JPS6154982A - Thermal transfer recording method and picture-receiving element - Google Patents

Abstract

PURPOSE:To obtain transferred color picture having good fastness to ultraviolet rays by a method in which thermal transfer recording medium containing a nonsublimable dye and a heat-meltable substance is lapped with a picture-receiving element containing a specific compound on a supporter, and a heat energy is given to them according to information of pictures to be recorded. CONSTITUTION:A thermal transfer recording medium containing a nonsublimable dye and a heat-meltable substance is lapped with a picture-receiving element with a picture-receiving layer containing at least a compound of the formula on a supporter. A heat energy is given to them according to information of pictures to be recorded to transfer all or part of the dye and the heat-meltable substance to the picture-receiving element to obtain a transferred color picture. In the formula, R1, R2, R3, R4 and R5 are each a monovalent atom or group. The pictures so obtained are excellent in fastness to ultraviolet rays, live storability of the recording medium with respect to heat resistance and light resistance, and storage stability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial 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 thermal transfer recording media have a serious drawback in that the dyes forming the images undergo significant fading, especially when exposed to ultraviolet light during storage.

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 and method of the present invention for solving the above technical problems include a thermal transfer recording medium having a non-sublimable dye and a heat-fusible substance on a support, and the following: An image receiving element having an image receiving layer containing at least one compound represented by the general formula (I) is superimposed on the non-sublimable dye and a heat-fusible dye. transferring some or all of the substance to the image receiving element;
It is characterized by obtaining a dye transfer image.

General Formula (I) In the formula, R5, R2, R3, R4 and R5 each represent a -valent atom or group.

Rt, R2, R3, R4, and R5 in the general formula (I) may be the same or different from each other, and the -valent atom is preferably a hydrogen atom or a halogen atom (chlorine, bromine, iodine, fluorine), - The valence group is a nitro group,
Hydroxy group, alkyl group (e.g. methyl, ethyl, n
-propyl, 1so-propyl, aminopropyl, n-
Butyl, 5eG-butyl, t-butyl, chlorobutyl,
n-7 mil, iao niamil, hexyl, octyl, nonyl, stearylamidobutyl, decyl, dodecyl, pentadecyl, hexadecyl, cyclohexyl, benzyl, phenylethyl, phenylpropyl, etc.), alkenyl groups (e.g. vinyl, allyl, methallyl) , dodecenyl, tetradecenyl, octadecenyl, etc.), aryl groups (e.g., phenyl, 4-methylphenyl, 4-ethoxyphenyl, 2-hexoxyphenyl, 3-hexoxyphenyl, etc.), alkoxy groups (e.g., methoxy , ethoxy, propoxy, chlorobutoxy, decoxy, diaminophenoxy, pentadecyl, octodecoxy, etc.), alkoxycarbonyl groups (e.g., carbumethoxy, carbobutoxy, carbohexoxy, carpopentadecoxy, etc.), aryloxy groups (e.g. phenoxy, 4-methylphenoxy, 2-propylphenoxy, 3-amylphenoxy, etc.), alkylthio groups (e.g., methylthio, ethylthio, t-butylthio, t-octylthio, benzylthio, etc.), arylthio groups (e.g. phenylthio, methylphenylthio, quaternary ethylphenylthio, methoxyphenylthio, ethoxyphenylthio, naphthylthio, etc.), mono- or dialkylamino groups (e.g. toethylamino, t-cutylamino, N,N-diethylamino, N, tri- t
-butylamino, etc.), a 5- or 6-membered heterocyclic group containing oxygen, sulfur, or nitrogen (e.g., piperidino, morpholino, pyrrolidino, piperazino, etc.), and R4 and R5 are closed ring groups. may form a 5- or 6-membered ring consisting of carbon atoms, and the substituents represented by R1 to Rs preferably have a total number of carbon atoms of 1 to 36, and the alkyl group has 1 to 36 carbon atoms. -18 is preferred.

Next, specific examples of the compound represented by the general formula (I) (hereinafter referred to as the compound of the present invention) used in the present invention will be shown, but the compounds are not limited thereto.

[Examples of compounds of the present invention] OH (3) OHcuH9(t)(4
) 0■CuH9(t)(5)
ou Cat(1r(t) C5H11(t) [8] OH (IIH9(t) Cu )(g(t) (12) (14) ou CfU(IIH
(see) OCgf (17C) [20] H H CH3 [26] The compounds of the present invention as described above are disclosed in, for example, Japanese Patent Publication No. 36-1
No. 0466, roJ42-26187, roJ48-54
No. 96, Mukai No. 48-41572, U.S. Patent No. 3,754
, No. 919, No. 4,220,711, etc., and can be synthesized by the method described in Kokura et al.

The compounds of the present invention may be used alone or in combination of two or more.

The amount of the compound of the present invention to be used is not limited, but it is preferably 0.1 to 100 mmol/m' to the image receiving element, preferably when superimposed on a thermal transfer recording medium having a tactile colorant layer and given thermal energy. In this case, any material may be used as long as it transfers at least a portion of the non-sublimable dye and the heat-fusible substance, and examples of the material include A1 paper, natural or synthetic polymers, etc. Examples of polymers include polyacrylates (e.g. polymethyl acrylate, polyethyl acrylate),
Polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyether chloride, polyvinylidene chloride, polyvinyl chloride, polyvinylcarbazole, polystyrene, styrene-butadiene copolymer, cellulose acetates, polyacetals ( polyvinyl butyral, polyvinyl formal), polytetrafluoroethylene, polychlorotrifluoroethylene, polyethylene, chlorinated polyethylene, polycarbonate, polyvinyl acetate, polyvinyl alcohol, polypropylene, polyvinylpyrrolidone, polymethacrylates (such as 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.),
Examples include polyamide, polyimide, polysulfone, etc., which are suitable for use as materials for support-integrated (dual-purpose) image-receiving elements. [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 polyvinylbutyral, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, polyvinyl acetate, oil-soluble polyvinylbutyral, acetylcellulose, polymethylacrylate, polybutyl 7-acrylate, polybutyl methacrylate, polystyrene, polyvinylpyridine, Polyethylene terephthalate, epoxy resins, etc. can also be used as materials for the image receiving element, and these are suitable for use as the image receiving element (image receiving layer) provided on the 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,
Examples include polyamides synthesized from hexamethylene diamine and diphenic acid, 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 matte whiteness, smoothness, and gloss. It may also contain other additives for the purpose of improving the fastness of the image or for other purposes.

The method of incorporating the compound of the present invention into the image-receiving element is not particularly limited, but may include [a method of coating or dipping the surface of the AI image-receiving element after forming it], or [B] a method of incorporating the compound of the present invention into the image-receiving element when forming the image-receiving element. There are ways to add it in advance. In the former case [A], the compound of the present invention is dissolved in a suitable organic solution (for example, acetone, methanol, ethanol, ethyl acetate, dimethylformamide, dibutyl phthalate, tricresyl phosphate, etc.). The additives 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 are methods in which paper is made 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 agent, a sizing agent, a filler, etc.; There is a method in which the compound of the present invention is added to a 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, the material with excellent morphology is molded into the form of a fresh pickle, and the compound of the present invention is applied thereon using this as a support. A layer containing can be formed. Materials with excellent morphology include the above-mentioned image receiving element material [A], metal, wood,
An appropriate material may be selected from 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 thermal 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 non-sublimable dye-containing layer may be used as long as part or all of the layer is transferred, and the main components of the heat-fusible coloring material layer include a heat-fusible substance (a low melting point substance or a low softening point substance), a non-sublimable dye= This is Nenjajuku.

The heat-melting substance used in the present invention preferably has a melting point (measured by the purlin MPJ-2 type) or a softening point (measured by the ring and ball method) of 40 to 120°C, more preferably 60 to 120°C. solid or semi-solid substance,
Specific examples include carnauba wax, wood wax, auriculie wax, vegetable wax such as esparto wax, animal wax such as beeswax, insect wax, shellac wax, spermaceti wax, paraffin wax, microcrystalline wax, ester wax, and oxidized wax. In addition to waxes such as petroleum waxes such as montan wax, osikerite, mineral waxes such as ceresin; higher fatty acids such as palmitic acid, stearic acid, margaric acid, and behenic acid; palmityl alcohol,
Higher alcohols such as stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate; acetamide, propionic acid amide, palmitic acid amide, Amides such as stearic acid amide and amide wax; rosin derivatives such as ester gum, rosin maleic acid resin, rosin phenol resin, and hydrogenated rosin; polymers such as phenol resin, terpene resin, cyclopentadiene resin, aromatic resin, etc. Compounds: higher amines such as stearylamine, behenylamine, palmitinamine; polyethylene oxides such as polyethylene glycol 4000 and polyethylene glycol 8000; these may be used alone,
Two or more kinds may be used in combination, and among these, higher amides such as palmitic acid amide, stearic acid amide, oleic acid amide, and amide wax are particularly preferred, and are also described in JP-A-54-68253. "Thermofusible solid component that is solid at room temperature" and JP-A-55-105579
The "vehicle" described in the publication may also be used.

Among the heat-melting substances used in the heat-melting coloring material layer of the present invention, the low melting point substance is a hard wax [25°C ( Penetration (JIS K 2
According to 530. ) is less than 8] Examples of ester waxes (natural ester waxes such as Carnapawanx and Montanwax, and manufactured by Hoechst) 1
oechst War E, F, KP.

KPS, BJ, OP, OM, X22. Synthetic ester wax such as UJ Yobi 0 etc.), ! 2) M wax (
Wax obtained by oxidizing wax such as paraffin wax and microcrystalline wax, NPS-9210, NPS-8115 manufactured by Hiki Seiro Co., Ltd., PETR0NABAΦC, CARDIS 31 manufactured by Toyo Petrolite Co., Ltd.
4, etc.), ■Low molecular weight polyethylene wax (especially those with a molecular weight of 300 to 1000, PO manufactured by Toyo Petrolite)
LYWAX 500 and 655, etc.), Acid wax (
Hoechst Wax S, L, P, etc.), or ■Diakaruna 3o or Diakaruna PA30
L (manufactured by Mitsubishi Kasei Corporation) and the like. Also,
Soft wax [25℃ (loOg) 28 points penetration - (
According to JIS K 2530. ) is 8 or more] Examples of microcrystalline wax (Nisseki Microwax 115°180 (manufactured by Nippon Oil Co., Ltd.),
Hl-MIG-1080, old-MIC-2085.

1(1-MIG-2H5, I(f-MIC-1070,
)If-M[-1045, Hl-MIC-2045 (manufactured by Hiki Seirosha), 5TARWAX 100. BE 5
QUARE175.185. VICTORY, ULT
RAFLEX (manufactured by Toyo Petrolite Co., Ltd.), stearic acid, behen alcohol, stearyl alcohol, white wax, beeswax, dodecyl stearate, stearone, sorbitan monostearate, polyoxyethylene monostearate, and the like. In addition, when using a combination of such hard wax and soft wax, the weight ratio used is 1:9 to 9:1 (more preferably 2:8 to
8:2) is preferred.

The non-sublimable dye to be contained in the heat-melting color material layer of the present invention is
The dyes and pigments may be appropriately selected from non-sublimable dyes, such as basic dyes, oil-soluble dyes (
(including oil-soluble metal complex dyes), acid dyes, direct dyes, disperse dyes, etc. These dyes may be ballasted dyes; Organic pigments such as phthalocyanine pigments can be used.

The dye to be contained in the heat-melting color material layer of the present invention is particularly non-sublimable, and as a non-sublimable dye, during heating recording,
The non-sublimable dye preferably used in the present invention may be any non-sublimable substance that can be transferred to the image receiving element together with a heat-fusible substance and has a color. This excludes pigments (including those that vaporize with melting or dissolution).

Basic dyes preferably used as non-sublimable dyes of the present invention include 1, for example, crystal violet (C, 1,4
2555), Malachite Green CC, 1,42000
), methyl violet (G, 1.42535),
Triphenylmethane dyes such as Victoria Blue (C, 144045) and Mazienta (C, 1, 42510), auramine (C, I.

Diphenylmethane dyes such as 655), Astraphloxin FFCC, 1,48070), Eisenkathylon Yellow 3GLH (product of Hodogaya Chemical Co., Ltd., C, 1,4
8055), Cramps Chiron Red 8BH (C, 1,
48020) Astrason Go JL/7” Yellow G
Methine-based and azamethine-based dyes such as L (/<Inil Co., Ltd. product, C, 1,48054).

Xanthine dyes such as Rhodamine B (C, 1, 45170), Rhodamine 6G (C, 145180), Astrazone Blue GL (C, 1, 11052),
Astrazone Red F3B, L (G, 1.11055)
Thiazole azo and triazole azo dyes such as Eisenki Chiron Blue-50H (C, l-11085)
, methylenebu A, -(C,l-52015) and other quinoneimine dyes, Eisencathilone Red GTLH ((
, 1, 11085), Cevron Yellow 3RL (DuPont product, C11,110B?), Astrazone Blue FGL (c, It will be done.

Oil-soluble metal complex dyes include, for example, symmetric l22 type azo metal complex dyes, asymmetric 1:2 type azo metal complex dyes, l
: I-type azo metal complex dyes, azomethine total complex dyes, formazan metal complex dyes, metal phthalocyanine dyes, and organic base salts of these dyes. Specifically, Eisenspiron Yellow 3RH (Hodogaya Chemical Co., Ltd. product, C,1, Solvent Yellow 25)
, Zapon Fast Yellow R (BASF product, C, 1
, 18890), Eisenspiron Orange 2RH (C
, 1, Solvent Orange 40), Pomelo Fast Scarlet B (C, 1, 12783), Eisens Bironlet GEH (G, 1. Solvent Red 84), Zapon Fast Red BE (C, 1, 12715), Zapon Fast Violet BE (C, 1, 1219B)
, Cyanine Blue〇B (Sumitomo Chemical Co., Ltd. product, C, 1,74
180), /Clifast Black 113804 (Orient Chemical Co., Ltd. product, C, 1, 12195), Aisenspirone Yellow 3RH Special (C, 1, Solvent Yellow 25:l), Isenspirone Orange 2R
H Special (C, 1, Solvent Orange 40:l)
, Eisensviron Blue-28NH (C,I, Solvent Blue 117), Zapon Fast Blue) IFL
(C, 1,74350), Eisenspiron Blafuku B
) I Special (C, 1, Solvent Black 22:1
) etc.

Acidic dyes include, for example, C,1, Acid Yellow 19,
Examples include C,1, Acid Red 37, C,1, Acid Blue 62, C,1, Acid Orange 1O1c,r, Acid Blue 83, c,r, and Acid Black 01.

The direct dye is C,1, Direct Yellow 44.0. I
.

Direct Yellow 142, G, 1. Direct Yellow 12, C,1, Direct Blue 15, C,1, Direct Blue 25, C,1, Direct Blue 248
,C0! , Direct Red 81, G, 1. Direct Red 8, (:, 1. Direct Red 31, C, 1,
Examples include Direct Black 154, C,t, Direct Black 17, and the like.

Disperse dye is C,1, Disboose Yellow 5°C,1
, Disbor's Yellow 51, C, 1, Disbor's Yellow 84.0.1. Disbos Red 43, C, 1
, Disbo's Red 54. C, 1, Disbors Red 135, G,! , Disbo's Blue 56, C, 1
, Disbor's Bluff 3, C, 1, Disbor's 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 groups with high solubility in heat-melting 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 preferable. Examples of the structure of the ballast dye preferably used in the present invention are given in Japanese Patent Application No. 81688/1988 filed by the present applicant. However, the present invention is not limited thereto.

Hot melt I41 of the present invention! It is preferable that a softening agent is contained in the coloring agent. The softening agent used in the present invention preferably has a softening point (measured by the ring and ball method) of 40 to 200°C, and a hydrophilic polymer. , hydrophobic polymers can be used. 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. synthetic water-soluble polymers such as polyvinyl compounds,
Further examples include vinyl-based and polyurethane-based polymer latexes. @Aqueous polymers include U.S. Patent Nos. 3,142,588, 3,143,388, and 3.
, QB2, 8? No. 4, No. 3,220,844, No. 3
, 287.288 and 3,411,911 can be cited as examples. Preferred polymers include polyvinyl butyral, polyvinyl formal, polyethylene, polypcopinone, polyamide, ethyl cellulose, cellulose acetate, etc., polyvinyl butyral, polyvinyl formal, polyvinylidene chloride, polyvinyl chloride, polyvinyl chloride, polyvinylidene chloride, etc. Acrylic resins such as ethylene-ethyl acrylate, ethylene-vinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid terpolymer, polymethyl methacrylate, polyisobutylene, rosin derivatives such as ester gum, petroleum Examples include resin, coumaron indene resin, cyclic rubber, and chlorinated rubber. In the present invention, one or a combination of two or more of these softeners may be used.

Although the composition ratio of the heat-melting coloring material layer of the present invention is not limited,
Relative to 100 parts (parts by weight, the same applies hereinafter) of the total solid content of the heat-melting coloring material layer, the heat-melting substance is 50 to 95 parts (more preferably 70 to 85 parts), and the non-sublimable dye is 5 to 20 parts. part, and the softener is 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, and olive oil, animal oils such as whale oil, and mineral oils are preferably 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. The heat-fusible coloring material layer is composed of an upper coloring material layer that does not contain a dye and a lower coloring material layer that substantially contains a dye, that is, the entire heat-melting coloring material layer of the upper and lower layers. The non-sublimable dye contained in the upper color material layer is 30% or less, preferably 10% or less, more preferably 0 to 5%, with the total amount of non-sublimable dye contained as 100%. It has a layer structure in which most of the non-sublimable dyes are contained in the lower coloring material layer, ■Patent Application No. 1987-192544, No. 58-192
As shown in No. 545, 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. This layer may contain a substance that assists the migration of the non-sublimable dyes present in the layer upon heating. Examples of the binder forming this layer include casein, gelatin, polyvinyl alcohol, polyvinyl butyral, methylcellulose,
gum arabic, polyester, polyvinyl formal,
Polypropylene, polystyrene.

Commonly known binding awns, such as polyvinyl chloride, are more stable for fishing.

The non-sublimable dyes contained in this layer include 45°C and below.
Any material may be used as long as it can be transferred to the heat-fusible material layer by the action of the transfer auxiliary substance, such as those mentioned above. Among them, those having a melting point of 45°C to 120°C are preferably used. Particularly preferred are azotoluene, azobenzene, azophenethole, N, N-
Dimethyl-m-nitroaniline, p-nitroanisole, m-7 minobenzophenone, p-nitrone-N, N-
Examples include dimethylanilide, 4-nitro-2-aminoanisole, 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 5 to 70% binder (weight ratio)
, a non-sublimable dye (1 to 80% (weight ratio)), particularly preferably a binder of 30 to 60% (weight ratio),
Advantageously, 1 part of the non-sublimable dye qao to 70% (by weight) is used. If necessary, two transfer aids may be added to assist the transfer of the non-sublimable dye.

Further, a middle 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 case of 72η, it can be transferred to the image receiving element together with a hot melt substance.

The support used in the thermal transfer recording medium of the present invention is preferably a support that has heat resistance strength, dimensional stability, and surface smoothness. Examples of the material include paperback paper, condenser paper, laminated paper, Paper such as coated paper, resin films such as polyethylene, polyethylene terephthalate, polystyrene, polypropylene, polyimide, etc., paper-resin film composites, metal sheets such as aluminum foil, etc. are all suitably used. The thickness of the support is usually about 80 Bm or less, especially 1.5 Bm or less in order to obtain good thermal conductivity.
The thermal transfer recording medium of the present invention may have an arbitrary structure on the back side of the support, and may be provided with a backing layer such as an anti-sticking layer.

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, and these techniques are known in the art. The known techniques can also be applied to the present invention↓ 6 For example, a constituent layer including a heat-melting coloring material layer can be coated by hot-melt coating the composition, or by dissolving or dispersing the composition in an appropriate solvent. This is a layer formed by solvent coating a liquid. As a coating method for each constituent layer of the present invention, a reverse roll coater is used.
Any technique can be employed, such as a coating method, an extrusion coater method, a gravure coater method, or a wire bar coating method. The heat-melting coloring material layer preferably has a molecular weight of 2oJLII or less, more preferably 1 to 15
It may be set to 7La. Further, the non-sublimable dye and the heat-fusible material layer each preferably have a density of 0.5 to 5 ILII.

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 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 component layer side containing the heat-melting substance of the heat-sensitive transfer recording medium and the image receiving element are overlapped, and a thermal recording device using a thermal head, a thermal vane, a laser, etc. Or, when energy is applied from the image receiving element side, the heat-fusible substance is transferred to the image receiving element along with non-sublimable dyes etc. by applying energy exceeding a certain value. A dye transfer image having good fastness to ultraviolet light is obtained on the image-receiving element in the form of a dye transfer image dissolved or dispersed in a heat-fusible substance.

The receiving layer of the present invention may be formed by the following general formula (A), (B) or (
At least one of the compounds represented by C) may also be included, in which case a synergistic effect is obtained.

General formula (A) General formula CB) General formula (C) In the formula, R1, Rs', Ri, R3' and Rs are each a hydrogen atom, an aliphatic group, an alicyclic compound residue, an aromatic group, a heterocyclic group , represents an acyl group, an alkylsulfonyl group, an arylsulfonyl group or an aralkylsulfonyl group, and R
2, R4, R4, R6 and R7 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, m, n and p each represents an integer from 1 to 3, and! +rn+n,
When P and q are each 2 or more, R2, R4, R4,
R8H and R74 may be the same or different, or may form a ring.

More specifically, the above R1, R1, and R3.

Examples of the aliphatic group represented by R3' and R5 include an alkyl group and an alkenyl group, and the alkyl group is a linear or branched group having 1 to 20 carbon atoms, and the alkenyl group is a straight chain or branched group having 62 to 20 carbon atoms. Those having straight or branched chains are preferred.

The alicyclic compound residues represented by R1, R1', R3, R3'' and R5 include 5- to cyclocyclo\sil groups, etc.
A 7-membered dichlorofurkyl group is preferred.

Further, the aromatic groups represented by Rt, R1', R3, R3' and R5 include phenyl groups, naphthyl groups, etc., and the heterocyclic groups represented by Rt, R1', R3, R3' and R5 above. Preferably, those containing a 5- to 6-membered nitrogen atom, oxygen atom, or sulfur atom, such as furyl, pyranyl, tetrahydropyranyl, imidazolyl, pyrrolyl, pyrimidyl, pyrazinyl,
Examples include triazinyl, chenyl, quinolyl, oxasilyl or pyridyl.

The acyl group represented by R1, R1', R3, R3' and R5 is preferably a furkylcarbonyl group or arylcarbonyl group having 2 to 20 carbon atoms, such as acetyl, pivaloyl, oleyl, lauroyl, benzoyl, etc. . Also, the above-mentioned R1 and Rt'.

Examples of the alkylsulfonyl group, arylsulfonyl group, and aralkylsulfonyl group represented by R3, R3', and Rs include methanesulfonyl, butanesulfonyl, benzenesulfonyl, toluenesulfonyl, benzylsulfonyl, and the like.

Next, the monovalent organic groups represented by R2, R4, R4', Ra and υR2 are 1, for example, each having 1 to 2 carbon atoms.
0 alkyl group, alkyloxy group, alkylthio group,
Examples include phenyl group, phenoxy group, acyl group, acylamino group, sulfonamide group, alkylamino group, and alkoxycarbonyl group.

Specific examples of compounds that can be used in combination with these include those described in the patent application (A) filed on the same date.
No. 034, rF149-8338, rF149-2097
No. 7, JP-A-52-35633, JP-A No. 52-14743
No. 4, No. 53-17729, No. 53-20327,
No. 54-48538, No. 55-89836, No. 47
It can be synthesized by the methods described in Publications No. 4-738 and No. 54-44521.

The compounds of the present invention may be used alone or in combination of two or more.

The amount of the compound of the present invention to be used is not limited, but is preferably 1 to 500 mol %, particularly preferably 10 to 2 mol %, based on 1 mol of the dye forming the maximum density image obtained on the image receiving element.
It is preferable to use 00 mol%.

[Effects of the Invention] The images obtained by the present invention not only have improved fastness to ultraviolet rays, but also have a high transfer density, are heat resistant, have excellent storage stability of thermal transfer recording media against both light, etc. Also, it is possible to obtain a dye image which is excellent in 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 35 g of carnauba wax and 15 g of beeswax were placed on a 5.3 pm thick polyethylene terephthalate film.
A thermal transfer recording medium sample (2) was prepared by mixing 5 g of cellulose diacetate and 1 g of non-sublimable dye (C-1) shown below.

On the other hand, as an image-receiving element, 8 g of cellulose diacetate and the compound of the present invention (shown in Table 1) were applied to a polyethylene terephthalate film (thickness loOgm) per 1 m''.
2.5 mmol of dibutyl phthalate Ig was applied.

The thermal transfer recording medium sample (1) and this image-receiving element sample were superimposed on each other, and a thermal printer (heating element density: 8d) was used.
Using a prototype machine equipped with an ot/am thin-film line thermal head, the applied power per heating element was 0.9W.
Recording was performed by applying energy for 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 for 48 hours with an 8000W xenon lamp (illuminance on the image surface was 6000 lux), and the optical density (Do before irradiation, D1 after irradiation) was measured by input o + ax before and after irradiation, and Dt /Do
The durability against ultraviolet rays was tested using X100 ($) as the survival rate.

The raw storage stability and storage stability of the transferred image were also tested, and the results are shown in Table 1.

Furthermore, in place of the non-sublimable dye in the thermal transfer recording medium sample (1), 1.8 g of the following sublimable dye (C-2) was added to prepare a thermal transfer recording medium sample (2).

Table 1 below shows the fastness to ultraviolet rays, storage stability, etc. of the transferred images obtained using the comparative thermal transfer recording medium sample (1).

In addition, raw storage stability (Y1) in Table 1 shows that when thermal transfer is performed after leaving the thermal transfer recording medium at 25°C and 40% RH for one month after creation, compared to when thermal transfer is performed immediately after creation.
13. Mark O when the degree decrease is less than 1%.

A three-step method was used: 0 mark for 1% or more and less than 10%, and jX mark for 10% or more.

In addition, the storage stability (02) in Table 1 indicates that when the image receiving element is left at 25°C and 40% RH for one month after obtaining a thermal transfer image, immediately after obtaining a thermal transfer image, compared.

In visual observation, a three-step method was used: if no bleeding of the transferred image was observed, the mark was ``■'', if a slight blurring was observed, the mark ``O'', and if the bleeding was noticeable, the mark was ``X''.

Non-sublimable dye'' (C-1) Sublimable dye (C-2) 〇-pen As is clear from Table 1, the image receiving element of the present invention uses a heat-melting coloring material containing a non-sublimable dye. It can be seen that when used in combination with a thermal transfer recording medium having a layer (Sample No., ■), the fastness to ultraviolet rays is improved and the storage stability of the recording medium and the transferred image is 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 prepared using the thermal transfer recording medium sample (■) of Example 1. As a result, similar to Example 1, good results were obtained.

Example 3 While stirring a solution in which gelatin Ig was dissolved in 20 ml of water at 80°C, 2 g of non-sublimable dye (C-1) was added thereto, and then the solution was cooled to 50°C. This liquid was dispersed in a sand mill for 2 hours while keeping it at 50°C.

Coating liquid 1 was obtained. 2g of beeswax in JP-A-56-1203
20 m according to the dispersion method described in Publication No. 93.
Coating liquid 2 was prepared by dispersing the liquid in 1 liter of water.

Coating liquid 1 was applied onto a polyethylene terephthalate film having a thickness of 134 m using a wire bar, and after drying, a layer of a heat-melting material having a thickness of 3.0 pm was provided. Coating liquid 2 was applied thereon with a wire bar and dried to obtain a heat-melting material having a thickness of 2.8 m, thereby obtaining a heat-sensitive transfer recording medium.

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 (2)

[Claims] (1) A heat-sensitive transfer recording medium having a non-sublimable dye and a heat-fusible substance on a support and an image-receiving element having an image-receiving layer containing at least one compound represented by the following general formula (I) are superimposed. . A thermal transfer recording method in which a part or all of the non-sublimable dye and heat-fusible substance are transferred to the image receiving element by applying thermal energy according to image information to be recorded, thereby obtaining a dye transfer image. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4 and R_5
each represents a monovalent atom or group. ] (2) An image-receiving element used in combination with a heat-sensitive transfer recording medium having a non-sublimable dye and a heat-fusible substance, characterized in that it contains at least one compound represented by the following general formula (I): . General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4 and R_5
each represents a monovalent atom or group. ]