JPH03126582A - Thermal transfer image-receiving material - Google Patents

Abstract

PURPOSE:To improve a transfer density and to enhance a resistance to light by a method wherein an image receiving layer is made of a composition obtained by dispersing a dye accepting substance in a water-soluble binder, and a codispersion of an ultraviolet absorber and a plasticizer having a specific (organic/inorganic) value is contained in an upmost layer of an image receiving material. CONSTITUTION:An image receiving layer is made of a composition obtained by dispersing a dye accepting substance in a water-soluble binder, and a codispersion of an ultraviolet absorber and a plasticizer is contained in an upmost layer of image receiving surface forming layers of an image receiving material. The substance capable of accepting a thermally migrating dye is a polymer having an ester linkage, a urethane linkage, an amide linkage, a urea linkage, or a sulfone linkage. As the water-soluble binder, a water-soluble polymer having a group capable of crosslinking by a hardener is preferably used. As the ultraviolet absorber, for example, a benzotriazole compound substituted by an aryl group can be used. The plasticizer is a compound having an (organic/inorganic) value of 1.5 or more. As the plasticizer, a high-boiling organic solvent having a boiling point of 180 deg.C or higher or a compound which is solid at an ordinary temp. and has a melting point of 35-250 deg.C but melts when being heated by a thermal head at the time of transfer is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermal transfer image-receiving material for thermal transfer recording, and particularly to a thermal transfer image-receiving material that has high image density and excellent image storage stability.

(Prior Art) In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and devices suitable for each information processing system have also been developed and adopted. The thermal transfer recording method is one of these recording methods.The equipment used is lightweight, compact, noiseless, easy to operate,
It has excellent maintainability and can be easily colored, so it has been widely used recently. This thermal transfer recording method is roughly divided into two types: a thermal)8 melting type and a thermal transfer type. In the latter method, a thermal transfer dye-providing material having a dye-providing layer containing a binder and a heat-transferable dye on a support is superimposed on a thermal transfer image-receiving material, and heat is applied from the support side of the dye-providing material to create a pattern formed by the thermal application. In this method, a transfer image is obtained by transferring a heat-transferable dye onto a recording medium (thermal transfer image-receiving material ff4).

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

(Problems to be Solved by the Present Invention) Organic solvent-soluble polymers are usually used in thermal transfer image-receiving materials used in this thermal transfer type thermal transfer recording method. However, the use of organic solvents increases production costs and is also undesirable in terms of health care for workers who handle organic solvents.For this reason, attempts have been made to use water-dispersed polymers as image-receiving materials. The dye does not have sufficient dyeability, and in order to obtain a high-density transferred image, an excessive amount of heat is required during transfer, resulting in a deterioration in the durability of the thermal head.

In order to obtain a high transfer density, a method has been proposed in which a polymer such as polyvinylpyrrolidone or hydroxyethyl cellulose is added to saturated polyester (Japanese Patent Application Laid-open No. 57107885 and Japanese Patent Application Laid-open No. 57-137191). However, image-receiving materials manufactured by these methods do not take into account the storage stability (lightfastness) of transferred images under light irradiation.
When exposed to sunlight, the image density often decreases significantly and the color of the image changes significantly.

It has been known for a long time to incorporate an ultraviolet absorber into an image-receiving material in order to improve light resistance (for example, JP-A-59-158289, JP-A-60-101090, JP-A-6L-229594). When UV absorbers are added to the image receiving material, the UV absorbers diffuse throughout the image receiving layer.

Since the transferred dye mainly exists on the surface of the image-receiving layer, the added ultraviolet absorber cannot fully exhibit its effect. When a large amount of ultraviolet absorber is added to the image-receiving layer to improve light resistance, the dye tends to diffuse, causing image smearing and heat fusion with the ink sheet. .

The present invention solves manufacturing cost and safety problems by reducing the use of organic solvents when manufacturing a thermal transfer image-receiving material, and provides a thermal transfer image-receiving material that can obtain high transfer density. It is an object of the present invention to provide a thermal transfer image-receiving material that has good light resistance without causing problems such as image bleeding and thermal fusion with an ink sheet.

(Means for Solving the Problems) The above object of the present invention is to provide at least one image-receiving layer on a support for receiving the dye transferred from the thermal transfer dye-providing material when heated to form an image. In the provided thermal transfer image-receiving material, the image-receiving layer is made of a composition in which a dye-receiving substance is dispersed in a water-soluble binder, and the uppermost layer of the image-receiving surface constituting layer of the image-receiving material contains an ultraviolet absorber and an [organic/
It has been found that this can be achieved by a thermal transfer image-receiving material characterized by containing a plastic co-dispersion having an inorganicity value of 1.5 or more.

The present invention will be explained in more detail below.

The thermal transfer image-receiving material of the present invention is provided with a dye image-receiving layer. This image-receiving layer receives the heat-transferable dye that migrates from the heat-transferable dye-providing material during printing, and is made of a material capable of receiving the heat-transferable dye that has the function of dyeing the heat-transferable dye. is dispersed and supported in a water-soluble binder.

Typical examples of polymers that can accept heat-transferable dyes 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-57-21462 and JP-A-57-21462.
-101395, 62-238790, 63-7
No. 971, No. 63-7972, No. 63-7973,
Examples include those described in No. 60-294862. In addition, as a commercially available product, Byron 290 manufactured by Toyobo
, Byron 200, Byron 280, Byron 300,
Byron 103, Byron GK-140, Byron GK
-13111'-, Pyronal MD-1200, Kao ATR-2009, ATR-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.

As the water-soluble binder of the present invention, various known water-soluble polymers can be used, and among them, water-soluble polymers having a group capable of crosslinking with a hardening agent are preferred.

Examples of water-soluble polymers that can be used in the present invention include vinyl polymers such as polyvinyl alcohol, polyvinylpyridinium, and cationic modified polyvinyl alcohol, and derivatives thereof (JP-A-60-145879, JP-A-60-220).
No. 750, No. 61-143177, No. 61-2351
No. 82, No. 61-245183, No. 61-23768
1, No. 61-261089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or its salt, acrylic acid-methacrylic acid copolymer or its salt, polymethacrylic acid or its salt, acrylic Acrylic group-containing polymers such as acid-vinyl alcohol copolymers or salts thereof (JP-A-60-168651, JP-A-62-9)
988), starch, oxidized starch, acetate starch, amine starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, cal, boxy Methyl cellulose, hydroxyethyl cellulose,
Natural polymers such as hydroxypropyl cellulose or derivatives thereof (JP-A-59-174382, JP-A No. 60-
No. 262685, No. 61-143177, No. 61-1
No. 81679, No. 61-193879, No. 61-28
7782), polyvinyl methyl ether, maleic acid-vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer,
Synthetic polymers such as maleic acid-alkyl vinyl ether copolymer and polyethyleneimine (JP-A-61-327
No. 87, No. 61-237680, No. 61-27748
3) and the water-soluble polymers described in JP-A No. 56-58869.

Also, SO, - group, C00- group, So! Various copolymers made water-solubilized by monomer components containing - groups, etc. can also be used.

The use of gelatin as the water-soluble binder is particularly preferable because it can be dried quickly, resulting in less drying load, and simultaneous multilayer coating can be easily performed.

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

Na16. Enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in P2O (1966) can be mentioned.

When using two or more types of water-soluble polymers as the water-soluble binder, they can be mixed in advance and used as the water-soluble binder. Alternatively, a dispersion may be prepared with an aqueous solution (for example, an aqueous gelatin solution) containing 1 m of polymer, and then an aqueous solution containing another polymer may be mixed.

The water-soluble binder and the receptive substance have a weight ratio of receptive substance/water-soluble binder -1 to 20, preferably 2 to 10.
Particularly preferably, it is used in a range of 2.5 to 7.

As a method for dispersing a receptive substance in a 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 receptive substance dissolved in an R-containing solvent that is immiscible with water and mixing it with an aqueous solution of a water-soluble binder; There is a method of mixing it with 18 liquid of water.

Examples of ultraviolet absorbers that can be used in the receiving layer of the present invention include benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, in the Nos. 3,344,794 and 3,352,681), hensifhenone compounds (e.g., JP-A-46
-2784), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805;
7.375), butadiene compounds (such as those described in U.S. Pat. No. 4,045,229), or hendioxazole compounds (such as those described in U.S. Pat. No. 3,700,455). can be used. Furthermore, those described in U.S. Pat. No. 3,499.762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used.

Further, a UV-absorbing polymer or the like may be used.

Ultraviolet absorbers suitable for use in the present invention are compounds represented by the following general formulas (U-1) to (U-IV).

General formula (1)-I) 11 General formula (U-11) General formula (U-[11) General formula (U-IV) In the above general formulas (U-1) to (U-IV), R, -
R, may be the same or different, hydrogen atom, halogen atom, acyloxy group, aliphatic group, aromatic group, R1
, 0- or R, ff5Ot-, and R6-R1 may be the same or different, hydrogen atom, halogen atom, hydroxy group, aliphatic group, aromatic group, carbonamide group, sulfonamide group, sulfo group , carboxy group, or R+? Represents O-, and R3゜ and Rl l may be the same or different and represent a hydrogen atom, an aliphatic group, a halogen atom, or R1? R1□, R1 and RI& may be the same or different and represent a hydrogen atom, an aliphatic group or an aromatic group; however, R+s and R16 are never hydrogen atoms at the same time. ), RI2 and R14 may be the same or different; cyano group, carbamoyl group, sulfamoyl group, formyl group, -COR, , SOR+q,
-5OtR+t, -5OzOR+t, or -COO
R+? , R, represents an aliphatic group or an aromatic group.

Here, the aliphatic group refers to a substituted or unsubstituted linear, branched, or cyclic alkyl group, and the aromatic group refers to a group consisting of a substituted or unsubstituted monocyclic or condensed benzene ring. .

Next, the general formula (U-1) used in the present invention, (tJ-
The ultraviolet absorbers represented by It), (U-111) and (U-rV) will be explained.

Substituents R1 to R1 used in compounds represented by general formulas (U-1) to (U-IV)? An example is shown below.

That is, halogen atoms (fluorine, chlorine, bromine, etc.), aliphatic groups (methyl, ethyl, n-propyl, I-propyl, 5ec-butyl, t-butyl, t-amyl, t-hexyl, n-octyl, 2 - Ethylhexyl, t-octyl, dodecyl, hexadecyl, trifluoroacetyl, benzyl, etc.), aromatic groups (phenyl, tolyl, 4-methoxyphenyl, naphthyl, etc.), acyloxy groups (acetyloxy, hendiyloxy, p-chlorobenzoyl) oxy, etc.), carbonamide groups (acetamide, benzamide, trifluoroacetamide, etc.), sulfonamide groups (methanesulfonamide, henzenesulfonamide, toluenesulfonamide, etc.), carbamoyl groups (carbamoyl, dimethylcarbamoyl, dodecylcarbamoyl, etc.), It is a sulfamoyl group (sulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.).

The compounds represented by the general formulas (U-1) to (U-r'/) may be bonded to each other in any of the substitutions Z Rl-Rlt to form a dimer or a multimer of more than that,
R1~R1 again? It may be bonded to the main chain of the polymer to form a polymeric compound.

Specific examples of compounds represented by general formulas (U-1) to (U) are shown below, but the invention is not limited thereto.

v V-2 U■ (t) CJq V V 0!1 V-5 V-9 11 V-6 0■ (t) CJv y-7; (weight ratio) UVII U■ 5 V-12 V 3 CIls C113 (-C
Il, -C, CIl□-Ch C-OCOOCH3 x:y=80:20 (N ratio) The plasticizer used together with the ultraviolet absorber in the present invention is:
(Organic/Inorganic) A compound with a value of 1.5 or more, and a high-boiling organic solvent with a boiling point of 180°C or more or a melting point of 35°C or more
A compound that has a temperature of 250°C and is solid at room temperature, but melts when heated by the thermal head during transfer (
(hereinafter referred to as a thermal solvent) is preferred. Here, organicity and inorganicity are concepts for predicting the properties of compounds.
It is described in.

Specific examples of high boiling point organic solvents and thermal solvents include JP-A-59-83154, JP-A-59-178451, and JP-A-59.
-178452, 59-178453, 59-
No. 178454, No. 59-178455, No. 59-1
No. 78457, No. 62174754, No. 62-245
No. 253, No. 61-209444, No. 61-2005
No. 38, No. 62-8145, No. 62-9348, No. 62-30247, No. 62-136646, etc. ), amides (for example, fatty acid amides, sulfamides), ethers, alcohols, paraffins, and the like.

Preferred specific examples of high boiling point organic solvents and thermal solvents that can be used in the present invention are listed below, but the invention is not limited thereto. Note that the values in parentheses are (organic/inorganic) values.

S-1 5-2 (n-C+JItJ"')Tp=.

(13,5) S-3 S 4 S S 1 S 2 5-13 113 C1l.

(3゜ 41) C.B.

CHl (2゜ 53) S S HS-9 S 0 S 4 S 5 ('J S 6 n C+JisCOOCH3 S 7 CIlz C00C+zllzs (Jlz　C00C+211□.

(2゜ 27) (6゜ 33) (4゜ 67) H3-22 C+, th+C00C b 1131 S 7 CH20COC.

11zz(n) 11 OCOC+ 11zs(n) CIl□ococ.

11□3(n) S-28 CH20COC tllzs(n) +10 C112 CH20COC ,11is(n) ozou (10°67) (4°33) (2°56) (3°29) (4°00) 5- 23 S 5 S 6 CHzOCOC+Jss(n) S 1 S 2 (C+JzsOsu-yP=0 S 3 S-35 (5°69) 1(S-36 H3-37) The above ultraviolet absorber and plasticizer are as described below. It is used as the top layer of the image-receiving layer as a co-dispersion in a form that can be dispersed in a water-based solvent.A co-dispersion is a co-dispersion in which both an ultraviolet absorber and a plasticizer are mixed in dispersed particles. For example, it is prepared by mixing a solution of a UV absorber and a plasticizer dissolved in a co-X11! solvent with an aqueous solution of a water-soluble binder and emulsifying and dispersing it. During emulsifying and dispersing, anion, Nonionic, cationic or amphoteric surfactants can be used as appropriate.

The ultraviolet absorber and plasticizer have a weight ratio of ultraviolet absorber/plasticizer=0.02 to 1.0, preferably 0°05 to 0.75.
Use within the range. Although it is essential that the co-dispersion of the ultraviolet absorber and the plasticizer be contained in the uppermost layer constituting the image-receiving layer, it may also be used in an intermediate layer. Moreover, each dispersion of an ultraviolet absorber or a plasticizer can also be added separately to layers other than the uppermost layer. The amount of the ultraviolet absorber is preferably 0.5 to 20 parts by weight, particularly 1 to 15 parts by weight, based on 100 parts by weight of the dye-receiving material in the uppermost layer. The plasticizer is the top layer dye-receiving material 10
It is preferably 5 to 40, particularly 7.5 to 30 parts by weight relative to 0 parts by weight.

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

The support used in the thermal transfer image-receiving material of the present invention is not particularly limited, and any known support can be used. Materials with high diffusivity for heat-transferable dyes can also be used as supports under the present invention.

General specific examples 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 Latinx impregnated paper, synthetic resin internal addition Paper supports such as paper, 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 the Japanese Society of Photographic Studies, ``Fundamentals of Photographic Engineering (for Silver Salt Photography)'' (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 is generally made of high-quality paper. 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 receptor layer is provided, but
It may be provided on both the front and back sides. Examples of polyolefins used include high density polyethylene, low density polyethylene, and polypropylene, and any of them 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 is usually preferably 5 to 1100 p on one side. However, in order to obtain a higher degree of transfer, it is preferable that the polyolefin coat on the receiving layer side be thinner.

Pigments and fillers such as titanium oxide and ultramarine blue may be added to the polyolefin coat to increase whiteness. Further, the polyolefin coat may have a thin gelatin layer of about 0.05 to 0.4 g/rd on its surface (the side on which the receptor layer is provided and/or the back surface thereof).

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 or more of the functions of a diffusion prevention layer for a heat-transferable dye, and in some cases also serves as an adhesive.

The heat-transferable dye diffusion prevention layer serves to prevent 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 a water-soluble binder is preferable, and an example thereof is the water-soluble binder mentioned above as the binder for the receptor layer, and gelatin is particularly preferable.

The porous layer is a layer that serves to prevent the heat applied during thermal transfer from diffusing from the receiving layer to the support, and to effectively utilize the applied heat.

When using a water-soluble polymer as a binder for a porous layer, 1) porous fine particles are dispersed in a water-soluble polymer and applied and dried; 2) a liquid of the water-soluble polymer is prepared in which air bubbles are generated by mechanical stirring. 3) A water-soluble polymer solution containing a foaming agent is foamed before coating or foamed during the coating drying process. 4) An organic solvent (preferably more than water) is added to the water-soluble polymer solution. It can be formed by a method such as emulsifying and dispersing a solvent (with a high boiling point) and forming microvoids in the process of coating and drying.

When using an organic solvent-soluble binder as the porous layer, l) a synthetic resin emulsion such as polyurethane, a synthetic rubber latte such as methyl methacrylate-butadiene, etc.
A liquid prepared by mechanically stirring Nox to generate air bubbles is applied onto a support and dried. 2) A liquid obtained by mixing the above synthetic resin emulsion or synthetic rubber latex with a foaming agent is applied onto a support and dried. 3) A mixture of synthetic resin such as PVC blastisol, polyurethane, or synthetic rubber such as styrene-butadiene with a foaming agent is applied onto the support and heated to foam, 4) Thermoplastic resin or synthetic rubber. is dissolved in an organic solvent, and a non-solvent (mainly water-based) that is less likely to evaporate than the organic solvent, is compatible with the organic solvent, and has no solubility in thermoplastic resins or synthetic rubbers. It is possible to use a method such as coating a mixed solution of a microporous layer (including a microporous layer) on a support and drying the mixture.

If the receiving layers are 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 50μ, particularly preferably X to 20μ.

In the present invention, a silicone compound can be included in the image-receiving layer or the intermediate layer.

Silicone compounds have siloxane bonds (-3i
-0-5i-), and silicone oil is particularly preferred. In addition to unmodified silicone oil, examples of silicone oil include olefin-modified, polyether-modified, alcohol-modified, fluoroalkyl-modified, amine-modified, carboxy-modified, and epoxy Modified silicone oils such as modified silicone oil and mercapto modified silicone oil can be used. Specific examples include various modified silicone oils described on pages 6 to 18B of the "Modified Silicone Oil" technical data published by Shin-Etsu Silicone. Among these silicone oils, polyether-modified silicone oil and epoxy-modified silicone oil give particularly preferable results in the present invention.

An antistatic agent can also be contained in the image-receiving layer on at least one side of the thermal transfer image-receiving material of the present invention or in the surface of the image-receiving layer. Antistatic agents include surfactants, such as cationic surfactants (quaternary ammonium salts, polyamine derivatives, etc.), anionic surfactants (alkyl phosphates, etc.), amphoteric ionic surfactants, or nonionic surfactants. In addition to surfactants, metal oxides such as aluminum oxide and tin oxide may be used. In a configuration in which the image-receiving layer is provided only on one side, an antistatic agent may also be used on the opposite side to the side on which the image-receiving layer is provided.

Constituent layers such as the image receiving layer, intermediate layer, protective layer, and bank layer of the thermal transfer image receiving material of the present invention include, for example, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, and synthetic zeolite. , zinc oxide, lithopone, titanium oxide, and the like may be added.

It is preferable that the water-soluble binder of the image-receiving layer, especially the outermost layer, contains fine silica powder. Here, silica refers to silicon dioxide or a substance containing silicon dioxide as a main component. The fine powder silica to be contained in the image receiving layer has an average particle size of 10 to 100 mμ and a specific surface area of less than 250 rd/g, more preferably an average particle size of 10 to 50 mμ and a specific surface area of 20 to 20 Or/g. It will be done. The content of fine powder silica is in the range of 5 to 90% by weight, preferably 10 to 60% by weight, based on the total weight of the layer containing it.

In the present invention, the above-mentioned image-receiving layer may further contain an anti-fading agent. It is preferable that the oil-soluble anti-fading agent and the heat-transferable dye receiving material be dissolved in a solvent, emulsified and dispersed in a water-soluble binder, and then incorporated into the image-receiving layer.

Antifading agents include, for example, antioxidants or certain metal complexes. Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (hindered phenols, etc.), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-1593644 are also effective.

Examples of metal complexes include U.S. Pat. No. 4,241,155, U.S. Pat.
No. 5, columns 3 to 8, JP-A-62-174741, No. 6
1-88256 pages (27) to (29), patent application 1982-
No. 234106, No. 6231096, No. 62-230
There are compounds described in No. 596 and the like.

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

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

Furthermore, in the present invention, a fluorescent whitening agent can be included in the above-mentioned image-receiving layer or intermediate layer. Examples of optical brighteners include K, VeenkataramanWrThe
Chemistry of 5ynthetic Dy
Compounds described in es J Vol. 5, Chapter 8, JP-A-61-143752, etc. can be mentioned. More specific examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. . Optical brighteners can be used in combination with antifade agents.

A hardening agent can be contained in the constituent layers of the thermal transfer image-receiving material of the present invention, such as the image-receiving layer, intermediate layer, and bank layer.

Examples of the hardening agent that can be used in the present invention include aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-5-)riazine, bis(vinylsulfonyl)methyl ether, N,N'-ethylenebis(vinylsulfonylacetamide), N , N'trimethylene-bis(vinylsulfonylacetamide), etc.], active halogen compounds (2,4-di[1-6-hydroquine-5-1-riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxy chloric acid, etc.), epoxy compounds, isoxazoles, dialdehyde starch, 1-
Examples include chloro-6-hydroxytriazinylated gelatin. A specific example is U.S. Patent No. 1゜870.
．． No. 354, No. 2,080,019, No. 2.726.
No. 162, No. 2,870,013, No. 2,983.6
No. 11, No. 2,992.109, No. 3.047,39
No. 4, same 3. 057. No. 723, 3,103.4
No. 37, No. 3.321313, No. 3,325.287
No. 3,362.827, No. 3,490,911, No. 3539.644, No. 3,543.292, British Patent No. 676.628, No. 825.544, No. 1,
270.578, German Patent No. 872.153, 1
, No. 090.427, No. 2.749260, Special Publication Show 3
It is described in No. 4-7133, No. 46-1872, etc.

Among these gelatin hardeners, aldehydes, active vinyl compounds, and active halogen compounds are particularly preferred.

The thermal transfer image-receiving material of the present invention is used in combination with a thermal transfer dye-providing material.

A thermal transfer dye-providing material basically has a thermal transfer layer containing a thermally transferable dye and a binder on a support. Thermal transfer dye-providing materials are prepared by preparing a coating solution by dissolving or dispersing a conventionally known heat-transferable dye and a binder resin in an appropriate solvent, and applying this to a support for conventionally known thermal transfer dye-providing materials. On one side of the body, for example about 0.
It can be obtained by coating and drying to form a thermal transfer layer in a coating amount such that the dry film thickness is 2 to 5 μm, preferably 0.4 to 2 μm.

Furthermore, if necessary, an antistatic layer described in EP 194106A or the like or a slippery layer described in JP-A No. 62-51490 or the like may be provided.

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
4 GL, Dianix Yellow H2G-FS,
Miketon Polyeltel Yellow 3GSL, Kayatsuset Yellow 937, Sumikaron Red EFBL, Dianix Resodo ACE, Miketon Polyeltel Red FB, Kayatsu Trend 126, Miketon Fast Brilliant Blue B, Kayatsuset Blue 136, etc. are suitable. used.

Also, JP-A No. 59-78895, No. 60-28451, No. 60-28453, No. 60-53564, No. 6
No. 1-148096, No. 60-239290, No. 60
-31565, 6030393, 60-535
No. 65, No. 60-27594, No. 61-262191
No. 60-152563, No. 61-244595, No. 62, -196186, No. 63-142062, No. 63-39380, No. 62-290583, No. 63-111094, No. 63-111095 , same 6
No. 3-122.594, No. 63-71392, No. 63
-74685, 63-74688, patent application 1986-
No. 41285 (describing the dye represented by the general formula below).

R1 2 In the formula, R1 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, R2 represents a hydrogen atom, an alkyl group, or an aryl group, and R3 represents an aryl group or It represents a heteryl group, and R4 and R2 may be the same or different and each represents a hydrogen atom or an alkyl group. The above substituents may be further substituted), etc., yellow dyes described in JP-A No. 60-2238 [i2, No. 62-28452],
6O-315 (i3, 59-78896, 6
No. 0-31564, No. 60-303391, No. 61-
No. 227092, No. 61-227091, No. 60-3
No. 0392, No. 6030694, No. 60-13129
No. 3, No. 61-227093, No. 60 15'909
No. 1, No. 61-262190, No. 62-33688, No. 63-5992, No. 61-12392, No. 62
-55194, 62-297593, 63-7
No. 4685, No. 63-74688, No. 62-9788
No. 6, No. 62-132685, No. 61-163895
No. 62-211190, No. 62-99195,
Japanese Patent Application No. 62-220793 (describing the dye of the following general formula).

\ / -4 In the formula, R + and Rz are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group,
Represents an aryloxy group, aralkyl group, cyano group, acylamino group, sulfonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amine group, R3, R4 represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. R3 and R1 may be bonded to each other to form a ring, or R2 and Rz and Rz and R4 may be bonded to each other to form a ring. n
represents an integer from O to 3, X, Y and Z represent -C= or a nitrogen atom (here, R2 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group,
represents an aryl group, alkoxy group, aryloxy group, or amino group), or when X and Y are 5 or y (!: When z is -C=, they combine with each other to form a saturated or unsaturated carbon ring. (The above substituents may be further substituted) Magenta dyes described in JP-A-5!178894, JP-A-59-227490,
No. 60-151098, No. 59-227493, No. 61-244594, No. 59227948, No. 60
°-131292, 60-172591, 60
-151097, 60-131294, 60-
No. 217266, No. 60-31559, No. 60-53
No. 563, No. 61-255897, No. 60-2392
89, 61-22993, 61-19396, 61-368493, 61-35994, 61-31467, 61-148269, 6m
-49893, 61-57651, 60-23
No. 9291, No. 60239292, No. 61-2844
No. 89, No. 62-191191, No. 62-13829
No. 1, No. 62-288656, No. 63-57293, No. 63-15853, No. 63-144089, No. 63-15790, No. 62-311190, No. 63
-74685, 63-74688, 62-13
No. 2684, No. 62-87393, No. 62-2551
No. 87, Japanese Patent Application No. 62-176625 (describing the dye of the following general formula).

R+ \ In the formula, Q represents an atomic group containing at least one nitrogen atom and necessary to form a 5-membered or more nitrogen-containing heterocycle with the bonded carbon atom, and R3 represents an acyl group or a sulfonyl group. R2 represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, R3 represents a hydrogen atom, a halogen atom, an alkoxy group, or an aliphatic group having 1 to 6 carbon atoms, and R4 represents a halogen atom, an alkoxy group, or It represents an aliphatic group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. R3 may be combined with R3 or R2 or R4 to form a ring. R
2 and R6 represent a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, or an aromatic group. Rs and Ra may be bonded to each other to form a ring. In addition, cyan dyes described in (R3 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-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-based resins (e.g., partially saponified polyvinyl alcohols such as polyvinyl alcohol and polyvinyl butyral), petroleum-based resins, rosin derivatives, coumaron-indene resins, terpene-based resins, polyolefin-based resins (e.g., 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, as the ink solvent for dissolving or dispersing the above pigment and binder resin, conventionally known ink solvents can be freely used. Specifically, alcohol-based ink solvents include methanol, ethanol, isopropyl alcohol, butanol, and isobuknol. Ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Aromatics include toluene, xylene, etc.
Examples of the halogen type include dichloromethane, trichloroethane, etc., dioxane, tetrahydrofuran, etc., and mixtures thereof. It is important to select and use these solvents in such a way that the dye used has a predetermined concentration or higher and the binder resin is sufficiently dissolved or dispersed.

For example, about 9 to 2 of the total weight of pigment and binder resin.
Preferably, 0 times the amount of solvent is used.

The thermal transfer dye-providing material obtained as described above is superimposed on the thermal transfer image-receiving material of the present invention, and is heated from either side, preferably from the back side of the thermal transfer dye-providing material, according to the image signal by heating means such as a thermal head. heated. As a result, the dye in the thermal transfer layer can be easily transferred to the receiving layer of the thermal transfer image-receiving material with relatively low energy depending on the amount of heating energy, resulting in excellent clarity and
Color images with high resolution gradations can be obtained.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used, such as polyester (polyethylene terephthalate, etc.), polyamide, polycarbonate, Krasin paper, condensate t-i, cellulose ester, chemical compound polyether, Examples include polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, cellophane, polyamide, and the like.

Support for thermal transfer dye-providing materials and generally has a thickness of 2 to 30 μm.
It is. It may also be coated with a subbing layer if desired. Further, the back surface may be coated with a slipping layer for preventing the thermal head from adhering to the base dye-providing material. Such slipping layers consist of lubricating substances, such as surfactants, liquid lubricants, solid lubricants or mixtures thereof, with or without polymeric binders.

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

The heating means is not limited to a thermal head, and 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, CR7 screens, etc.

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 way of Examples below.

Example 1 (Preparation of thermal transfer dye-providing material (A)) A 5.5 μm thick polyethylene terephthalate film (Lumirror: manufactured by Toshi) having a heat-resistant slipping layer made of a thermosetting acrylic resin on one side was used as a support, A coating composition (A) for forming a thermal transfer dye-providing layer having the following composition was coated on the opposite side of the support from the side on which the heat-resistant slipping layer was provided, so that the coated amount after drying was 1 g/rd. A thermal transfer dye-providing material (A) was obtained by coating and forming.

Rest color removal (λ)
Cyan disperse dye (a) (below) 4 parts Polyvinyl butyral resin 4.5 parts (Suresoku BX-1: Shimizu Chemical) Methyl ethyl ketone 45 parts Toluene 45 parts Polyisocyanate 0.2 parts (Takenate DIION:
Takeda Pharmaceutical) Cyan disperse dye (at 2nd layer: Pyronal MD-1200 100g 40% liquid (saturated polyester aqueous dispersion Toyobo n) Dispersion-1 Preparation of thermal transfer image-receiving material (101-109)) Thickness 200
Polyethylene coated for μm photographs (base paper is 150 μm)
laminate with polyethylene of 27 μm on the front side and 23 μm on the back side, and undercoat with gelatin on the front side), and coat the surface with a coating solution for an image-receiving layer (the first layer and the second layer from the support side) with the following composition. Image-receiving materials (101 to 107) were prepared by coating and drying so that the dry film thicknesses were 1 μm and 7.5 μm, respectively.

1st layer: lO% gelatin water? Yon (tE 10
0g water
40d hardener t1) 14% aqueous solution 6
0+d polyether modified silicone oil 3gK
F-615A (Shin-Etsu Chemical side) Surfactant 12+"" 5% aqueous solution 20M1
water 34
5m In the above, the ultraviolet absorber +11 and plasticizer fl) shown in Table 1 were used.

Note-1) 1 Hardener (11:1,2-bis(vinylsulfonium acetamide)ethane O surfactant (1): O surfactant in sodium dodecylbenzenesulfonate (21: CI+117SO2NCII
□CIl□C00KCz II q Note-2) Preparation method of dispersion-1 Dissolve the ultraviolet absorber and plasticizer in ethyl acetate. A mixed solution of 10% gelatin aqueous solution, surfactant and water was added to this solution while stirring, and emulsification and dispersion was carried out at 15,000 rpm for 9 minutes using a homogenizer.

Next, image-receiving materials (108 and 109) in which an ultraviolet absorber was added to the image-receiving layer by a conventional method were prepared using the coating liquid shown below as the second layer and in the same manner as above.

Coating liquid for image-receiving material 108 (for second layer) Pyronal MD-120040% liquid ong Image-receiving material 103 river dispersion liquid 202g (Table-1
Reference) Polyether modified silicone oil 3gKF-6
15A Ultraviolet absorber UV-6 10% liquid 25-Surfactant (2) 5% aqueous solution 20-Water
320-Image receiving material 1
Coating liquid for 09 (for second layer) Pyronal MD-1200 40% liquid 00g Molecules for image receiving material 103 l't, /&, 202g (Table ~ 1
Reference) Polyether modified silicone oil 3gKF-6
15A Ultraviolet absorber UV-6 10% liquid 50d Surfactant (2) 5% aqueous solution 20 Water resistant
295-The thermal transfer dye-providing material and the thermal transfer image-receiving material obtained as described above are superimposed so that the dye-providing layer and the image-receiving layer are in contact with each other, and the thermal transfer dye-providing material is heated using a thermal rad from the support side of the thermal transfer dye-providing material. Head output 0.25 W/dot, pulse width 0°15~15 m5ec, dot density 6 dots/dot
Printing was carried out under the conditions of mm, and the cyan dye was dyed imagewise on the image-receiving layer of the thermal transfer image-receiving material.

(Performance Evaluation) Todoroki 1 Skin: The reflection density of the saturated portion (Dsax) of the obtained recorded thermal transfer image-receiving material was measured using a Status A filter.

The recorded thermal transfer image-receiving material thus obtained was stored in an incubator at 60° C. for one month, and bleeding of the color image was observed.

The evaluation criteria for bleeding are as follows.

×: Significant blurring.

Δ: Slight blurring.

O: No bleeding was observed.

15.00 for the recorded thermal transfer image-receiving material for 7 days.
The stability of the color image was examined by irradiating it with a 0 lux fluorescent lamp.

Status A reflection density was measured before and after irradiation, and the stability was evaluated based on the ratio.

The results are shown in Table-1.

As is clear from Table 1, the image-receiving sort produced according to the present invention had a high transfer degree and good color image stability, and no image stains were observed. Compared to this,
Image-receiving sheets (108, 109) in which an ultraviolet absorber was directly added to the coating solution by a conventional method had poor color image stability and smudges were observed in the image.

Example-2 (Preparation of polyester aqueous dispersion) ■/&: 10% gelatin aqueous solution 50g Surfactant (2) 5% aqueous solution 501#1 water
40-■
'4. : Polyester resin (1) 40 g
After dissolving 60 g of toluene and 60 g of methyl ethyl ketone (2), liquid (2) was added to the first solution while stirring and emulsified and dispersed at 15,000 rpm for 9 minutes using a homogenizer to prepare a polyester aqueous dispersion A.

Polyester resin (1r monomer composition (mol%) TP
A IPA 5IPA BTS-A-BD
BG25 25 1 24.5
24.5 molecular weight approximately 20,000 where TPA-terephthalic acid IPA-isophthalic acid 0 Ja CH.

BG = ethylene glycol It is.

(Preparation of thermal transfer image-receiving material (201-203)) Example-
On the same support as used in Example 1, a coating solution for an image receiving layer having the following composition (for the second layer, the second layer is the same as in Example 1) was applied by Giesser coating, so that the dry film j1 had a thickness of 1 μm in the second layer. , the second layer is coated to a thickness of 7.5 μm and dried to form an image-receiving material (2
01-2o3) were produced.

Coating liquid for image receiving material (201) (for second layer) Polyester aqueous dispersion A 300g Magnet 10 of Example-1
Dispersion liquid for 4 205g Polyether-modified silicone oil 3gKF-615A Surfactant (2) 5% aqueous solution 20ad water 140-
Coating liquid for image-receiving material (202) (for second layer) Polyester aqueous dispersion A 300g Example-1 No. 10
Dispersion liquid for 6 205g Polyether modified silicone oil 3gKF-615A Surfactant (2) 5% aqueous solution 201R1
water 14
Coating liquid for 0d image receiving material (203) (for second layer) Polyester aqueous dispersion A 300g Dispersion liquid for floor 103 of Example-1 205g Polyether modified silicone oil 3g KF-615A Ultraviolet absorber UV-6 10% liquid 25- Surfactant (2) 5% aqueous solution 20-water
115-Image receiving material (2
01 to 203) were superimposed on the thermal transfer dye-providing material (A) in the same manner as in Example 1, and printing was performed using a thermal spatula to obtain a cyan dyed image. The obtained transferred image was evaluated for maximum density, image bleeding, and color image stability in the same manner as in Example-1. The results are shown in Table-2.

As is clear from Table 2, the image-receiving sheet prepared according to the present invention had good transfer density, image bleeding, and color image stability.

Example 3 (Preparation of thermal transfer dye-providing materials (B, C)) The following magenta disperse dye fbl or yellow disperse dye ( A magenta thermal transfer dye-providing material (B) and a yellow thermal transfer dye-providing material (C) were produced using Example e) and in the same manner as in Example-1.

Magenta disperse dye (bl) Coating liquid for image-receiving material (302) (comparative example) Image-receiving material (30
3) Coating liquid (comparative example) for thermal transfer image-receiving material (301-3
03)) Synthetic paper with a thickness of 150μ (Seiji Yuka Co., Ltd.: y
upo-FGP-150), and coated the surface with a coating solution for an image-receiving layer having the following composition (layer 1, layer 2, and layer 3 from the support side) by Giesser coating to give a dry film thickness of 1 μm, 4 μm, and 3 μm, respectively. Image-receiving materials (101 to 103) were prepared by coating to a thickness of .5 mμ and drying.

Coating 1 for image-receiving materials (301) (invention) For these image-receiving materials, thermal transfer dye-providing materials (A>, (B) and (
C) and printed using a thermal head in the same manner as in Example 1 to obtain dyed images of cyan, magenta, and yellow, respectively. The obtained transferred image was evaluated for maximum density, image bleeding, and color image stability in the same manner as in Example-1. The results are shown in Table-3.

Procedural amendment Display of incidents Heisei 1 Hand-held application No. 26μ771, name of invention Thermal transfer image receiving material person who makes corrections Relationship with the incident

Claims (1)

[Scope of Claims] A thermal transfer image-receiving material comprising at least one image-receiving layer provided on a support for forming an image by receiving a dye that migrates from a thermal transfer dye-providing material when heated, the image-receiving material comprising: The layer is made of a composition in which a dye-receiving substance is dispersed in a water-soluble binder, and the uppermost layer of the image-receiving surface constituting layer of the image-receiving material contains an ultraviolet absorber and an [organic/inorganic] value of 1.5.
A thermal transfer image-receiving material characterized by containing a co-dispersion of the above plasticizer.