JPH0452799B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a thermal transfer recording method and an image receiving element. Specifically, the present invention relates to a thermal transfer recording method for obtaining a dye transfer image having good fastness to ultraviolet light, and an image receiving element suitable for use in carrying out the method. [Prior Art] A thermal transfer recording medium has been conventionally used as a recording medium for transferring and forming an image onto an image receiving element such as a recording sheet by a thermal printer, a thermal facsimile, or the like. As this heat-sensitive transfer recording medium, one containing, for example, a dye such as a pigment and a heat-melting substance on a support is known. Techniques for obtaining dye transfer images on image-receiving elements using these heat-sensitive transfer recording media have a serious drawback in that the dyes forming the image develop a significant brown color during storage, particularly when exposed to ultraviolet light. Therefore, there is a need for the development of a technique for obtaining a dye transfer image with good light resistance using a heat-sensitive transfer recording medium containing a non-sublimable dye and a heat-fusible substance. [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and uses a non-sublimable dye and a dye that has good fastness to ultraviolet light, that is, exists stably under ultraviolet irradiation. The technical problem is to make it possible to obtain a dye transfer image that can [Means for Solving the Problems] The thermal transfer recording method of the present invention for solving the above technical problems includes a thermal transfer recording medium having a non-sublimable dye and a heat-melting substance on a support, and the following: The non-sublimable dye and the image receiving element having an image receiving layer containing at least one of the compounds represented by the general formula () are superimposed on each other, and thermal energy is applied according to the image information to be recorded. A dye transfer image is obtained by transferring part or all of the dye substance to the image receiving element. General formula () In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. Examples of the halogen atoms representing R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in the general formula () include chlorine, bromine, iodine, and fluorine. Examples of alkyl groups include methyl, ethyl,
n-propyl, iso-propyl, aminopropyl,
n-butyl, sec-butyl, t-butyl, chlorobutyl, n-amyl, iso-amyl, hexyl,
Octyl, nonyl, stearylamide butyl, decyl, dodecyl, pentadecyl, hexadecyl,
Examples include groups such as cyclohexyl, benzyl, phenylethyl, and phenylpropyl. Examples of the aryl group include phenyl, 4-methylphenyl, 4-ethoxyphenyl, 2-hexoxyphenyl, and 3-hexoxyphenyl. Examples of alkoxy groups include methoxy, ethoxy, propoxy, chlorobutoxy, decoxy,
Examples include groups such as diaminophenoxy, pentadecoxy, and octodecoxy. Examples of the aryloxy group include phenoxy, 4-methylphenoxy, 2-propylphenoxy, and 3-amylphenoxy. Further, the substituents represented by R ₁ to _{R 5} preferably have a total number of carbon atoms of 1 to 36, and the alkyl group preferably has 1 to 18 carbon atoms. Next, the compound represented by the general formula () used in the present invention (hereinafter referred to as the compound of the present invention)
Specific examples are shown below, but the invention is not limited to these. [Examples of compounds of the present invention] The compounds of the present invention as described above can be used, for example, in
No. 36-10466, No. 42-26187, No. 48-5496, No. 48-5496, No.
No. 48-41572, U.S. Patent No. 3754919, U.S. Patent No. 4220711
It can be synthesized by the methods described therein. The compounds of the present invention may be used alone or in combination of two or more. Although the amount of the compound of the present invention used is not limited,
It is preferable to use 0.1 to 100 mmol/m ² , preferably 1 to 10 mmol/m ² for the image receiving element. For example, when the image receiving element of the present invention is overlaid with a heat-sensitive transfer recording medium having a heat-fusible coloring material layer containing a non-sublimable dye and thermal energy is applied, at least one of the non-sublimable dye and the heat-fusible material is produced. Any material is sufficient as long as it transfers the part, and the material is [A]
Examples include paper, natural or synthetic polymers, and the like. Examples of polymers include polyacrylates (e.g. polymethyl acrylate, polyethyl acrylate),
Polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-
Styrene copolymers, polyether chloride, polyvinylidene chloride, polyvinyl chloride, polyvinylcarbazole, polystyrene, styrene-butadiene copolymers, cellulose acetates, polyacetals (e.g. polyvinyl butyral, polyvinyl formal), polytetrafluoroethylene, Chlorotrifluoroethylene, polyethylene, chlorinated polyethylene, polycarbonate, polyvinyl acetate, polyvinyl alcohol, polypropylene,
Polyvinylpyrrolidone, polymethacrylates (e.g. polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate,
Polyisopropyl methacrylate, poly-t-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl dimethacrylate, etc.), polyesters (e.g. polyethylene terephthalate, etc.), polyamide, polyimide, polysulfone, etc. These are suitable for use as materials for support-integrated (combined-type) image-receiving elements. In addition, [B] casein, vegetable protein, gum tragacanth, gum arabic, starch, starch, dextrin, gelatin, glue, alginic acid, agar, polyethylene glycol, polyethylene glycol ester, propylene glycol ester, polyacrylamide, polyacrylic acid,
polyvinyl alcohol, polyvinylpyrrolidone,
Water-soluble polyvinyl butyral, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl acetate, oil-soluble polyvinyl butyral, acetyl cellulose, polymethyl acrylate, polybutyl acrylate, polybutyl methacrylate, polystyrene, polyvinyl pyridine, polyethylene terephthalate, Epoxy resins and the like can also be used as materials for the image-receiving element, and these are suitable for use as an image-receiving element (image-receiving layer) provided on a support. Furthermore, [C] a thermofusible substance described below can also be used as a material for the image receiving element. These materials may be used alone or as a mixture. Among these, particularly preferred are polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyethylene terephthalate, cellulose acetates such as triacetate and diacetate, heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid, and hexamethylene diamine. and diphenic acid, polyamides synthesized from hexamethylene diamine and isophthalic acid, polyesters synthesized from diethylene glycol and diphenylcarboxylic acid, and ethylene glycol and bis-p-carboxyphenoxybutane. Furthermore, various additives can be added to the image receiving element.
For example, inorganic additives such as titanium white, silica, talc, clay, talc, barium sulfate, calcium carbonate, glass powder, kaolin, and zinc oxide are added to give mattness, whiteness, smoothness, and gloss. It's okay. Further, other additives may be included for the purpose of improving image fastness or for other purposes. The method of incorporating the compound of the present invention into the image-receiving element is not particularly limited, but [A] the method of coating or dipping the surface of the image-receiving element after forming the image-receiving element, or [B] the method of incorporating the compound of the present invention when forming the image-receiving element. There is a method of adding it in advance. In the case of the former [A], the compound of the present invention is dissolved in a suitable organic solvent (e.g., acetone, methanol, ethanol, ethyl acetate, dimethylformamide, dibutyl phthalate, tricresyl phosphate, etc.). They can be added by dipping the image receiving element or by applying these solutions to the image receiving element. On the other hand, in the case of the latter [B], there is a method of making paper using a paper machine using a mixed solution (slurry) in which the compound of the present invention is added to natural or synthetic pulp together with a paper strength enhancer, a sizing agent, a filler, etc.
There is a method in which the compound of the present invention is added to a synthetic polymer melt or solution and formed into a film to form the image receiving element of the present invention. When the material of the image-receiving element has poor morphology as in [B] and [C] above, a material with excellent morphology is molded into the desired shape, and the compound of the present invention is applied thereon using this as a support. A layer containing the above-mentioned properties can be formed. Materials with excellent morphology may be appropriately selected from the above-mentioned image-receiving element material [A], metal, wood, glass, and the like. Preferably, the shape of the image receiving element has a surface that matches the surface of the thermal transfer recording medium to be superimposed. The image receiving element of the present invention is placed in a stacked relationship with a thermal transfer recording medium at least during thermal transfer, and can be used with any thermal transfer recording medium containing a non-sublimable dye and a heat-melting substance. However, they can be used in combination. A preferred embodiment of the heat-sensitive transfer recording medium of the present invention has a heat-melting coloring material layer containing a non-sublimable dye on a support, and the heat-melting coloring material layer is applied to an image receiving element by heat. Any layer containing a non-sublimable colorant to which part or all of the colorant is transferred may be sufficient, and the main components of the heat-melting coloring material layer may include a heat-melting substance (a low melting point substance or a low softening point substance), a non-sublimable coloring material, It is a pigment. The thermofusible substance used in the present invention preferably has a melting point (value measured by Yanagimoto MP-2 model) or a softening point (value measured by ring and ball method) of 40 to 120.
℃, more preferably 60 to 120℃, and specific examples include vegetable waxes such as carnauba wax, wood wax, auricilla wax, and espalt wax, beeswax, insect wax, In addition to waxes such as animal waxes such as seratzu wax and spermaceti wax, petroleum waxes such as paraffin wax, microcrystalline wax, ester wax, and oxidized wax, and mineral waxes such as montan wax, ozokerite, and ceresin; palmitic acid and stearin. Higher fatty acids such as acids, margaric acid, behenic acid; Higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol; cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate Higher fatty acid esters such as acetamide, propionic acid amide, palmitic acid amide, stearic acid amide, amide wax, etc.; rosin derivatives such as ester gum, rosin maleic acid resin, rosin phenolic resin, hydrogenated rosin; phenolic resin, terpene Polymer compounds such as resins, cyclopentadiene resins, and aromatic resins; higher amines such as stearylamine, behenylamine, and palmitinamine; and polyethylene oxides such as polyethylene glycol 4000 and polyethylene glycol 6000. They may be used, or two or more types may be used in combination. Among these, palmitic acid amide, stearic acid amide,
Higher amides such as oleic acid amide and amide wax are particularly preferred. Furthermore, the "thermofusible solid component that is solid at room temperature" described in JP-A-54-68253 and the "vehicle" described in JP-A-55-105579 may also be used. . Among the heat-melting substances used in the heat-melting coloring material layer of the present invention, a combination of a hard wax and a soft wax (one type or two or more types of each) is particularly preferable as a low-melting substance. Hard wax [measured by wax ball method with penetration (according to JIS K 2530) of less than 8 at 25°C (100 g)] is preferably 40 to 120
℃, more preferably 60 to 120℃, and specific examples include vegetable waxes such as carnauba wax, wood wax, auricilla wax, and espalt wax, beeswax, insect wax, In addition to waxes such as animal waxes such as seratzu wax and spermaceti wax, petroleum waxes such as paraffin wax, microcrystalline wax, ester wax, and oxidized wax, and mineral waxes such as montan wax, ozokerite, and ceresin; palmitic acid and stearin. acids, higher fatty acids such as margaric acid, behenic acid; higher alcohols such as palmitic alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol; cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate, etc. higher fatty acid esters; amides such as acetamide, propionic acid amide, palmitic acid amide, stearic acid amide, amide wax; rosin derivatives such as ester gum, rosin maleic acid resin, rosin phenolic resin, hydrogenated rosin; phenolic resin, terpene resin , cyclopentadiene resin, aromatic resin, etc.; higher amines such as stearylamine, behenylamine, palmitinamine; polyethylene oxide such as polyethylene glycol 4000, polyethylene glycol 6000, etc., and these may be used alone. or two or more types may be used in combination. Among these, palmitic acid amide, stearic acid amide,
Higher amides such as oleic acid amide and amide wax are particularly preferred. Furthermore, the "thermofusible solid component that is solid at room temperature" described in JP-A-54-68253 and the "vehicle" described in JP-A-55-105579 may also be used. . Among the heat-melting substances used in the heat-melting coloring material layer of the present invention, a combination of a hard wax and a soft wax (one type or two or more types of each) is particularly preferable as a low-melting substance. Examples of hard waxes [waxes with a penetration degree (according to JIS K 2530) of less than 8 at 25°C (100g)] include ester waxes (natural ester waxes such as carnauba wax and Montan wax, and Hoechst waxes). Hoechst Wax
Synthetic ester waxes such as E, F, KP, KPS, BJ, OP, OM, NPS-9210, NPS- manufactured by Nippon Seirosha
6115, PETRONABA manufactured by Toyo Petrolite Co., Ltd.
C, CARDIS 314, etc.), low molecular weight polyethylene waxes (especially those with a molecular weight of 300 to 1000, such as POLYWAX 500 and 655 manufactured by Toyo Petrolite)
etc.), acid wax (Hoechst), acid wax (Hoechst
Wax S and LP, etc.) or Diakaruna 30
and Diakaruna PA30L (manufactured by Mitsubishi Kasei Corporation). In addition, soft wax [25℃
(100g) (according to JIS K 2530)
As an example of waxes with a diameter of 8 or more, microcrystalline waxes (Nisseki Microwaxes)
115, 180 (manufactured by Nippon Oil Co., Ltd.), HI-MIC-1080, HI
−MIC−2065, HI−MIC−2095, HI−MIC−
1070, HI-MIC-1045, HI-MIC-2045 (manufactured by Nippon Seirosha), STAR WAX 100, BE SQUARE
175, 185, VICTORY, ULTRAFLEX (manufactured by Toyo Petrolite, etc.), stearic acid, behenic acid,
Examples include stearyl alcohol, white wax, beeswax, dodecyl stearate, stearon, sorbitan monostearate, and polyoxyethylene stearate. In addition, when such a hard wax and a soft wax are used in combination, the weight ratio used is preferably 1:9 to 9:1 (more preferably 2:8 to 8:2). The non-sublimable dye to be contained in the heat-melting color material layer of the present invention may be appropriately selected from non-sublimable dyes and pigments. Examples of the dye include basic dyes, oil-soluble dyes (oil-soluble (including metal complex dyes), acid dyes, direct dyes, disperse dyes, etc., which are non-sublimable. These dyes may also be ballasted dyes. On the other hand, as the pigment, organic pigments such as phthalocyanine pigments can be used. The pigment contained in the heat-melting coloring material layer of the present invention is
In particular, the non-sublimable dye may be any non-sublimable dye that can be transferred to the image-receiving element together with a heat-fusible substance during heating recording and has a color. Non-sublimable dyes preferably used in the present invention are sublimable dyes used in mordant dyes, etc. (including those that vaporize with solvent or dissolution)
This excludes pigments. Basic dyes preferably used as non-sublimable dyes in the present invention include, for example, crystal violet (CI42555), malachite green (C.
I.42000), Methyl Violet (CI42535), Victoria Blue (CI44045), Mazienta (C.
Triphenylmethane dyes such as I.42510), diphenylmethane dyes such as Auramine (CI655), Astraphloxine FF (CI48070), Eisenkatylon Yellow 3GLH (Hodogaya Chemical Industry Co., Ltd. product, CI48055), Eisenkathyronretsu Do 6BH
(CI48020) Astrazone Golden Yellow
Methine and azamethine dyes such as GL (Bayer product, CI48054), Rhodamine B (C.
I.45170), xanthene dyes such as Rhodamine 6G (CI45160), Astrazone Blue GL (C.
I.11052), Astrazone Red F3BL (CI11055)
Thiazole and triazole azo dyes such as
Quinoneimine dyes such as Eisenkatilone Blue 5GH (CI11085), Methylene Blue (CI52015), Eisenkatilone Red GTLH (CI11085),
Cevron Yellow 3RL (DuPont product, C.
I.11087), Astrazone Blue FGL (CI61512)
Examples include insulating azo dyes and anthraquinone dyes having an onium group at the structural end. Examples of oil-soluble metal complex dyes include symmetrical 1:2 type azo metal complex dyes, asymmetrical 1:2 type azo metal complex dyes, 1:1 type azo metal complex dyes, azomethine metal complex dyes, and formazan metal complex dyes. Examples include complex salt dyes, metal phthalocyanine dyes, and organic base salts of these dyes. Specifically, Eisenspiron Yellow 3RH (Hodogaya Chemical Co. product, CI Solvent Yellow 25), Zapon Fast Yellow R (BASF product, CI18690), Eisenspiron Orange 2RH (CI Solvent Orange 40), Zapon Fast Scarlet B (C.
I.12783), Eisenspiron Red GEH (CI Solvent Red 84), Zaponphastrone BE
(CI12715), Zapon Fast Violet BE (C.
I.12196), Cyanine Blue BB (Sumitomo Chemical Co., Ltd. product,
CI74160), Variable Asto Black #3804 (Orient Chemical Company product, CI12195), Eisenspiron Yellow 3RH Special (CI Solvent Yellow 25:1), Eisenspiron Orange 2RH Special (CI Solvent Orange 40:1), Eisenspiron Blue 2BNH (CI Solvent Blue 117), Zapon Fuasto Blue HFL (C.
I.74350), Eisenspiron Black BH Special (CI Solvent Black 22:1), etc. Acidic dyes such as CI Acid Yellow
19, CI Assisted Red 37, CI Assisted Blue
62, CI Acid Orange 10, CI Acid Blue 83, CI Acid Black 01, etc. Direct dyes are CI Direct Yellow 44, CI
Direct Yellow 142, CI Direct Yellow 12, CI Direct Blue 15, CI Direct Blue 25, CI Direct Blue 249, CI Direct Red 81, CI Direct Red 9, CI Direct Red 31, CI Direct Black 154,
Examples include CI Direct Black 17. The disperse dyes are CI Dispose Yellow 5, C.
I. Dispose Yellow 51, CI Dispose Yellow 64, CI Dispose Yellow 43, CI Dispose Red 54, CI Dispose Red
135, CI Dayspose Blue 56, CI Dayspose Blue 73, CI Dayspose 91, etc. The ballasted dyes used in the present invention are dyes having at least one ballast group in the dye matrix, such as azo dyes, azomethine dyes, indoaniline dyes, anthraquinone dyes, naphthoquinone dyes, sterine dyes, quinophthalo dyes, and phthalocyanine dyes. It is. Ballast groups are, for example, groups that are highly soluble in heat-fusible substances such as alkyl groups, cycloalkyl groups, aralkyl groups, alkoxy groups, alkylsulfonylamino groups, alkylsulfonyl groups, hydroxylalkyl groups, cyanoalkyl groups, and alkoxycarbonylalkyl groups. group, an alkyl group having 6 or more carbon atoms, such as an alkoxyalkyl group, an alkylthio group, or an alkylene group. In particular, a ballast group having at least one alkyl group having 6 or more carbon atoms in the molecule is preferred. Examples of the structure of the ballasted dye preferably used in the present invention include those described in Japanese Patent Application No. 81688/1988 filed by the present applicant, but the present invention is not limited thereto. It is preferable that the heat-melting color material layer of the present invention contains a softener. The softener used in the present invention has a softening point (measured by the ring and ball method) of 40 to 200°C.
It is preferable to use either a hydrophilic polymer or a hydrophobic polymer. Examples of hydrophilic polymers include gelatin, gelatin derivatives, cellulose derivatives, proteins such as casein, natural products and natural product derivatives such as polysaccharides such as starch, water-soluble nylon, polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Examples include synthetic water-soluble polymers such as polyvinyl compounds, and vinyl-based and polyurethane-based polymer latexes. As hydrophobic polymers, US Pat. No. 3,142,586, US Pat.
No. 3062674, No. 3220844, No. 3287289, No.
The synthetic polymers described in No. 3411911 may be mentioned by way of example. Preferred polymers include polyvinyl butyral, polyvinyl formal, polyethylene, polypropylene, polyamide, ethyl cellulose, cellulose derivatives such as cellulose acetate, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, ethylene-
Ethyl acrylate, ethylene-vinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Examples include vinyl acetate-maleic acid terpolymers, acrylic resins such as polymethyl methacrylate, polyisobutylene, rosin derivatives such as ester gum, petroleum resins, coumaron indene resins, cyclic rubbers, chlorinated rubbers, and the like. In the present invention, one or a combination of two or more of these softeners may be used. The composition ratio of the heat-melting coloring material layer of the present invention is not limited, but the heat-melting substance may be 50 to 100 parts (parts by weight, same hereinafter) of the total solid content of the heat-melting coloring material layer.
95 parts (more preferably 70 to 95 parts), non-sublimable dye 5 to 20 parts, and softener 0 to 30 parts (more preferably 1 to 10 parts). The heat-melting coloring material layer of the present invention may contain various additives in addition to the above-mentioned components. For example, vegetable oils such as castor oil, linseed oil, olive oil, animal oils such as whale oil, and mineral oils may be suitably used. However, in the present invention, the content of the additives other than the above-mentioned main components is preferably less than 50% by weight. The heat-sensitive transfer recording medium to which the method of the present invention is applied may have two or more heat-melting coloring material layers. For example, as shown in Japanese Patent Application No. 58-204708 filed by the present applicant, an upper color material layer containing substantially no pigment;
The heat-melting coloring material layer is composed of a lower coloring material layer that substantially contains a dye, that is, the total amount of the non-sublimable dye contained in the entire heat-melting coloring material layer of the upper and lower layers is 100%. %, the non-sublimable dye contained in the upper color material layer is 30% or less, preferably 10% or less, more preferably 0 to 5%, and most of the non-sublimable dye is contained in the lower color material layer. Patent Application No. 58-192544, No. 58-
As shown in No. 192545, two or more heat-melting colors, such as that the heat-melting coloring material layer is composed of an upper coloring material layer containing a heat-melting substance and a lower coloring material layer containing a resin. The method of the present invention can also be applied to a thermal transfer recording medium having a material layer. Another preferred embodiment of the thermal transfer recording medium of the present invention includes a layer containing a non-sublimable dye (hereinafter referred to as a non-sublimable dye layer) and a layer consisting of a heat-melting substance as essential layers on the support. (hereinafter referred to as a heat-fusible material layer). Here, the non-sublimable dye layer is capable of holding the non-sublimable dye in, for example, a particulate or molecular state, and is formed by a binder in which the non-sublimable dye can migrate during heating. It is not transferred onto the image receiving element upon heating. This layer may contain a substance that assists the non-sublimable dye present in the layer to migrate upon heating. Examples of binders forming this layer include casein, gelatin, polyvinyl alcohol, polyvinyl butyral, methylcellulose, gum arabic, polyester, polyvinyl formal, polypropylene, polystyrene, polyvinyl chloride, and other commonly known binders. It is preferable to use one that is stable. The non-sublimable dye contained in this layer is a substance that can be melted by itself and/or transferred to the heat-fusible substance layer by the action of the above-mentioned transfer aid substance when heated to 45°C or higher. For example, the above-mentioned ones may be mentioned. Among them, the melting point is 45
C. to 120.degree. C. is preferably used. Particularly preferred are azotoluene, azobenzene, azophenethole, N,N-dimethyl-m-nitroaniline, p-nitroanisole, m-aminobenzophenone, p-nitroso-N,N-dimethylanilide, 4-nitro-2- aminoanisole,
Examples include nitrophenylhydrazine and p-nitrobenzyl acetate. Moreover, the above-mentioned materials can be used as the heat-melting material. The composition of the non-sublimable dye layer is preferably in the range of 5 to 70% (by weight) binder and 1 to 90% (by weight) non-sublimable dye, particularly preferably 30 to 60% binder.
(by weight), a proportion of non-sublimable dyes from 40 to 70% (by weight) is advantageous. A migration auxiliary substance that assists the migration of the non-sublimable dye can be added thereto, if necessary. Also, an intermediate layer can be provided between the non-sublimable dye layer and the heat-fusible material layer. The intermediate layer may or may not melt when heated. In the former case, it may be transferred to the image receiving element together with the hot melt material. The support used in the thermal transfer recording medium of the present invention preferably has heat-resistant strength, high dimensional stability, and high surface smoothness. Materials include, for example, papers such as plain paper, condenser paper, laminated paper, coated paper, resin films such as polyethylene, polyethylene terephthalate, polystyrene, polypropylene, polyimide, paper-resin film composites, aluminum foil, etc. Metal sheets and the like are preferably used. The thickness of the support is preferably about 60 .mu.m or less, particularly 1.5 to 15 .mu.m, in order to obtain good thermal conductivity. Furthermore, in the thermal transfer recording medium of the present invention, the structure on the back side of the support may be optional, and a backing layer such as a sticking prevention layer may be provided. In the heat-sensitive transfer recording medium of the present invention, techniques suitable for applying a constituent layer containing a non-sublimable dye and/or a heat-fusible substance to a support such as a polymer film are known in the art; The known techniques can also be applied to the present invention. For example, the constituent layer including the heat-melting coloring material layer is a layer formed by hot-melt coating the composition or by solvent coating a coating solution obtained by dissolving or dispersing the composition in an appropriate solvent. be. As a coating method for each constituent layer of the present invention, any technique such as a reverse roll coater method, an extrusion coater method, a gravure coater method, a wire bar coating method, etc. can be adopted. The heat-melting coloring material layer preferably has a thickness of 20 μm or less,
More preferably, the thickness is 1 to 15 μm. or,
Non-sublimable dye and heat-fusible material layer each have a thickness of 0.5 to 5μ
m is preferred. The thermal transfer recording medium of the present invention may have other constituent layers such as an undercoat layer (for example, a layer for improving film adhesion), an intermediate layer, and an overcoat layer. A method for thermal transfer recording using the image receiving element of the present invention and the thermal transfer recording medium will be described below. The side of the constituent layer containing the heat-melting substance of the heat-sensitive transfer recording medium and the image receiving element are overlapped, and the side of the heat-sensitive transfer recording medium is layered with a thermal recording device using a thermal head, a thermal pen, a laser, etc. according to the image information. When energy is applied from above and/or from the image-receiving element side, the heat-fusible substance is transferred to the image-receiving element together with the non-sublimable dye etc. by applying energy above a certain value. A dye transfer image having good fastness to ultraviolet light is obtained on the image-receiving element in a form dissolved or dispersed in a heat-fusible substance. The image receiving layer of the present invention has the following general formula (A), (B) or (C).
At least one of the compounds represented by may be included, in which case a synergistic effect can be obtained. General formula (A) General formula (B) General formula (C) In the formula, R ₁ , R ₁ ′, R ₃ , R ₃ ′ and R ₅ each represent a hydrogen atom, an aliphatic group, an alicyclic compound residue, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an aryl group. represents a sulfonyl group or an aralkylsulfonyl group, R ₂ , R ₄ , R ₄ ', R ₆ and R ₇ each represent a hydrogen atom, a halogen atom or a monovalent organic group, x represents an integer of 1 to 4, q represents an integer of 1 to 6, and m, n and p each represent an integer of 1 to 3. Also, x, m, n, p and q are each 2
In the above cases, R ₂ , R ₄ , R ₄ ′, R ₆ and R ₇ may be the same or different, or may form a ring. To explain more specifically, the above R ₁ , R ₁ ′,
Examples of the aliphatic group represented by R ₃ , R ₃ ', and R ₅ include alkyl groups and alkenyl groups, and the alkyl groups include straight-chain or branched groups having 1 to 20 carbon atoms; has a carbon number of 2 to 20
Those having straight or branched chains are preferred. Said
The alicyclic compound residue represented by R ₁ , R ₁ ', R ₃ , R ₃ ' and R ₅ is preferably a 5- to 7-membered cycloalkyl group such as a cyclohexyl group. Furthermore _, the aromatic groups represented by R ₁ , R ₁ ′, R ₃ , _{R 3} ′, and R ₅ include _phenyl group, naphthyl group, etc. ₃ ′ and
The heterocyclic group represented by R ₅ is preferably one containing a 5- to 6-membered nitrogen atom, oxygen atom, or sulfur atom, such as furyl, pyranyl, tetrahydropyranyl, imidazolyl, pyrrolyl, pyrimidyl, pyrazinyl, triazinyl, Thienil,
Examples include quinoline, oxazolyl or pyridyl. The acyl group represented by R ₁ , R ₁ ', R ₃ , R ₃ ' and R ₅ is preferably an alkylcarbonyl group or arylcarbonyl group having 2 to 20 carbon atoms, such as acetyl, pivaloyl, oleyl, lauroyl, benzoyl etc. In addition, the above R ₁ , R ₁ ′,
Examples of the alkylsulfonyl group, arylsulfonyl group, and aralkylsulfonyl group represented by R ₃ , R ₃ ', and R ₅ include methanesulfonyl, butanesulfonyl, benzenesulfonyl, toluenesulfonyl, benzylsulfonyl, and the like. Next, the monovalent organic groups represented by R ₂ , R ₄ , R ₄ ', R ₆ and R ₇ each have, for example, 1 carbon number.
~20 alkyl groups, alkyloxy groups, alkylthio groups, phenyl groups, phenoxy groups, acyl groups,
Examples include an acylamino group, a sulfonamide group, an alkylamino group, and an alkoxycarbonyl group. Specific examples of compounds that can be used in combination with these include:
Examples of compounds that can be used in combination include those described in the patent application (A) filed on the same date.
No. 52-35633, No. 52-147434, No. 53
−17729, No. 53-20327, No. 54-48538, No.
It can be synthesized by the methods described in Publications No. 55-89836, No. 47-4738, and No. 54-44521. The compounds of the present invention may be used alone or in combination of two or more. Although the amount of the compound of the present invention used is not limited,
It is preferably used in an amount of 1 to 500 mol %, particularly preferably 10 to 200 mol %, based on 1 mol of the dye forming the maximum density image obtained on the image-receiving element. [Effects of the Invention] Images obtained by the present invention not only have improved fastness to ultraviolet rays, but also have a high transfer density, and have excellent shelf life of thermal transfer recording media with respect to heat resistance, light resistance, etc. It is also possible to obtain a dye image which is excellent in terms of storage stability and storage stability of the dye transfer image. It is possible to incorporate the compound of the present invention into the heat-melting coloring layer of the heat-sensitive transfer recording medium or its transferable constituent layer without incorporating it into the image-receiving element; The method of the present invention is better because it is not superior to the present invention in this respect. [Example] Examples are given below, but the embodiments of the present invention are not limited thereto. Example 1 On a 5.3 μm thick polyethylene terephthalate film, 35 g of carnauba wax, 15 g of bees wax, and 5 g of cellulose diacetate were mixed, and to this, 1 g of the following non-sublimable dye (C-1) was added and applied. A thermal transfer recording medium sample was prepared. On the other hand, as an image-receiving element, 8 g of cellulose diacetate per 1 m ² and the compound of the present invention (Table
2.5 mmol (shown in 1) and 1 g of dibutyl phthalate were applied. The heat-sensitive transfer recording medium sample and this image-receiving element sample were superimposed on each other, and a thermal printer (prototype machine equipped with a thin-film line thermal head with a heating element density of 8 dots/mm) was used to apply electric power per heating element. Recording was performed by applying energy of 0.9 W and an application time of 2 milliseconds. As a result, a dye transfer image was obtained on the image receiving element. The obtained transferred image was irradiated with a 6000W xenon lamp for 48 hours (illuminance on the image plane was 6000 lux), and the optical density (D ₀ before irradiation, D ₁ after irradiation) was measured by λmax before and after irradiation. , D ₁ /D ₀ ×100 (%) as the survival rate, and the fastness to ultraviolet rays was tested. The raw storage stability and the retention stability of the transferred image were also tested, and the results are shown in Table 1. Furthermore, the following sublimable dye (C-2) was used instead of the non-sublimable dye in the thermal transfer recording medium sample.
A sample to which 1.6 g of the above-mentioned compound was added was prepared and used as a thermal transfer recording medium sample. Table 1 below shows the fastness to ultraviolet rays, storage stability, etc. of the transferred images obtained using this comparative thermal transfer recording medium sample. Furthermore, raw storage stability ( ^* 1) in Table 1 shows that when thermal transfer recording media are left at 25°C and 40% RH for one month after creation and then thermally transferred, compared to when thermal transfer is performed immediately after creation. When the concentration decrease is less than 1%◎
A three-step method was used: mark: 1% or more and less than 10%, ○ mark, and 10% or more: × mark. In addition, the storage stability ( ^* 2) in Table 1 indicates that after obtaining a thermal transfer image, the image receiving element is kept at 25°C and 40% RH for 1 time.
When left for several months, compared to immediately after obtaining a thermal transfer image, visual observation shows that no bleeding is observed at all in the transferred image, marked ◎, and cases where slight bleeding is observed, marked ○, marked bleeding is noticeable. A three-step method was used, with cases marked with an X. Non-sublimable dye (C-1) Sublimable dye (C-2)

【table】

[Table] As is clear from Table 1, when the image-receiving element of the present invention is used in combination with a thermal transfer recording medium (sample No.) having a heat-fusible coloring material layer containing a non-sublimable dye, It can be seen that the fastness to ultraviolet rays is improved, and the storage stability of the recording medium and the storage stability of the transferred image are excellent. Example 2 An image-receiving element sample was prepared in the same manner as in Example 1, except that the compounds of the present invention and their amounts were changed as shown in Table 2 below, and a dye transfer image was formed using the thermal transfer recording medium sample of Example 1. As a result, similar to Example 1, good results were obtained.

[Table] Example 3 A solution in which 1 g of gelatin was dissolved in 20 ml of water was stirred at 80°C, and non-sublimable dye (C-1) 2 was added to it.
After adding g, cool the liquid to 50℃. This liquid
Disperse in a sand mill for 2 hours while keeping at 50℃,
Coating liquid 1 was obtained. 2g of beeswax in Japanese patent publication 1983-
According to the dispersion method described in Publication No. 120393
Coating liquid 2 was prepared by dispersing it in 20 ml of water. Coating liquid 1 was applied onto a polyethylene terephthalate film with a thickness of 6 μm using a wire bar, and after drying, a layer of heat-fusible material with a thickness of 3.0 μm was provided. Apply coating liquid 2 on top of it with a wire bar,
A heat-melting material having a thickness of 2.8 μm was obtained by drying, and a heat-sensitive transfer recording medium was obtained. Using this, a dye transfer image was obtained in the same manner as Test No. 2 of Example 1, and similarly good results were obtained.

Claims (1)

[Scope of Claims] 1. A thermal transfer recording medium that does not contain a sublimable dye and contains a non-sublimable dye and a heat-melting substance, and at least one of the compounds represented by the following general formula ().
A part or all of the non-sublimable dye and the heat-fusible substance are transferred to the image-receiving element by overlapping the image-receiving element with an image-receiving layer containing an image-receiving layer and applying thermal energy according to the image information to be recorded. A thermal transfer recording method in which a dye transfer image is obtained. General formula () [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. . ] 2 An image receiving element used in combination with a heat-sensitive transfer recording medium that does not contain a sublimable dye and contains a non-sublimable dye and a heat-fusible substance, containing at least one compound represented by the following general formula () An image receiving element characterized by: General formula () [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. . ]