JPH03101993A - Heat-transfer image pickup material - Google Patents

Abstract

PURPOSE:To obtain high transfer density while preventing the heat fusion of an image pickup material and a dye donative material on heat transfer by composing an image pickup layer of a composition, in which a dye acceptable substance is dispersed in a water-soluble binder, and the co-dispersion matter of a silicone compound and a specific plasticizer being contained in an uppermost layer. CONSTITUTION:An image pickup layer provided in a heat transfer image pickup material carries in a water-soluble binder a substance which in the case of printing, receives a heat migrating dye which migrates from a heat transfer dye donating material, and has a function of dying with the heat migrating dye. Various watersoluble polymers can be used as the water-soluble binder, and the water-soluble polymer having a group capable of conducting a crosslinking reaction by a hardener is particularly preferable. The co-dispersion matter of a silicone compound and a plasticizer having a [organic/inorganic] value of 1.5 or more is contained in the uppermost layer of the image-pickup surface forming layer of said image-pickup material. A compound having a siloxane bond in a molecule thereof is used as the silicone compound, and silicone oil is particularly preferable.

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 excellent film properties and provides high transfer density. .

(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.
It has excellent maintainability and can be easily colored, and has recently been widely used. This thermal transfer recording method can be divided into two broad types: 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 diffusion in a sublimation case or medium.

(Problems to be Solved by the Invention) The thermal transfer image-receiving material used in this thermal transfer type thermal transfer recording method usually uses an organic solvent-soluble polymer. However, the use of organic solvents not only increases manufacturing costs, but also is not favorable from the viewpoint 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, but the dyes do not have sufficient dyeability (to obtain a high-density transferred image, an excessive amount of heat is required during transfer, and thermal There was a drawback that the durability of the head deteriorated.

Image-receiving materials using water-dispersed polymers have the disadvantage that they tend to thermally fuse with the thermal transfer dye-providing material during transfer.

In order to solve these drawbacks, a method of adding polymers such as polyvinylpyrrolidone or hydroxyethyl cellulose to saturated polyester (JP-A-Sho J; 7-/07tri,
JP-A-J7-137tY/'), Method of incorporating fine silica, synthetic sodium aluminosilicate, light calcium carbonate pigment, etc. into image-receiving material ← JP-A-KAI! 1-/4 #7 ta ψ, Suikai Sho J-r-/97019% Tokukai Sho rr-irebu? ! ) has been proposed.

However, with these methods, it has been difficult to obtain an image-receiving material that has a high-density transferred image and also has good film quality that does not cause thermal fusion with the thermal transfer dye-providing material.

Therefore, the present invention solves the above-mentioned problems that occur when a dye-receiving substance is coated with an organic solvent, and also provides a thermal transfer image-receiving material that can obtain a high transfer density, and furthermore, it An object of the present invention is to provide an improved thermal transfer image-receiving material that does not undergo thermal fusion.

(Means for Solving the Problems) The above object of the present invention is to provide an image-receiving layer on a support for receiving the dye that migrates from the thermal transfer dye-providing material when heated and for controlling the shape of the image. The thermal transfer image-receiving material has at least one layer, and 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 a silicone compound and ( organic/inorganic) value is /. It has been found that a thermal transfer image-receiving material characterized by containing a co-dispersion of a plasticizer of J or more is violated.

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 contains a substance that can accept heat-transferable dyes that migrate from the heat-transfer dye-providing material during printing and has the function of dyeing the heat-transferable dyes. It is dispersed and supported in a water-soluble binder.

Typical examples of polymers that can accept heat-transferable dyes include the following resins.

(b) Dicarboxylic acids with ester bonds, such as terephthalic acid, isoheptalic acid, and succinic acid (some of these dicarboxylic acids 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 , polyacrylic acid ester resins such as polybutyl acrylate! or polymethacrylic acid ester resin: polycarbonate resin; polyvinyl acetate resin: tin acrylate resin: vinyltoluene acrylate resin, etc. Specifically, Japanese Patent Application Publication No. 37-17-, J/!
A 2, same j5'-/0/35P! No. 12-, 2j
r7PQ, same, 43-7! P7/No., J-7F7.
Examples include those described in No. 2, No. J-7973, and No. 2Q-22φt6. In addition, commercially available products include Byron 2PO, Byron 2θ0, and Byron. 2rO, Byron SOO, Byron/03, Byron GK-74!0% Byron GK-/3θ, Pyronal MD-tko θ01 Kao ATR-λooy, ATR
- JOIO etc. can be used.

←) Those with urethane bonds polyurethane resin, etc.

← Something 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 with highly polar bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

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

Various known water-soluble polymers can be used as the water-soluble binder of the present invention, and among them, a water-soluble polymer having a group capable of crosslinking with a hardening agent is preferred.

Examples of water-soluble polymers that can be used in the present invention include vinyl polymers such as polyvinyl alcohol, polyvinylpyridinium, and cationically modified polyvinyl alcohol, and derivatives thereof (%Kasho 60-/φ!r7? No. 40-220)
7jO issue, same A/-/! 3l77, 4/-2361
No. 12, same one. 24L! /No.13, 7/-237
61/No. 61/261012), polyacrylamide, boridimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid case or its salt, acrylic acid-methacrylic acid copolymer case or its salt, polymethacrylate Acrylic group-containing polymers such as acid casings or salts thereof, acrylic acid-vinyl alcohol copolymers or salts thereof (JP-A No. 1, No. 1, J.2-
991t), starch, oxidized starch, acetate starch, amine starch, carboxyl starch, dialdehyde starch, cationic starch, dextrin, sodium alginate, gelatin, gum arabic, casein, pullulan, dextran, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxy Natural polymers such as ethyl cellulose and hydroxypropyl cellulose are derivatives thereof (Japanese Patent Application Laid-open No. ShojF-/7ψ312, lo-x
tatrz issue, A/-/4Cj/77, al-irit'yta, 4/-/Pjza 72, A/-217712), polyvinyl methyl ether, maleic acid-acetic acid a Vinyl copolymer, mono-N-vinylpyrrolidone maleate copolymer,
Synthetic polymers such as maleic acid-alkyl vinyl ether copolymer and polyethyleneimine (% Kaisho A/-327
No. 17, No. 6/-237610, No. j/-2774'
Examples include water-soluble polymers described in Japanese Patent Application Laid-Open No. 2003-120002 (see No. RJ) and Japanese Patent Application Laid-Open No. 2003-110003.

Furthermore, various copolymers made water-solubilized by monomer components containing S03 groups, COO groups, so2 groups, etc. can also be used.

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

As for seratin, the following 7s gelatin sheets and gelatin derivatives can be used. Specifically, lime-treated gelatin,
Gelatin p and its derivatives such as decalcified lime-treated gelatin, acid-treated gelatin, phthalated gelatin, acetylated gelatin, succinated gelatin, Bull,
Soc. Photo, Japan, A/4, PJ
Enzyme-treated gelatin, gelatin hydrolyzate, and enzymatic decomposition product as described in O(/PAj) can be mentioned.

As a water-soluble binder. When using a water-soluble polymer of 281 or higher, the two can be mixed in advance and used as the water-soluble binder. Alternatively, a dispersion may be prepared from an aqueous solution containing one type of polymer (for example, an aqueous seratin solution), and then an aqueous solution containing another polymer may be mixed therein.

The weight ratio of the water-soluble binder and the receptive substance is receptive substance/water-soluble binder=/~20, preferably 1L, or λ~/0
,% preferably Ko. Use in the range of j 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 organic solvent that is immiscible with water and mixing it with an aqueous solution of a water-soluble binder; There are ways to mix it with.

The silicone compound that can be used in the present invention is a molecular epoxy-modified silicone oil compound, and silicone oil is particularly preferred.

As the silicone oil, in addition to unmodified silicone oil, modified silicone oils such as olefin-modified, polyether-modified, alcohol-modified, fluoroalkyl-modified, amine-modified, carboxy-modified, epoxy-modified, and mercapto-modified silicone oils can be used. Specific examples include various modified silicone oils described on pages 6 to FB of the "Modified Silicone Oil" technical data published by Shin-Etsu Silicone ■. Among these silicone oils, polyether-modified silicone oil and 7% epoxy-modified silicone oil give favorable results for the present invention.

Examples of modified silicone oils include those having the following skeleton structures and compounds thereof, such as alkyl-modified silicone oil R; alkyl, aralkyl, for example (4) 7"-# modified silicone oil, polyether-modified silicone oil, R': bonding group (e.g. -CH2- (same below) POA
: Polyoxyalkylene group such as oxyethylene/oxypropylene (same below) Amino-modified silicone oil NH2 For example (7) Fluorine-modified silicone oil (8) Higher fatty acid-modified silicone oil R : CH3 or FiOCH3 (6) Carboxyl-modified silicone oil R ; Aliphatic hydrocarbon group (9) Epoxy/polyether modified silicone oil e.g. aO Alkyl/polyether modified silicone oil The plasticizer used together with the silicone compound in the present invention has an (organic/rootless) value of / ．． ! The above compound is a high boiling point organic solvent 1 having a boiling point of 0C or more or a melting point of 3!0C-coJ-. A compound having a temperature of 0° C. and solid at room temperature but melting when heated by a thermal head during transfer (hereinafter referred to as a thermal solvent) is preferable. Here, organicity and inorganicity are concepts for predicting the properties of compounds.
/F page (lta!7).

Specific examples of high-boiling point organic solvents and thermal solvents include JP-A-19-13/1989! II No., same j9-/7rll-J-7, same! Tar 17t4! ．． rko issue, same JP-/71g! 3
No., same j9'-/7IrlAj44, same! ? 1/7r
lljj issue, same j''?-/7r'tjT issue, same 2-/
7μ7317, same 62-coφ! 2!3, same A/-2
09←p<z issue, same 4/-200!31, same t. 2-
rips, AJ-431Ar, 6J-30 4
T7 issue, same A! - Esters (e.g. phthalate esters, phosphate esters, fatty acid esters), amides (e.g. fatty acid amides, sulfamides), ethers, alcohols as described in /J4bu4t No. 6 etc. , paraffins and other compounds.

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.

Compound A/Compound Hire (n-CIBH370YP=0 (/J.!) Compound A3 Compound Skin← Compound Aio (Co.Co7) Compound 16// (3.Dal) Compound A/λ Compound 413 UH3 (J.jJ) Compound Ab Compound & 7 Compound At Compound A Compound Edition l4! Compound AI! Compound 16/6 n-C17H35α)OCH3 Compound 417 (6.3 3) Compound Ken/t Compound I6 Co3 Compound Todoroki/ ? Compound Todoroki Compound AJO Compound A! Compound Kencol (J, 7/ Compound store = 6 Compound & 22 CH20COC17H35(n) I C15H31 COOC16H33 (/0.t7) CH20COC17H35(n) Compound A, 27 Compound 163/ CH20COC41H23(n) CH-OCOC 1 1 H23 ( n) - CH20COC 11 H23 (n) (4!.jJ) (Co.!g) Compound 42F Compound 4JJ CI{20COC17H35(n) I HOCH2 -C-CH20COC 17H35 (n
)1 cH20H (Ko.!bu) (C12H250op=o Compound A33 (!.bu9) Compound consideration λta Compound Ajp (3. Kota) Compound shop 30 Compound I63yo0 Compound AJ & Compound 437 Compound Aj.r Above The silicone compound and the plasticizer are used in the top layer of the image-receiving layer as a co-dispersion in a form that can be dispersed in a water-based solvent as described below. It is a dispersion in which both the silicone compound and the plasticizer are mixed together in the dispersed particles.For example, it is prepared by mixing a solution of a silicone compound and a plasticizer in a common solvent with an aqueous solution of a water-soluble binder, and emulsifying and dispersing it. During emulsification and dispersion, anionic, nonionic, cationic or amphoteric surfactants can be used as appropriate.

The silicone compound and plasticizer have a weight ratio of silicone compound/plasticizer=0. 02~/. o, Yoshikazu or o. or
Use in the range of ~0,j. Although it is essential that the co-dispersion of a silicone compound and a plasticizer be contained in the uppermost layer constituting the image-receiving layer, it may be used in an intermediate layer. It is also possible to separately add each dispersion of the silicone compound 1 or the plasticizer to layers other than the uppermost layer of the casing. The silicone compound is added in an amount of o. I-CoQ parts by weight, especially 0.2~/! Parts by weight are preferred. Plasticizer is based on the pigment-receptive substance ioo parts by weight of the uppermost eyebrow! ~G0, especially 7. ! The amount is preferably 1 to 30 parts by weight.

The thickness of the image-receiving layer is /-40 μm in total, especially 3 to 30 μm.
The range is good. In the case of a configuration with two or more layers, the outermost layer
．． /~IOpm, especially 0. Preferably, the thickness is in the range of 2 to 1 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.

A common example is manure.

■ Laminated paper (polyolefin-based, polystyrene-based laminated paper, etc.), ■ 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 Paper supports such as resin-coated paper, paperboard, cellulose fiber paper, polyolefin-coated paper (especially paper coated on both sides with polyethylene), ■
Various plastic film casing sheets made of polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate, etc., and film casings or sheets made of these plastics to give them white reflective properties.

A laminate made of any combination of the above items (1) to (2) can also be used.

Among these, polyole 7 in-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, /ta 72), pages 223-0. 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 that can be 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.

There is no particular limit to the thickness of the polyolefin coat, but it is usually one-sided! ~/00 pm is preferred. However, in order to obtain a higher transfer density, it is preferable that the polyolefin coating 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. In addition, polyole 7 in-coated paper has 0.0! A thin gelatin layer of about 0.4<g/m2 may be provided.

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 may be a cushion layer, a porous layer, or
It is a layer having one or more of these functions as a diffusion prevention layer for a heat-transferable dye, and may also serve as an adhesive depending on the case.

The heat-transferable dye diffusion prevention layer serves to prevent the heat-transferable dye from diffusing into the support. The binder forming this anti-diffusion layer may be either water-soluble or organic solvent-soluble, but water-soluble binders are preferred, examples of which include the water-soluble binders mentioned above as binders for the receptor layer, especially gelatin. I like it.

The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the receptor layer to the support and effectively utilizes the applied heat.

When using a water-soluble polymer as a binder for a porous layer, the following methods are used: /) Disperse porous fine particles in a water-soluble polymer and apply and dry; 2) Add a water-soluble polymer liquid to which air bubbles have been generated by mechanical stirring. 3) foam the water-soluble polymer solution to which a foaming agent has been added before application, or foam the case or during the coating drying process; g) add an organic solvent (preferably) to the water-soluble polymer solution; It can be formed by emulsifying and dispersing a solvent (with a boiling point higher than that of water) and forming microvoids during the coating and drying process.

When using an organic solvent-soluble binder as the porous layer, l) a liquid obtained by mechanically stirring a synthetic resin emulsion such as polyurethane, or a synthetic rubber latex such as methyl methacrylate-butadiene to generate air bubbles; Coating on the support and drying; c) Coating the liquid mixture of the above-mentioned resin emulsion or synthetic rubber latex with a foaming agent on the support and drying; c) Synthetic resin such as PVC plastisol or polyurethane, or A mixture of a foaming agent and a foaming rubber such as styrene-butadiene is applied onto a support and foamed by heating. Non-solvents (including those whose main component is water) that are less likely to evaporate than organic solvents, are compatible with the organic solvents, and have no solubility in thermoplastic resins or synthetic rubbers. A method such as applying a mixed solution onto a support and drying it to form a microporous layer can be used.

If the 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 o. Z-to[mu], especially /~20[mu] is preferred.

An antistatic agent can also be contained in the casing of the image-receiving layer or the surface of the image-receiving layer on at least one side of the thermal transfer image-receiving material of the present invention. Antistatic agents include surfactants, such as cationic surfactants (μ-class ammonium salts, polyamine derivatives, etc.), anionic surfactants (alkyl phosphates, etc.), amphoteric surfactants, or non-ionic surfactants. In addition to ionic 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 of the image-receiving layer, intermediate layer, and protective layer of the thermal transfer image-receiving material of the present invention. For example, fine powders such as silica, clay, Merck, diatomite, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithobon, titanium oxide, etc. are added to the constituent layers such as the back layer. Good too.

It is preferred 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 diameter of lθ to ioomμ and a specific surface area of 2! Om2
/g is more preferable, and the average particle size lθ~! O
mμ and a specific surface area of 20 to 200 m 2 7 g are used. 1. The content of finely powdered silica is based on the total weight of the layer containing it. ~P0 weight, preferably <Fiio~60 weight flies.

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 is dissolved in an organic solvent together with a heat-transferable dye receiving substance, emulsified and dispersed in a water-soluble binder, and then contained in the image-receiving layer.

Antifading agents include, for example, antioxidants, ultraviolet absorbers, 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. Also, JP-A-Sho t/-/jF
The compound described in No. J61Aφ is also effective.

As ultraviolet absorbers, penzotriazole compounds (
U.S. Patent No. 31337, etc.), φ-thiazolidone compounds (U.S. Pat. No. 33126, etc.), bezophenone compounds (Japanese Patent Application Laid-open No. 2711!, etc.)
, and other published works by Akira. T! -4IjJj issue, same AJ-/
There are compounds described in J7A4 (/, No. 6/1rr2zt, etc.). Also effective are ultraviolet absorbing polymers described in JP-A-62-2tO/12.

Examples of metal complexes include U.S. Patent Nos. θ/r No. 3-3 columns, same No. ψ. 2! μ／
Pj No. 3-l columns, JP-A-Sho tco 17g No. 711/, same No. J/-r. r. 2jA (.27) ~ (j2) pages, Patent Application No. 1972-231 I/Ot, No. t2-sioyt,
There are compounds described in t2-2 JOJ; No. 96 and the like.

Examples of useful anti-fading agents are disclosed in Japanese Patent Application Laid-open No. Sho AJ-2/Ta 272 (
/27) to (/J7) pages.

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

Furthermore, in the present invention, a fluorescent whitening agent can be contained in the above-mentioned image receiving layer or intermediate layer. Examples of optical brighteners include K. Veenkataraman m “The
Chemistry of Synthetic D
yes J number! Volume Chapter T, JP-A-1/-/Da 37! Compounds described in item a etc. can be mentioned.

More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, penzoxazolyl compounds,
Naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, λ. ! -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 back layer.

Nuclear hardening agents that can be used in the present invention include, for example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds [/, J, j-triacryloyl-hexahydro S - } riazine, bis(hinylsulfonyl) methyl ether, N,N'-ethylene-bis(vinylsulfonylacetamide), N,N '−
IJ methylenebis(vinylsulfonylacetamide)
etc.], active halogen compounds (2, dichlor-2-
hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), epoxy compounds, inoxazoles, dialdehyde starch, /-chloro-6-hydroxytriazinylated gelatin, etc. I can list them. Specific examples include U.S. Patent No. 1, t70, Jj4A, U.S. Patent No. 2,010,0/9, U.S. Patent No. J,7JA,/42, U.S. Pat.
, Wr3, t// issue, 2.992, /09, 3.
0μ7.3 tag number, same J, Oj7,723, same 3, /
03, μ37 issue, same j, 32/, 3/3 issue, same 3,3
No. 21,217, No. 3,3zλ, tco No. 7, No. 3. φもO. Tal/No. 3. ! 3 ta. 6ψg, 1ji 3, j name 3.42λ, British patent j7,4,621, rx
s, tp+ issue, same/, co70,. No. t7r, German patent t7co. /j No. 3, same i, oji O. ψ27, same 2
．． 7g No. 7.240, % Kosho j4Z-7/Jj No. 4
It is described in the ZJ-/r7λ issue etc.

Among these gelatin hardeners, aldehydes, active vinyl compounds, and active vinyl 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. A thermal transfer dye-providing material is produced by dissolving a dye that becomes a conventionally known heat-transferable dye and a binder resin in an appropriate solvent.
A coating solution is prepared by dispersing Tappa, and this is coated on one side of a support for a conventionally known thermal transfer dye-providing material, for example, in a coating solution of about Q.
．． 2~! .mu., good housing is obtained by coating and drying the coating amount to give a dry film thickness of 0.4t-.lamda..mu. to form a thermal transfer layer.

Additionally, if necessary, an antistatic layer described in EP/DiptOAk or the like or a slippery layer described in JP-A No. 12-311770 may be provided.

Dyes useful for forming such a thermal transfer layer include:
Any of the dyes conventionally used in thermal transfer dye-providing materials can be used, but particularly preferred in the present invention are dyes of about ij
It has a molecular weight as low as o-too, 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
φGL, Dianix Yellow HJG-F8, Miketon Polyel Terui Milow 30SL. Kayatsuset Yellowta 37, Sumi Chikaraguchi/Re? EFBL, Dianic Red ACE, Miketo/Polyeltel Red FB, Kaya Set Red/IA% ■Katon Fast Brilliant Plue B1 Kaya Set Blue-l3t, etc. are preferably used.

Puta Tokukai Akira! No. 7119j, No. 40-Jr! No. l, No. 6θ-2U x 3, No. 60-1JjA4c, No. A
I-/ltr09t, 40-232290, 0-Jlj41, to-303'? No. J, same tO-
! 3ltj issue, same to-27 tag issue, same t/-26l
iyi issue, same Oichi izλ! No. 63, same t/-24!1
7! 2! No. A, 2-lytirt No. 43-/1
No. 72062, No. t3-39310, No. 1, 2-29
No. 0jlJ, No. 63-/l/No. OY'l, No. Aj-//
No. 109j, same J! -/JJtyu issue, 43-773
No. 9'λ, No. 43-71613, No. 4j-7!76I
T issue, special request Showa 4J-! No. r/21r (Describes the dye represented by the general formula below.

In the formula, R1ri hydrogen atom, alkyl group, alkoxy group,
Represents an aryl group, alkoxycarbonyl group, cyano group, residue or carbamoyl group, R2 is a hydrogen atom, an alkyl group represents an aryl group, R3 represents an aryl group and a heteroheteryl group, R4 and R5 are the same But it can be different,
Each represents a hydrogen atom or an alkyl group. The above substituent may be further substituted), etc., the yellow dye described in
JP-A No. 1θ-JJjJ'42, AO-2f4A! 2
No. 40-J/jjJ No. 40-J/jj? -7rIP No. 6, same No. o-sizt, same No. 0-30332/, same No. 1
-ko270?2, same6l-λko7091, sametO-
No. 3032λ, No. 60301.914, No. 60-/3
/293, same l/-227023, same 1,0-/j
909/No., j/-2A21PO, No. 4.2-JJ
trr, Aj-j5'l2, t/-/. 2j5
'． No. 2, T-cota tri tag No., same 2-kota 7j No. 3, same l3-7 da trr No., same 43-7 Vtry No.,
Same + s-y'yrrt issue, Same 4. 2-/JJA
lr j number, same number J/-/43191, same number ax-2i
II Tao No. 62-Tata IYS No. Tokkun Showa Tλ-22
07ta No. 3 (describes the dye of the general formula below.

In the formula, R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, a cyano group, an acylamino group, a sulfonylamino group, a ureido group, an alkylthio group, and an arylthio group. R3, R4Fi represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group. R3 and R4 may be combined with each other to form a ring. R2 and R3, or R2 and R4 may be combined with each other to form a ring. n
Id represents an integer from O to 3. X, Y and R5 1 and Z represent C=1 or a nitrogen atom (where R5 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group,
represents an aryl group, alkoxy group, aryloxy group, or amino group). When X and Y are R5 or Y and Z are -C=, they may be bonded to each other to form a saturated or unsaturated carbon ring.The above substituents may be further substituted. ) etc., magenta dyes described in JP-A No. 39-2.271AtaO, JP-A No. 60-/!/0jig, JP-A No. 5>-.2274, etc.
No. 1j, same l/- cog μ! Same tag number! 2 pieces 72φ
! No., same tO-/3/2 Octopus No., same O1/7! Day issue, same issue 0-/j/097, same issue 60-/J/291/
- issue, 1,0-2/72tt issue, 60-j/jrj
rta, tO-J-3j63, 6l-2jry2
No. 7, same 1hO-. 2J9 Kozata, same 6/-2λL?
No. 23, No. 6l-/No. 32t, No. A/-, J/;♂←
No. 73, A/-3j Tata No., J/-J/G No. 67, No. 4/-+9?23, No. 6l-7tj/ No. 40 -23929/issue, same to
-2J92Y2, same t/-. 2rlllltrY No. 62-/9/19/, tGJ-/3129/, No. 62-81lIj6. mJt3-r7r23, same a
3-izrrJ issue, same 63-/4#Or? No., same buj-
/! 7 Ta O, same t 2-J / / / Ta O, same 1
, J-71161! No., same tj-7lA Art No., same t
2-7JJtrφ, JJ-47393, ts-
．． 2zzir'y issue. % GanshojJ-/7662! No. (describes the dye with the general formula below.

R, where Q1 contains at least l nitrogen atoms, together with the bonding carbon atoms! Represents an atomic group necessary to form a nitrogen-containing heterocycle with more than one member ring, R1 represents an acyl group 1 or a sulfonyl group, R2Fi represents a hydrogen atom box or an aliphatic group having carbon number/~t, R3 represents 1 hydrogen atom, a halogen atom, an alkoxy group, or an aliphatic group having up to 4 carbon atoms, R4
represents a halogen atom, an alkoxy group, or an aliphatic group having a carbon number of 1 to 2, and n represents an integer of O-V. R3tiR1
If ( may be combined with FiR 2 i or R4 to form a ring. R5 and R6 represent a hydrogen atom, an aliphatic group or an aromatic group having a carbon number of 1 to 100 carbon atoms. R5 and R6 are bonded to each other. may form a ring.R5 and/1 or R
6 may be combined with R4 to form a ring) and the like are also preferably used.

Furthermore, as the binder resin to be used with the above-mentioned dyes, any of the binder resins conventionally known for this purpose can be used, and they usually have high heat resistance and are capable of preventing transfer of dyes when heated. Those that do not interfere are selected. For example, polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins including polyvinylpyrrolidone, Vinyl chloride resins (e.g. vinyl chloride-vinyl acetate copolymer), polycarbonate resins, polystyrene, polyphenylene oxide, cellulose resins (e.g. tif
Methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate,
Cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resins (e.g. partially saponified polyvinyl alcohols such as polyvinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, coumaron-inde/resins, terubone resins, polyole 7-yne resins Resin (e.g. polyethylene, polypropylene)
etc. are used.

Such binder resins are preferably used, for example, in a proportion of about to-+00 parts by weight per part by weight of dye/OO.

According to 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, and specifically, alcohol-based ink solvents include methanol, ethanol, improvyl Alcohol, butanol, isoptanol, etc. Ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone L. Aromatics include toluene, xylene, etc.
Examples of the halogen type include dichloromethane, trichloroethane, dioxane, 5-tetrahydride, 7-ran, etc., and mixtures thereof. It is important to select and use these solvents so that the dye used has a predetermined concentration or higher and the binder resin is sufficiently dissolved or dispersed.

For example, about 2 to 2
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 heated from either side, preferably from the back side of the thermal transfer dye-providing material, by heating means such as a thermal head. It is heated according to the image signal. 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 sharpness and resolution. Color images can be obtained.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. For example, polyester (polyethylene terephumerate, etc.), phoramide, polycarbonate, glassine paper, condenser paper, cellulose ester.弗1 Polymer polyether, polyacetal,
Examples include polyolefin, polyimide, polyphenylene chloride, polypropylene, polysulfone, cellophane, polyamide, and the like.

The support for thermal transfer dye-providing materials generally has a thickness of 2 to 30 μm.
It is. It may also be coated with a subbing layer if desired. Additionally, the back surface may be coated with a slipping layer to prevent the thermal head from adhering to the base dye-providing material. Such slibbing layers consist of lubricating substances, such as surfactants, liquid lubricants, solid lubricant housings 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 corresponding to image information is applied from either side, preferably from the back side of the thermal transfer dye-providing material, using a heating means such as a thermal head. 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 the heating energy, and a color image with excellent sharpness, two-resolution, and gradation can be obtained.

The heating means is not limited to a thermal head, and any known means such as a laser beam (for example, a semiconductor laser), an infrared flash heat 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 using various thermal printing printers, facsimiles, or by magnetic recording, magneto-optical recording, optical recording, etc. Alternatively, it can be used to create prints from television or CRT screens.

For details on the thermal transfer recording method, see JP-A-Sho tθ-J'l
lY! You can refer to the description in the issue.

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

Example/ (Preparation of thermal transfer dye-providing material (A)) Thickness with a heat-resistant slipping layer made of thermosetting acrylic resin on one side! ，! A µm polyethylene terephthalate film (Lumirror: manufactured by Toray Industries, Ltd.) is used as a support, and a coating composition (A) for forming a thermal transfer dye-donating layer having the following composition is applied to the side opposite to the side on which the heat-resistant slipping layer is provided. A thermal transfer dye-providing material (A) was obtained by wire bar coating so that the coating amount after drying was /g/m2.

Disperse dye (MS Red G: manufactured by Mitsui Toatsu) (Disperse Red Ao) 3# Partially disperse dye (Macrol
ex Violet R: made by Bayer) (7” Ispers Red Co6) 2.2 parts polyvinyl petyral resin (Eslec BX-/: made by Shimizu Chemical) g.3 parts methyl ethyl keto 7 ←! parts toluene
μ! (Thermal transfer image receiving material (B')
(Preparation) Thickness. Polyethylene coated paper for photographs of zoθμm (base paper is /j O pm, 27μm on the front side, 13μm on the back side)
The dry film thickness was adjusted by coating the image-receiving layer coating solution with the following composition (the first layer and the second layer from the support side) on the surface using Giesser coating. /μm, 7.7 μm, and dried to prepare an image-receiving material B-/.

Coating solution 1st layer for image receiving material B-/: /θ multi-gelatin aqueous solution ioog water
Hardening agent (1)
Layer Pyronal MD-/Co00 4AO% liquid (saturated polyester/θoz aqueous dispersion Toyobo ■) 10 polygelatin aqueous solution/00g surfactant (1)**t aqueous solution CoOml water
Next, image-receiving materials B-2 to B-7 were prepared in the same manner as described above, except that the second layer of the image-receiving material coating solution was changed to the following composition. Here, image-receiving materials B-/B-Jk and B-7 are comparative samples, and B-ψ to B-AFi are samples of the present invention.

Coating liquid 2nd layer for image-receiving material B-λ: Pyronal MD-/200 μO excellent liquid /00 fl dispersion 1 liter Surfactant (1)! Coating liquid second layer for aqueous solution water image-receiving material B-J: Pyronal MD-/Co00 ←O% liquid dispersion-2 CoOml 311! ml /00 g Surfactant (1)! Polyaqueous solution. 20ml Coating liquid for water image receiving material B-1 Layer λ: Pyronal MD-/u00 go% liquid dispersion-3 Surfactant (l)! Multi-aqueous solution water image receiving material B-! Coating liquid 2nd layer: Pyronal MD-l2oθ Guo liquid dispersion-l! 4! jtml ioo g Surfactant (1)! Aqueous solution Oml 20ml Second layer of coating liquid for water image-receiving material B-4: Pyronal MD-lxoo φ0% liquid dispersion-! 3g! ml iooy, 3←jml /00fl Surfactant (1)j Coating liquid second layer for multi-aqueous solution water image-receiving material B-7: Pyronal MD-/200 ti. o% liquid dispersion-2 dispersion-7 ko Oml 3g! ml /00g Surfactant (1)! Polyaqueous solution 20ml water
3φjml
Note-7) *Hardening agent (1): /, J-His(hinylsulfonium acetamide)ethane** Surfactant (1): C8H17SO2NC
H2C} f2cOOK No. C3H7 *This book Surfactant (2): Sodium dodecylbenzenesulfonate injection) Preparation method of dispersion/~7 Dissolve the silicone oil and/or the compound of the present invention in ethyl acetate. A mixed solution of 0% gelatin aqueous solution, surfactant and water was added to this solution without stirring, and emulsification and dispersion was carried out for 2 minutes at iroθorpm using a homogenizer.

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 a thermal head is used from the support side of the thermal transfer dye-providing material, and the output of the thermal head is θ． ．． lJ-W
/dot, pulse width O. /j ~/! msec
, Printing was performed under the conditions of dot density t dots/mm,
The image-receiving layer of the thermal transfer image-receiving material was imagewise dyed with macenta dye.

The transferred dye density of the obtained recorded image-receiving material was measured using a reflective Macbeth densitometer, and the results (Dmax values) are shown in Table 11.

Furthermore, the output of the thermal head is o. Transfer was carried out under the same conditions as above except that the temperature was 3W, and the thermal fusion properties of the dye-donating layer of the thermal transfer dye-donating material to the surface of the image-receiving material were examined. The evaluation was as follows: ○: No heat fusion; Δ: Partial fusion; ×: A considerable portion fused; as shown in Table -/.

Table 1 As is clear from Table 1, the image receiving sheet produced according to the present invention had a high transfer density and good heat fusion properties. In comparison, image-receiving sheets (B-λ, B-.y) Fi, D containing a silicone compound case or a plasticizer alone
The max value is low, and the heat fusion properties are also poor. The image-receiving sheet (B-7) containing the silicone compound and plasticizer as separate dispersions has good thermal adhesion, but Dma
It can be seen that the x value is low.

Example 1 (Preparation of aqueous polyester dispersion A) Solution I: Aqueous gelatin solution JOg surfactant (2)! Excellent water solution! j'Oml water
←Omll■ solution: Polyester resin (11 og toluene ≦Og methyl ethyl ketone After dissolving the tog river solution, add the ■ solution into it while stirring the I solution, and use a homogenizer to emulsify and disperse it in an iroθOrmp for a minute to make the polyester. Aqueous dispersion A was prepared.

Monomer composition (mol%) of polyester resin (1)* T
PA IPA SIPA BI8-A-BD
BG Ko! r2jr/2da. j 2≠． j Molecular weight: about 20,000. $% where TPA=terephthalic acid IPA=isophthalic acid BIS-A-BD=BG=ethylene glycol.

(Preparation of thermal transfer image-receiving material (C)) On the same support as used in Example 1l, apply a coating solution for image-receiving layer having the following composition (for the second layer, the first layer is the same as in Example 1). By applying Giesser, the dry film thickness was reduced to 1iil.
/μm, second layer 7,! An image receiving material C-/-C-← was prepared by coating and drying to a thickness of μm.

Layer λ of coating liquid for image-receiving material C-t: Polyester aqueous dispersion A Dispersion of JOOg Example 1/l Surfactant (1)! Coating liquid λ layer for fly aqueous solution water image receiving material C-co. Dispersion of polyester aqueous dispersion Example 1/1 Surfactant (l}! Coating liquid for multi-aqueous solution water image receiving material C-3 2nd layer: Polyester aqueous dispersion A Dispersion of Example 1/3 Surfactant (1)!Multi-aqueous solution water image-receiving material C-G coating liquid 2nd layer: Polyester aqueous dispersion A Dispersion of Example 11 Surfactant (1)!Multi-aqueous solution 200g 20ml/φOml 3 θOg 200g 20m/1 /lIOml 300g +2001 2Oml /uOml 300g 200g 20mI! Water /4tO
mlj Here, image-receiving materials (C-/) and (C-2) are comparison materials, and (C-J) and (C-μ) are samples of the present invention. These image-receiving materials were superimposed on a thermal transfer dye-providing material in the same manner as in Example-/. Printing was performed using a thermal head to obtain a magenta dyed image. Table 2 shows the results of the transfer dye density value (Dmax) and thermal fusion properties measured using a reflective Macbeth densitometer.

Table 2 As is clear from Table 2, the image receiving sheet produced according to the present invention had a high transfer density and good heat fusion properties.

Example-3 (Preparation of thermal transfer image-receiving material (D)) Thickness/! θμ synthetic paper (Oji Yuka: YUPO-FGP
-yro), and the surface is coated with the image-receiving layer solution (
The first layer, second layer, and third layer (based on the support measurement) were coated with Giesser to give a dry film thickness of /μm% and μm, respectively.
%J. It is coated so as to have a thickness of jmμ and dried to form an image receiving material D-
/~D-j was produced.

First layer of coating liquid for image-receiving material D-/: io multi-gelatin aqueous solution ioog water
Hardening agent (1) Multi-aqueous solution tOml second layer Binal MD-/200/00g Example 1/Dispersion-2 200g Surfactant (1
) t% aqueous solution λOml water
3≠! ml third layer: Pyronal MD-/. 200/0
0 f<1 liter of dispersion of Example 1/Surfactant (1)! Multi-aqueous solution water-receiving material D-coating liquid first layer: /0% Seratin aqueous solution Water hardener (1) Aqueous solution second layer: Pyronal MD-t2oo Example 1 Dispersion-2 Interface Activator (1)! Multi-aqueous solution water third layer: Pyronal MD-/JOO Example 1 l dispersion-2 Surfactant (1) j Multi-aqueous solution water coating liquid first layer for image-receiving material D-s: 200y 20ml j41! ml /00g DaOml AOml ioo g aoo g 20ml JIIjmlJ /00g 200 g KoOml 3〆yoml /Ots Gelatin aqueous solution i o o g water
110ml hardener (1
) 4'% aqueous solution &Omll second layer: Dispersion of Pyronal MD-i2oo /oog Example-/Cooog surfactant (1
)! Polyaqueous solution 20ml water
3μ! ml third layer: Pyronal MD-1200 /00g Example 1 liter dispersion-3 Coog surfactant (1
)! Polyaqueous solution 20ml water
Here, image-receiving materials D-/ and DJ are comparative samples, and D-3 is a sample of the present invention. These image-receiving materials were superimposed on the thermal transfer dye-providing material in the same manner as in Example 1, and printing was performed using a thermal head to obtain a magenta dyed image. Transfer dye density value measured using a reflective Macbeth densitometer (
Dmax) and thermal fusion properties are shown in Table 3.

Table 3 As is clear from Table 3, the image receiving sheet produced according to the present invention had a high transfer density and good heat fusion properties.

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 layer of the image-receiving material contains a silicone compound and an [organic/inorganic] value of 1.
．． A thermal transfer image-receiving material comprising a co-dispersion of plasticizers of 5 or more.