JPH04310793A - Image-receiving sheet for thermal transfer recording - Google Patents

Abstract

PURPOSE:To provide an image receiving sheet for thermal transfer recording which is excellent in a transfer property of a pigment from an ink sheet for thermal transfer recording in thermal transfer, excellent also in shelf life of an obtained image, and excellent in durability for a white ground of an image receiving layer in preservation. CONSTITUTION:An image-receiving sheet for thermal transfer is composed of a base material and an image-receiving layer. Vinyl cholride resin and a heat stabilizer are contained in the image receiving layer.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to an image-receiving sheet for thermal transfer recording, and more specifically, the present invention relates to an image-receiving sheet for thermal transfer recording. The present invention relates to an image receiving sheet for thermal transfer recording for recording.

0002

[Prior Art and Problems to be Solved by the Invention] In recent years, inkjet,
Color recording technologies using electrophotography, thermal transfer, etc. are being considered.

[0003] Among these, the thermal transfer method in particular has a number of advantages such as ease of operation and maintenance, ability to reduce the size of the device, and ability to reduce costs.

In this thermal transfer method, a transfer sheet having a meltable ink layer on a support is imagewise heated by a laser or a thermal head to melt and transfer the meltable ink layer onto a transfer sheet. Thermal diffusion transfer method (sublimation transfer method) uses a transfer sheet having an ink layer containing a heat diffusible dye (for example, a sublimable dye) on a support to diffusely transfer only the heat diffusible dye to the transfer sheet. There are two types: (transfer method).

The latter thermal diffusion transfer method can control the gradation of an image by changing the amount of thermally diffusible dye transferred in response to changes in the thermal energy of the thermal head.

[0006] Therefore, this thermal diffusion transfer method has recently attracted attention as a method that can transfer and record a color image having continuous changes in color shading by overlapping recording of cyan, magenta, and yellow. There is.

[0007] By the way, the biggest problem with the thermal diffusion transfer method, which has been attracting attention in recent years, is to obtain high image quality and high image storage stability in an image-wise and high-speed manner according to electrical signals. Material technology is still under development.

For example, when a polyester resin is used as the resin for the image-receiving layer, a relatively high transfer density can be obtained, but there are problems in that it is easy to fuse and has poor light resistance. Therefore, it is conceivable to use vinyl chloride resin, which has good light-resistant storage properties for images, but it is difficult to obtain images with high transfer density. Furthermore, there is a method of copolymerizing vinyl chloride with other monomers to improve dye dyeing properties as a means of increasing the transfer density of images in the image-receiving layer made of vinyl chloride resin. Problems arise in that the heat-resistant storage stability, which is an advantage, deteriorates and the image fades or changes color, or the white background of the image-receiving sheet itself deteriorates.

The present invention aims to solve the above-mentioned problems. That is, an object of the present invention is to provide an image-receiving sheet for thermal transfer recording which has a high transfer density and is excellent in heat-resistant storage stability of images and white background durability of the image-receiving sheet.

0010

[Means for Solving the Problems] The present invention for solving the problems described above is an image-receiving sheet for thermal transfer recording characterized by having an image-receiving layer containing a vinyl chloride resin and a heat stabilizer. . The present invention will be explained in detail below.

[1. ] Image-receiving sheet for thermal transfer recording The image-receiving sheet for thermal transfer recording can be formed from a base material and an image-receiving layer formed thereon.

[0012] In some cases, an image-receiving sheet for thermal transfer recording can also be formed from a self-supporting image-receiving layer.

[0013] In the image-receiving sheet for thermal transfer recording comprising this self-supporting image-receiving layer, since no base material is used, the number of parts and manufacturing steps can be reduced.

-Image-receiving layer- This image-receiving layer can generally be formed from a binder, a stabilizer, and various additives. In addition, depending on the case, it can also be formed from a binder and a stabilizer.

1. Binder In the present invention, a vinyl chloride resin is used as the binder.

[0016] Examples of the vinyl chloride resin include vinyl chloride resins and vinyl chloride copolymers.

The vinyl chloride copolymer has a vinyl chloride monomer content of 50 to 100% by weight and a polymerization degree of 2.
A value of about 00 to 800 is preferable.

Preferred monomers that can be copolymerized include vinyl acetate, vinyl propionate, vinyl esters of fatty acids such as vinyl acetate and vinyl tallow, acrylic acid, methacrylic acid, methyl acrylate, and ethyl methacrylate. , acrylic acid or methacrylic acid and its alkyl esters such as butyl acrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, maleic acid, diethyl maleate, dibutyl maleate, dioctyl maleate, etc. Examples include maleic acid and its alkyl alkyl esters, alkyl vinyl ethers such as methyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, palmityl vinyl ether, and stearyl vinyl ether. Furthermore, the comonomer may include ethylene, propylene, acrylonitrile,
Methacrylonitrile, styrene, chlorostyrene, itaconic acid and its alkyl esters, crotonic acid and its alkyl esters, dichloroethylene, trifluoroethylene, etc., halogenated olefins, cycloolefins such as cyclopentene, aconitic acid esters, vinyl Examples include benzoate and benzoyl vinyl ether.

The vinyl chloride copolymer may be a block copolymer, a graft copolymer, an alternating copolymer, or a random copolymer. Further, in some cases, it may be a copolymer with a material having a peeling function such as a silicon compound.

In the present invention, it is possible to use the resin in combination with other resins to the extent that the object of the present invention is not impaired.

[0021] In that case, it is desirable that the amount of vinyl chloride resin is 10% by weight or more based on the total amount of vinyl chloride resin and other resins.

Other resins mentioned here include polyester resins, acrylic esters, polyvinylpyrrolidone,
Examples include polycarbonate, cellulose triacetate, styrene-acrylate resin, vinyltoluene-acrylate resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, styrene-maleic anhydride resin, and polyacrylonitrile resin.

[0023] As polyester resins that can be used in the present invention, Japanese Patent Application Laid-open No. 188695/1983,
Compounds described in JP-A-62-244696 can be mentioned. Polycarbonate resins can also be used as binders, for example:
Various compounds described in JP-A-62-169694 can be used.

These resins may be newly synthesized and used, but commercially available products may also be used.

For example, commercially available polyester resins include Byron 200, Byron 290, and Byron 60.
0 etc. [all manufactured by Toyobo Co., Ltd.], KA-1038C [
Arakawa Kagaku Co., Ltd.], TP220, TP235 [all manufactured by Nippon Gosei Co., Ltd.], and the like.

In any case, from the viewpoint of physical properties, other resins for the image-receiving layer are preferably resins having a Tg of -20 to 150°C, and more preferably resins having a Tg of 40 to 120°C. In addition, the binder has a molecular weight of 2,000 to 1
Preferably, it is 00,000. If the above-mentioned various resins have reactive active sites, they may be used to utilize the reactive active sites, or if there are no reactive active sites, they may be added to crosslink or cure using radiation, heat, moisture catalysts, or the like.

In that case, a radiation active monomer such as epoxy or acrylic or a crosslinking agent such as isocyanate can be used.

2. Stabilizer In the present invention, the image-receiving layer contains a heat stabilizer. By incorporating this heat stabilizer, sufficient image durability and white background durability can be obtained.

Examples of the heat stabilizer include lead-based stabilizers, metal soaps, composite soaps, metal salt liquid stabilizers, organotin stabilizers, other metal stabilizers, and non-metal stabilizers.

As a lead-based stabilizer, lead white (2PbCO3.
Pb(OH)2), tribasic lead sulfate (3Pb0/PbS
O4・H2O), dibasic lead phosphite (2PbO・PbH
PO3・1/2H2O), basic lead sulfite (nPbO
・PbSO3), dibasic lead phthalate (2PbO・P
b (C8H404)), tribasic lead maleate (3Pb
O.Pb(C4H2O2)H2O), silica gel coprecipitated silicate (PbSiO3.mSiO2), and the like.

[0031] As the metal soap, lithium stearate,
Magnesium stearate, calcium stearate,
Stearates such as barium stearate, cadmium stearate, strontium stearate, zinc stearate, laurates such as calcium laurate, barium laurate, cadmium laurate, zinc laurate, calcium ricinoleate, barium ricinoleate, ricinol Examples include cadmium acid, ricinoleate salts such as zinc ricinoleate, naphthenate salts such as cadmium naphthenate, zinc 2-eyorhexoate, and the like. As the composite metal soap, two or more of the above metal soaps can be used in combination. By using two or more kinds in combination, the characteristics of each can be taken into account, the drawbacks of each can be covered, and various functions such as colorability and thermal stability of the image-receiving layer can be improved. Combinations with synergistic effects include Pb/Ba, Pb/
Ca, Pb/Ba/Ca, Ba/Zn, Ba/Ca/
Zn, Ba/Ca/Sn (organotin compound), Ca/
Mg/Zn, Ca/Zn, Ca/Zn/Sn, Zn/K
In addition, tribasic sulfate (TS)/Pb (dibasic)/Pb, TS/Pb/Ba, TS/Pb/Ba/C
a, Cd/Ba, Cd/Ba/Pb, Cd/B
There are also a/Zn and TS/Pb/Ca/Ba.

[0032] Metal salt liquid stabilizer is a name for a powder type or granular type stabilizer, and the acid group of the metal compound constituting the powder type or granular type stabilizer is a lead salt whose acid group is an inorganic acid or an organic acid. The metal soap is a higher fatty acid, whereas the acid group of the metal salt, which is the main component of the metal salt liquid stabilizer, is a branched fatty acid, an unsaturated fatty acid, an alicyclic acid, an aromatic acid, an alkylphenol, etc. Is it liquid itself?
or soluble in other liquid components. Specifically, single metal systems include barium, zinc, and cadmium, and composite metal systems include Ba-Zn, Ca/Zn, Cd/Ba, and Cd/
Ba/Zn, Zn/K, Zn/Na Ba/Zn/Sn
, Ca/Zn/Sn, etc. The branched fatty acids of organic acids are ethylhexoic acid, isodecaic acid,
Examples of unsaturated fatty acids include oleic acid, ricinoleic acid, and linoleic acid; examples of alicyclic acids include naphthenic acid; and examples of aromatic acids include carbolic acid, alkylphenolic acid, benzoic acid, and alkylbenzoic acid. . It is usually desirable to use two or more types of organic acids.

The organotin stabilizer is a compound in which at least one carbon atom is directly bonded to a tetravalent tin atom, and is represented by the following general formula.

Rm SnY4-m where R represents an alkyl group such as methyl, n-butyl,
Examples include n-octyl.

[0035] Y can be a fatty acid salt type, a maleate type, or a sulfur-containing type. Fatty acid salt types include laurate and stearate, and maleate types include maleic acid and maleic acid alkyl esters. Sulfur-containing systems include dialkyltin sulfide polymers, alkylmercapto,
Examples of organic tin using mercaptocarboxylic acid alkyl esters include di-n-octyltin bis(thioglycolic acid isooctyl ester) salt, dimethyltin bis(thioglycolic acid isooctyl ester) salt, Examples include monomethyltin tris(thioglycolic acid isooctyl ester), mono-n-octyltin tris(thioglycolic acid isooctyl ester) salt, di-n-octyltin bis(thioglycolic acid isooctyl ester) salt, etc. may be used together.

Other metal stabilizers include antimony mercapto compounds.

[0037] As the non-metallic stabilizer, epoxy compounds,
Examples include organic phosphite esters, phenol derivatives, polyhydric alcohols, nitrogen-containing compounds, sulfur-containing compounds, keto compounds, etc., and epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid alkyl esters, trialkyl phosphites, thoria, etc. lylphosphite, various polyphosphites, hindered phenols, hindered amines, polyols such as trimethylolpropane and pentaerysyltol, β-aminocrotonic acid ester,
2-phenylindole, triazines, isocyanuric acid derivatives, dialkylthiopropionate esters,
Typical examples include acetoacetic acid ester, dehydroacetic acid, and β-diketones.

The above stabilizers can be used alone or in combination of two or more.

Among the above-mentioned stabilizers, organic tin compounds, complex metal soaps, phosphorous esters, and the like are preferable in terms of improving heat-resistant storage stability and preventing discoloration of the white background of the image-receiving layer, which are the objects of the present invention.

The amount of the stabilizer blended is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the image-receiving layer.
It is.

If the amount of the stabilizer is less than 0.01% by weight, sufficient heat stability cannot be obtained, and if the amount exceeds 10% by weight, the light storage stability may deteriorate or the image-receiving layer may deteriorate. This is not preferable because it may cause problems such as coloring of the white background.

3. Additives A release agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles), and a pigment may be added to the additive image-receiving layer.

[0043] The release agent can improve the releasability between the sublimation type heat-sensitive transfer ink sheet and the image-receiving layer, which will be described later.

Such release agents include silicone oil (including those called silicone resins); solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants; Among them, silicone oil is preferred.

[0045] There are two types of silicone oil: a type in which it is simply added (simple addition type) and a type in which it is cured or reacted (curing reaction type).

In the case of the simple addition type, it is preferable to use modified silicone oil in order to improve compatibility with the binder.

Examples of the modified silicone oil include polyester modified silicone resin (or silicone modified polyester resin), acrylic modified silicone resin (or
silicone-modified acrylic resin), urethane-modified silicone resin (or silicone-modified urethane resin), cellulose-modified silicone resin (or silicone-modified cellulose resin), alkyd-modified silicone resin (or silicone-modified alkyd resin), epoxy-modified silicone resin ( or silicone-modified epoxy resin).

Namely, polyester-modified silicone resin containing polysiloxane resin in the main chain and copolymerized with polyester in block form, silicone-modified polyester resin having dimethylpolysiloxane moiety as a side chain bonded to the polyester main chain. , block copolymers, alternating copolymers, graft copolymers, random copolymers, etc. of dimethylpolysiloxane and polyester can also be used as the modified silicone oil or resin.

If a vinyl chloride resin is used as a binder, a polyester-modified silicone resin is preferred as a combination.

Typical polyester-modified silicone resins include, for example, a copolymer of diol and dibasic acid, or a block copolymer of polyester, which is a ring-opening polymer of caprolactone, and dimethylpolysiloxane (both dimethylpolysiloxane and dimethylpolysiloxane). (Contains a copolymer in which the terminal or one terminal is blocked with the above polyester moiety, or conversely, the above polyester is blocked with dimethylpolysiloxane), or the above polyester is the main chain and the side chain is (dimethyl)polysiloxane. A copolymer formed by bonding siloxane can be mentioned.

[0051] The amount of these simple addition type silicone oils cannot be uniformly determined because it may vary depending on the type of silicone oil, but generally speaking, the amount of the binder in the image-receiving layer 0.5-5 for
0% by weight, preferably 1 to 20% by weight.

[0052] As curing reaction type silicone oil,
Examples include reaction curing type, photo curing type, catalyst curing type, and the like.

[0053] As a reaction-curing silicone oil, there is one obtained by reaction-curing an amino-modified silicone oil and an epoxy-modified silicone oil.

[0054] Also, as catalyst curing type or photo curing type silicone oil, KS-705F-PS, KS-70
5F-PS-1, KS-770-PL-3 [both catalytic curing silicone oils: manufactured by Shin-Etsu Chemical Co., Ltd.],
Examples include KS-720 and KS-774-PL-3 [both photocurable silicone oils: manufactured by Shin-Etsu Chemical Co., Ltd.].

The amount of these curable silicone oils added is preferably 0.5 to 30% by weight of the binder for the image-receiving layer.

A release agent layer can also be provided on a part of the surface of the image-receiving layer by dissolving or dispersing the above-mentioned release agent in a suitable solvent and applying the solution, followed by drying.

[0057] Next, as the antioxidant, JP-A-59
No.-182785, No. 60-130735, JP-A-1
Antioxidants described in Japanese Patent No. 127387 and the like, and compounds known to improve image durability in photographs and other image recording materials can be mentioned.

[0058] The UV absorber and light stabilizer include:
JP-A-59-158287, JP-A No. 63-74686,
No. 63-145089, No. 59-196292, No. 62-229594, No. 63-122596, No. 61
Examples include compounds described in publications such as No. 283595 and JP-A No. 1-204788, and compounds known to improve image durability in photographs and other image recording materials.

[0059] Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina, etc., and examples of the organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicone resin particles. can be mentioned. These inorganic/organic resin particles vary depending on their specific gravity, but are preferably added in an amount of 0.1 to 70% by weight.

Typical examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay.

-Substrate- Examples of the support for the image-receiving sheet for thermal transfer recording include paper, coated paper, synthetic paper (polypropylene, polystyrene, or a composite material made by gluing these together with paper or plastic film), white polyethylene, etc. Synthetic paper such as terephthalate base film, transparent polyethylene terephthalate base film, transparent polyethylene naphthalate base film, ABS, AS, PP, and PS. Examples include polyolefin-coated paper. The thickness of the support is usually 20 to 300 μm, preferably 30 to 300 μm.
It is m.

[2. ] Manufacture of image-receiving sheet for thermal transfer recording Image-receiving sheets for thermal transfer recording are prepared by dispersing or dissolving the components forming the image-receiving layer in a solvent to prepare a coating solution for the image-receiving layer, and then applying the coating solution for the image-receiving layer. It can be manufactured by a coating method in which a liquid is applied to the surface of a base material and dried.

[0063] The image receiving layer can also be produced by a lamination method in which a mixture containing the components forming the image receiving layer is melt extruded and laminated onto the surface of a base material. Examples of the solvent used in the coating method include conventionally known solvents such as water, alcohol, methyl ethyl ketone, toluene, dioxane, and cyclohexanone.

[0064] When employing the lamination method, a coextrusion method may also be employed.

The image-receiving layer may be formed over the entire surface of the base material, or may be formed on a part of the surface of the base material.

The thickness of the image receiving layer formed on the surface of the base material is:
Generally, it is about 2 to 50 μm, preferably about 3 to 20 μm.

On the other hand, when the image-receiving layer is self-supporting and therefore forms an image-receiving sheet for thermal transfer recording, the thickness of the image-receiving layer is about 60 to 200 μm, preferably about 90 to 150 μm.

[0068] In this image-receiving sheet for thermal transfer recording, in order to more effectively prevent fusion with the ink layer of the ink sheet for thermal transfer recording, a release material (the above-mentioned silicone resin, modified A release layer containing a silicone resin, a silicone oil film, or a cured product thereof may be further laminated.

[0069] The thickness of this peeling layer is usually 0.03 to 2.
It is 0 μm.

Further, in the image-receiving sheet for thermal transfer recording of the present invention, a cushion layer may be provided between the base material and the image-receiving layer.

[0071] By providing a cushion layer, noise is reduced and an image corresponding to image information can be transferred and recorded with good reproducibility.

Examples of the material constituting the cushion layer include urethane resin, acrylic resin, ethylene resin, butadiene rubber, and epoxy resin. The thickness of the cushion layer is usually 1 to 50 μm, preferably 3 to 30 μm.
It is μm.

[3. ] Ink sheet for thermal transfer recording The ink sheet for thermal transfer recording can be composed of a support and an ink layer formed thereon. - Ink layer - The ink layer basically contains a heat-diffusible dye and a binder.

1. Heat-diffusible dyes Examples of heat-diffusible dyes include cyan dyes, magenta dyes, and yellow dyes.

[0075] As the cyan dye, JP-A-59-7
No. 8896, No. 59-227948, No. 60-249
No. 66, No. 60-53563, No. 60-130735
No. 60-131292, No. 60-239289, No. 61-19396, No. 61-22993, No. 6
No. 1-31292, No. 61-31467, No. 61-3
No. 5994, No. 61-49893, No. 61-1482
No. 69, No. 62-191191, No. 63-91288
Examples include naphthoquinone dyes, anthraquinone dyes, and azomethine dyes described in publications such as No. 63-91287 and No. 63-290793.

[0076] As the magenta dye, JP-A-59-
No. 78896, JP-A-60-30392, JP-A-60
-30394, JP 60-253595, JP 61-262190, JP 63-5992, JP 63-205288, JP 64-159, JP 64-63194 Examples include anthraquinone dyes, azo dyes, azomethine dyes, etc., which are described in various publications such as No.

[0077] As a yellow dye, JP-A-59-78
No. 896, JP-A-60-27594, JP-A-60-3
No. 1560, JP-A-60-53565, JP-A-61-
Examples include methine dyes, azo dyes, quinophthalone dyes, and anthrisothiazole dyes described in publications such as No. 12394 and JP-A-63-122594.

Particularly preferred as the heat-diffusible dye is a compound having an open-chain or closed-chain active methylene group, and an oxidized product of a p-phenylenediamine derivative or a p-phenylenediamine derivative.
Azomethine dye obtained by a coupling reaction with an oxidized product of an aminophenol derivative and indoaniline obtained by a coupling reaction with an oxidized product of a phenol or naphthol derivative or a p-phenylenediamine derivative or an oxidized product of a p-aminophenol derivative. It is a pigment.

The heat-diffusible dye contained in the ink layer may be any of yellow, magenta, and cyan dyes as long as the image to be formed is monochromatic. Furthermore, depending on the color tone of the image to be formed, it may contain two or more of the three types of dyes or other heat-diffusible dyes.

[0080] The amount of the heat-diffusible dye used is usually 0.1 to 20 g, preferably 0.2 to 20 g per m2 of support.
It is 5g.

2. Binder As a binder, cellulose resin such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate;
Vinyls such as polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinylpyrrolidone, polyvinyl acetate, polyacrylamide, polyvinyl acetoacetal, styrene resin, styrene copolymer resin, polyacrylic acid ester, polyacrylic acid, acrylic acid copolymer, etc. Examples include resins based on resins, rubber resins, ionomer resins, olefin resins, and polyester resins.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal or cellulose resins are preferred because of their excellent storage stability.

[0083] The above-mentioned various binders can be used singly or in combination of two or more.

The weight ratio of the binder to the heat-diffusible dye is preferably from 1:10 to 10:1, particularly preferably from 2:8 to 8:2.

3. Other Optional Components Furthermore, various additives may be added to the ink layer within a range that does not impede the object of the present invention.

The additives include silicone resin, silicone oil (reactive curing type is also possible), silicone modified resin, fluororesin, surfactant, and peeling compounds such as waxes, fine metal powder, silica gel, and metal oxide. Examples include fillers such as carbon black and fine resin powder, and curing agents that can react with binder components (for example, radiation active compounds such as isocyanates, acrylics, and epoxies).

Furthermore, examples of additives include heat-melting substances for promoting transfer, such as waxes and higher fatty acid esters, which are described in JP-A-59-106997.

-Support- The support used in the present invention may be anything as long as it has good dimensional stability and can withstand the heat during recording with a thermal head, such as condenser paper or glassine paper. Tissue paper, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polycarbonate,
polysulfone, polyvinyl alcohol, cellophane,
A heat resistant plastic film such as polystyrene can be used.

The thickness of the support is preferably 2 to 10 μm, and the support has a subbing layer for the purpose of improving adhesion with the binder and preventing transfer and dyeing of the dye to the support. You can leave it there.

Furthermore, the back side of the support (the side opposite to the ink layer)
An anti-sticking layer may be provided for the purpose of preventing adhesion or sticking of the head to the support or generation of wrinkles on the thermal transfer recording medium. The thickness of this anti-sticking layer is usually 0.1 to 1 μm.The shape of the support is not particularly limited and may be of any shape, such as a wide sheet or film, a narrow tape or card.

[4. ] Manufacture of ink sheet for thermal transfer recording Ink sheets for thermal transfer recording are prepared by dispersing or dissolving the various components forming the ink layer in a solvent to prepare a coating liquid for forming an ink layer, and applying this to a support. It can be manufactured by coating the surface of the surface and drying it. Note that one or more of the binders can be used by dissolving them in a solvent or dispersing them in a latex form.

Examples of the solvent include water, alcohols (eg, ethanol, propanol), cellosolves (eg, methyl cellosolve, ethyl cellosolve), and aromatics (eg, methyl cellosolve, ethyl cellosolve).
(e.g., toluene, xylene, chlorobenzene), ketones (e.g., acetone, methyl ethyl ketone), ester solvents (e.g., ethyl acetate, butyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane), chlorinated solvents (e.g., chloroform, trichloroethylene)
etc. can be mentioned.

[0093] For the above-mentioned coating, conventional methods such as a surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method, etc. can be employed.

The ink layer may be formed as a layer containing a monochromatic heat-diffusible dye on the entire surface or a part of the surface of the support, or may be formed as a layer containing a monochromatic heat-diffusible dye, or a layer containing a yellow ink containing a binder and a yellow dye. A magenta ink layer containing a binder and a magenta dye and a cyan ink layer containing a binder and a cyan dye are formed on the entire surface or a part of the surface of the support in a constant repetition along the plane direction. You can leave it there.

[0095] In addition to the three ink layers arranged in the plane direction, a black ink layer containing a black image forming substance may be interposed. Note that with regard to the black ink layer, clear images can be obtained with either the diffusion transfer type or the melt transfer type.

The thickness of the ink layer thus formed is usually 0.2 to 10 μm, preferably 0.3 to 3 μm.
It is μm.

[0097] It is also possible to make the ink sheet for thermal transfer recording easier to use by forming perforations or providing detection marks for detecting the positions of areas with different hues.

The ink sheet for thermal transfer recording is not limited to the structure consisting of a support and a heat-sensitive layer formed thereon, and other layers may be formed on the surface of the ink layer. For example, an overcoat layer may be provided for the purpose of preventing fusion with the image-receiving sheet for thermal transfer recording and setting-off (blocking) of the heat-diffusible dye.

[5. ] Image formation (thermal transfer recording) To form an image, the ink layer of the ink sheet for thermal transfer recording and the image-receiving layer of the image-receiving sheet for thermal transfer recording are overlapped,
Image-wise thermal energy is applied to the interface between the ink layer and the image-receiving layer. Then, the heat-diffusible dye in the ink layer is vaporized or sublimated in an amount corresponding to the applied thermal energy, transferred to the image-receiving layer side, and received, thereby forming an image on the image-receiving layer.

In the present invention, since the image-receiving layer of the image-receiving sheet for thermal transfer recording contains a vinyl chloride resin and a heat stabilizer, the fixability of the heat-diffusible dye from the ink sheet for thermal transfer recording is good. Moreover, the image-receiving sheet for thermal transfer recording of the present invention not only can reliably prevent the dye from bleeding due to light and heat during storage, but also has excellent image storage stability.

[0101] As the heat source for providing the thermal energy,
A thermal head is generally used, but other known devices such as a laser beam, an infrared flash, and a thermal pen can also be used.

When a thermal head is used as a heat source for applying thermal energy, the applied thermal energy can be varied continuously or in multiple stages by modulating the voltage or pulse width applied to the thermal head.

[0103] When using laser light as a heat source for providing thermal energy, the heat energy provided can be changed by changing the amount of laser light and the irradiation area.

In this case, in order to facilitate the absorption of laser light, a laser light absorbing material (for example, in the case of a semiconductor laser, carbon black, an infrared absorbing substance, etc.) may be present in the ink layer or near the ink layer. When using a laser beam, it is preferable to bring the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording into close contact with each other.

[0105] If a dot generator incorporating an acousto-optic element is used, thermal energy can be applied depending on the size of halftone dots.

[0106] When an infrared flash lamp is used as a heat source for providing thermal energy, heating is preferably performed through a colored layer such as black, as in the case of using laser light. Alternatively, heating may be performed through a pattern or halftone dot pattern that continuously expresses the shading of an image, such as black, or a colored layer such as black and a negative pattern corresponding to the negative of the above pattern. Heating may be performed in combination.

Thermal energy may be applied from the ink sheet side for thermal transfer recording, from the image receiving sheet side for thermal transfer recording, or from both sides, but priority is given to effective use of thermal energy. If so, it is desirable to do so from the ink sheet side for thermal transfer recording.

[0108] By the above thermal transfer recording, a one-color image can be recorded on the image-receiving layer of an image-receiving sheet for thermal transfer recording, but according to the method described below, it is possible to obtain a color photo-like color image consisting of a combination of each color. You can also do it.

For example, by sequentially replacing yellow, magenta, cyan, and, if necessary, black thermal transfer recording sheets and performing thermal transfer according to each color, a photographic color image consisting of a combination of each color is obtained. You can also do that.

The following method is also effective. That is, instead of using ink sheets for heat-sensitive transfer recording of each color as described above, an ink sheet for heat-sensitive transfer recording is used that has areas pre-painted in each color.

[0111] First, the yellow area is used to thermally transfer the yellow color separation image, and then the magenta area is used to thermally transfer the magenta color separation image. , and, if necessary, a method of thermally transferring the black color image in this order.

[0112] Although it is possible to obtain a color photographic-like color image with this method, a further advantage of this method is that there is no need to replace the heat-sensitive sheet for heat-sensitive transfer recording as described above. There is.

[0113]

[Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

[0114] In the following, "parts" means "parts by weight."

(Example 1) A polyethylene terephthalate film with a thickness of 6 μm [manufactured by Toray Industries, Inc.] was used as a support.
On the corona-treated surface of One or two drops of [X-41, 4003A, manufactured by Shin-Etsu Silicone Co., Ltd.] were applied with a dropper and spread over the entire surface, and a back surface treatment coating was performed to obtain an ink sheet for thermal transfer recording.

Coating liquid for ink layer formation Disperse dye [manufactured by Nippon Kayaku Co., Ltd....4 parts Kayaset Blue 714] Polyvinyl butyral...5 parts [degree of polymerization 1
700, trade name BX-1: manufactured by Sekisui Chemical Co., Ltd.] Methyl ethyl ketone 90 parts Cyclohexanone 5 parts.

[0117] Next, a coating solution for forming an image-receiving layer having the following composition was coated on a 100 μm thick White PET [trade name W400; manufactured by Diafoil Co., Ltd.] as a base material by a wire bar coating method, and then coated with a dryer. After temporary drying, it was dried in an oven at a temperature of 100° C. for 1 hour to obtain an image-receiving sheet for thermal transfer recording, in which an image-receiving layer with a thickness of 5 μm was formed on synthetic paper.

Coating liquid for forming image-receiving layer Vinyl chloride copolymer 9.45
Part [Nippon Zeon Co., Ltd., MR-110] Methyltin isooctylthioglycolate...0.05 part
[Manufactured by Katsuta Chemical Co., Ltd., TM-181FSJ] Polyester modified silicone oil 0.5 part
[Manufactured by Shin-Etsu Silicon Co., Ltd., X-24-8310]
Methyl ethyl ketone...75 parts
Cyclohexanone・・・・・・・・・15 parts・
Next, the ink sheet for heat-sensitive transfer recording and the image-receiving sheet for heat-sensitive transfer recording are overlapped so that the surface of the ink layer of the former is in contact with the surface of the image-receiving layer of the latter, and the support side of the ink sheet for heat-sensitive transfer recording is Output 0.4W/dot, pulse width 0.3-10msec using thermal head
Image recording was performed by heating at a dot density of 6 dots/mm.

After recording the image, the transfer density on the surface of the image-receiving layer of the image-receiving sheet for thermal transfer recording, the heat-resistant storage stability of the image, and the white background durability of the image-receiving layer were evaluated according to the following criteria. The results are shown in Table 1.

Transfer density: Reflection density OD value was measured using an optical densitometer. ◎・・・OD value is 2.0 or more. ○...OD value is 1.7 to 2.0. X...OD value is 1.7 or less.

Heat resistance (heat-resistant image storage stability): The image-receiving sheet for thermal transfer recording on which an image has been recorded is stored at 77°C and relative humidity 80%.
The sample was kept in this environment for 72 hours, and fading and discoloration of the dye was visually evaluated. ×: The pigment was significantly faded or discolored. ○: There was little fading or discoloration of the pigment.

White Background Durability of Image-Receiving Layer The image-receiving sheet for thermal transfer recording on which an image was recorded was kept in an environment of 77° C. and 80% relative humidity for 30 days, and the reflection density of the white background was measured. Reflection density is Sakura Densitometer P
Blue density was measured using DA-65 (Example 2) The same procedure as in Example 1 was carried out except that the coating solution for forming an image-receiving layer in Example 1 had the following composition. The results are shown in Table 1.

Coating liquid for forming image-receiving layer: Vinyl chloride copolymer: 6 parts [manufactured by Tosoh Corporation, Luron Q640] Vinyl chloride resin: ......4 parts [manufactured by Shin-Etsu Chemical Co., Ltd., TK-600 tris tridecyl phosphite] ...1 part [manufactured by Daihachi Chemical Co., Ltd., T
TDP-1] Polyester modified silicone oil 1 part [manufactured by Shin-Etsu Silicon Co., Ltd., X-24-8300] Methyl ethyl ketone 90 parts.

(Example 3) The same procedure as in Example 1 was carried out except that the composition of the coating liquid for forming an image-receiving layer in Example 1 was changed to the following composition. The results are shown in Table 1.

Coating liquid for forming image-receiving layer Vinyl chloride copolymer 6 parts [BAS
F Co., Ltd., Laroflex-MP25] Polyvinyl chloride 3 parts [Shin-Etsu Chemical Co., Ltd., TK-300] Ba/Zn composite stabilizer... ...0.2 part [manufactured by Akishima Chemical Co., Ltd., LT-700R] Polyester modified silicone oil ...0.5 part [manufactured by Shin-Etsu Silicon Co., Ltd., X-24]
-8300] Methyl ethyl ketone 4
0 parts Cyclohexanone...10 parts.

(Example 4) The same procedure as in Example 1 was carried out except that the composition of the coating liquid for forming an image-receiving layer in Example 1 was changed to the following composition. The results are shown in Table 1.

Coating liquid for forming image-receiving layer Vinyl chloride copolymer...6 parts [BAS
Manufactured by F Co., Ltd., Laroflex-MP25] Polyvinyl chloride 3 parts [Shin-Etsu Chemical Co., Ltd.
Co., Ltd., TK-300] Methyltin isooctylthioglycolate 0.05 part [Katsuta Chemical Co., Ltd., TM-18
1FSJ] Plasticizer・・・・・・・・・・・・・・・0
．． Part 5 [ADK CIZER C manufactured by Asahi Denka Co., Ltd.
-79] Polyester modified silicone oil...0.
5 parts [manufactured by Shin-Etsu Silicon Co., Ltd., X-24-8300] Methyl ethyl ketone 40 parts cyclohexanone 10 parts.

(Comparative Example 1) The same procedure as in Example 1 was carried out except that the stabilizer TM-181FSJ was removed from the composition of the coating solution for forming an image-receiving layer in Example 1. The results are shown in Table 1.

(Comparative Example 2) The same procedure as in Example 1 was carried out except that the stabilizer TTDP-1 was omitted from the composition of the coating liquid for forming an image-receiving layer in Example 2. The results are shown in Table 1.

(Comparative Example 3) The same procedure as in Example 1 was carried out except that the composition of the coating liquid for forming an image-receiving layer was changed to the following composition. The results are shown in Table 1.

Coating liquid for forming image-receiving layer: Vinyl chloride resin: 9.5 parts [manufactured by Shin-Etsu Chemical Co., Ltd., TK-600] Polyester-modified silicone oil: 0.5 part [Shin-Etsu Silicon Co., Ltd.
X-24-8300] Methyl ethyl ketone...
・・・・・・80 parts cyclohexanone・・・・・・・・・
・20 copies.

[0132]

[Table 1]

[0133]

[Effect of the invention] The image-receiving sheet for thermal transfer recording of the present invention has the following features:
Excellent transferability of dyes from thermal transfer recording ink sheets during thermal transfer, excellent storage stability of the resulting images, and good durability of the white background of the image-receiving layer during storage.

Claims (1)

[Claims] 1. An image-receiving sheet for thermal transfer recording, comprising an image-receiving layer containing a vinyl chloride resin and a heat stabilizer.