JPH044187A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To obtain a high-density image by a method wherein a polymerization initiator initiating a polymerization reaction by being heated at the time of thermal transfer and a polymerizable compound are incorporated in an image receiving layer or an intermediate layer provided between the image receiving layer and a substrate. CONSTITUTION:As a polymerization initiator used for a thermal transfer image receiving material, an azo compound and a peroxide are exemplified. The use of those acting as a polymerization initiator at approximately 40 deg.C or higher prevents a heat generation effect of the polymerization reaction of the thermal transfer image receiving material from deteriorating under storage before conducting thermal transfer. As a polymerizable compound used for the thermal transfer image receiving material, an ethylene unsatd. group-containing compound, an epoxy group-containing compound, or the like is used. The polymerization initiator and the polymerizable compound contained in the dye receiving layer or an intermediate layer initiate a polymerization reaction by being heated by a thermal heat at the time of thermal transfer. A heat generation subsequent to the reaction increases an average temp. in the dye receiving layer during thermal transfer and extends a high temp. holding time after heat application, thus realizing a high-density image.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermal transfer image-receiving material used in a thermal transfer recording method, and particularly to a thermal transfer image-receiving material capable of obtaining high-density images.

(Prior art) In recent years, 2. With rapid development, 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. . 20 There are two main types of thermal transfer recording methods: thermal melting type and thermal transfer type. In the latter method, a thermal transfer dye-providing material having a dye-providing layer containing a binder and a heat-transferable dye on a support is superimposed on a thermal transfer image-receiving material, and heat is applied from the support side of the dye-providing material to create a pattern formed by the thermal application. This is a method of obtaining a transferred image by transferring a heat-transferable dye onto a recording medium (thermal transfer image-receiving material).

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

(Problems to be Solved by the Invention) However, conventional thermal transfer image-receiving materials have a problem in that the obtained images do not have sufficient density. Furthermore, if the energy applied to the thermal head during thermal transfer is increased in order to improve the density of the image on the thermal transfer image-receiving material where the transferred image density is insufficient, there is a problem that the durability of the thermal head deteriorates.

(Means for Solving the Problems) The above-mentioned problems can be solved in a thermal transfer image-receiving material having an image-receiving layer capable of receiving a dye on a support.
The problem was solved by a thermal transfer image-receiving material characterized in that an intermediate layer provided between the image-receiving layer and the support contains a polymerization initiator and a polymerizable compound that initiates a polymerization reaction when heated during thermal transfer.

In the present invention, the polymerization initiator and polymerizable compound contained in the dye image-receiving layer and the intermediate layer are compounds that initiate a polymerization reaction when heated from a thermal head during thermal transfer. A polymerization reaction between a polymerization initiator and a polymerizable compound generally generates heat along with the reaction. When an exothermic polymerization reaction occurs in the dye image-receiving layer or intermediate layer during thermal transfer,
The average temperature in the dye image-receiving layer during thermal transfer increases, and the high temperature retention time after heat application also increases. As a result, a thermal transfer image-receiving material containing a polymerization initiator that causes an exothermic polymerization reaction and a polymerizable compound can provide a higher image density than a thermal transfer image-receiving material that does not contain the polymerization initiator and polymerizable compound.

Therefore, it is essential that the polymerization initiator and the polymerizable compound that initiate the polymerization reaction by heating the thermal head are compounds that cause an exothermic polymerization reaction.

Examples of polymerization initiators used in thermal transfer image-receiving materials include:
Examples include ab compounds and peroxides.

Among the polymerization initiators, those that act as an initiator for polymerization at about 40"C or higher are preferable. This prevents the exothermic effect of the polymerization reaction of the thermal transfer image-receiving material from deteriorating during storage before thermal transfer. 80°C
Examples of polymerization initiators that act as polymerization initiators at higher temperatures include cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, and di-t-butyl peroxide. Typical polymerization initiators that act as initiators include hendyl peroxide, lauroyl peroxide, potassium persulfate, and azobisisobutyronitrile.

Specific examples of the polymerization initiator are shown below, but the polymerization initiator of the present invention is not limited thereto.

Examples of polymerizable compounds used in thermal transfer image-receiving materials include compounds having ethylenically unsaturated groups and compounds having epoxy groups.

Examples of compounds having ethylenically unsaturated groups that can be used in thermal transfer image-receiving materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, anhydrous maleic acid, maleic esters,
Examples include itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

Preferred specific examples of polymerizable compounds include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, dicyclohexyloxyethyl Acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate,
Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diacrylate of polyoxyethylated bisphenol A, diacrylate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane condensate, 2,2-dimethyl- Triacrylate of 3-hydroxypropionaldehyde and pentaerythritol condensate, triacrylate of propylene oxide adduct of trimethylolpropane, polyacrylate of hydroxypolyether,
Examples include polyester acrylate and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, Examples include pentaerythritol tetramethacrylate and polyoxyalkylenated bisphenol A dimethacrylate.

The above polymerization initiators and polymerizable compounds may be used singly and in combination, or two or more polymerization initiators and two or more polymerizable compounds may be used in combination.

The content of the polymerizable compound is 0.5 g/rtf to 10 g
/rd is preferred, and the polymerization initiator is preferably contained in an amount of 0.1% to 100% by weight based on the content of the polymerizable compound.

When the content of the polymerizable compound is 0.5 g/rrr or less, even if the polymerization initiator is contained from 0.1% to 100% by weight based on the polymerizable compound, the image density will not improve due to the heat generated by the polymerization reaction. The inside becomes smaller. In addition, the content of polymerizable compounds is 1
0g/n (in the case above, the polymerizable compound seeps into the image-receiving layer of the image-receiving material, causing defects such as blocking.

As the polymerization initiator and the polymerizable compound, either an organic solvent-soluble compound or a water-soluble compound can be used.

When both the polymerization initiator and the polymerizable compound are compounds soluble in an organic solvent, the following methods can be mentioned as the addition method.

■ A method of applying a liquid obtained by dissolving a polymerization initiator and a polymerizable compound in an organic solvent ■ A method of applying a liquid in which a polymerization initiator and a polymerizable compound are dissolved or dispersed in a resin dissolved in an organic solvent■ A method of applying a liquid in which a polymerization initiator and a polymerizable compound are dissolved or dispersed in a resin In the method ■ ■ of applying a dispersion obtained by dispersing a liquid dissolved in a polymerizable compound or a liquid obtained by adding an organic solvent or a resin dissolved in an organic solvent to this liquid in a water-soluble binder, a polymerization initiator and Method for applying a liquid obtained by microcapsulating oil droplets of a polymerizable compound Various known techniques can be applied to the microcapsules without any particular limitations. Examples include U.S. Pat. No. 2,800,457 and U.S. Pat. -19
Interfacial polymerization methods described in U.S. Pat. No. 574, No. 42-446, and Miscellaneous Publication No. 42-771; Methods by precipitation of polymers described in U.S. Pat. Nos. 3,418,250 and 3,660,304; Described in U.S. Pat. A method using the isocyanate-polyol wall material described in U.S. Pat. No. 3,914,511; A method using the isocyanate wall material described in U.S. Pat. No. 4,001,140, U.S. Pat. No. 4,087,376, and U.S. Pat. Alternatively, a method using a urea-formaldehydelene-lucinol-based wall forming material; melamine-
Method using wall-forming materials such as formaldehyde resin and hydroxypropyl cellulose; in-5-itu method by polymerization of monomers described in Japanese Patent Publication No. 36-9168 and Japanese Patent Application Laid-Open No. 51-9079; British Patent No. 927807
Polymerization dispersion cooling method described in the specifications of No. 1 and No. 965,074; US Pat. No. 3,111,407 and British Patent No. 9
Examples include the spray drying method described in the specification of 30422 Miscellaneous Notes. Although the method of microencapsulating oil droplets of a polymerizable compound is not limited to the above,
Particularly preferred is a method in which a core substance is emulsified and then a polymer membrane is formed as the microcapsule wall.

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

General specific examples of supports are listed below.

■Synthetic paper (polyolefin-based, polystyrene-based, etc. synthetic paper), ■High-quality paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin interior Paper supports such as paperboard, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene);
Various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc., and films or sheets processed to give white reflective properties to these plastics.

Moreover, a laminate formed by any combination of the above items (1) to (2) can also be used.

Among these, polyolefin coated paper is preferred because it has features such as not causing concave deformation due to heating during thermal transfer, excellent whiteness, and little curling.

Polyolefin coated paper is described, for example, in "Fundamentals of Photographic Engineering (Silver Salt Photography Edition)" edited by the Photographic Society of Japan (published by Corona Publishing, 1979), pages 223-240.

This polyolefin coated paper basically consists of a support sheet and a polyolefin layer coated on the surface of the support sheet. The support sheet is made of something other than synthetic resin, and -
High-quality paper is used for boat fishing. The polyolefin coat may be applied by any method as long as the polyolefin layer is in close contact with the surface of the support sheet, but it is usually applied by an extrusion method. The polyolefin coat layer may be provided only on the surface of the support sheet on which the receiving layer is provided, but it may also be provided on both the front and back surfaces. Examples of polyolefins used include high density polyethylene, low density polyethylene,
Examples include polypropylene, but any material may be used. However, considering the heat insulation effect during transfer, it is preferable to use low-density polyethylene, which has lower thermal conductivity, on the side where the receiving layer is provided.

The thickness of the polyolefin coat is not particularly limited, but it is usually preferably 5 to 100 microns on one side. However, in order to obtain a higher transfer density, the thickness of the polyolefin coat on the receiving layer side is preferably thinner.

Pigments and fillers such as titanium oxide and ultramarine may be added to the polyolefin coat to increase whiteness, and the polyolefin coated paper has a pigment of 0.05 to A thin gelatin layer of about 0.4 g/rd may be provided.

The thermal transfer image-receiving material is provided with a dye image-receiving layer.

This image-receiving layer receives 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 hardness of about 50-50.

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 Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK140, Byron GK-130 manufactured by Toyobo, ATR-2009 and ATR manufactured by Kao.
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.

Examples of high boiling point organic solvents include JP-A-59-83154;
No. 59-178451, No. 59-178452, No. 59-178453, No. 59-178454, No. 5
Ester 1 as described in No. 9-178455, No. 59-178457, etc. (For example, compounds such as phthalic acid esters, phosphoric acid esters, fatty acid esters, amides (such as fatty acid amides, sulfamides, ethers, alcohols, paraffins, silicone oils, etc.) can be mentioned.

As a thermal solvent, it must be: - compatible with the dye but incompatible with the water-soluble binder; - solid at room temperature, but melts when heated by the thermal head during transfer (i.e., does not mix with other components). Compounds are used that have the following properties: (1) they do not decompose when heated with a thermal head; Preferably 35
~250"C1 exhibits a melting point of especially 35-200°C, (
Compounds having an inorganic/organic) value of <1,5 are preferred.

Here, inorganicity and organicity are concepts for predicting the properties of compounds.
9 (1957).

Specific examples of high boiling point organic solvents and thermal solvents include JP-A-62-174754, JP-A-62-245253, and JP-A-62-245253.
No. 1-209444, No. 61-200538, No. 62
-8145, 62-9348, 62-3024
No. 7 and No. 62-136646.

The high-boiling organic solvent and/or thermal solvent can be used alone in microdispersed form in the image-receiving layer, or can be used in combination with a heat-accepting polymer.

Further, the above-mentioned high boiling point organic solvent may be used for the purpose of improving slipperiness, peelability, curl balance, etc.

The image-receiving layer of the thermal transfer image-receiving material of the present invention 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 a water-soluble polymer having a group capable of crosslinking with a hardening agent is preferred.

The water-soluble polymers used in the present invention include vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyridinium, cation-modified polyvinyl alcohol, and derivatives thereof (Japanese Patent Application Laid-Open No. 60-14587
No. 9, No. 60-220750, No. 61143177, No. 61-235182, No. 61-245183,
61-237681, 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid-methacrylic acid copolymer or its salt, polymethacrylic acid or its salt. salt, acrylic acid
Polymers containing acrylic groups such as vinyl alcohol copolymers or salts thereof (JP-A No. 60-168651, No. 62
-9988), starch, oxidized starch, acetic acid starch, amine starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin,
Natural polymers or their derivatives such as sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose (JP-A-59-174
No. 382, No. 60-262685, No. 61-1431
No. 77, No. 61-181679, No. 61-19387
No. 9, No. 61-287782), polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, maleic acid-acetate M-vinyl comonomer, maleic acid-N-vinylpyrrolidone copolymer, maleic acid-alkyl vinyl ether copolymer , synthetic polymers such as polyethyleneimine (JP-A-61-32787, JP-A-61-32787;
237680, 61-277483) and the water-soluble polymers described in JP-A-56-58869.

Furthermore, various copolymers made water-solubilized by heptamer components containing SO3- groups, COO- groups, SO2- groups, etc. can also be used.

It is particularly preferable to use gelatin as the water-soluble binder because it can be dried in a set manner and the drying load is much lower. Specifically, gelatin and its derivatives such as lime-treated gelatin, decalcified lime-treated gelatin, acid-treated gelatin, phthalated gelatin, acetylated gelatin, succinated gelatin, Bull, Soc, Phot,
Japan, No. 16. Enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in P2O (1966) can be mentioned.

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

The water-soluble binder and the dye-receiving substance have a weight ratio of dye-receiving substance/water-soluble binder=1 to 2o, preferably 2o.
~IO1 is particularly preferably used in the range of 2.5 to 7.

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 providing two or more layers, use a synthetic resin with a low glass transition point for the image-receiving layer closer to the support, or use a high-boiling point organic solvent or hot solvent to increase the dyeability of the outermost layer. Use synthetic resins with higher glass transition points, minimize the amount of high-boiling point organic solvents and thermal solvents required, or avoid using them to prevent surface stickiness, adhesion with other substances, and dyes after transfer. It is desirable to have a structure that prevents failures such as retransfer to other substances and blocking with the thermal transfer dye-providing material.

The total thickness of the image receiving layer is 0.5 to 50-1, especially 3 to 30μ.
, in the case of a two-layer structure, the outermost layer is 0.1 to 20I! a, especially 0.2-10I! It is preferable to set it in the range of m.

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

Depending on the material it is made of, the intermediate layer may be a Kunjeong layer, a porous layer, or a porous layer.
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.

When using a water-soluble polymer as a binder for a porous layer, there are two methods: 1. Dispersing porous particles in a water-soluble polymer and coating and drying. 2. Applying a water-soluble polymer liquid with air bubbles generated by mechanical punching. 3) The water-soluble polymer solution containing a foaming agent is foamed before coating or foamed during the coating drying process. 4) An aqueous solvent (preferably one with a boiling point lower than water) is added to the water-soluble polymer solution. high solvent)
It can be formed by a method such as emulsifying and dispersing, forming microvoids in the process of coating and drying.

When using an organic solvent-soluble binder as the porous layer, 1) a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate-butadiene system is mechanically stirred to support a liquid in which air bubbles are generated; 2) Apply the above synthetic resin emulsion or synthetic rubber latex mixed with a foaming agent onto the support and dry it. 3) Synthetic resin such as PVC plastisol, polyurethane, or styrene-butadiene type. 4) A solution of thermoplastic resin or synthetic rubber mixed with a foaming agent is applied onto a support and foamed by heating. A mixed solution with a non-solvent (including those whose main component is water) that is easily compatible with the organic solvent and has no solubility in the thermoplastic resin or synthetic rubber is applied onto the support. A method such as drying to form a microporous layer can be used.

If the image-receiving layer is on both sides of the support, the intermediate layer may be provided on both sides, or may be provided on only one side.

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

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

A fluorescent whitening side may be used in the thermal transfer image receiving material.

Examples include K. Veenkataraman, ed.
The Chewistry of 5yntheti
c Dyes” Volume Chapter 8, JP-A-61-1437
Examples include compounds described in No. 52 and the like. More specifically, stilbenzene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dihenzoxazolethiophene compounds, etc. can be mentioned. The fluorescent whitening side can be used in combination with an anti-fading agent.

The thermal transfer dye-providing material used in the present invention is a thermal transfer dye-providing material having a dye-providing layer containing a heat-transferable dye on a support, in which the dye is transferred in a pattern by applying heat to the image-receiving material of the thermal transfer image-receiving material. A thermal transfer dye-providing material having a heat-melting ink layer (dye-donating layer) on a support and a thermal transfer image-receiving material in which the ink is melted in a pattern by applying heat. This includes two types that are recorded by being transferred to a computer.

The dye-donor layer is formed by selecting a dye so that the desired hue can be transferred when printed, and if necessary, arranging two or more dye-donating layers with different dyes on one thermal transfer dye-donating material. Good too. For example, when printing each color repeatedly according to color separation signals to form an image such as a color photograph, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing the dye to be provided are arranged.

Alternatively, a dye-donating layer containing a dye that gives a black hue in addition to cyan, magenta, and yellow may be added; however, when forming these dye-donating layers, the formation of any one of the dye-donating layers and It is preferable to provide a mark for position detection at the same time, since no ink or printing process separate from the formation of the dye-donating layer is required.

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

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 mm.
-, an undercoat layer may be provided if necessary. Further, a dye diffusion prevention layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer, thereby further improving 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-donor material; this slipping layer may contain a lubricating material, such as a surfactant, solid or liquid, with or without a polymeric binder. Consists of lubricants or mixtures thereof.

A thermal transfer dye-providing material using a heat-transferable dye basically has a dye-providing layer on a support containing a dye that sublimes under heat but becomes mobile and a binder. This thermal transfer dye-providing material is prepared by preparing a coating solution by dissolving or dispersing a dye that sublimes under heat but becomes mobile and a binder resin in an appropriate solvent, and applying this to one side of a support. The thermal transfer layer can be obtained by applying and drying the coating amount to give a dry film thickness of, for example, about 0.2 to 5-1 m, preferably 0.4 to 2 m, 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, for example, disperse dyes, basic dyes, oil-soluble dyes, etc. can be mentioned, but in particular, Sumikaron Yellow E
4GL, Dianix Yellow 82G-FS.

Miketon Boliertel Yellow 3GSL, Kayasset Yellow 937, Sumikalon Red EFBL, Dianix Red ACE, Miketon Boliertel Red FB.

Kayasset Red 126, Miketon Fast Brilliant Plue B, Kayasset Blue 136, etc. are preferably used. Other known heat-transferable dyes can also be 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-2-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride resins (e.g. vinyl chloride-vinyl acetate) copolymers), polycarbonate resins, polystyrene, polyphenylene oxide, cellulose resins (e.g. methylcellulose, ethylcellulose, carboxymethylcellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate), polyvinyl Alcohol resins (for example, partially saponified polyvinyl alcohols such as polyvinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, coumaron-indene resins, terpene resins, and polyolefin resins (for example, polyethylene and polypropylene) are used.

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

In the present invention, any conventionally known ink solvent can be freely used as the ink solvent for dissolving or dispersing the above pigment and binder resin.

A second embodiment of the thermal transfer dye-providing material is an embodiment in which the thermal transfer layer is a thermal melt transfer layer composed of an ink for forming a thermal transfer layer consisting of a wax containing a coloring agent such as a dye or a pigment. This ink is made by distributing and dispersing colorants such as carbon black and various dyes and pigments using waxes with appropriate melting points, such as paraffin wax, microcrystalline wax, carnauba wax, and urethane wax, as a binder. It is what it is. The ratio of the colorant and wax used is preferably such that the colorant accounts for about 10 to 65% by weight in the hot-melt transfer layer to be formed, and the thickness of the layer to be formed is about 1.5 to 6.0 tm. The manufacture of the ink and its application to the support, in which the range is preferred, can be carried out according to known techniques.

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, in order to prevent stinking due to the heat of samarheside and improve slippage.

For example, polyvinyl butyral resin is preferably provided with a heat-resistant slip layer mainly consisting of: ■ main reaction product of polyvinyl butyral resin and isocyanate, ■ alkali metal salt or alkaline earth metal salt of phosphoric acid ester, and ■ filler. It is preferable to have a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110°C, and a vinyl butyral moiety of 15 to 40% by weight from the viewpoint of having many reaction sites with incyanate. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafac RD720 manufactured by Toho Chemical Co., Ltd. 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. .

It is desirable that the lower layer of the heat-resistant slip layer has heat resistance.
A combination of a synthetic resin that can be cured by heating and its curing agent,
For example, a combination of polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelate, or polyester and organic titanium compound may be provided by coating.

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 gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly(vinyl alcohol), poly(ethyleneimine), poly(acrylic acid), poly(vinyl alcohol) and poly(vinyl acetate) It is obtained by using a mixture, a mixture of poly(vinyl alcohol) and poly(acrylic acid) or a mixture of cellulose monoacetate and poly(acrylic #). Particularly preferred are poly(acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has the desired effect, but preferred specific examples include (acrylonitrile-vinylidene chloride-acrylic 1!I) copolymer Combined (weight ratio 14:80
:6), (butyl acrylate-methacrylate #-2-aminoethyl-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear/saturated polyester such as Bostick 7650 (Mhart) , Bostic 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
~2.0g/n? used in amounts of

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.

Examples of mold release agents include solid or waxy substances such as polyethylene wax, amide wax, and Teflon powder; surfactants such as fluorine-based and phosphate esters; and conventionally known oils such as paraffin-based, silicone-based, and fluorine-based oils. 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 on pages 6 to 18B of the "Modified Silicone Oil" technical data published by Shin-Etsu Silicone ■. When used in an organic solvent-based binder, amino-modified silicone oil having a group that can react with the crosslinking agent of this binder (for example, a group that can react with isocyanate) is used after being emulsified and dispersed in a water-soluble binder. For example, carboxy-modified silicone oil (for example, Shin-Etsu Silicone ■: trade name X-22-3710) is effective.

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. Pat.
No. 39, column 41, JP-A-59-116655, JP-A No. 62
Hardeners described in Japanese Patent Nos. 245261 and 61-18942 are suitable for use. More specifically, aldehyde-based hardeners (such as formaldehyde), aziridine-based hardeners, epoxy-based hardeners, and vinylsulfone-based hardeners (N,N'-ethylene-bis(
(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), and polymer hardeners (compounds described in JP-A-62-234157, etc.).

Antifading agents may be used in thermal transfer dye-providing materials and thermal transfer image-receiving materials, such as antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compound disclosed in Japanese Patent Application Laid-open No. 159644/1983 is also effective.

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, benzophenone compounds (JP-A-56-2784, etc.), and other JP-A-54-48535, JP-A No. 62-13
There are compounds described in No. 6641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
Same No. 4,245,018 No. 3-366! , No. 4, 2
No. 54,195, columns 3 to 8, JP-A-62-174741
No. 61-88256, pages (27) to (29), Japanese Patent Application No. 62-234103, No. 62-31096, No. 6
There are compounds described in No. 2-230596 and the like.

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

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

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

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

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

In addition, when dispersing substances that can accept heat-transferable dyes, mold release agents, anti-fading agents, ultraviolet absorbers, optical brighteners, and other hydrophobic compounds in a water-soluble binder, the interface is used as a dispersion aid. It is preferable to use surfactants; 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, etc. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57 -9053 No. 8 to 1711
, JP-A-61-20944, JP-A No. 62-135826
Hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil, or solid fluorine compound resins such as tetrafluoroethylene resin are mentioned.

A capping 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 corresponding to image information is applied from either side, preferably from the back side of the thermal transfer dye-providing material, by a heating means such as a thermal helad. By applying this, the dye in the dye-donating layer can be transferred to the thermal transfer image-receiving material according to the magnitude of heating energy, and a color image with excellent clarity and resolution and gradation can be obtained.

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

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

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

EXAMPLES The present invention will be explained in more detail by way of Examples below.

Example 1 (Preparation of thermal transfer dye-providing material) A 5.5-thick polyethylene terephthalate film with a heat-resistant slipping layer made of a thermosetting acrylic resin on one side (
Lumirror Nitoshi Co., Ltd.) was used as a support, and on the side opposite to the side on which the heat-resistant slipping layer was provided, a coating composition for forming a thermal transfer dye-donating layer having the following composition was coated with a wire bar, after drying. A thermal transfer dye-providing material was obtained by coating to a thickness of 2-.

Disperse dye-a Polyvinyl butyral resin 5000-A: manufactured by Denki Kagaku) Methyl ethyl ketone toluene polyisocyanate product] Disperse dye-a g (Denka butyral g 0yd 0m (Takenate DIION: Takeda Yakuhin 0.2+d Preparation) As a support, synthetic paper with a thickness of 150 mm (manufactured by Tamago Yuka Co., Ltd.) was used.
Thermal transfer image-receiving material 1 was prepared by applying a coating composition for an image-receiving layer having the following composition to the surface using wire bar coating so that the dry thickness was 15 - using Y[1PO-FPG-150). . Drying was performed in an open air condition at a temperature of 50° C. for 16 hours after temporary drying with a dryer.

As a polymerization initiator, 1,1'-azobis(cyclohexane-1-carbonitrile) was used, and as a polymerizable compound, compound A was used.

Polyester resin a 20g1,1
'-azobis(cyclohexane-1-carbonitrile)
0.5 g Compound A
5g amino-modified silicone oil (KF-857: manufactured by Shin-Etsu Silicone)
1g polyisocyanate (KP-907
(manufactured by Dainippon Ink) g Methyl ethyl ketone 85H1 Toluene 85m The structure of polyester resin a and the compound is shown below (the numerical value of each monomer component of polyester resin a is mol%).

TPA TPA SIP^ EG BrS-A-EG Polyester resin-a 24.3 24.3 1.6TPA
: Terephthalic acid [PA : Isophthalic acid EG: Ethylene glycol Example 2 The same content as in Example 1 was used as the thermal transfer dye-providing material.

(Preparation of Thermal Transfer Image-Receiving Material 2) On the surface of a support having the same contents as Image-receiving material 1, a coating composition for the lower layer of the image-receiving layer having the following composition was applied by wire bar coating so that the dry thickness was 10-.

Polyester resin a 20g1.1
'-azobis(cyclohexane-1-carbonitrile)
0.5g compound A
5g amino-modified silicone oil (KF-8577 manufactured by Shin-Etsu Silicone)
1 g Polyisocyanate (KP-90: manufactured by Dainippon Ink) g Methyl ethyl ketone 85 m Toluene 85 m On the lower layer of the above image-receiving layer, apply a coating composition for the upper layer of the image-receiving layer having the following composition by wire bar coating to a dry thickness of 5-. Thermal transfer image-receiving material 2 was prepared by coating as follows.

The drying method was the same as in Example 1.

Polyester resin a 20g Amino-modified silicone oil (KF-857: manufactured by Shin-Etsu Silicone) 1g Polyisocyanate (KP-90: manufactured by Dainippon Ink) g Methyl ethyl ketone 85d Toluene 85M1 Example 3 The thermal transfer dye-providing material was the same as in Example 1. I used something.

(Preparation of thermal transfer image-receiving material 3) A composition having the same content as the coating composition for the lower layer of the image-receiving layer of image-receiving material 2 was applied to the surface of a support having the same content as image-receiving material 1 so that the dry thickness was 110 l1. Then, a composition having the same contents as the image-receiving layer coating composition of image-receiving material 1 was coated thereon so that the dry thickness was 5-5, to prepare thermal transfer image-receiving material 3. The drying method was the same as in Example 1.

Example 4 The same thermal transfer dye-providing material as in Example 1 was used.

(Preparation of thermal transfer image-receiving material 4) Prepare resin-coated paper in which polyethylene is laminated to a thickness of 15t1m and 25mm on both sides of a 200m paper, and image-receiving material 2 is placed on the laminated surface of 15μ thickness as a lower layer of the image-receiving layer. A composition in which the polyester resin a of the paint composition for the image receiving layer was replaced with Vylon 280 manufactured by Toyobo was applied to a dry thickness of 10 m, and on top of this, the polyester resin of the paint composition for the image receiving layer of the image receiving material 1 was applied. a,
Thermal transfer image-receiving material 4 was prepared by applying a composition substituted with Toyobo's Vylon 280 so that the dry thickness was 5-.

The drying method was the same as in Example 1.

Example 5 The thermal transfer dye-providing material used was the same as in Example [1].

(Preparation of thermal transfer image-receiving material 5) A coating composition for an image-receiving layer having the following composition was coated on the surface of a support having the same contents as image-receiving material 1 by wire bar coating so that the dry thickness was 15 m to prepare a thermal transfer image-receiving material. 5
was created. The drying method was the same as in Example 1.

Polyester resin a 10g Vinyl chloride-vinyl acetate copolymer resin 10g 1.1'-azobis (cyclohexane-1-carbonitrile)
0.5g compound A
5g amino-modified silicone oil (KF-
857: Made by Shin-Etsu Silicone)
1 g Polyisocyanate (KP-90: manufactured by Dainippon Ink) g Methyl ethyl ketone 85id Toluene 85M1 Example 6 The same content as in Example 1 was used as the thermal transfer dye-providing material.

(Preparation of Thermal Transfer Image-Receiving Material 6) A coating composition for the lower layer of the image-receiving layer having the following composition was coated on the surface of a support having the same content as that of image-receiving material 1 by wire bar coating so that the dry thickness was 104.

The following coating composition is prepared by mixing Preparation Liquid A and Preparation Liquid B,
The mixture was heated to 60°C and stirred for 10 minutes using a high-speed stirrer (10,000 rpm) to form a dispersion.

Cm liquid A>1.1'-azobis(cyclohexane-1-carbonitrile') 1. Og compound A
10.0 g (1i liquid B) Polyvinylpyrrolidone 10 wt% aqueous solution 100 g Compound B 15 wt% aqueous solution 7.0 g The structure of compound B is shown below.

Compound B ~=206.3 Furthermore, a composition having the same contents as the coating composition for the image-receiving layer of Image-receiving material 1 was applied thereon so that the dry thickness was 5a to prepare thermal transfer image-receiving material 6. .

The drying method was the same as in Example 1.

Comparative Example 1 The same thermal transfer dye-providing material as in Example 1 was used.

(Preparation of thermal transfer image-receiving material 7) A composition having the same contents as the coating composition for the upper layer of the image-receiving layer of Example 2 was applied to the surface of a support having the same contents as image-receiving material 1 so that the dry thickness was 151 m. A thermal transfer image-receiving material 7 was prepared.

Comparative Example 2 The same thermal transfer dye-providing material as in Example 1 was used.

(Preparation of thermal transfer image-receiving material 8) A composition in which the polyester resin a of the coating composition for the upper layer of the image-receiving layer of Example 2 was replaced with Vylon 280 manufactured by Toyobo was applied to the surface of a support having the same contents as image-receiving material 4. The thickness of
A thermal transfer image-receiving material 8 was prepared by applying the coating to a thickness of 5 m.

Comparative Example 3 The same thermal transfer dye-providing material as in Example 1 was used.

(Preparation of thermal transfer image-receiving material 9) A coating composition for an image-receiving layer having the following composition was coated on the surface of a support having the same content as in Example 1 by wire bar coating so that the dry thickness was 15-1, and thermal transfer was performed. Image receiving material 9
was created. The drying method was the same as in Example 1.

Tun polyester resin a 10g Vinyl chloride-vinyl acetate copolymer resin 10g Amino-modified silicone oil (KF-857: manufactured by Shin-Etsu Silicone)
Ig polyisocyanate (K
P-90: Dainippon Ink) g Methyl ethyl ketone 85m Toluene 85d Comparative example 1.2 above
．． The method for drying the thermal transfer image-receiving material in Example 3 was the same as in Example 1.

The thermal transfer dye-providing material and the thermal transfer image-receiving material obtained as described above are superimposed so that the dye-providing layer and the image-receiving layer are in contact with each other. Output 0.25W/dot, pulse width 0.15-15ssec, dot density 6
Confidence printing was performed under the conditions of dot/■-, and the magenta dye was imagewise dyed on the image-receiving layer of the thermal transfer image-receiving material.

The reflection density of the saturated portion (Dmax) of the recorded thermal transfer image-receiving material was measured using a Status A filter, and the results are shown in Table 1.

Claims (1)

[Claims] In a thermal transfer image-receiving material having an image-receiving layer capable of receiving a dye on a support, a polymerization reaction is initiated in the image-receiving layer or an intermediate layer provided between the image-receiving layer and the support by heating during thermal transfer. A thermal transfer image-receiving material characterized by containing a polymerization initiator and a polymerizable compound.