JPH0624151A - Manufacture of image receiving sheet for thermal transfer recording - Google Patents

Abstract

PURPOSE:To provide a method for producing an image receiving sheet for thermal transfer recording which has good adhesion between a polyolefine resin layer and an emulsion layer and is prevented from peeling of an image receiving layer by flexural stress and a method for producing the image receiving sheet for thermal transfer recording which is free from cissing in the application of a coating liquid for forming the image receiving layer and has a good coating property. CONSTITUTION:When an image receiving layer is laminated on a substrate which has a polyolefine surface for the lamination, the polyolefine surface treated before the image receiving layer is formed by a coating method. The method for the surface treatment is preferably selected from treatment methods including corona discharge, flame, ozone, primer, ultraviolet, radiation, roughening, low-temperature plasma, and grafting treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording image-receiving sheet, and more particularly to a method for producing a heat-sensitive transfer recording image-receiving sheet having a polyolefin resin layer on a substrate and an image-receiving layer laminated thereon.

[0002]

2. Description of the Related Art Conventionally, various methods are known as image forming (printing / copying) methods. In recent years, various methods have been studied for efficiently forming not only monochrome images but also high-quality full-color images.

For example, as a method for obtaining a color hard copy, a color recording technique such as ink jet, electrophotography, thermal transfer recording and the like is being studied. Of these, especially the thermal transfer recording method is not limited to monochrome recording,
Easy operation and maintenance even for color recording,
It has advantages such as miniaturization and cost reduction of the device.

In the thermal transfer recording system, the ink layer surface of the thermal transfer recording ink sheet (transfer sheet) having an ink layer on the substrate and the image receiving layer surface of the thermal transfer recording image receiving sheet are superposed, and from the back surface of the ink sheet. Imagewise heating is performed by a thermal head (or heat supply means such as laser) to transfer the ink (dye) to the image receiving sheet,
This is a method of forming a desired image.

This thermal transfer recording system includes a thermal fusion transfer system and a thermal diffusion transfer system. The former is a method of using an ink sheet having a heat-fusible ink layer on a base material, and melt-transferring a portion of the ink layer heated by a thermal head or the like onto an image receiving sheet, and the latter is a method of transferring the part on the base material. An ink sheet having an ink layer containing a heat diffusible dye (sublimation dye) is used, and the heat diffusible dye is sublimated (vaporized) from the ink layer by heating with a thermal head or the like, and is diffusion-transferred to an image receiving sheet. It is a method to do. The thermal diffusion transfer method is also called a sublimation transfer method.

Among them, the thermal diffusion transfer system can control the gradation of an image by changing the transfer amount of the dye according to the change of thermal energy of the thermal head and the like, so that the gradation of a photographic image or the like can be controlled. It is suitable for forming an image.
Further, according to this method, not only a monochrome image but also a full-color image can be easily formed. For example, by superimposing recording of three primary colors such as cyan, magenta and yellow, it is possible to obtain a continuous change in shade of color. A color image for color printing can be easily formed. From this point of view, the thermal diffusion transfer method has recently been particularly attracting attention.

That is, with the development of the thermal diffusion transfer system, the thermal transfer recording method is not limited to the formation of a normal image such as a character image by the thermal fusion transfer system, but a multicolor gradation color image by the thermal diffusion transfer system. It can also be used to create (eg, color facial photographs). Moreover, the formation of images having these different characteristics can be performed extremely efficiently by a simple operation of appropriately selecting an ink sheet using a simple device such as a thermal transfer printer.

Due to these advantages, the thermal transfer recording method using the thermal diffusion transfer method has recently been actively used for producing an image recording body having a gradation color image such as a color photographic image. I began to be hurt. Of course, in the case of ID cards such as membership cards and identification cards, not to mention image-receiving sheets for various printers, it is important to record face photographs in addition to various information such as codes to identify the person. Therefore, it has attracted particular attention as its application field.

By the way, in the thermal transfer recording of the thermal diffusion transfer system, the dye used in the thermal transfer recording material is important, and in the conventional ones, the stability of the obtained image, that is, the light resistance and the fixing property are not good. It has the drawback of

In order to improve these points, JP-A-59-7
8893, 59-109394, 60-2398, etc. use a chelating heat-diffusible dye and form an image with the chelated dye on the image-receiving sheet for thermal transfer recording. A method is disclosed.

Further, the conventional image-receiving sheet for thermal transfer recording is
Polyester resin, polyvinyl chloride resin, copolymer of vinyl chloride and other monomers as binder for image receiving layer,
Polyvinyl butyral, polyvinyl pyrrolidone and the like are used, and a coating method has been widely used as a method of forming an image receiving layer from the viewpoints of thinning and surface uniformity.

By the way, as the base material of the image-receiving sheet for thermal transfer recording, paper containing pulp as a main component, JP-A-62-158095
No. 4, etc., Japanese Patent Publication No. 46-40794, JP-A-57-40
-149363, Japanese Patent Publication No. 60-36173, etc., synthetic paper comprising a stretched film of a polyolefin resin containing inorganic fine powder, JP-A-60-245593, JP-A-63-1595,
A laminate of resin films described in 1-108040 and 2-241740 has been devised.

Among them, polyolefin resin film, synthetic paper or resin film laminated with polyolefin resin is excellent in cushioning property and therefore advantageous in preventing transfer omission, and is widely used because of high transfer density. Further, in order to have a heat insulating effect, a polyolefin resin layer containing inorganic fine particles, stretched and voided has a higher heat insulating property than the above-mentioned ones, so that those effects are further increased and high sensitivity is obtained. It is supposed to be.

However, when it is attempted to form an image receiving layer by a coating method on a substrate having a surface on which these image receiving layers are laminated made of a polyolefin resin, the adhesive force between the interface between the polyolefin resin layer and the image receiving layer is increased. However, the image receiving layer may be peeled off when the image receiving sheet is deformed, or cissing may occur when the image receiving layer forming coating solution is applied (particularly in the case of an aqueous coating solution).

[0015]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a method for producing a heat-sensitive transfer image-receiving sheet which has excellent adhesion between the polyolefin resin layer and the image-receiving layer and is free from peeling of the image-receiving layer due to bending stress. Another object of the present invention is to provide a method for producing an image-receiving sheet for heat-sensitive transfer recording, in which no flicker is observed at the time of application of the image-receiving layer forming coating solution and good coatability is obtained.

[0016]

The above object of the present invention is to, after laminating an image-receiving layer on a substrate having a polyolefin resin on the surface on which the image-receiving layer is laminated, after surface-treating the resin surface of the polyolefin,
This is achieved by a method for producing an image-receiving sheet for thermal transfer recording, in which an image-receiving layer is laminated and formed by a coating method. At this time, the surface treatment method used is any one of corona discharge treatment, flame treatment, ozone treatment, primer treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, low-temperature plasma treatment or graft treatment. It is preferable to use a chemical treatment.

The items described in claims 6 to 10 are preferable measures in the production of the heat-sensitive transfer recording image-receiving sheet of the present invention.

Corresponding to the use of thermoplastic resin as the core material,
It is an effective form for slightly thick things such as cards,
Cushioning properties and heat insulating properties are provided on the printed surface side as described above, and the back surface has a paper-like form, which is also good against the touch, and because it contains a large amount of inorganic pigments, it is also writable. It is excellent. Hereinafter, the present invention will be described more specifically.

(1) Image-Receiving Sheet for Thermal Transfer Recording The image-receiving sheet for thermal transfer recording of the present invention basically comprises an image receiving layer laminated on a substrate having a polyolefin surface.

As a support for a base material whose surface on which the image-receiving layer is laminated is a polyolefin resin, a paper containing pulp as a main component, Japanese Patent Publication No. 46-40794, Japanese Patent Publication No. 57-149363, and Japanese Examined Patent Publication No. 60. -36173 etc. may be such as synthetic paper consisting of a stretched film of a polyolefin resin containing inorganic fine powder, the thermoplastic resin, polyethylene terephthalate, polybutylene terephthalate, such as polyethylene terephthalate ester-based Resin; PV
Vinyl chloride resin such as C, vinyl chloride-vinyl acetate copolymer, PVC-EVA graft polymer; vinylidene chloride resin such as polyvinylidene chloride; polystyrene, AB
Styrene resins such as S and AS; polyolefin resins such as polyethylene and polypropylene; cellulose resins such as nitrocellulose and methyl cellulose; PMM
(Meth) acrylic resin such as A; ionomer resin,
Polyvinyl alcohol, polyarylate, polyacetal, polyamide, polysulfone, polyether nitrile, polyether ether ketone, polycarbonate,
Examples thereof include modified polyphenylene oxide, polyoxybenzylene, polyetherimide, polyamide, polyphenylene sulfide, and polyparabanic acid resin.
Depending on the thickness of the support, when flexibility is required, ester resins, vinyl chloride resins, styrene resins, polyolefin resins, etc. are preferred, and when relatively rigid is required. Examples include (meth) acrylic resin, polyarylate, polyacetal, polyamide, polysulfone, polyether nitrile, polyether ether ketone, polycarbonate, modified polyphenylene oxide, polyoxybenzylene, polyetherimide, polyamideimide, polyphenylene sulfide,
Polyparabanic acid resin and the like are preferable. When heat resistance is required, polyamide, PET, polyarylate,
Polyacetal, polyamide, polysulfone, poly-
Ternitrile, polyetheretherketone, polycarbonate, modified polyphenylene oxide, polyoxybenzylene, polyetherimide, polyamideimide,
Polyphenylene sulfide, polyparabanic acid resin and the like are preferable, and when heat resistance is not required so much, polyolefin, PVC, polyvinylidene chloride, PVA, acrylic resin, cellulose resin, styrene resin, ionomer resin and the like are preferable.

In the base material, white pigments such as titanium white, magnesium sulfate, zinc oxide, barium sulfate, silica, talc, clay and sulfuric acid are added in order to enhance the sharpness of the image formed in the subsequent step. Calcium or the like may be added.

The thickness of the substrate is usually 20 to 1000 μm, preferably 20 to 800 μm, and is appropriately selected from such a range.

As the polyolefin resin forming the polyolefin resin layer, polyethylene, polypropylene, polybutene-1, polyisobutylene, polypentene-
1, polyhexene-1, poly (3-methylbutene-1), poly (4-methylpentene-1), poly (4-methylhexene-)
1) etc. and their copolymers, polystyrene, ethylene-vinyl acetate copolymers, etc., among which homopolymers or copolymers of unsaturated aliphatic olefins such as polyethylene, polypropylene, ethylene-propylene copolymers, etc. It is preferable in terms of cushioning property and prevention of blocking. Examples of the inorganic filler contained in the polyolefin resin layer include metal oxides such as silica, alumina, titanium oxide and zinc oxide; metal salts such as calcium carbonate, barium sulfate, aluminum sulfate and aluminum hydroxide; acid clay and activated clay. , Talc, clay, kaolin, etc., and can be arbitrarily selected depending on the required whiteness and surface gloss.

In the present invention, in order to improve the wettability of the coating solution for the image receiving layer on the surface of the base material, the adhesion to the image receiving layer, and the like, corona discharge treatment, flame treatment, ozone treatment, primer treatment, and ultraviolet treatment. , Radiation treatment, surface roughening treatment, or chemical treatment improves the wettability of the coating solution or the poor adhesion between the image receiving layer and the substrate. (Especially for polyolefins).

The above method may be any method as long as it achieves those objects. Other,
For details, refer to “Basics and Applications of Polymer Surfaces (below)”, Kagaku Dojin, Chapter 2 and / or “Handbook of Polymer New Materials”, Maruzen, Chapter 8.

Surface treatment by low temperature plasma is roughly classified into plasma surface treatment and plasma polymerization, and any of them can be used. In the low temperature plasma reaction, the chemical structure and physical structure of the polymer surface layer can be modified to suit the purpose by appropriately selecting the type of gas to be plasma and the plasmaization conditions. For example, (1) surface etching, (2) surface layer cross-linking, (3) surface chemical modification,
It is possible to say (4) graft polymerization and (5) plasma polymerization coating. Examples of the plasma reactor include a glow discharge device, a sputtering method, an ion plating method and a plasma CVD method. The polymer surface modification by plasma includes surface cross-linking structure, functional group imparting, etching, etc., and achieves the object of the present invention to improve the wettability of the image receiving layer coating solution and the adhesiveness with the image receiving layer. Any method may be used as long as it is one. In plasma polymerization, a low-temperature plasma state is created by glow discharge, the monomers are dissociated and recombined in the polymerization to perform polymerization, and when the image-receiving layer is coated on the image-receiving layer coating surface, adhesion with the image-receiving layer is achieved. A thin film having a functional group for strengthening can be obtained. For other details, refer to “Basics and Applications of Polymer Surfaces (above)”, Kagaku Dojin, Chapter 8 and / or “Handbook of New Polymer Materials”, Maruzen, Chapter 8.

Improving the wettability of the coating solution for the image receiving layer by introducing a graft chain into the surface in contact with the surface of the image receiving layer by graft polymerization or the like.
A method of achieving improved adhesion with the image receiving layer is also effective. Graft polymerization methods include radiation methods (γ-rays, accelerated electrons, etc.), low temperature plasma methods, methods of graft polymerizing monomers such as light / ultraviolet methods, and graft coupling methods of grafting polymers. It can be used if a functional group capable of achieving the object of the present invention can be introduced. For other details, refer to "Basics and Applications of Polymer Surfaces (above)" Kagaku Dojin, Chapter 9 and / or "Handbook of New Polymer Materials" Maruzen, Chapter 8.

The image-receiving layer in the image-receiving sheet for heat-sensitive transfer recording of the present invention is not particularly limited except that it is provided by a coating method, and has various materials, compositions, layer constitutions, etc. depending on the purpose of use. can do. For example, it may be the same as the image-receiving layer having various materials, compositions, layer constitutions, etc., which have been proposed for the conventional image-receiving sheet for thermal transfer recording of this kind, or those obtained by appropriately improving them. Good.

Needless to say, when the image-receiving sheet for heat-sensitive transfer recording of the present invention is used for recording gradation color images such as color face photograph images such as ID cards such as ID cards, at least thermal diffusion transfer is used. The image receiving layer is provided so that a clear color image can be easily formed by the method. In such a case, the image receiving layer is formed of a material having a sufficient dyeing property for at least the heat diffusible dye (sublimable dye) transferred from the ink sheet, and usually,
A suitable resin is used as the main component.

Examples of such resins include polyvinyl chloride resins, copolymer resins of vinyl chloride and other monomers (eg alkyl vinyl ether, allyl glycidyl ether, vinyl propionate, etc.), polyvinylidene chloride resins, Polyester resin, acrylic ester,
Methacrylic acid ester, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate, polysulfone, polyarylate, polyparabanic acid, cellulose triacetate, styrene acrylate resin, vinyltoluene acrylate resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone Examples thereof include resins, styrene-maleic anhydride resins, polyacrylonitrile resins, and the like. These resins can be used alone or in combination of two or more.

The above various resins may be newly synthesized and used, or commercially available products may be used.

In forming the image-receiving layer, the various resins described above utilize their reaction active points (if there are no reaction active points, they are imparted to the resin), and radiation, heat, moisture, catalysts are used. You may bridge | crosslink or harden | cure by etc. In that case, a radiation-active monomer such as epoxy or acrylic, or a crosslinking agent such as isocyanate can be used.

When the heat diffusible dye undergoes a chelating reaction with a metal ion, the resin may contain a compound containing a metal ion, if necessary.

Examples of the metal ions constituting the metal ion-containing compound include divalent and polyvalent metals belonging to Groups I to VIII of the Periodic Table, among which Co and C
r, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti, Zn and the like are preferable, and Ni, Cu, Co, Cr, Zn and the like are particularly preferable.

The compound containing these metal ions is preferably an inorganic or organic salt of the metal and a complex of the metal. As a specific example, a complex represented by the following general formula and containing Ni ²⁺ , Cu ²⁺ , Co ²⁺ , Cr ²⁺ and Zn ²⁺ is preferably used.

[0036] _{[M (Q 1) k (} Q 2) m (Q 3) n] p + · P (L) - However, M in the formula represents a metal _{ion, Q 1, Q 2, Q} 3 each M Represents a coordination compound capable of forming a coordination bond with a metal ion, and these coordination compounds may be selected from the coordination compounds described in, for example, “Chelate Chemistry (5) (Nankodo)”. it can. Particularly preferred is a coordination compound having at least one amino group that forms a coordinate bond with a metal, and more specifically, ethylenediamine and its derivatives, glycinamide and its derivatives,
Picolinamide and its derivatives are mentioned.

L is a counter anion capable of forming a complex,
Examples thereof include inorganic compound anions such as Cr, SO ₄ , and ClO ₄ , and organic compound anions such as benzenesulfonic acid derivatives and alkylsulfonic acid derivatives. Particularly preferred are tetraphenylboron anion and its derivatives, and alkylbenzenesulfonic acid anion and its derivatives. It is a derivative. k
Represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0. These are tetradentate or hexadentate in the complex represented by the general formula. Position, or the number of Q ₁ , Q ₂ , and Q ₃ ligands. p represents 1, 2 or 3.

As this kind of metal ion-containing compound,
Mention may be made of those exemplified in US Pat. No. 4,987,049.

When the metal ion-containing compound is added, the addition amount thereof is preferably 0.5 to 20 g / m ^{2 and} more preferably 1 to 15 g / m ² with respect to the image receiving layer.

If necessary, additives such as 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 image receiving layer. Further, a plasticizer, a heat-fusible substance or the like may be added as a sensitizer.

The release agent is for improving the releasability between the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet, and in the case of the present invention, it is preferably contained in the outermost layer.

Examples of such release agents include silicone oils (including those called silicone resins); solid waxes such as polyethylene wax, amide wax, Teflon powder; fluorine-based and phosphoric ester-based surfactants. And the like, among which silicone oil is preferable.
This silicone oil is a type that cures or reacts with a type that is simply added (simple addition type) (curing reaction type)
There is.

In the case of the simple addition type, it is preferable to use a modified silicone oil (for example, polyester modified silicone resin, urethane modified silicone resin, acrylic modified silicone resin, etc.) in order to improve the compatibility with the resin. .

The addition amount of these simple addition type silicone oils cannot be uniformly determined because it may vary depending on the type, but generally speaking, the resin for the image receiving layer is usually used. To 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

As the curing reaction type silicone oil,
Reaction-curable type (for example, one obtained by reaction-curing amino-modified silicone oil and epoxy-modified silicone oil),
Examples include photo-curing type and catalyst-curing type.

The amount of the curable silicone oil added is preferably 0.5 to 30% by weight of the resin for the image receiving layer.

A release agent layer may be provided on a part of the surface of the image receiving layer by dissolving or dispersing the release agent in an appropriate solvent and applying the solution, followed by drying.

Next, as the above-mentioned antioxidant, JP-A-59-1 is used.
82785, 60-130735, JP-A-1-127387, and other antioxidants, and compounds known to improve the image durability of photographs and other image recording materials can be mentioned.

Examples of the UV absorber and the light stabilizer include JP-A-59-158287, JP-A-63-74686, JP-A-63-145089, and JP-A-59-115889.
-196292, 62-229594, 63-122596, 61-2835
The compounds described in JP-A No. 95-2004, JP-A 1-204788, etc., and compounds known to improve the image durability of photographs and other image recording materials can be mentioned.

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 organic fine particles include resin particles such as fluorine resin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. Can be mentioned. These inorganic and organic resin particles differ depending on the specific gravity, but it is preferable to add 0 to 30% 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.

As the plasticizer, phthalic acid esters,
Trimellitic acid ester, adipic acid ester, other saturated or unsaturated carboxylic acid ester, citric acid ester, epoxidized soybean oil, epoxidized linseed oil, epoxy stearic acid epoxy, orthophosphoric acid ester, phosphite ester And glycol esters.

Examples of the heat-fusible substance include alcohols such as terpineol, menthol, 1,4-cyclohexanediol and phenol, amides such as acetamide and benzamide, coumarin and esters such as benzyl cinnamate, diphenyl ether and crown ether. Ethers such as camphor, ketones such as p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, higher fatty acids such as margaric acid, higher alcohols such as eicosanol, cetyl palmitate Higher fatty acid esters such as, higher fatty acid amides such as stearic acid amide, monomolecular compounds represented by higher amines such as behenylamine, carnauba wax, beeswax, paraffin wax, ester wax, montan wax, Waxes such as dowax, ester gum, rosin maleic acid resin, rosin derivative such as rosin phenol resin, phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene resin, aliphatic hydrocarbon resin, cyclopentadiene resin, polyolefin Resin, polyethylene glycol,
Examples thereof include polymer compounds represented by polyolefin oxides such as polypropylene glycol.

In the present invention, the above-mentioned heat-meltable substance preferably has a melting point or softening point of 10 to 150 ° C.

In the present invention, it is usually preferable to select the total amount of the additives added in the range of 0.1 to 30% by weight based on the resin for the image receiving layer.

The thickness of the image receiving layer is usually 3 to 30 μm.
It is suitable to select m, preferably 5 to 20 μm.

The image-receiving layer may be a single layer, or may have the same composition or different compositions as required.
You may provide as a multilayer structure more than a layer.

In the present invention, the image receiving layer can be formed by a known coating method. For example, the image-receiving layer is prepared by dispersing or dissolving the forming components in a solvent to prepare an image-receiving layer-forming coating liquid, and the image-receiving layer-forming coating liquid is added to the surface-treated polyolefin resin layer on the substrate. It can be formed by coating on the surface and drying.

As the solvent used in the above coating method, for example, water, alcohols (eg ethanol, propanol etc.), cellosolves (eg methyl cellosolve, ethyl cellosolve etc.), aromatics (eg toluene, xylene, chlorobenzene etc.) , Ketones (eg acetone,
Methyl ethyl ketone, etc.), ester solvents (eg ethyl acetate, butyl acetate etc.), ethers (eg tetrahydrofuran, dioxane etc.), chlorine solvents (eg methylene chloride, chloroform, trichloroethylene etc.) and the like.

For the coating, conventionally known gravure roll coating methods, extrusion coating methods, wire bar coating methods, roll coating methods and the like can be adopted. After this coating, by appropriately drying, an image receiving layer having a predetermined dry film thickness is formed.

The image receiving layer is not limited to a single layer structure,
It is also possible to have a structure having more layers. Further, the image receiving layer may be formed over the entire surface of the porous layer on the substrate,
If necessary, it may be formed on part of the surface.

In the image-receiving sheet of the present invention, in addition to the above-mentioned polyolefin resin substrate and image-receiving layer, an intermediate layer (if necessary) is further provided between the polyolefin resin substrate and the image-receiving layer for the purpose of improving whiteness. An undercoat layer) may be provided.

Further, an overcoat layer may be laminated on the surface of the image receiving layer for the purpose of preventing fusion between the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet. When the above-mentioned intermediate layer and overcoat layer are provided, it is preferable that the thickness of each layer is usually selected in the range of 0.1 to 20 μm.

If necessary, the back surface of the image-receiving sheet of the present invention may be provided with a backing layer such as an antistatic layer, a writing layer and a curl preventing layer. There is no particular limitation on the material, structure, forming method, etc. of this backing layer, and it may be formed as the same as the backing layer used for a known image receiving sheet of this type, or may be appropriately selected according to the purpose and the like. You can also Note that the backing layer is not limited to a single layer structure and can have a structure of two or more layers. The backing layer is usually formed over the entire back surface of the base material, but in some cases, it may be formed on a part of the back surface. This backing layer may be formed at any point in the manufacturing process of the image-receiving sheet of the present invention. Of course, the image-receiving sheet of the present invention may be manufactured using a substrate having a predetermined backing layer in advance, or may be formed after the image-receiving layer is formed.

(2) Ink sheet for thermal diffusion transfer As the support for the ink sheet, any material may be used as long as it has good dimensional stability and can withstand the heat at the time of recording with the thermal head, such as condenser paper or glassine paper. Thin paper, polyethylene terephthalate, polyethylene naphthalate,
A heat resistant plastic film such as polyamide, polyimide, polycarbonate, polysulfone, polyvinyl alcohol cellophane, or polystyrene can be used. The thickness of the ink sheet support is preferably 2 to 10 μm.

The shape of the ink sheet support is not particularly limited, and may be any shape such as a wide sheet or film, a narrow tape or a card.

When the ink layer is transferred to a heat-sensitive transfer recording image-receiving sheet by a thermal diffusion transfer method, it contains a thermal diffusion dye and a binder as essential components.

Examples of sublimable dyes include cyan dyes, magenta dyes and yellow dyes. Examples of cyan dyes include JP-A-59-78896, JP-A-59-227948, and JP-A-60-24.
966, 60-53563, 60-130735, 60-131292
No. 60, No. 60-239289, No. 61-19396, No. 61-22993, No. 6
1-31292, 61-31467, 61-35994, 61-49893
No. 61, No. 61-148269, No. 62-191191, No. 63-91288, No.
Examples thereof include naphthoquinone dyes, anthraquinone dyes, azomethine dyes and the like described in 63-91287 and 63-290793.

As the magenta dye, JP-A-59-78896 is available.
No. 60, No. 60-30392, No. 60-30394, No. 60-253595, No. 6
1-262190, 63-5992, 63-205288, 64-159
No. 64-63194 and the like, anthraquinone dyes, azo dyes, azomethine dyes and the like.

As a yellow dye, JP-A-59-78896
No. 60, No. 60-27594, No. 60-31560, No. 60-53565, No. 61
-12394, 63-122594, etc., include methine dyes, azo dyes, quinophthalone dyes, and anthryothiazole dyes.

Particularly preferred as the sublimable dye is
A compound having an active methylene group of open chain type or closed type,
An azomethine dye obtained by a coupling reaction with an oxidized form of a p-phenylenediamine derivative or a p-aminophenol derivative, and a phenol or naphthol derivative,
It is an indoaniline dye obtained by a coupling reaction with an oxidized form of a p-phenylenediamine derivative or a p-aminophenol derivative.

The sublimable dye contained in the sublimable dye-containing ink layer can be used if the image to be formed is a single color.
Any of yellow dye, magenta dye, and cyan dye may be used.

When a metal ion-containing compound is contained in the image-receiving layer of the heat-sensitive transfer recording image-receiving sheet, the sublimable dye is preferably a dye compound capable of forming a chelate with the metal ion-containing compound.

As the dye compound forming a chelate with the metal ion-containing compound, various known compounds can be appropriately selected and used. Specifically, for example, JP-A-59-78893, 59-109349, Japanese Patent Application No. 2-213303, 2
-214719 and 2-203742 cyan image forming dyes (hereinafter referred to as cyan dyes), magenta image forming dyes (hereinafter referred to as magenta dyes), yellow image forming dyes (hereinafter referred to as yellow dyes) ) And the like.

Among the above dyes, it is preferable to use at least a dye compound capable of forming a bidentate chelate with the above metal ion-containing compound. Examples of such dyes include dyes represented by the following general formula.

[0076]

[Chemical 1]

In the formula, at least one ring of X ₁ is 5 to 7
Represents a group of atoms necessary to complete an aromatic carbocycle or heterocycle composed of 6 atoms, and at least one of the adjacent positions of the carbon atoms bonded to the azo bond is substituted with a nitrogen atom or a chelating group. It is a carbon atom. X ₂ represents an aromatic heterocycle or an aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms. G represents a chelating group.

Whichever dye compound is used,
Depending on the color tone of the image to be formed, any two or more of the above three types of dyes or another sublimable dye may be contained.

The amount of the sublimable dye used is usually 0.1 to ²⁰ g, preferably 0.2 to 5 g, per m ^{2 of} the support.

As a binder for the ink layer, a cellulose-based compound such as a cellulose addition compound, a cellulose ester or a cellulose ether; a polyvinyl acetal resin such as polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal or polyvinyl butyral, polyvinyl pyrrolidone or polyvinyl acetate, Polyacrylamide, styrene resin, poly (meth) acrylic acid ester, poly (meth) acrylic acid, vinyl resin such as (meth) acrylic acid copolymer, rubber resin, ionomer resin, olefin resin, polyester resin Etc.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal, and cellulosic resins which are excellent in storage stability are preferable.

The various binders may be used alone or in combination of two or more.

The weight ratio of the binder to the heat-diffusible dye is preferably 1:10 to 10: 1, and particularly preferably 2: 8 to 7: 3.

Further, various additives can be appropriately added to the ink layer. As the additive, silicone resin, silicone oil (reaction-curable type is also possible), silicone-modified resin, fluororesin, surface-active agent and peelable compounds such as waxes, fine metal powder, silica gel, metal oxide,
Examples thereof include fillers such as carbon black and resin fine powder, and curing agents capable of reacting with a binder component (for example, radiation-active compounds such as isocyanates, acryls and epoxies).

Further, as an additive, a heat-melting substance for promoting transfer, for example, a compound described in JP-A-59-106997 such as wax or higher fatty acid ester can be mentioned.

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

Further, the support may have an undercoat layer for the purpose of improving the adhesiveness with the binder and preventing the dye from being transferred to the support and dyeing.

Further, a backing layer may be provided on the back surface of the support (on the side opposite to the ink layer) for the purpose of running stability, dimensional stability, heat resistance, antistatic and the like.

The thickness of the above-mentioned overcoat layer, subbing layer and backing layer is usually 0.1 to 1 μm.

For the thermal transfer recording ink sheet, an ink layer-forming coating liquid prepared by dispersing or dissolving the various components forming the ink layer in a solvent is applied to the surface of the support. It can be produced by drying.

The binder may be used alone or in combination of two or more in a solvent or dispersed in a latex form. Examples of the solvent include water, ethanol, tetrahydrofuran, methyl ethyl ketone, toluene, xylene, chloroform, dioxane, acetone, cyclohexane, and normal butyl acetate.

For the coating, conventionally known surface sequential coating by gravure roll coating method, extrusion coating method, wire bar coating method, roll coating method and the like can be adopted.

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 a yellow ink containing a binder and a yellow dye. A layer, 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 at regular intervals along the plane direction. May be. Further, in addition to the three ink layers arranged along the plane direction, a black ink layer containing a black image forming substance may be interposed.

With respect to the black ink layer, a clear image can be obtained by 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.

Incidentally, the ink sheet for thermal transfer recording may be formed with perforations or provided with detection marks for detecting the positions of areas having different hues, thereby facilitating use.

(3) Formation of Image (Thermal Transfer Recording) To form an image, the ink layer of the thermal transfer recording ink sheet and the image receiving layer of the thermal transfer recording image receiving sheet are superposed to form an ink layer and an image receiving layer. Imagewise heat energy is applied to the interface. Then, the heat diffusible dye in the ink layer is vaporized or sublimated by an amount corresponding to the applied heat energy, and is transferred to the image receiving layer side and received, and as a result, an image is formed on the image receiving layer.

As a heat source for giving the heat energy,
A thermal head is generally used, but other known ones such as a laser beam, an infrared flash, and a hot pen can be used.

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

When laser light is used as the heat source for giving heat energy, the heat energy to be given can be changed by changing the light quantity of the laser light or the irradiation area. In this case, a laser light absorbing material (for example, carbon black or a near infrared absorbing substance in the case of a semiconductor laser) may be present in the ink layer or in the vicinity of the ink layer in order to easily absorb the laser light.

If a dot generator with a built-in acousto-optical element is used, it is possible to give heat energy according to the size of the halftone dot.

When an infrared flash lamp is used as a heat source for giving heat energy, it is preferable to heat through a colored layer such as black as in the case of using laser light. Alternatively, heating may be performed via a pattern or a halftone dot pattern in which the shade of the image is continuously expressed, such as black, or a negative pattern corresponding to the negative of the above-mentioned pattern and a colored layer such as black on one surface. You may heat by combining.

The thermal energy may be applied from the thermal transfer recording ink sheet side, from the thermal transfer recording image receiving sheet side, or from both sides. If priority is given, it is desirable to carry out from the thermal transfer recording ink sheet side.

By the above thermal transfer recording, an image of one color can be recorded on the image-receiving layer of the image-receiving sheet for thermal transfer recording. According to the following method, a color photographic tone color image formed by combining the respective colors is obtained. You can also

For example, by replacing yellow, magenta, cyan and, if necessary, black heat-sensitive transfer recording heat-sensitive sheets in sequence and performing heat transfer corresponding to each color, a color image having a color photographic tone is obtained by combining each color. You can also

Further, instead of using the heat-sensitive transfer recording ink sheet of each color as described above, it is also effective to use a heat-sensitive transfer recording ink sheet having an area formed separately for each color.

That is, first, the yellow color-separated image is thermally transferred using the yellow area, and then the magenta color-separated image is thermally transferred using the magenta area. And, if necessary, the black color-separated image is thermally transferred in order.

This method also makes it possible to obtain a color image of a color photographic tone, but more conveniently, this method does not require the replacement of the heat-sensitive sheet for heat-sensitive transfer recording as described above. There is.

Further, after forming an image by the method described above, heat treatment may be performed by the method described above for the purpose of improving the image storability. For example, over the entire image forming surface, heat treatment may be performed using a portion of the ink sheet where the ink layer is not provided by the thermal head, or heat treatment such as a heat roll may be newly performed. Further, when the near infrared ray absorbent is contained, the image forming surface may be exposed by using an infrared flash lamp.

In any case, the heating means is not limited,
Since the purpose is to further diffuse the dye inside the image receiving layer, it is effective and preferable to heat from the support side of the image receiving layer.

[0111]

The present invention will be described in more detail with reference to the following examples.

Example 1 (Production of image-receiving sheet for thermal transfer recording) a) Polypropylene 85 having melt index (MI) 1.2
15 parts by weight of titanium oxide (average particle size: 1.0 μm) was mixed in the above parts, sufficiently kneaded by an extruder at 270 ° C., extruded into a sheet and cooled by a cooling device to obtain an unstretched sheet. Then, the sheet was heated to 150 ° C. and stretched 5 times in the longitudinal direction to obtain a polypropylene resin sheet having a thickness of 300 μm.

One surface of the polypropylene resin sheet obtained as described above was subjected to corona discharge treatment, and then an image receiving layer forming coating solution having the following composition was applied onto the above corona-discharged substrate and dried, An image receiving layer having a thickness of 10 μm was formed to obtain an image receiving sheet for thermal transfer recording. Image-receiving layer-forming coating solution Polyvinyl chloride 5.0 parts [Shin-Etsu Chemical Co., Ltd., TK-600] Vinyl chloride resin 4.5 parts [BASF, Laroflex MP25] Modified silicone resin 0.5 parts [Shin-Etsu Silicone Co., Ltd.] X-24-8300] Methyl ethyl ketone 40 parts Dioxane 40 parts Cyclohexanone 10 parts (Production of thermal transfer recording ink sheet) Coating of ink layer containing heat diffusible dye by mixing each of the following raw material compositions A liquid was prepared.

Ink layer forming coating solution Thermal diffusion dye 4.0 parts [Nippon Kayaku Co., Ltd., Kayaset Blue 714] Polyvinyl butyral 4.0 parts [Sekisui Chemical Co., Ltd., S-REC BX-1] Methyl ethyl ketone 82 parts Cyclohexanone 10 parts Next, the above ink layer-forming coating liquid was applied onto a polyethylene terephthalate film [manufactured by Toray Industries, Inc.] having a thickness of 6 μm and having a thickness of 1 μm after drying using a wire bar. As shown in the figure, it is applied and dried at intervals in the plane direction to form a dye-containing layer on the support, and silicone resin [SP-2105 manufactured by Dainichiseika Co., Ltd.] is included on the back surface that has not been subjected to corona discharge treatment. An ink sheet for heat-sensitive transfer recording was obtained by dropping 1 or 2 drops of the nitrocellulose solution with a dropper and spreading it over the entire surface, followed by backside treatment coating.

(Image formation) First, the heat-sensitive transfer recording ink sheet and the heat-sensitive transfer recording image-receiving sheet are superposed so that the former ink layer surface and the latter image-receiving layer surface are in contact with each other. An image was formed by applying a thermal head from the support side of the ink sheet under the following conditions.

Next, the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet were peeled off, and the image was transferred onto the thermal transfer recording image receiving sheet.

The evaluation of the transfer density on the surface of the recorded image, the adhesive force between the polyolefin resin layer and the image receiving layer of the formed thermal transfer recording image receiving sheet, and the coatability at the time of coating were evaluated according to the following criteria. The results are shown in Table 1.

Linear density in main scanning and sub-scanning: 8 dots / mm Recording power: 0.6 W / dot Heating time of thermal head: 20 msec (applied energy about 11.2)
X 10 ^-3 J) to 2 msec (applied energy approx. 1.12 x 10)
^-3 J), the heating time was adjusted stepwise.

<Transfer Density> The reflection density OD value was measured with an optical densitometer.

◎ ・ ・ ・ OD value is 2.5 or more ◯ ・ ・ ・ OD value is 2.0 to 2.5 △ ・ ・ ・ OD value is 1.7 to 2.0 × ・ ・ ・ OD value is 1.7 or less <Between the polyolefin resin layer and the image receiving layer Adhesive strength> The image-receiving layer was peeled from the substrate when a bending stress was applied, or the surface of the image-receiving layer was cut into a grid of 2 × 2 mm, and this surface was tape-peeled to determine the adhesive strength.

∘: No problem was found in the bending test and the peeling test.

B: There was no problem in the bending test, but some peeled off in the peeling test.

Δ: No problem was found in the bending test, but some were peeled off in the peeling test.

X: There was a problem in both the bending test and the peeling test.

<Coatability at the time of coating> The wettability of the coating liquid at the time of coating and the film state of the image receiving layer at the time of forming the image receiving layer were visually judged.

◯: The image receiving layer was formed uniformly without any flicker during coating. Fair: flicker occurred during coating, or the coated surface was uneven. X ... A cissing occurs at the time of application and the application surface is not uniform.

Example 2 b) MI 5.0 polypropylene 90 parts by weight, density 0.956, M
A composition in which 5 parts by weight of high-density polyethylene of I6.0 and 5 parts by weight of calcium carbonate (average particle size 1.5 μm) are mixed, c) 45 parts by weight of polypropylene of MI5.0, density of 0.956,
A composition prepared by mixing 15 parts by weight of high-density polyethylene with MI 6.0 and 40 parts by weight of calcium carbonate (average particle size 1.5 μm) is used.
Melt kneading with separate extruder at ℃, stack in a die,
The sheet was coextruded into a sheet and laminated on the polypropylene resin sheet stretched in Example 1 so that b) was on the outside, and cooled. Then, the mixture was heated to 170 ° C., stretched 7.5 times in the transverse direction with a tenter, and annealed to obtain a polyolefin resin sheet having a three-layer structure (thickness: a / c / b = 40 /
100/10 μm).

Next, the surface b) of the above-mentioned three-layer structure polyolefin resin sheet was flame-treated with a flame having a molar ratio of air / methane = 107 (“New Polymer Handbook” 50).
See page 8).

Separately, an image-receiving layer coating liquid having the following composition was prepared, and an image-receiving layer was formed on the surface of the treated substrate as described in Example 1. Next, after forming an image using the ink sheet used in Example 1, the same evaluation as in Example 1 was performed. The results are shown in Table 1. Image-receiving layer forming coating solution Vinyl chloride latex 22.5 parts [Zeon Corporation, ZEON 150 × 15] Vinyl chloride latex 20.0 parts [ZEON Corporation, G-576] Modified silicone resin 2.5 parts [Shin-Etsu] Silicone Co., Ltd., X-24-8300] Water 50.0 parts Example 3 A density of 0.918 containing 15% titanium oxide (average particle size: 1.0 μm) d) on the surface of 200 g / m ² of fine wood paper. , MI7 low density polyethylene was melt extruded with a weight of 30 g / m ² , and e) 10% titanium oxide (average particle size: 1.0 μm) on the back surface.
Low density polyethylene with a density of 0.922 and MI3.5 containing
Melt extrusion was performed at 30 g / m ² to obtain a polyolefin-coated substrate.

The substrate is then heated to 220 ° C., d)
The surface of is sprayed with air containing 25 g / m ³ of ozone,
d) The surface was treated with ozone.

Separately, an image-receiving layer coating solution having the following composition was prepared, and an image-receiving layer was formed on the surface of the treated substrate as described in Example 1. Next, after forming an image using the ink sheet used in Example 1, the same evaluation as in Example 1 was performed. The results are shown in Table 1. Coating liquid for forming image-receiving layer Water-dispersed polymer Polyester 25.0 parts [Toyobo Co., Ltd., Bayronal MD1220] Phthalic acid alkyl ester 3.5 parts [Dahachi Chemical Co., Ltd., DOP] Modified silicone resin 1.5 parts [Shin-Etsu Silicone Ltd., X-24-8300] 70 parts of water Example 4 One side of a biaxially stretched white polyethylene terephthalate resin film containing an inorganic filler with a thickness of 350 μm, f) 10%
Density 0.91 containing titanium oxide (average particle size: 1.0 μm)
8. MI8.5 low density polyethylene was melt extruded at a weight of 30 g / m ² , and 10% titanium oxide (average particle size: 1.0 μm) was included on the back side. Density 0.918, MI 7.0 low density Polyethylene was melt extruded at 30 g / m ² to obtain a polyolefin-coated substrate.

Then, titanium tetraisopropoxide was applied to the surface of f) of this substrate so as to have a film thickness of 0.2 μm, and the surface of f) was treated with a primer.

Separately, an image-receiving layer coating solution having the following composition was prepared, and an image-receiving layer was formed on the surface of the treated substrate as described in Example 1. Next, after forming an image using the ink sheet used in Example 1, the same evaluation as in Example 1 was performed. The results are shown in Table 1. Image receiving layer forming coating Polyvinyl chloride resin 7.0 parts [Shin-Etsu Chemical Co., Ltd., TK300] Vinyl chloride-vinyl acetate copolymer 1.5 parts [Union Carbide Co., VYHH] Phthalic acid alkyl ester 1.0 part [Dahachi Chemical Co., Ltd., DOP] Polyester-modified silicone resin 0.5 part [Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone 80 parts Cyclohexanone 10 parts Example 5h) MI0.8 polypropylene 50 parts, density 0.955, MI1 .
5 parts high density polyethylene 40 parts, titanium oxide (average particle size:
1.0 μm) 10 parts by weight are mixed and sufficiently kneaded by an extruder at 270 ° C., then extruded into a sheet and cooled by a cooling device,
An unstretched sheet was obtained. Next, the sheet was heated to 150 ° C. and stretched 5 times in the longitudinal direction to obtain a polyolefin resin sheet having a thickness of 360 μm.

Separately, i) 25 parts by weight of MI5.0 polypropylene, 20 parts of high density polyethylene having a density of 0.955 and MI1.5,
50 parts by weight of high density polyethylene having a density of 0.954 and MI6.0 and 5 parts by weight of calcium carbonate (average particle size 1.5 μm), j) 50 parts by weight of high density polyethylene having a density of 0.954 and MI6.0, calcium carbonate ( 5 parts by weight of an average particle diameter of 1.5 μm) were mixed and melt-kneaded at 270 ° C. in separate extruders,
The polyolefin resin sheet (h) was laminated in a die, coextruded into a sheet shape, and laminated on both sides of the polyolefin resin sheet (h) previously stretched 5 times in the longitudinal direction so that j) was on the outside and cooled. Then heated to 170 ℃, stretched 6.0 times in the transverse direction with a tenter,
Annealing treatment was performed to obtain a five-layer structure polyolefin resin sheet (thickness: j / i / h / i / j = 15/30/60 /
30/15 μm). Then, 1) ultraviolet light (low wavelength type: 189 nm) is applied to one surface of j) laminated on both sides of this base material.
Irradiation was carried out for 0 minutes, and the surface of j) was treated with ultraviolet rays.

The image-receiving layer-forming coating solution used in Example 2 was applied to the surface j) which had been surface-treated as described above and dried to form an image-receiving layer on the substrate. Next, after forming an image using the ink sheet used in Example 1, the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Example 6 Density containing k) 10% titanium oxide (average particle size: 1.0 μm) on one side of a white polyvinyl chloride resin film containing a 550 μm thick uniaxially stretched inorganic filler. 0.918, M
I8.5 low-density polyethylene was melt extruded at a weight of 30 g / m ² and 1) 30% titanium oxide (average particle size: 1.
A low density polyethylene having a density of 0.918 and MI 7.0 containing 0 μm) was melt extruded at 30 g / m ² to obtain a polyolefin-coated substrate.

Then, the k) surface of this substrate was irradiated with an electron beam from an electron beam accelerator of 750 kv to subject the k) surface to radiation treatment.

Separately, an image receiving layer coating solution having the following composition was prepared, and an image receiving layer was formed on the surface of the treated substrate as described in Example 1. Next, after forming an image using the ink sheet used in Example 1, the same evaluation as in Example 1 was performed. The results are shown in Table 1. Image- receiving layer forming coating solution Polyvinyl chloride resin 3.0 parts [Shin-Etsu Chemical Co., Ltd., TK300] Vinyl chloride-vinyl acetate copolymer 1.5 parts [Union Carbide Co., VYHH] Phenoxy resin 5.0 parts [Toto Kasei Co., Ltd. ), Epotote YP-50] Polyester-modified silicone resin 0.5 part [Shin-Etsu Silicone Co., Ltd., X-24-8300] Dioxane 80 parts Cyclohexanone 10 parts Example 7 of 500 μm thick uniaxially stretched ABS resin film M15.0 polypropylene containing m) 10% titanium oxide (average particle size: 1.0 μm) was melt extruded on one side at a weight of 30 g / m ² and n) 30% titanium oxide (average particle size) on the back side. Diameter: 1.0 μm) MI30.0 polypropylene containing 30
Melt extrusion was performed at g / m ² to obtain a polyolefin-coated substrate.

Then, chromium was vapor-deposited on the m) surface of this substrate and a chromium metal thin film having a thickness of 50 Å was applied. Next, this chromium-deposited polyolefin-coated substrate was placed in an oxygen atmosphere and subjected to sputter etching to roughen the surface m).

Separately, an image-receiving layer coating solution having the following composition was prepared, and an image-receiving layer was formed on the surface of the treated substrate as described in Example 1. Next, after forming an image using the ink sheet used in Example 1, the same evaluation as in Example 1 was performed. The results are shown in Table 1. Image-receiving layer forming coating liquid Vinyl chloride resin 5.5 parts [BASF Corporation, Laroflex MP25] Vinyl chloride-benzyl methacrylate copolymer 4.0 parts [Vinyl chloride content 83.7 parts, Tg: 51 ° C, degree of polymerization 520] Modified silicone Resin 0.5 parts [X-24-8300 manufactured by Shin-Etsu Silicone Co., Ltd.] Methyl ethyl ketone 40 parts Dioxane 40 parts Cyclohexanone 10 parts Example 8 White polyvinyl chloride resin film containing 550 μm thick uniaxially stretched inorganic filler O) 10% titanium oxide (average particle size: 1.0 μm) on one side, density 0.952, M
I11 high density polyethylene was melt extruded at a weight of 30 g / m ² and 30% titanium oxide (p) on the back surface (average particle size: 1.
A low density polyethylene having a density of 0.918 and MI 7.0 containing 0 μm) was melt extruded at 30 g / m ² to obtain a polyolefin-coated substrate.

Next, the surface o) of this substrate was treated with a chromic acid mixed solution for 60 minutes, and the surface o) was treated with a chemical agent.

Separately, an image receiving layer coating solution having the following composition was dispersed and prepared using a sand grinder. Next, an image receiving layer was formed on the surface of the treated substrate as described above in the same manner as in Example 1. Next, after forming an image using the ink sheet used in Example 1, the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Coating liquid for forming image receiving layer Vinyl chloride latex 25.0 parts [Nippon Zeon Co., Ltd., G-576] Polyvinyl acetoacetal resin 15.0 parts [Sekisui Chemical Co., Ltd., KW-1] Modified silicone resin 2.5 parts [Shin-Etsu Silicone Co., Ltd., X-24-8300] Silicone resin fine powder 2.5 parts [Toshiba Silicone Co., Ltd., Tospearl 104] UV absorber 5.0 parts [BASF Corporation, Ubinar N-35] Water 45.0 Parts ethanol 5.0 parts Example 9 q) 10 on one surface of a white polyethylene terephthalate film containing a 350 μm thick biaxially stretched inorganic filler
Density containing 0.1% titanium oxide (average particle size: 1.0 μm)
918, MI7.0 low density polyethylene melted and extruded with a weight of 30 g / m ² , r) containing 30% titanium oxide (average particle size: 1.0 μm) density 0.918, MI7.0 low density Polyethylene was melt extruded at 30 g / m ² to obtain a polyolefin-coated substrate.

Then, the surface q) of the base material was set in a plasma reactor of a cylindrical flow type / polarized external electrode system under Ar atmosphere, subjected to Ar plasma treatment for 5 minutes, and then taken out into the air. , Q) was subjected to low temperature plasma treatment.

Separately, an image receiving layer coating solution having the following composition was dispersed and prepared using a sand grinder, and an image receiving layer was formed on the surface of the treated substrate as described in Example 1. Then, an ink layer-forming coating solution having the following composition was prepared, and Example 1 was used.
An ink layer was formed in the same manner as in. An image was formed using the image receiving sheet and the ink sheet in the same manner as in Example 1, and then the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Coating liquid for forming image-receiving layer Vinyl chloride latex 27.5 parts [Nippon Zeon Co., Ltd., G-351] Metal ion-containing compound 20.0 parts [[Ni (C ₂ H ₅ NHCH ₂ CH ₂ NH ₂ ) ₃ ] ²⁺ 2 [(C ₆ H ₅ ) ₄ B] ^- ] Modified silicone resin 2.5 parts [Shin-Etsu Silicone Co., Ltd., X-24-8300] Water 45.0 parts Ethanol 5.0 parts Ink layer forming coating heat diffusion Sex dye [PCY-20] 3.0 parts Polyvinyl butyral 3.0 parts [Sekisui Chemical Co., Ltd. Esslec BX-1] Methyl ethyl ketone 44.0 parts Dioxane 40.0 parts Cyclohexanone 10.0 parts.

Example 10 Using the base material used in Example 9, the surface q) was set in a plasma reactor of a cylindrical flow type / polarized external electrode system under Ar atmosphere, and acrylonitrile was used as a monomer. By flowing to form a plasma polymerized thin film of acrylonitrile on the surface of q), and the surface of q) was subjected to low temperature plasma treatment.

Separately, an image receiving layer coating solution having the following composition was dispersed and prepared using a sand grinder, and an image receiving layer was formed on the surface of the treated substrate as described in Example 1. Then, an ink layer-forming coating solution having the following composition was prepared, and Example 1 was used.
An ink layer was formed in the same manner as in. An image was formed using the image receiving sheet and the ink sheet in the same manner as in Example 1, and then the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Coating liquid epoxy resin for image receiving layer formation 10.8 parts [Topot Kasei Co., Ltd., Epototo YD-017] Metal ion-containing compound 8.0 parts [[Ni (NH ₂ COCH ₂ NH ₂ ) ₃ ] ²⁺ 2 [ _{(C 6 H 5) 4 B} ] -] modified silicone resin 1.0 parts [Shinetsu silicone Co., Ltd., X-24-8300] dispersing agent 0.2 parts water 80.0 parts ink layer coating solution thermally diffusible dye [PCM -37] 2.94 parts Polyvinyl butyral 3.0 parts [Sekisui Chemical Co., Ltd., Eslec BX-1] Modified silicone resin 0.06 parts [Toagosei Co., Ltd., Cymac US-270] Methyl ethyl ketone 44.0 parts Dioxane 40.0 parts Cyclohexanone 10.0 parts Example 11 Using the substrate used in Example 8, ⁶⁰ Co having a dose rate of 1.8 × 10 4 rad / hr −1 was pre-irradiated in the air as a radiation source, and the surface was degassed for 60 minutes. O) Graft polymerization of acrylamide on the surface with 25% acrylamide solution It was washed with water and dried o) surface was treated grafted.

Separately, an image-receiving layer coating solution having the following composition was dispersed and prepared using a sand grinder, and an image-receiving layer was formed on the surface of the treated substrate as described in Example 1. Then, an ink layer-forming coating solution having the following composition was prepared, and Example 1 was used.
An ink layer was formed in the same manner as in. An image was formed using the image receiving sheet and the ink sheet in the same manner as in Example 1, and then the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Coating liquid for forming image-receiving layer Vinyl chloride-mono-2-ethylhexyl maleate copolymer 7.8 parts [Vinyl chloride content: 85.1%, Tg: 75 ° C, degree of polymerization: 500] Metal ion-containing compound 8.0 parts _{[[Ni (C 2 H 5} NHCH 2 CH 2 NH 2) 3] 2+ 2 [(C 6 H 5) 4 B] -] 1.0 parts modified silicone resin [Shinetsu silicone Co., Ltd., X-24-8300 ] UV absorber 3.0 parts [BASF Corporation, Ubinal N-35] Dispersant 0.2 parts Water 70.0 parts Ethylene glycol monomethyl ether 10.0 parts Ink layer forming coating liquid thermal diffusion dye [PCC-37] 3.0 parts Polyvinyl butyral 3.0 Part [Sekisui Chemical Co., Ltd., Esslec BX-1] Methyl ethyl ketone 44.0 parts Dioxane 40.0 parts Cyclohexanone 10.0 parts The heat diffusible dyes used in Examples 9 and 10 are as follows.

[0152]

[Chemical 2]

Comparative Example 1 An image was formed using the ink sheet used in Example 1 except that the surface treatment was not performed in Example 1, and then the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 2 After the image was formed using the ink sheet used in Example 1 except that the surface treatment was not performed in Example 2, the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 3 After forming an image using the ink sheet used in Example 9 except that the surface treatment was not performed in Example 9, the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 4 The same evaluation as in Example 1 was performed after forming an image using the ink sheet used in Example 11 except that the surface treatment was not performed in Example 11. The results are shown in Table 1.

Table 1 Transfer Density Adhesive Strength Coatability Transfer Density Adhesive Strength Coatability Example 1 ◎ ◎ ◎ ○ Example 9 ◎ ◎ ◎ Example 2 ◎ ○ ○ Example 10 ◎ ◎ ○ ○ Example 3 ◎ ○ ○ Example 11 ◎ ◎ ○ Example 4 ◎ ◎ ◎ Comparative Example 1 ○ △ △ Example 5 ◎ ○ ○ Comparative Example 2 △ × × Example 6 ◎ ◎ ○ Comparative Example 3 △ × × Example 7 ◎ ◎ ○ Comparative Example 4 △ × × Example 8 ◎ ◎ ○

[0158]

According to the manufacturing method of the present invention, (1) the adhesive force between the polyolefin resin layer and the image receiving layer is sufficiently maintained, and the image receiving layer is not peeled off even when bending stress is applied. (2) When the coating liquid for the image-receiving layer is applied, no repellency is observed and good coatability is obtained, whereby an image-receiving sheet for thermal transfer recording having excellent transferability can be obtained.

Claims (10)

[Claims] 1. A heat-sensitive transfer recording image-receiving sheet comprising an image-receiving layer laminated on a substrate having an image-receiving layer laminated with a polyolefin resin, the polyolefin-side resin surface being surface-treated, and then the image-receiving layer being laminated by a coating method. A method for producing an image-receiving sheet for thermal transfer recording, which comprises forming the image-receiving sheet. 2. The surface treatment is performed by any one of corona discharge treatment, flame treatment, ozone treatment, primer treatment, ultraviolet treatment, radiation treatment, surface roughening treatment and chemical treatment. The method for producing an image-receiving sheet for thermal transfer recording according to claim 1. 3. The method for producing an image-receiving sheet for thermal transfer recording according to claim 1, wherein the surface treatment is performed by low temperature plasma. 4. The method for producing an image-receiving sheet for thermal transfer recording according to claim 1, wherein the surface treatment is a grafting treatment. 5. A laminate in which a polyolefin resin layer containing 5 to 40% by weight of an inorganic filler or a laminate having a polyolefin resin layer containing 5 to 40% by weight of an inorganic filler as a surface layer is laminated on both sides of a support. One side of a base material is claimed in claims 1 to 4.
After surface treatment by any of the surface treatment methods described,
A method for producing an image-receiving sheet for thermal transfer recording, comprising laminating image-receiving layers by a coating method. 6. The method for producing an image-receiving sheet for thermal transfer recording according to claim 5, wherein the polyolefin resin layer containing the inorganic filler is laminated by a melt laminating method. 7. A polyolefin resin layer containing an inorganic filler or a laminate having a polyolefin resin layer containing an inorganic filler as a surface layer, wherein the polyolefin resin layer containing an inorganic filler is stretched in at least one axial direction. An image receiving sheet for thermal transfer recording according to claim 5, which is a sheet. 8. The image-receiving sheet for thermal transfer recording according to claim 5, wherein the support is a sheet of thermoplastic resin. 9. The image-receiving sheet for thermal transfer recording according to claim 8, wherein the thermoplastic resin sheet contains an inorganic filler. 10. The thermoplastic resin sheet has a thickness of 10 to 10.
The image-receiving sheet for thermal transfer recording according to claim 8, which is a sheet having a thickness of 1000 μm and stretched in at least one axial direction.