-670
, ES-675, ES-850, Eastman Chemical Company +7) FPY6762, MPS7762, WD36
52, WJL6342, WNT9519, WMS511
3 etc. can be used.

The aqueous polyester resin of the present invention may be mixed and dispersed and supported in a water-soluble binder. As the water-soluble binder, various known water-soluble polymers can be used,
Among these, water-soluble polymers having a group capable of crosslinking with a hardening agent are preferred.

Examples of water-soluble polymers that can be used in the present invention include vinyl polymers such as polyvinyl alcohol, polyvinylpyridinium, and cationic modified polyvinyl alcohol, and derivatives thereof (JP-A-60-145879, JP-A-60-220).
No. 750, No. 61-143177, No. 61-2351
．． No. 82, No. 61-245183, No. 61-2376
81, No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid-methacrylic acid copolymer or its salt, polymethacrylic acid or its salt, acrylic Acrylic group-containing polymers such as acid-vinyl alcohol copolymers or salts thereof (JP-A-60-168651, JP-A-62-9)
988), starch, oxidized starch, acetate starch, amine starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin, sodium alginate, seratin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, calfoquin methylcellulose , hydroquine ethyl cellulose, human pheasant propyl cellulose and other natural polymers or derivatives thereof (JP-A-59-174382, JP-A-60-2)
No. 62685, No. 61-143177, No. 61-18
No. 1679, No. 61-193879, No. 61-287
782), polyvinyl methyl ether, maleic acid-vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer,
Synthetic polymers such as maleic acid-alkyl vinyl ether copolymer and polyethyleneimine (JP-A-61-327
No. 87, No. 61-237680, No. 61-27748
3) and the water-soluble polymers described in JP-A No. 56-58869.

Various copolymers made water-soluble by monomer components containing 503-groups, COO-groups, 502-groups, etc. can also be used.

The use of gelatin as the water-soluble binder is particularly preferable because it can be dried in a set manner, reducing the drying load, and also because simultaneous multilayer coating can be easily performed.

As the gelatin, various gelatins and gelatin derivatives such as those described below can be used. Specifically, lime-treated gelatin,
Gelatin and its derivatives such as decalcified lime-treated gelatin, acid-treated gelatin, phthalated gelatin, acetylated gelatin, succinated gelatin, Bull,
Soc, Phot, Japan.

No, 16. Enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in P.30 (1966) can be mentioned.

When using two or more types of water-soluble polymers as the water-soluble binder, they can be mixed in advance and used as the water-soluble binder. Alternatively, a dispersion may be prepared with an aqueous solution containing one type of polymer (for example, an aqueous gelatin solution) and then mixed with an aqueous solution containing another polymer.

The water-soluble binder and the water-based polyester resin have a weight ratio of water-based polyester resin/water-soluble binder = 1 to 20.
It is preferably used in a range of 2 to IO1, particularly preferably 2.5 to 7.

The amphoteric surfactant used in the present invention refers to a surfactant that has both an anionic group and a cationic group in its molecule to form an inner salt, and is represented by the following general formula (1). It can be done.

General formula (I) Ae (e) (wherein, Ao is an anionic residue containing an anionic group such as a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, etc., C0
represents an organic cation residue. ) The amphoteric surfactant used in the present invention preferably contains at least one saturated or unsaturated hydrocarbon group having 4 or more carbon atoms in one molecule. Fluorine amphoteric surfactants having a fluorine atom in the molecule are particularly preferred.

Specific examples of the amphoteric surfactants used in the present invention will be described below.

CH.

HI ■ CH.

CH.

Hs CH3 ■ CH.

CH.

" CH.

(I-13) CH.

(I-15) CH20COCzH2゜CH3 (I-17) CH3 CH.

" CH.

■ CH.

(I-23) The amphoteric surfactant is dissolved in a suitable solvent such as water, ethanol, methanol, ethyl acetate, etc., and added to the image-receiving layer coating solution. Alternatively, it may be used as an emulsifying and dispersing agent for various water-insoluble additives described below, and added to the image-receiving layer coating solution in the form of a dispersion. The amount of the amphoteric surfactant added is preferably 0.05% to 20% by weight, particularly preferably 0.5% to 10% by weight, based on the weight of the solid components of the image-receiving layer. When two or more image-receiving layers are provided, it may be added to all of the layers or only to the surface layer.

The total thickness of the image-receiving layer is 1 to 50 μm, particularly 3 to 30 μm.
A range of is preferred. In the case of a configuration with two or more layers, the outermost layer is 0
．． It is preferably in the range of 1 to 10 μm, particularly 0.2 to 6 μm.

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

General specific examples of supports are listed below.

■Synthetic paper (polyolefin-based, polystyrene-based, etc. synthetic paper), ■High-quality paper, art paper, coated paper, cast 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.

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

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

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

Here, inorganicity and organicity are concepts for predicting the properties of compounds.
9 (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.
]-209444, No. 61-200538, No. 62
-8145, 62-9348, 62-3024
No. 7 and No. 61-136646.

The high-boiling organic solvent and/or thermal solvent can be used in micron-dispersed form in the image-receiving layer. for example,
A high-boiling organic solvent and/or a thermal solvent is dissolved in a solvent such as ethyl acetate, mixed with an aqueous solution of an aqueous polyester and/or a water-soluble binder, emulsified and dispersed to obtain a dispersion, and this is added to the image-receiving layer coating solution. do. During emulsification and dispersion, anionic, nonionic, cationic or amphoteric surfactants can be used as appropriate.

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

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

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

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

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 only on one side.

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

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

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

Examples include The Chemistry of 5yntheti, edited by K. Veenkataraman.
c Dyes J Volume 5 Chapter 8, JP-A-61-1437
Examples include compounds described in No. 52 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds,
Examples include carbostyryl compounds and 2,5-dibenzoxazolethiophene compounds.

Optical brighteners can be used in combination with antifade agents.

The thermal transfer dye-providing material used in the present invention is a thermal transfer dye-providing material having a layer containing a heat-transferable dye on a support, in which the dye is applied in a pattern to the image-receiving layer of the thermal transfer image-receiving material. A thermal transfer dye-providing material having a heat-melting ink layer on a support, which performs recording by applying heat to melt the ink in a pattern and transferring it to a thermal transfer image-receiving material. Two things are included.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. Examples include polyethylene terephthalate, polyamide, polycarbonate, glassine paper, 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.
μ. 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.

=25= 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 an appropriate solvent, and then using this as a coating solution. On one side of the support for the material,
For example, about 0.2-5μ, preferably 0°4-2μ
The thermal transfer layer is obtained by coating and drying the coating amount to give a dry film thickness of .

Further, thermal transfer dye-providing materials are disclosed in JP-A-2-586, JP-A-2-24192, JP-A-2-25389, and JP-A-2-2.
As described in US Pat. No. 2,729, two or more dye-containing layers may be provided.

Multilayer thermal transfer dye-donor materials are particularly useful for repeated transfers.

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 H2 (, -F S, Miketon Polyester Yellow 3GSL, Kaya Set Yellow 927, Sumikagel Red EFBL, Dianix Red ACE, Miketon Polyel Tell Red FB, Kaya Set Red 126, Miketon Fast Brilliant Blue B, Kayaset Blue 136, etc. are preferably used.

In addition, for example, the following yellow dyes can be used.

(In the formula, R' 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 (Represents a heteryl group, and R4 and R5 represent a hydrogen atom or an alkyl group. The above group may be further substituted.) Specific compound examples are shown below.

Il CH.

As the macenta dye, a dye represented by the following general formula (If) can be used.

(In the formula, R6 to RI Q are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, an annulamino group, a sulfonylamino group,
Represents a ureido group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, or amino group, and R'' and R12 represent a hydrogen atom, an alkyl group, or an aryl group. . Rl l and R12 may be bonded to each other to form a ring (and R8 and R" or/and R9 and Rl 2 may be bonded to each other to form a ring.

l 3 X, Y and Z represent -C- or a nitrogen atom (R13
is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
(represents an aryloxy group or an amine group).

They may be bonded to each other to form a saturated or unsaturated carbon ring. The above groups may be further substituted. ) Specific examples of compounds are shown below.

l CH,0 C,Hrt Further, as the cyan dye, a dye of the following general formula (III) can be used.

In the formula, Rl 1 to R21 are the same as R11-RIo,
R'', R23 is the same as R''X R12. ) Specific examples of compounds are shown below.

llCH3 IC2H5 C4! C2H5 Cjl’ CH.

Cjl’ CHs CH.

C-9 Regarding the compounds of the above general formulas (Y), (M), (C),
It is preferable to introduce an anti-fading group as described in Japanese Patent Application No. 1-271078 because light fastness is improved.

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

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

In the present invention, any conventionally known ink solvent can be freely used as the ink solvent for dissolving or decomposing the above-mentioned 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 a mold release agent, conventionally known solid or waxy substances such as polyethylene wax, amide wax, and Teflon powder; surfactants such as fluorine-based and phosphate ester-based, paraffin-based, silicone-based, and fluorine-based oils, etc. Although any of the above mold release agents can be used, silicone oil is particularly preferred.

As the silicone oil, in addition to unmodified silicone oils, modified silicone oils such as carboxy-modified, amine-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 ■. Among these, particularly carboxy-modified silicone oil (for example, Shin-Etsu Silicone (manufactured by Kiki), product name ,
K1-615 (A), X-21-6008, Tou μ・
5H-3749, 5F-8410 (manufactured by Silicone ■), and epoxy-polyether modified silicone oil (for example, 5F-84, 21, manufactured by Tonmu Silicone) are effective.

-;l 2- 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.

For example, the hardening agents described in U.S. Pat. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, nylsulfone hardeners (N, N'-ethylene-bis(vinylsulfonylatamido)ethane, etc.) , N-methylol hardeners (such as dimethylol urea), or polymer hardeners (compounds described in JP-A-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.

As metal complexes, US Pat. No. 4,241,155,
No. 4,245,018, columns 3 to 36, No. 4,25
No. 4,195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), Japanese Patent Application No. 1983-234103, JP-A No. 62-31096, Japanese Patent Application No. 1983 There are compounds described in No.-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 61-215272 (
125) to (137).

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

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

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

Nonionic surfactants, anionic surfactants, and cationic surfactants can be used. Specific examples of these are described in JP-A-62-173463 and JP-A-62-183457.

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

The constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static electricity, improving releasability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17;
Fluorine surfactants described in JP-A-61-20944 and JP-A-62-135826, oily fluorine compounds such as fluorine oil, solid fluorine compound resins such as tetrafluoroethylene resin, etc. Examples include hydrophobic fluorine compounds and aqueous dispersions thereof. A specific example is Daikin Industries' Daifree ME-3.
13, ME-413, ME-414, ME-810, M
S-443, MS-743, MS-043, MS-84
3. Asahi Glass (Asahi Guard AG-530, AG-
533(S), AG-550, AG-650, AG-7
10, AG-730, AG-740, AG-780, A
Examples include G-800 and Erasgard 100 manufactured by Daiichi Kogyo Seiyaku ■.

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), Japanese Patent Application No. 110064/1982, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 62-110065.

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

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

In the case of thermal transfer using laser light, it is preferred to include a photothermal conversion material in the dye-providing material. Examples of preferred photothermal conversion materials include carbon black and infrared absorbing compounds.

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

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

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

Example 1 (Preparation of thermal transfer dye-providing material (A)) A 6 μm thick polyester film (manufactured by Teijin ■) having a heat-resistant slipping layer made of a thermosetting acrylic resin on one side was used as a support, and the heat resistance of this support was The ink composition (A) for forming a dye-donating layer having the following composition is applied to the side opposite to the side on which the slipping layer is provided so that the coating amount after drying is 1.2 g/rd to provide a thermal transfer dye. Material (A) was obtained.

Magenta ink composition for forming dye-donating layer (A) Dye-M
-42.5 parts Polyvinyl butyral resin (Nislex BX-1: Sekisui Chemical) 2.5 parts Polyisocyanate (KP-90: Dainippon Ink Chemical) 0.1 part Silicone oil (KF-857: Shin-Etsu Chemical) ) 0.004 parts methyl ethyl ketone 70 parts toluene
30 parts (preparation of thermal transfer image-receiving material) Synthetic paper with a thickness of 150μ as a support (manufactured by Tamago Yuka Co., Ltd.: Y
UPO-FPG-150), a coating composition for the image-receiving layer having the following composition (the first layer and the second layer from the support side) was coated on the surface by Giesser coating to a dry film thickness of 1 μm each.
The coating was applied to a thickness of 7.5 μm and dried to produce thermal transfer image-receiving materials (1) to (5) and thermal transfer image-receiving materials (a) to (c) for comparison.

1st layer: 10% gelatin aqueous solution 100g water
401nl hardener (1) 4% aqueous solution 6〇-Second layer/10% solution of the compound of the present invention Type and amount listed in Table 1 Fluorine-based anti-moisture oil agent AG-730 (Asahi Glass Co., Ltd.) l〇 −Water
335-Note-l
) *Hardening agent (1): 1,2-bis(vinylsulfonium acetamide) ethane **Surfactant (1) Sodium nidodecylbenzenesulfonate Note-2) Preparation of dispersion-1 Phthalate ester and silicone oil Dissolve in ethyl acetate. A mixed solution of 10% gelatin aqueous solution, surfactant and water was added to this solution while stirring, and emulsification and dispersion was carried out at 15,000 rpm for 9 minutes using a homogenizer.

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 Printing was carried out under the conditions of 0.25 W/dot, pulse width of 0°2 to 15 m5 ec, and dot density of 6 dots/mm to dye the image-receiving layer of the thermal transfer image-receiving material with magenta dye in an imagewise manner.

The portion (Dmax) where the density of the obtained recorded thermal transfer image-receiving material is saturated is measured with Status A reflection density,
The results are shown in Table 1. The recorded thermal transfer image-receiving material was then stored at 20° C. in a dark place for 8 weeks, and the color transfer of the dyed area was evaluated by the following method. The results are shown in Table 1.

Note 3) Color transfer evaluation method: Plain white paper was brought into contact with the D max portion of the recorded thermal transfer image-receiving material, and the paper was moved back and forth once while applying a load to evaluate the degree of color transfer of the dye to the paper. Load: 200 g, contact area: 1+ffl, reciprocating distance: 100 m00 = almost no dye adhesion observed, Δ - slight dye adhesion observed. ×= Considerable amount of dye attached.

Next, the recorded thermal transfer image-receiving material was stored at 60° C. and 70% in the dark for one week, and the degree of blurring of the image processing and edges was evaluated and the results are shown in Table 1.

○=no blurring, △-edges are slightly blurred, ×=edges are very blurry.

/ Zu3- =54- As is clear from Table 1, the image-receiving material to which the amphoteric surfactant of the present invention is added does not cause color transfer without decreasing the D max value or worsening image blur. Improved. In comparison, image-receiving materials to which anionic surfactants or nonionic surfactants are added tend to blur images and worsen color transfer.

Example 2 (Preparation of thermal transfer image-receiving material) A photographic polyethylene coated paper with a thickness of 200 μm (150 μm base paper, laminated with 27 μm polyethylene on the front side and 23 μm polyethylene on the back side, gelatin undercoat on the front side) was used, and the surface was coated with the following: A coating liquid for the image-receiving layer (from the support side, the first layer and the second layer) having the composition was applied by keyer coating to a dry film thickness of 11 m and 7.5 μm, respectively, and dried to form a thermal transfer image-receiving material (6 ) to (thermal transfer image-receiving materials (d) to (f) for ID and comparison were produced.

The first layer is the same as the first layer of Example-1.

Second layer: Water 350-Dispersion-2 was prepared in the same manner as Dispersion-1 in Example-1.

The thermal transfer image-receiving material obtained as described above was used in Example-
The image-receiving layer of the dye-donating layer of the same thermal transfer dye-donor material as in Example 1 was superimposed so that they were in contact with each other, and printing was carried out under the same conditions as in Example 1. The image-receiving layer of the thermal transfer image-receiving material was dyed imagewise with magenta dye. I made him wear it.

Regarding the recorded thermal transfer image-receiving material, the reflection density of D max was measured in the same manner as in Example-1, and the results were
Shown in the table. Next, in the same manner as in Example-1, the recorded thermal transfer image-receiving material was observed for color transfer and image blur over time, and
The results are shown in Table 2.

As is clear from Table 2, the image-receiving material not using the compound of the present invention has poor color transfer over time, and this is not improved by the addition of a nonionic surfactant. Nonionic surfactant is D
This results in a slight increase in the max value, but the image blur worsens. In contrast, in the image receiving material using the amphoteric surfactant of the present invention, color transfer is improved without deterioration of the D max value or image blur.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment filed on May 1, 1991, 1991, Case description: Japanese Patent Application No. 299264, 1990, 2,
Title of the invention: Thermal transfer image-receiving material 3, Relationship with the person making the amendment Patent application: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd., Tokyo Head Office 4, Subject of the amendment
Column 5 of the "Detailed Description of the Invention" of the description and contents of the amendment The description in the "Detailed Description of the Invention" section of the description is amended as follows.

■) Page 9, line 2 "Reaction chemistry system" "Gouou Kagaku" and correct it.

2) The chemical structural formula of (i7) on page 15 is r
CH20H ■I Cl6Jl+30cHzcHcHz-N-CHzOH0
HC)IZCOOθ”.

3) Page 20, line 1 Before "Methacrylate" [Poly J Insert.

4) Page 21, line 14 “Inorganic and organic” "Inorganic/Organic" and correct it.

5) Page 22, line 4 "micron" "micro" and correct it.

6) Page 31, 3rd line from the bottom [General formula (U)J "General formula (M)" and correct it.

7) Page 36, 3rd line from the bottom "General formula (■)" "General formula (C)" and correct it.

8) Page 54, line 5 "(C) Comparative compound-1" "(C) Comparative compound-2" and correct it.

Claims (1)

[Claims] A thermal transfer image-receiving material comprising at least one image-receiving layer formed on a support to form an image by receiving the dye that migrates from the thermal transfer dye-providing material when heated, wherein the image-receiving layer is made of an aqueous polyester resin. A thermal transfer image-receiving material characterized by containing an amphoteric surfactant.