JPH03277587A - Thermal transfer material and thermal transfer image forming method - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer image having good light fastness and high image density by bringing a thermal transfer dye donating material containing an ultraviolet absorber and a thermal transfer image receiving material into contact with each other to heat both of them imagewise and transferring a dye and the ultraviolet absorber from the thermal transfer dye donating material to the thermal transfer image receiving material. CONSTITUTION:A thermal transfer dye donating material is formed by applying a coating composition for an yellow dye donating layer containing an ultraviolet absorber to the surface of a polyethylene terephthalate film having a thickness of 6mum by wire coating so that thickness at the time of drying becomes 1.5mum to dry the coating layer and a thermal transfer image receiving material is formed by preparing resin coated paper obtained by laminating polyethylene to both surfaces of paper having thickness of 200mum respectively in thicknesses of 15mum and 25mum and applying a coating composition for an image receiving layer containing the ultraviolet absorber to the laminated surface with thickness of 15mum of the resin coated paper in dry thickness of 10mum by wire bar coating to dry the coating layer. These materials are superposed one upon another so that the thermal transfer dye donating layer and the image receiving layer come into contact with each other and a thermal head is used on the support side of the thermal transfer dye donating material to heat said material and full-color transfer recording is applied to the image receiving layer of the thermal transfer image receiving material.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermal transfer material for thermal transfer recording and a thermal transfer image forming method using the same, and in particular to a thermal transfer image forming method with excellent light resistance and high density. The present invention relates to a thermal transfer material and a method for forming a thermal transfer image.

(Background 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, and has recently become widely used because the equipment used is lightweight, compact, noiseless, has excellent operability and maintainability, and can be easily converted to color. . There are two types of thermal transfer recording methods: heat-melting type and heat-transfer type. This is a method in which a transferred image is obtained by superimposing the dye on a thermal transfer image-receiving material, applying heat from the support side of the dye-providing material, and transferring the heat-transferable dye to a recording medium (thermal transfer image-receiving material) in the form of a heat-applied pattern.

Note that the term "thermally transferable dye" as used herein refers to a dye that can be transferred from a thermal transfer dye-providing material to a thermal transfer image-receiving material by sublimation or diffusion in a medium.

(Problems to be Solved by the Invention) However, the image-receiving material obtained in this manner did not have sufficient storage stability (light resistance) of the transferred image under light irradiation. That is, when a transferred image is left indoors under a fluorescent light or exposed to sunlight for a long time, the image density often decreases significantly or the color of the image changes significantly. In order to improve light resistance, a method of incorporating an ultraviolet absorber into an image-receiving material (for example, Japanese Patent Laid-Open No. 59-158289
, JP-A-60-101090, JP-A-6L-22959
4) and a method in which an ultraviolet absorber is contained in the dye-donating layer of the dye-donating material so that the ultraviolet absorber is transferred to the image-receiving material simultaneously with the transfer of the dye has been proposed. However, regarding the former, the transferred dye mainly exists on the surface of the image-receiving layer, whereas simply adding an ultraviolet absorber to the image-receiving material causes the ultraviolet absorber to be dispersed throughout the image-receiving layer. It is not possible to make full use of its effects. On the other hand, if a large amount of ultraviolet absorber is added to the image-receiving layer in order to improve needle shine, the dyed pigment will be more likely to diffuse, causing image smearing or thermal fusion with the ink sheet. . Regarding the latter, in normal transfer, the amount of ultraviolet absorber transferred from the dye-donating layer to the image-receiving layer is small, and light resistance cannot be sufficiently improved. If a large amount of ultraviolet absorber is added to the dye-donating layer to improve light resistance, the front and back surfaces of the ink sheet will adhere to each other during storage.

Furthermore, the image density of sublimation thermal transfer is determined by the amount of heat given to the dye, that is, the amount of current flowing through the thermal head. Therefore, in order to obtain a high-density transferred image, an image-receiving material with low dyeability requires an excessive amount of heat during transfer, and the durability of the thermal head deteriorates.

(Means for Solving the Problems) An object of the present invention is to provide a thermal transfer material and a thermal transfer image forming method capable of obtaining a thermal transfer image having good light resistance and high image density without causing the above-mentioned difficulties. This is the purpose.

The object of the present invention is to provide a thermal transfer dye-providing material having a dye-donating layer containing a heat-transferable dye on a support, and a thermal transfer image-receiving material having a dye-receiving layer on the support that receives the dye that migrates during heating. A thermal transfer material characterized in that both the thermal transfer dye-providing material and the thermal transfer image-receiving material contain an ultraviolet absorber, and the thermal transfer dye-providing material and the thermal transfer image-receiving material are brought into contact and imagewise This was accomplished by a thermal transfer imaging method characterized by heating to transfer dyes and ultraviolet absorbers from a thermal transfer dye-providing material to a thermal transfer image-receiving material.

The present invention will be explained in more detail below.

In the thermal transfer dye-providing material of the present invention, the ultraviolet absorber may be contained in the dye-providing layer or in a layer separate from the dye-providing layer. For full-color thermal transfer recording, the dye-donating layer is usually provided as a set of a yellow layer, a magenta layer, and a cyan layer (and in some cases, a black layer), or the ultraviolet absorber is contained in one of these dye-donating layers. or may be contained in two or more layers. In addition, when it is contained in a layer separate from the dye-providing layer (
In other words, when the ultraviolet absorber layer is provided separately), the ultraviolet absorber layer may be provided at a position where the ultraviolet absorber is transferred before, during, or after the dye transfer.

The ultraviolet absorber is preferably added to the dye image-receiving layer in the thermal transfer image-receiving material.

UV absorbers suitable for use in the present invention have the following general formula [
These are compounds represented by I) to [IV).

For the thermal transfer dye-providing material, a heat transferable ultraviolet absorber is selected from among these compounds and used.

One of the criteria for selecting a heat-transferable UV absorber is the molecular weight of the UV absorber. It is preferable to use an ultraviolet absorber with a molecular weight of 1000 or less, especially 600 or less in the thermal transfer dye-providing material.

For the thermal transfer image-receiving material, it is preferable to select and use ultraviolet absorbers that are relatively less susceptible to thermal transfer among the compounds represented by formulas m to (IV).

Only one type of ultraviolet absorber may be used, or two or more types may be used in combination.

0.1-10g of ultraviolet absorber for thermal transfer dye-providing material
/rrI', particularly preferably in the range of 0.2 to 5 g/rd. Thermal transfer image-receiving material contains 0.1 g/I, especially 1
~6g/rr? It is preferable to use the range of . Further, the amount is 1 to 100% by weight, preferably 10 to 60% by weight, based on the binder polymer of the layer used.

General formula [1 General formula [■] General formula General formula [rV] In the above general formulas CI) to [IV], R7'' to R7s
may be the same or different and may be a hydrogen atom, /"t rogene atom, acyloquine group, aliphatic group, aromatic group, R"O-
or R"SO2-, R7" to R79 may be the same or different, and include a hydrogen atom, a hydrogen atom, a hydrogen atom, an aliphatic group, an aromatic group, a carbonamide group,
Sulfonamide group, sulfo group, carboxy group, or R
``O-'', RI O and RI l may be the same or different and represent a hydrogen atom, an aliphatic group, a halogen atom, or R870-, and R12, R85 and R'' may be the same or different and represent hydrogen represents an atom, an aliphatic group, or an aromatic group (provided that R'' and RI6 are not hydrogen atoms at the same time), R'' and R84 may be the same or different, and may be a cyano group, a carbamoyl group, or a sulfamoyl group. , formyl group, -CORs7-3OR"5o2
R17-8o20R17, also represents C0OR''. RI T represents an aliphatic group or an aromatic group. Here, the aliphatic group refers to a substituted or unsubstituted linear, branched or cyclic alkyl group. The aromatic group refers to a group consisting of a substituted or unsubstituted monocyclic or condensed benzene ring.

Specific examples will be shown below, but the present invention is not limited thereto.

V-1 ○H V H V H (t) Ct 89 (t)C,H UV UV 0 CH3 CH.

Go CH.

, CH2 0] C00CH.

UV 5 UV 7 CH.

CH.

6CH2 , C.H.

0] C00CH.

1 amount ratio) In the present invention, there is no particular restriction on the amount of ultraviolet absorber used, and preferably about 0.05 rays per heat transfer sheet.
g to 20 g, more preferably 0.1 g to 5 g.

A thermal transfer dye-providing material is a thermal transfer dye-providing material that has at least one dye-providing layer containing a heat-transferable dye and a binder on a support, and is a thermal transfer dye-providing material that transfers the dye in a heat-applied pattern to an image-receiving material. The recording is performed by transferring the data to a layer.

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

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.

This thermal transfer dye-providing material is prepared by preparing a coating solution by dissolving or dispersing a dye that sublimes or becomes mobile by heat and a binder resin in a suitable solvent, and then applying this coating solution to the thermal transfer dye-providing material. On one side of the support for the material,
For example, it can be obtained by coating and drying the coating amount to give a dry film thickness of about 0.2 to 5 μm, preferably 0.4 to 2 μm to form a thermal transfer layer.

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, examples include disperse dyes, basic dyes, oil-soluble dyes, and especially Sumikalon Yellow E.
4GL, Dianix Yellow H2G-FS, Miketone Polyeltel Yellow 3GSL, Kayasset Yellow 9
37, Sumikaron Red EFBL, Dianix Red ACE, Miketon Polyeltel Red FB, Kayasse Tread 126, Miketon Fast Brilliant Blue B
, Kayaset Blue 136, etc. are preferably used.

Also, JP-A No. 59-78895, No. 60-28451, No. 60-28453, No. 60-535, No. 4, No. 6
No. 1-148096, No. 60-239290, No. 60-
3] No. 565, No. 60-30393, No. 60-535
No. 65, No. 60-27594, No. 61-262191
No. 60152563, No. 61-244595,
No. 62-196186, No. 63-142062, No. 63-39380, No. 62-290583, No. 63
-111094, 63-111095, 63-
No. 122594, No. 63-71392, No. 63-74
No. 685, No. 63-74688, Patent Application No. 61-512
No. 85 (Describes the dye represented by the general formula below.

In the formula, Rho is a hydrogen atom, an alkyl group, an alkoxy group,
represents 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, R3 represents an aryl group or a heteryl group, and R1 and R6 may be the same or different. often,
Each represents a hydrogen atom or an alkyl group. The above substituent may be further substituted), etc., the yellow dye described in
JP 60-223862, JP 60-28452,
No. 60-31563, No. 59-78896, No. 60
-31564, 60-303391, 61-2
No. 27092, No. 61-227091, No. 60-30
No. 392, No. 6030694, No. 60-131293
No. 61-227093, No. 60-159091, No. 61-262190, No. 62-33688,
No. 63-5992, No. 61-12392, No. 62-
No. 55194, No. 62-297593, No. 63-74
No. 685, No. 63-74688, No. 62-97886
No. 62-132685, No. 61-163895, No. 62-211190, No. 62-99195, and Japanese Patent Application No. 62-220793 (describing the dye of the following general formula.

In the formula, R1R2 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an ano group, anruamino group, a sulfonylamine group, a ureido group, an alkylthio group, an arylthio group , alkoxycarbonyl group,
It represents a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, or an amino group, and R3 and R represent an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. R
3 and R4 may be combined with each other to form a ring (and R
2 and R, , R, and R4 may be combined to form a ring.

n represents an integer of 0 to 3. X, Y and Z represent -C= or a nitrogen atom (here, R6 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group,
represents an aryl group, alkoxy group, aryloxy group, or amino group).

5 When X and Y or Y and Z are -C-, they may be bonded to each other to form a saturated or unsaturated carbon ring. The above substituents may be further substituted), etc., magenta dyes described in JP-A No. 59-78894, JP-A No. 60-31559, JP-A No. 60-53563, JP-A No. 61-19396, JP-A No. 61-
No. 22993, No. 61-31467, No. 61-359
No. 94, No. 61-49893, No. 61. -57651
No. 62-87393, No. 63-15790, No. 63-15853, No. 63-57293, No. 63-
No. 74685, No. 63-74688, No. 59-227
No. 490, No. 59-227493, No. 59-2279
No. 48, No. 60-131292, No. 60-13129
No. 4, No. 60-151097, No. 60-151.09
No. 8, No. 60-172591, No. 60-217266
No. 60-239289, No. 60-239291, No. 60-239292, No. 61-148269,
No. 61-244594, No. 61-255897, No. 61-284489, No. 61-368493, No. 6
No. 2-132684, No. 62-138291, No. 62
-191191, 62-255187, 62-
No. 288656, No. 62-311190, No. 63-1
No. 44089, Japanese Patent Application No. 62176625 (describing the dye of the following general formula).

In the formula, Ql contains at least one nitrogen atom and represents an atomic group necessary to form a nitrogen-containing heterocycle of 5 or more members or a carbon ring together with the bonded carbon atom, R1 represents an acyl group or a sulfonyl group, particularly a nitrogen-containing or oxygen heterocyclic carbonyl group, R2 represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, and R8 represents a hydrogen atom or a halogen atom, an alkoxy group or a carbon Number 1
~6 aliphatic group, R4 represents a halogen atom, an alkoxy group, or a C1-6 aliphatic group, and n is 0-4
represents an integer. R3 may be combined with R8, R2, or R1 to form a ring. R5 and R6 represent a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, or an aromatic group. R,
, R, may be combined with each other to form a ring. Also R5
and/or R6 may be combined with R4 to form a ring) are also preferably used.

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

The dye-donor layer is formed by selecting a dye so that a desired hue can be transferred when printed, and if necessary, arranging two or more dye-donor layers with different hues on one thermal transfer dye-donor material. Good too. For example, when printing each color repeatedly according to color separation signals to form an image such as a color photograph, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers, each containing a dye to be provided, are arranged. Alternatively, a dye-donating layer containing a dye that provides a black hue in addition to cyan, magenta, and yellow may be added. It is preferable to provide a mark for position detection at the same time as the formation of any of the dye-donating layers, since this eliminates the need for an ink or printing process separate from the formation of the dye-donating layer.

In order to prevent sticking due to the heat of the thermal head and improve slippage when printing from the back side of the dye-donating material, it is preferable to apply an anti-sticking treatment to the side of the support on which the dye-donating layer is not provided.

For example, it is preferable to provide a heat-resistant slip layer mainly consisting of (1) a reaction product of a polyvinyl butyral resin and an isocyanate, (2) an alkali metal salt or alkaline earth metal salt of a phosphoric acid ester, and (2) a filler. Polyvinyl butyral resins have a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110°C, and have a vinyl butyral portion of 15 to 40% by weight from the viewpoint of having many reaction sites with isocyanate. Good. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Toho Kagaku type Kafaq RD 720 or the like is used, and it is preferably used in an amount of about 1 to 50% by weight, preferably about 10 to 40% by weight based on the polyvinyl butyral resin. .

The heat-resistant slip layer may be functionally separated into a slip layer and a heat-resistant layer, and in this case, it is preferable that the heat-resistant layer be the one closer to the support. The heat-resistant layer contains a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral, polyvalent incyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and a titanium chelating agent, or polyester and an organic titanium compound. Can be used.

The dye-donor element may also be provided with a hydrophilic barrier layer to prevent diffusion of the dye towards the support. Hydrophilic dye barrier layers contain hydrophilic materials useful for their intended purpose. Generally excellent results with gelatin, poly(acrylamide), poly(isopropylacrylamide)
, Butyl Methacrylate Grafted Seratin, Ethyl Methacrylate Grafted Seratin, Cellulose Monoacetate, Methyl Cellulose, Poly(vinyl alcohol), Poly(ethyleneimine), Poly(acrylic acid), Poly(vinyl alcohol) and Poly(vinyl acetate) , a mixture of poly(vinyl alcohol) and poly(acrylic acid) or a mixture of cellulose monoacetate and poly(acrylic acid). Particularly preferred are poly(acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with a subbing layer. In the present invention, any undercoat layer may be used as long as it has the desired effect, but a preferred specific example is (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14:80:6).
), (butyl acrylate-2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear/saturated polyester such as Bostik 7650 (Emhart, Bostic) stick chemical group) or chlorinated high density poly(ethylene-trichloroethylene) resins.

There is no particular limit to the amount of undercoat layer applied, but it is usually 0.1
It is used in an amount of ~2.0 g/rri.

The thermal transfer image-receiving material used together with the thermal transfer dye-providing material of the present invention in carrying out the thermal transfer recording method will be described. This thermal transfer image-receiving material has an image-receiving layer capable of receiving at least one heat-transferable dye on a support.

The support used in the thermal transfer image-receiving material of the present invention can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, denting after transfer, etc. You can use anything. For example, synthetic paper (polyolefin-based, polystyrene-based, etc.), high-quality paper, art paper, coated paper, cast coated paper,
wallpaper, lined paper, synthetic resin or emulsion impregnated paper,
Paper supports such as synthetic rubber latex-impregnated paper, synthetic resin-loaded paper, paperboard, cellulose fiber paper, polyolefin-coated paper (especially paper coated on both sides with polyethylene), polyolefins, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, Various plastic films or sheets such as polycarbonate, films or sheets treated to impart white reflective properties to the plastic, and laminates made of any combination of the above may 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 is provided with a dye image-receiving layer.

This image-receiving layer accepts the heat-transferable dye transferred from the thermal transfer dye-providing material during printing, and contains a dye-receiving substance that functions to dye the heat-transferable dye alone or Thickness 0,5 including with other binder substances
It is preferable that the film has a thickness of about 50 μm.

Examples of dye-receiving polymers that are representative examples of dye-receiving substances include the following resins.

(a) Dicarboxylic acid components having ester bonds such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components contain sulfonic groups,
Polyester resins obtained by condensation of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc. with carboxyl groups (which may be substituted with carboxyl groups, etc.): polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl Polyacrylic acid ester resin or polymethacrylic acid ester resin such as acrylate: Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A No. 59-101395, No. 63-7971, No. 63-7972, and No. 63-79.
Examples include those described in No. 73 and No. 60-294862. In addition, commercially available products include Toyobo's Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130, Kao's ATR-2009, AT
R-2010 etc. can be used.

(b) Those with urethane bonds polyurethane resin, etc.

(c) Those with an amide bond polyamide resin, etc.

(d) Those with urea bonds urea resin etc.

(e) Those with a sulfone bond.

polysulfone resin, etc.

(f) Others having highly polar bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resins mentioned above, mixtures or copolymers thereof can also be used.

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

Specific examples of high boiling point organic solvents and thermal solvents include JP-A No. 6
No. 2-174754, No. 62-245253, No. 61
-209444, 61-200538, 62-
No. 8145, No. 62-9348, No. 62-30247
No. 62-136646.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which a dye-receiving substance is dispersed and supported in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but water-soluble polymers having a group capable of crosslinking with a hardening agent are preferred, and among them, gelatins are particularly preferred.

As a method for dispersing the dye-receiving substance in the water-soluble binder, any known dispersion method for dispersing a hydrophobic substance in a water-soluble polymer can be used. Typical methods include emulsifying and dispersing a dye-receiving substance dissolved in an organic solvent that is immiscible with water and mixing it with an aqueous solution of a water-soluble binder; There are methods such as mixing with an aqueous solution of

The image receiving layer may be one layer or may be composed of two or more layers. When two or more layers are provided, a synthetic resin with a low glass transition point is used for the layer near the support, or a high-boiling point organic solvent or a hot solvent is used to increase the dyeability of the dye.
For the outermost layer, use a synthetic resin with a higher glass transition point, or minimize the amount of high-boiling point organic solvents or hot solvents necessary, but do not use them to prevent stickiness on the surface, adhesion with other substances, and post-transfer. It is desirable to have a structure that prevents failures such as re-transfer of the dye to other substances and blocking with the thermal transfer dye-providing material.

The total thickness of the image-receiving layer is 0.5 to 50 μm, especially 3 to 30 μm.
In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to lum.

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.

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 theolite, 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 No. Shungiku Chapter 8, JP-A-61'-143
Examples include compounds described in No. 752 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyril compounds, and 2,5-dibenzooxazolethiophene compounds. Examples include.

Optical brighteners can be used in combination with antifade agents.

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 wax-like substances such as polyethylene wax, amide wax, and Teflon powder, difluorine-based surfactants, phosphate ester-based surfactants, paraffin-based, silicone-based oils, 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 oil, modified silicone oils such as carboxy-modified, amino-modified, and epoxy-modified silicone oils can be used.

Examples include various modified silicone oils described in the technical data "Modified Silicone Oil" published by Shin-Etsu Silicone ■, pages 6 to 188, page 1m. When used in an organic solvent-based binder, amino-modified silicone oil having a group that can react with the crosslinking agent of the binder (for example, a group that reacts with isocyanate) is also emulsified and dispersed in a water-soluble binder. is a carboxy-modified silicone oil (e.g. manufactured by Shin-Etsu Silicone):
Product name X, -22-3710) is valid.

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 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.

As metal complexes, US Patent No. 4. 241. 155
No. 4,245,018, columns 3 to 36, No. 4,
No. 254,195, columns 3 to 8, JP-A-62-17474
There are compounds described in Japanese Patent Application No. 1, No. 61-88256, pages (27) to (29), Japanese Patent Application No. 62-234103, Japanese Patent Application No. 62-31096, and Japanese Patent Application No. 62-230596.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
It is described on pages 125) to 137.

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

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

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be hardened with a hardening agent.

When curing organic solvent-based polymers, JP-A-61
Hardeners described in Japanese Patent No. 199997 and No. 58-215398 can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For curing water-soluble polymers, U.S. Patent No. 4,678.7
No. 39, column 41, JP-A-59-116655, 61
Hardeners described in Japanese Patent Nos. 245261 and 61-18942 are suitable for use.

More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, etc.), vinylsulfone hardeners (N, N'-ethylene-bis(vinylsulfonylatamide, etc.) ) ethane etc.)
, N-methylol hardener (dimethylol urea, etc.),
Alternatively, polymer hardeners (compounds described in JP-A No. 62-234157, etc.) may be used.

The thermal transfer image-receiving material may contain a fading inhibitor as described above in advance.

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, amphoteric surfactants, and cationic surfactants can be used. Specific examples of these are disclosed in JP-A-62-173463 and JP-A-62-173463.
It is described in No. 183457, etc.

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.

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 on page 29 of No. 1-88256, Japanese Patent Application No. 110064/1988, 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. Further, the anti-fading agent can also be transferred in the same manner.

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

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

For details on the thermal transfer recording method, see Japanese Patent Application Laid-open No. 603489.
You can refer to the description in No. 5.

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

Example 1 (Preparation of thermal transfer dye-providing material) A support with a thickness of 6 μm and whose back surface was subjected to heat-resistant slipping treatment
Using a polyethylene terephthalate film (manufactured by Ondai), a yellow dye-donating layer coating composition (1-1) having the following composition was coated on the surface of the film with a wire bar to a dry thickness of 1.5 μm. I applied it to make it look like this.

Coating composition for yellow dye-donating layer (1-1) Yellow dye 5g polyvinyl butyral 2.5g (electrification type Denka Butyral 5000A>Toluene
50g and 5g of yellow dye (Y) and magenta dye (
Coating compositions for magenta and cyan dye-donating layers were prepared in the same manner except that 2 g of cyan dye (C) was used, and a magenta layer (dry thickness: 1 g) was prepared next to the yellow layer.
．． 5μm), next to which is a cyan layer (dry thickness 1.5μm)
A thermal transfer dye-providing material Nα1 was prepared by coating in the following order.

Similarly, a thermal transfer dye-providing material Nα2 was prepared using a coating composition for a thermal transfer dye-providing layer (■-2) having the following composition.

Coating composition for thermal transfer dye-donating layer (1-2) (Denka Butyral 5000A manufactured by Denki Kagaku Co., Ltd.) The following were used as yellow dye (Y), magenta dye (M), and cyan dye (C).

Yellow dye (Y) l Magenta dye (M) Cyan dye (C) (Preparation of thermal transfer image-receiving material) Prepare resin-coated paper in which polyethylene is laminated to a thickness of 15 μm and 25 μm on both sides of a 200 μm paper, and An image-receiving layer coating composition (Hl) having the following composition was applied to the laminated surface by wire bar coating to a dry thickness of 10 μm, and dried to prepare a thermal transfer image-receiving material Nα101.

Coating composition for image-receiving layer (■~l) Polyester resin A" 15g Amino-modified silicone oil 0.3g (KF-85
7: Shin-Etsu Silicone) Polyisocyanate 1.4g (KP
-90: Dainippon Ink) Methyl ethyl ketone 40g toluene 40. g Polyester resin A' Similarly, a coating composition for thermal transfer image-receiving layer (I
[-2), thermal transfer image-receiving materials k102 to k105 were produced.

Coating composition for image-receiving layer (■ 2) (KP-90 manufactured by Dainippon Ink) Thermal transfer dye-providing material Nαl~ obtained as above
2 and the thermal transfer image-receiving material Nα101 to 105 are superimposed so that the thermal transfer dye-providing layer and the image-receiving layer are in contact with each other, and using a thermal head from the support side of the thermal transfer dye-providing material, the output of the thermal head is 0° 25 W/dot, Pulse width 0. 15-15m5ec, dot density 6 dots/II
Heating was performed under the conditions of Im to perform full color transfer recording on the image receiving layer of the thermal transfer image receiving material.

These transferred materials were transferred to a fluorescent lamp tester (150001ux
) for 7 days to examine light resistance. The results when the yellow dye was transferred are shown in Table 3, 1 to 3.

Table 1 Table (Performance evaluation in yellow) Ultraviolet absorber tc, Hs (2) tc, He (3) tc, He From the above examples, it can be seen that by the present invention, ultraviolet rays are applied to both the thermal transfer dye-providing material and the thermal transfer image-receiving material. It has been found that recording using a thermal transfer material containing an absorber significantly improves the light fastness and density of images compared to when an ultraviolet absorber is used alone or when no ultraviolet absorber is used.

Further, when similar experiments were conducted using the image-receiving material 106 and the dye-donating material 1, the dye residual rate was 80.0%, and the Dma
x2. It was 22. This shows that the effects of the present invention cannot be obtained simply by increasing the amount of ultraviolet absorber used in the image-receiving material.

Furthermore, similar experiments were conducted with the type of ultraviolet absorber changed to the one shown below, and it was found that by adding it to both the dye-providing material and the image-receiving material, improvements in fading and image density were observed.

Optical dye-donating material (effects of the invention) Since the thermal transfer material of the present invention contains an ultraviolet absorber in both the thermal transfer dye-providing layer and the thermal transfer image-receiving layer, the recorded image has high light resistance. This makes it possible to provide notebook copies whose colors do not easily fade even when stored for a long period of time. The ultraviolet absorber also acts as a plasticizer and can provide a highly concentrated hard copy.

Claims (5)

[Claims] (1) Thermal transfer consisting of a thermal transfer dye-providing material having a dye-donating layer containing a heat-transferable dye on a support and a thermal transfer image-receiving material having a dye-receiving layer on the support that receives the dye that migrates during heating. A thermal transfer material, characterized in that an ultraviolet absorber is used in both the thermal transfer dye-providing material and the thermal transfer image-receiving material. (2) The thermal transfer material according to claim 1, wherein the thermal transfer dye-providing material contains an ultraviolet absorber in the dye-providing layer. (3) The thermal transfer dye-providing material according to claim 1, wherein the thermal transfer dye-providing material contains an ultraviolet absorber in a layer separate from the dye-providing layer. (4) The thermal transfer image-receiving material according to claim 1, wherein the thermal transfer image-receiving material contains an ultraviolet absorber in the dye image-receiving layer. (5) Thermal transfer, characterized in that the thermal transfer dye-providing material according to claim 1 and the thermal transfer image-receiving material are brought into contact and imagewise heated to transfer the dye and ultraviolet absorber from the thermal transfer dye-providing material to the thermal transfer image-receiving material. Image forming method.