Intermediate transfer medium, printed matter, and method for producing printed matter

Abstract

Provided is an intermediate transfer medium capable of achieving, in a region of a transfer target body to be transferred to, both adhesion between the transfer target body and a patch, and good covering characteristics at the outer edge of the patch. The intermediate transfer medium comprises a release member and a transfer sheet, wherein: the transfer sheet has a protective base material and a transfer layer, in order from the release member side; a slit that penetrates through the transfer sheet to the release member is provided from the surface of the transfer sheet on the opposite side to the release member side; a region of the transfer sheet that is defined by the slit, as the outer periphery of said region, can be transferred, as a patch, to the transfer target body; the transfer layer has at least a receiving layer and an intermediate layer; the receiving layer contains a vinyl chloride-vinyl acetate copolymer; the intermediate layer contains a (meth)acrylic resin; the glass transition temperature of the (meth)acrylic resin is 120°C or more; and the acid value of the (meth)acrylic resin is 15 mgKOH / g or more.

Description

Intermediate transfer medium, printed matter, and method for manufacturing printed matter CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority based on Japanese Patent Application No. 2024-058195, filed on March 29, 2024, the entire disclosures of which are incorporated herein by reference.

[0002] The present invention relates to an intermediate transfer medium, a print, and a method for producing the print.

[0003] In ID cards and credit cards, it is required to form an image on the entire surface of the card as much as possible to minimize the margins at the outer edges, and to appropriately protect the image by forming a protective layer or the like.

[0004] Patent Literature 1 discloses an intermediate transfer medium capable of forming a thermal transfer image with reduced margins on the outer edge of a transferee (sometimes referred to as "edge-to-edge printing"). The intermediate transfer medium disclosed in Patent Literature 1 includes a release member and a transfer sheet that can be peeled off from the release member. The transfer sheet has, in this order from the release member side, a protective substrate and a transfer layer. The intermediate transfer medium has a slit that runs from the surface of the transfer sheet through the transfer sheet to the surface of the release member. The intermediate transfer medium is capable of transferring an area of ​​the transfer sheet defined by the slit as an outer periphery to a transferee as a patch. Furthermore, the transfer layer has, from the protective substrate side, a release layer, a protective layer, and a receiving layer.

[0005] When the intermediate transfer medium disclosed in Patent Document 1 is brought into close contact with a transferee and then peeled off, in the transfer region within the patch frame, peeling occurs at the interface between the release member and the transfer sheet. As a result, the transfer layer within the patch frame is protected by the protective substrate. In contrast, in the transfer region located outside the patch frame (the outer edge of the patch), peeling occurs at the interface between the protective substrate and the transfer layer in the transfer sheet. The interface between the protective substrate and the transfer layer in the transfer sheet is the interface between the protective substrate and the release layer. Therefore, by using this intermediate transfer medium, a printed product with little margin at the outer edge can be obtained.

[0006] Japanese Patent Application Laid-Open No. 2020-163781

[0007] However, in the case of a printed product obtained using the intermediate transfer medium disclosed in Patent Document 1, after the print is cooled to the operating temperature after transfer, adhesion between the protective substrate and the transfer layer in the patch area is weak, and there is a risk that the patch will peel off from the transferee. In contrast, adjusting the components of the release layer to improve adhesion between the protective substrate and the release layer may deteriorate the transferability of the transfer layer to the transfer area outside the patch frame (the outer edge of the patch). Thus, with the technology disclosed in Patent Document 1, it was difficult to adequately cover the transfer area of ​​the transferee located at the outer edge of the patch while maintaining adhesion between the transferee and the patch.

[0008] The present disclosure has been made in consideration of the above circumstances, and aims to provide an intermediate transfer medium that can achieve both good adhesion between the transferee and the patch and good coverage of the outer edge of the patch in the transfer area of ​​the transferee. Another aim of the present disclosure is to provide a printed object in which the transfer area of ​​the transferee has good adhesion between the transferee and the patch and the outer edge of the patch is properly covered, and a method for manufacturing the same.

[0009] The intermediate transfer medium of the present disclosure includes a release member and a transfer sheet laminated on the release member, the transfer sheet having, in this order from the release member side, a protective substrate and a transfer layer, and a slit is provided in the transfer sheet from the surface opposite the release member side, penetrating the transfer sheet to the release member, and an area of ​​the transfer sheet defined by the slit as an outer periphery can be transferred as a patch to a transferee, the transfer layer having at least a receiving layer located on the surface opposite the protective substrate and an intermediate layer in contact with the receiving layer, the receiving layer containing a vinyl chloride-vinyl acetate copolymer, and the intermediate layer containing a (meth)acrylic resin, the (meth)acrylic resin having a glass transition temperature of 120°C or higher and an acid value of 15 mgKOH / g or higher. The printed matter disclosed herein comprises a transferee and a patch laminated so as to cover a portion of a transfer area of ​​the transferee, the patch having, from the transferee side, a transfer layer and a protective substrate in this order, the transfer layer having, from the transferee side, at least a receiving layer on which a thermal transfer image is formed and an intermediate layer in contact with the receiving layer, the receiving layer being exposed in a region of the transfer area outside the region covered by the patch. The manufacturing method of the printed matter disclosed herein is a method for manufacturing a printed matter using the above-mentioned intermediate transfer medium, which includes forming a thermal transfer image on the receiving layer of the intermediate transfer medium, integrating the transfer sheet and the transferee so that the receiving layer is in contact with the transfer area of ​​the transferee, and then removing the transfer sheet other than the receiving layer in the transfer area outside the patch to expose the receiving layer.

[0010] According to the present disclosure, it is possible to provide an intermediate transfer medium that can achieve both good adhesion between the transferee and the patch and good coverage of the outer edge of the patch in the transfer area of ​​the transferee. Also, according to the present disclosure, it is possible to provide a printed object in which the transfer area of ​​the transferee has good adhesion between the transferee and the patch and the outer edge of the patch is properly covered, and a method for manufacturing the same.

[0011] Fig. 1 is a schematic cross-sectional view showing one embodiment of an intermediate transfer medium of the present disclosure. Fig. 2 is a diagram showing one embodiment of a method for producing a printed matter of the present disclosure. Fig. 3 is a diagram showing one embodiment of a method for producing a printed matter of the present disclosure. Fig. 4 is a diagram showing one embodiment of a method for producing a printed matter of the present disclosure.

[0012] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure can be implemented in many different forms, and should not be construed as being limited to the description of the following exemplary embodiments. For clarity of explanation, the drawings may show the width, thickness, shape, etc. of each layer more schematically than in the embodiments, but these are merely examples and do not limit the interpretation of the present disclosure. In this specification and each drawing, elements similar to those already described with reference to the previous drawings are designated by the same reference numerals, and detailed descriptions may be omitted as appropriate.

[0013] In the present disclosure, when multiple upper limit candidates and multiple lower limit candidates are listed for a certain parameter, the numerical range of the parameter may be constructed by combining any one upper limit candidate with any one lower limit candidate. Examples of the parameters include physical properties, component content ratios, and layer thicknesses. As an example, the following statement will be explained: "Parameter B is preferably A1 or greater, more preferably A2 or greater, and even more preferably A3 or greater. Parameter B is preferably A4 or less, more preferably A5 or less, and even more preferably A6 or less." In this example, the numerical range of parameter B may be A1 or greater and A4 or less, A1 or greater and A5 or less, A1 or greater and A6 or less, A2 or greater and A4 or less, A2 or greater and A5 or less, A2 or greater and A6 or less, A3 or greater and A4 or less, A3 or greater and A5 or less, or A3 or greater and A6 or less.

[0014] In this specification, each of the components (for example, resin materials and additives such as colorants) appearing in the following description may be used alone or in combination of two or more.

[0015] [Intermediate Transfer Medium] The intermediate transfer medium of the present disclosure includes a release member and a transfer sheet laminated on the release member. The transfer sheet includes, in this order from the release member side, a protective substrate and a transfer layer. The intermediate transfer medium has a slit extending from the surface of the transfer sheet opposite the release member through the transfer sheet to the release member. The intermediate transfer medium is capable of transferring an area of ​​the transfer sheet defined by the slit as a patch to a transferee. The transfer layer includes at least a receiving layer located on the surface opposite the protective substrate and an intermediate layer in contact with the receiving layer. The receiving layer contains a vinyl chloride-vinyl acetate copolymer. The intermediate layer contains an acrylic resin having a glass transition temperature of 120°C or higher and an acid value of 15 mgKOH / g or higher. Preferred embodiments of the intermediate transfer medium of the present disclosure will be described in more detail below.

[0016] Fig. 1 is a cross-sectional view showing one embodiment of an intermediate transfer medium according to the present disclosure. In Fig. 1, the intermediate transfer medium 1 includes a release member 10 and a transfer sheet 20 provided on the release member 10. The transfer sheet 20 includes a protective substrate 21, a primer layer 22, an intermediate layer 23, and a receiving layer 24, in this order from the release member 10 side in the thickness direction of the intermediate transfer medium 1. The primer layer 22, the intermediate layer 23, and the receiving layer 24 form a transfer layer. The receiving layer 24 also forms the surface of the transfer layer.

[0017] In one embodiment, the release member 10 includes a liner substrate 11, an adhesive layer 12, and a release layer 13, in this order in the thickness direction of the intermediate transfer medium 1, from the opposite side to the transfer sheet 20. The configuration of the release member is not particularly limited to the above-described embodiment. For example, the release member may be configured in such a way that the lamination order of the release layer and the adhesive layer is reversed from that of the above-described embodiment, or may be configured to include a single layer that functions as both an adhesive layer and a release layer.

[0018] The intermediate transfer medium 1 of the present disclosure has a slit S that extends from the surface of the transfer sheet 20 opposite the release member 10, through the transfer sheet 20, and reaches the release member 10. The intermediate transfer medium 1 can transfer an area of ​​the transfer sheet 20 defined by the slit S as a patch onto a transfer recipient P (see FIG. 3). Each layer of the intermediate transfer medium of the present disclosure will be described below.

[0019] <Release member> (Liner substrate) The liner substrate can be used without any particular restrictions as long as it has heat resistance to the thermal energy applied during thermal transfer and has the mechanical strength to support a transfer sheet or the like placed on the release member including the liner substrate.

[0020] The liner substrate can be, for example, a film made of a resin material (hereinafter also referred to as a "resin film"). Examples of the resin material include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, 1,4-polycyclohexylene dimethylene terephthalate, and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer; polyamide; polyimide; polycarbonate; polyolefins such as polyethylene, polypropylene, and polymethylpentene; polystyrene; vinyl resins such as vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, and polyvinylpyrrolidone; vinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral; (meth)acrylic resins such as poly(meth)acrylate; cellulose resins such as cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate; and ionomers.

[0021] Among the above resin materials, polyester is preferred from the viewpoint of heat resistance and mechanical strength, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are more preferred, and PET is even more preferred.

[0022] In the present disclosure, "(meth)acrylic" encompasses both "acrylic" and "methacrylic," and "(meth)acrylate" encompasses both "acrylate" and "methacrylate."

[0023] A resin film laminate may be used as the liner substrate, and the resin film laminate can be produced by, for example, dry lamination, wet lamination, or extrusion.

[0024] The resin film may be a stretched film or an unstretched film. From the viewpoint of strength, the resin film is preferably a stretched film that is stretched uniaxially or biaxially.

[0025] The liner substrate may be subjected to a surface treatment on the surface of the liner substrate facing the adhesive layer in order to enhance adhesion to the adhesive layer. Examples of surface treatment methods include corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, plasma treatment, low-temperature plasma treatment, primer treatment, and grafting treatment.

[0026] The thickness of the liner substrate is preferably 1 μm or more and 50 μm or less, more preferably 3 μm or more and 25 μm or less, which can improve, for example, the mechanical strength of the liner substrate and the transfer of thermal energy during thermal transfer.

[0027] (Adhesive Layer) In one embodiment, the intermediate transfer medium of the present disclosure includes an adhesive layer on the surface of the liner substrate facing the transfer sheet, which can improve the adhesion between the liner substrate and the release layer of the release member.

[0028] The adhesive layer preferably contains a resin material. Examples of the resin material include (meth)acrylic resin, vinyl resin, polyolefin, polyester, polyurethane, epoxy resin, urea resin, melamine resin, and phenolic resin. The adhesive layer may contain one or more resin materials.

[0029] The content of the resin material in the adhesive layer is preferably 70% by mass or more and 100% by mass or less, and more preferably 80% by mass or more and 100% by mass or less.

[0030] The adhesive layer may be a layer obtained by curing a resin material with a curing agent, such as an isocyanate compound, an aliphatic amine, a cyclic aliphatic amine, an aromatic amine, or an acid anhydride.

[0031] The thickness of the adhesive layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 2 μm or less. The adhesive layer can be formed, for example, by dispersing or dissolving the components described above in an appropriate solvent to prepare a coating liquid, which is then applied to a liner substrate and dried. Examples of coating methods include roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, and rod coating.

[0032] (Release Layer) In one embodiment, the intermediate transfer medium of the present disclosure includes a release layer on the surface of the release member facing the transfer sheet. The release layer is a layer that does not constitute the transfer sheet and remains on the release member when the transfer sheet is transferred onto the transfer recipient. By providing the release layer, the intermediate transfer medium of the present disclosure further improves the thermal transferability of the transfer sheet including the protective substrate and the transfer layer.

[0033] The release layer preferably contains a resin material. Examples of the resin material include (meth)acrylic resin, melamine resin, polyol resin, cellulose resin, silicone resin, acetal resin, polyurethane, polyamide, and polyester. The release layer may contain one or more resin materials.

[0034] The content of the resin material in the release layer is preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass or less.

[0035] The release layer preferably contains a release agent. Examples of the release agent include silicone oil, wax, fluorine compounds, phosphate ester compounds, higher fatty acid amide compounds, and metal soaps. The release layer can contain one or more types of release agents.

[0036] The content of the release agent in the peel layer is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, thereby improving the thermal transferability of the transfer sheet of the intermediate transfer medium of the present disclosure.

[0037] The release layer may contain an additive. Examples of the additive include a filler, a plasticizer, an antistatic agent, an ultraviolet absorber, and a dispersant. The release layer may contain one or more additives. The thickness of the release layer is preferably 0.1 μm or more and 5 μm or less.

[0038] The release layer can be formed, for example, by applying a coating liquid obtained by dispersing or dissolving the above-mentioned components in an appropriate solvent onto an adhesive layer provided on a liner substrate using the known coating method described above, and drying the resulting coating liquid.

[0039] (Back Layer) In one embodiment, the intermediate transfer medium of the present disclosure may have a back layer on the surface of the release member opposite the surface on which the transfer sheet is provided. Note that the surface of the release member opposite the surface on which the transfer sheet is provided refers to the surface of the liner substrate opposite the surface on which the adhesive layer is provided. This allows the intermediate transfer medium of the present disclosure to suppress sticking and wrinkles caused by heating during thermal transfer.

[0040] The back surface layer preferably contains a resin material. Examples of the resin material include (meth)acrylic resin, styrene resin, vinyl resin, cellulose resin, polyester, polyurethane, polyvinyl acetal, silicone-modified polyurethane, and fluorine-modified polyurethane. The back surface layer may contain one or more resin materials.

[0041] The back layer may contain additives such as release agents such as silicone oil, wax, fluorine compounds, phosphate ester compounds, higher fatty acid amide compounds, and metal soaps; curing agents such as isocyanate compounds; organic particles such as fluorine resins; and inorganic particles such as silica, clay, talc, and calcium carbonate. This can improve the slip properties of the back layer in the intermediate transfer medium of the present disclosure. The back layer can contain one or more additives.

[0042] The thickness of the back layer is preferably 0.01 μm or more and 5 μm or less, more preferably 0.03 μm or more and 2 μm or less, so that the intermediate transfer medium of the present disclosure can further suppress sticking and wrinkles while maintaining the transferability of thermal energy during thermal transfer.

[0043] The back layer can be formed, for example, by dispersing or dissolving the above-mentioned components in a suitable solvent to prepare a coating liquid, which is then applied onto a liner substrate by the above-mentioned known coating method, and then dried.

[0044] <Transfer Sheet> (Protective Substrate) The protective substrate can be any substrate that has heat resistance to the thermal energy applied during thermal transfer and mechanical strength sufficient to protect the surface of the transfer layer to be transferred onto the transfer recipient.

[0045] As the protective substrate, a resin film similar to that described above for the liner substrate can be used.

[0046] The thickness of the protective substrate is not particularly limited, but is preferably from 0.5 μm to 100 μm, more preferably from 10 μm to 40 μm, which can improve, for example, the mechanical strength of the protective substrate and the transfer of thermal energy during thermal transfer.

[0047] (Primer Layer) In one embodiment, the intermediate transfer medium of the present disclosure includes a primer layer on the surface of the protective substrate opposite the release member, which can improve adhesion between the protective substrate and the transfer layer in the transfer sheet.

[0048] The primer layer preferably contains a resin material. The resin material is not particularly limited as long as it can improve the adhesive strength between the protective substrate and the transfer layer. As such a resin material, those listed above for the adhesive layer can be used.

[0049] The thickness of the primer layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 2 μm or less. The primer layer can be formed, for example, by applying a coating liquid obtained by dispersing or dissolving the above-mentioned components in an appropriate solvent onto the protective substrate by the above-mentioned known coating method, and drying the resulting coating liquid.

[0050] (Intermediate Layer) In one embodiment, the intermediate transfer medium of the present disclosure includes an intermediate layer between the primer layer and the receptor layer in the transfer layer, which protects the receptor layer on which the thermally transferred image is provided.

[0051] The intermediate layer contains, as a resin material, one or more (meth)acrylic resins having a glass transition temperature (Tg) of 120° C. or higher and an acid value of 15 mg KOH / g or higher. When the intermediate layer contains a (meth)acrylic resin with the above properties, the intermediate layer exhibits excellent cold adhesion to the receiving layer described below, and when the patch is transferred to a receiving material, the patch exhibits excellent adhesion to the receiving material.

[0052] Examples of the (meth)acrylic resin include a polymer of (meth)acrylic acid, a polymer of a (meth)acrylic acid ester, a copolymer of (meth)acrylic acid and another monomer, and a copolymer of a (meth)acrylic acid ester and another monomer. Specific examples of the (meth)acrylic resin include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, polyisobutyl (meth)acrylate, an ethyl (meth)acrylate-methyl (meth)acrylate copolymer, a butyl (meth)acrylate-methyl (meth)acrylate copolymer, an ethylene-methyl (meth)acrylate copolymer, and a styrene-methyl (meth)acrylate copolymer. Among these, preferred are those containing structural units obtained from at least one alkyl methacrylate selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Commercially available (meth)acrylic resins include, for example, MB7930, MB7931, MB7932, and MB7948 (manufactured by Mitsubishi Chemical Corporation).

[0053] The glass transition temperature (Tg) of the (meth)acrylic resin is preferably 120°C or higher, more preferably 125°C or higher. The upper limit of Tg is preferably 180°C or lower. Specifically, the Tg of the (meth)acrylic resin can be 120°C or higher and 180°C or lower. In the present disclosure, the glass transition temperature (Tg) is a value obtained by DSC in accordance with JIS K7121:2012.

[0054] The acid value of the (meth)acrylic resin is preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more. The acid value of the (meth)acrylic resin is preferably 60 mgKOH / g or less. Specifically, the acid value of the (meth)acrylic resin can be 15 mgKOH / g or more and 60 mgKOH / g or less. In the present disclosure, the acid value (mgKOH / g) is a value obtained in accordance with JIS K0070:1992.

[0055] The weight-average molecular weight (Mw) of the (meth)acrylic resin has a lower limit of preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more. The upper limit is preferably 300,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. Specifically, the weight-average molecular weight (Mw) of the (meth)acrylic resin can be 10,000 or more and 300,000 or less. When the weight-average molecular weight of the (meth)acrylic resin is 10,000 or more, the patch exhibits excellent adhesion to the transfer target when transferred onto the transfer target. Furthermore, when the weight-average molecular weight of the (meth)acrylic resin is 300,000 or less, the patch exhibits excellent coverage of the outer edge of the patch. In the present disclosure, the weight-average molecular weight (Mw) is the average molecular weight measured by gel permeation chromatography (GPC) analysis and converted into standard polystyrene.

[0056] In one embodiment, the content of the (meth)acrylic resin in the entire resin material is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, which can further improve cold adhesion to the receiving layer described below.

[0057] In one embodiment, the intermediate layer may contain one or more resin materials other than the (meth)acrylic resin. Examples of the resin materials include polyester, polyurethane, polystyrene, (meth)acrylic resin, and (meth)acrylic polyol resin.

[0058] The content of the resin material in the intermediate layer is preferably 80% by mass or more and 99% by mass or less, more preferably 85% by mass or more and 98% by mass or less, which can further improve the cold adhesion to the receiving layer described later.

[0059] In one embodiment, the intermediate layer preferably contains a release agent. This can improve the thermal transferability of the receiving layer, which will be described later. The thermal transferability of the receiving layer refers to the releasability between the receiving layer and the intermediate layer.

[0060] Examples of the release agent include fluorine compounds, phosphate ester compounds, higher fatty acid amide compounds, metal soaps, silicone oils, and waxes such as polyethylene wax and paraffin wax.

[0061] Examples of silicone oils include straight silicone oils such as dimethylsilicone oil and methylphenylsilicone oil, as well as modified silicone oils such as amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified silicone oil, (meth)acrylic-modified silicone oil, mercapto-modified silicone oil, carbinol-modified silicone oil, fluorine-modified silicone oil, methylstyryl-modified silicone oil, and polyether-modified silicone oil. Modified silicone oils include single-end, double-end, and side-chain single-end types. The intermediate layer can contain one or more release agents.

[0062] The content of the release agent in the intermediate layer is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, which can improve, for example, the thermal transferability of the receptor layer.

[0063] The intermediate layer may contain one or more of the above additives. The content of the additive per 100 parts by mass of the resin material contained in the intermediate layer is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less.

[0064] The thickness of the intermediate layer is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, which can further improve the cold adhesion to the receiving layer described later.

[0065] The intermediate layer can be formed, for example, by dispersing or dissolving the above-mentioned components in an appropriate solvent to prepare a coating liquid, which is then applied onto the primer layer by the above-mentioned known coating method, and then dried.

[0066] (Receptor Layer) In one embodiment, the thermal transfer sheet of the present disclosure includes a receptor layer on the surface of the intermediate layer in the transfer layer. The receptor layer constitutes a surface layer on one side of the intermediate transfer medium.

[0067] The receiving layer contains one or more vinyl chloride-vinyl acetate copolymers as a resin material. By containing the vinyl chloride-vinyl acetate copolymer, the receiving layer has excellent cold adhesion with the intermediate layer, and when the patch is transferred to a transfer recipient, the patch has excellent adhesion to the transfer recipient. In other words, the receiving layer has excellent cold adhesion to the transfer recipient.

[0068] The vinyl chloride-vinyl acetate copolymer resin may have a hydroxyl group. A vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group can be obtained by copolymerizing vinyl chloride and a vinyl acetate resin and then partially hydrolyzing the copolymer to introduce a hydroxyl group, or by adding a component having a hydroxyl group other than vinyl chloride or vinyl acetate, such as 2-hydroxyethyl methacrylate, during polymerization and copolymerizing the copolymer.

[0069] Specific examples of vinyl chloride-vinyl acetate copolymers include Solbin C, Solbin CL, Solbin CLL3, Solbin CN, Solbin CNL, Solbin C5R, and Solbin TA5R (manufactured by Nissin Chemical Industry Co., Ltd.).

[0070] In one embodiment, the content of the vinyl chloride-vinyl acetate copolymer in the entire resin material is preferably 70% by mass or more and 100% by mass or less, and more preferably 80% by mass or more and 100% by mass or less, which can further improve the cold adhesion between the intermediate layer and the transfer-receiving object.

[0071] In one embodiment, the receiving layer may contain one or more resin materials other than vinyl chloride-vinyl acetate copolymer. Examples of resin materials include polyolefins such as polyethylene and polypropylene, vinyl resins other than vinyl chloride-vinyl acetate copolymer, such as polyvinyl chloride and polyvinyl acetate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polystyrene, (meth)acrylic resins, polyamides, polyimides, polycarbonates, polyurethanes, cellulose resins, and ionomer resins. The receiving layer can contain one or more of the above resin materials.

[0072] The content of the resin material in the receiving layer is preferably 80% by mass to 99% by mass, more preferably 85% by mass to 98% by mass, which can further improve the receptivity of, for example, sublimation dyes.

[0073] In one embodiment, the receiving layer preferably contains a release agent. This improves the thermal transferability of the receiving layer. Furthermore, when a thermal transfer image is formed on the receiving layer, the release ability from the thermal transfer sheet having a sublimation transfer colorant layer can be improved. The receiving layer can contain one or more of the release agents exemplified for the intermediate layer.

[0074] The content of the release agent in the receiving layer is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, which can improve, for example, the thermal transferability of the receiving layer.

[0075] The receiving layer may contain one or more of the additives described above. The content of the additive per 100 parts by mass of the resin material contained in the receiving layer is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less.

[0076] The thickness of the receiving layer is preferably 0.5 μm to 20 μm, more preferably 1 μm to 10 μm, which can improve the density of the image formed on the receiving layer and the transferability of the transfer layer.

[0077] The receiving layer can be formed, for example, by dispersing or dissolving the components described above in a suitable solvent to prepare a coating liquid, which is then applied onto the intermediate layer by the known coating method described above, and then dried.

[0078] In one embodiment of the intermediate transfer medium of the present disclosure, the receptor layer constituting the transfer layer of the transfer sheet contains a vinyl chloride-vinyl acetate copolymer, and the intermediate layer contains an acrylic resin having a glass transition temperature (Tg) of 120° C. or higher and an acid value of 15 mg KOH / g or higher. This provides excellent cold adhesion between the intermediate layer and the receptor layer in the intermediate transfer medium of the present disclosure.

[0079] In one embodiment, the intermediate transfer medium of the present disclosure has a peel force f1 at 23° C. when the intermediate layer and the receiving layer are peeled off from each other, preferably 70 gf / cm or more, more preferably 100 gf / cm or more, and even more preferably 200 gf / cm or more. When the peel force f1 at 23° C. is 200 gf / cm or more, peeling at the interface between the intermediate layer and the receiving layer can be prevented after transfer of the patch.

[0080] In one embodiment of the intermediate transfer medium of the present disclosure, at least one of the receiving layer and the intermediate layer constituting the transfer layer of the transfer sheet contains a release agent, thereby providing excellent thermal transferability of the receiving layer.

[0081] In one embodiment, the intermediate transfer medium of the present disclosure has a peel force f2 at 50°C when the intermediate layer and the receiving layer are peeled off, which is smaller than the peel force F when the transfer sheet (protective substrate) and the release member (peeling layer) are peeled off. As a result, during transfer, when the intermediate transfer medium (receiving layer) and the transfer recipient are brought into close contact with each other and then the intermediate transfer medium is peeled off from the transfer recipient, peeling can be achieved at the interface between the intermediate layer and the receiving layer around the periphery of the patch. Therefore, when producing a printed product using the intermediate transfer medium of the present disclosure, the patch can be transferred to the transfer region of the transfer recipient, and the receiving layer can be transferred to the transfer region outside the patch, making it possible to support edge-to-edge printing.

[0082] In one embodiment, the intermediate transfer medium of the present disclosure has a peel force f2 at 50° C. when the intermediate layer and the receiving layer are peeled off, of preferably 10 gf / cm or less, more preferably 8 gf / cm or less, and even more preferably 5 gf / cm or less. When the peel force f2 at 50° C. is 10 gf / cm or less, the intermediate transfer medium of the present disclosure can be peeled off at the interface between the intermediate layer and the receiving layer in the peripheral portion of the patch during transfer.

[0083] In one embodiment, the intermediate transfer medium of the present disclosure preferably has a peel force F of more than 0.5 gf / cm at 50° C. when the transfer sheet (protective substrate) and the release member (peel layer) are peeled off. Furthermore, the peel force F is preferably 10 gf / cm or less, more preferably 7 gf / cm or less, and even more preferably 5 gf / cm or less. When the peel force F at 50° C. is 10 gf / cm or less, the intermediate transfer medium of the present disclosure can easily transfer a patch to a transfer recipient.

[0084] The peel force can be measured by a flat plate cross-stage method using a peel tester having the structure described in Japanese Patent No. 4717156. Specifically, the target layer is peeled at an angle of 90° from the target layer while the target layer (printed object) after patch transfer is heated to 50°C, and the load required for peeling is measured.

[0085] In one embodiment of the intermediate transfer medium of the present disclosure, when the intermediate layer and the receiving layer are peeled off, the average of the water contact angle on the surface of the intermediate layer (see reference numeral 23a in FIG. 4 ) and the water contact angle on the surface of the receiving layer (see reference numeral 24a in FIG. 4 ) is preferably 65° or more and 95° or less. The upper limit of this average is more preferably 70° or more, and even more preferably 75° or more. The lower limit of this average is more preferably 90° or less, and even more preferably 85° or less.

[0086] Here, the water contact angles on the surfaces of the intermediate layer and the receiving layer are indicators of the effect of the release agent contained in the intermediate layer and the receiving layer. When the average value is within the above range, hot peelability between the intermediate layer and the receiving layer can be ensured.

[0087] The contact angle of water is measured at three points on the surface of each of the intermediate layer and the receiving layer using a DropMaster series DM-300 (manufactured by Kyowa Interface Science Co., Ltd.), and the average of the measured values ​​is calculated. Specifically, water (approximately 2 μL / droplet) is dropped at 23° C. by the sessile drop method, and the contact angle is measured one second after the drop.

[0088] (Patch) In one embodiment of the intermediate transfer medium of the present disclosure, a patch is a region of the transfer sheet defined by a slit that penetrates the transfer sheet and reaches the release member (at least the surface of the release member that comes into contact with the transfer sheet). When the intermediate transfer medium of the present disclosure is viewed in a plan view in the thickness direction, the shape of the patch is not particularly limited, but can be, for example, a shape similar to the transfer area of ​​the transfer object (see FIG. 3). The area of ​​the patch is also not particularly limited, but is preferably smaller than the entire transfer area of ​​the transfer object, for example, so as to cover a portion slightly inside the transfer area of ​​the transfer object.

[0089] In one embodiment, the intermediate transfer medium of the present disclosure can form a patch on the transfer sheet of the intermediate transfer medium by a conventionally known method, for example, as described in the above-mentioned Patent Document 1.

[0090] [Method for manufacturing a printed product] The method for manufacturing a printed product of the present disclosure includes forming a thermal transfer image on the receiving layer of the intermediate transfer medium described above, integrating the intermediate transfer medium and the transferee so that the receiving layer is in contact with the transfer area of ​​the transferee, transferring a patch to the transfer area, and transferring the receiving layer to the transfer area outside the patch. Furthermore, in the method for manufacturing a printed product of the present disclosure, it is preferable to use a thermal transfer sheet having at least one colorant layer when forming a thermal transfer image on the receiving layer.

[0091] <Preparation Step> The method for producing a print product according to the present disclosure may include a preparation step of preparing the intermediate transfer medium according to the present disclosure, a transfer receiving body, and a thermal transfer sheet. Details of the intermediate transfer medium according to the present disclosure are as described above.

[0092] (Receiving Body) In the present disclosure, examples of the receiving body include metal plates such as aluminum plates; ceramic plates such as pottery; wood; glass substrates; paper substrates such as plain paper, fine paper, and tracing paper; and resin plates or resin films made of resin materials such as polycarbonate, polyester, (meth)acrylic resin, acrylonitrile-butadiene-styrene (ABS) copolymer resin, and polyvinyl chloride. Among these, resin cards such as polycarbonate and polyvinyl chloride are preferred.

[0093] (Transfer Sheet) In the present disclosure, the transfer sheet preferably has at least one colorant layer. In one embodiment, the thermal transfer sheet has one or more colorant layers provided in surface order on one surface of a base layer. By using the thermal transfer sheet of this embodiment, a thermal transfer image can be formed on the receiving layer of an intermediate transfer medium.

[0094] As the substrate layer, the same resin films as those explained above for the liner substrate and protective substrate can be used.

[0095] For example, when a thermal transfer image is formed by a sublimation thermal transfer method, the colorant layer is a sublimation transfer type colorant layer containing a sublimation dye and a binder resin.

[0096] The sublimation dye preferably has sufficient color density and does not discolor or fade due to light, heat, etc. Examples of such sublimation dyes include red dyes, yellow dyes, and blue dyes. The sublimation transfer colorant layer can contain one or more sublimation dyes. The content of the sublimation dye in the sublimation transfer colorant layer is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less.

[0097] Examples of binder resins in the sublimation transfer colorant layer include cellulose resins, vinyl resins, vinyl acetal resins, (meth)acrylic resins, polyurethanes, polyamides, polyimides, and polyesters. The sublimation transfer colorant layer can contain one or more binder resins. The content of the binder resin in the sublimation transfer colorant layer is preferably 20% by mass or more and 75% by mass or less, more preferably 30% by mass or more and 60% by mass or less.

[0098] The sublimation transfer colorant layer may be cured with a curing agent. Examples of the curing agent include epoxy resin, isocyanate, and carbodiimide. One or more types of curing agents may be used.

[0099] The sublimation transfer colorant layer may contain one or more types of particles, such as inorganic particles and organic particles. Examples of inorganic particles include carbon black, silica, alumina, titanium dioxide, and molybdenum disulfide. Examples of organic particles include polyethylene particles.

[0100] The sublimation transfer colorant layer may contain one or more release agents. Examples of the release agent include fluorine compounds, phosphate ester compounds, higher fatty acid amide compounds, metal soaps, silicone oils, and waxes such as polyethylene wax and paraffin wax. The content of the release agent in the sublimation transfer colorant layer is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less.

[0101] For example, when a thermal transfer image is formed by a melting type thermal transfer method, the color material layer is a melting type color material layer containing a colorant and a binder resin.

[0102] The colorant preferably has sufficient color density and does not discolor or fade due to light, heat, or the like. Examples of colorants include organic pigments, inorganic pigments, and dyes. The colorant color is not limited to, for example, cyan, magenta, yellow, or black, and various colors can be used. The melt-transfer colorant layer can contain one or more colorants. The content of the colorant in the melt-transfer colorant layer is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less.

[0103] Examples of binder resins in the melt-transfer colorant layer include polyolefins, vinyl resins, vinyl acetal resins, (meth)acrylic resins, polystyrene, polycarbonate, cellulose resins, and petroleum resins. The melt-transfer colorant layer can contain one or more binder resins. The content of the binder resin in the melt-transfer colorant layer is preferably 20% by mass or more and 75% by mass or less, more preferably 30% by mass or more and 60% by mass or less.

[0104] The melt transfer colorant layer may further contain a conventionally known wax. The colorant layer may contain one or more of the above-mentioned additives.

[0105] The thermal transfer sheet of the present disclosure may have one colorant layer on one surface of a substrate layer, or may have multiple colorant layers of different hues, such as a yellow colorant layer, a magenta colorant layer, a cyan colorant layer, and a black colorant layer, arranged in face order. The thickness of the colorant layer is preferably 0.1 μm or more and 5 μm or less.

[0106] The thermal transfer sheet of the present disclosure may be provided with a glittering material layer having an interference color and an adhesive layer after the coloring material layer. The adhesive layer is a layer for adhering the image pattern to the transfer surface of the information recording medium when the image pattern, which is composed of the coloring material image pattern and the glittering material image pattern transferred to the intermediate transfer medium in the primary transfer step, is retransferred to the information recording medium in the secondary transfer step.

[0107] In a preparation step, a thermal transfer image is formed on the receptor layer of the intermediate transfer medium of the present disclosure (hereinafter also referred to as an "image forming step").

[0108] Specifically, in the image forming process, an intermediate transfer medium having a receiving layer and a thermal transfer sheet having a colorant layer are superimposed so that the receiving layer and the colorant layer face each other, and a heating means such as a thermal head is used to transfer the sublimation dye contained in the sublimation transfer colorant layer to the receiving layer, or to transfer the melt transfer colorant layer onto the receiving layer, thereby forming a thermal transfer image.

[0109] In the image forming step, as described above, a thermal transfer sheet having one or more color material layers provided in face-sequential order on one surface of a substrate layer may be used to form a thermal transfer image on the receiving layer of the intermediate transfer medium of the present disclosure. Alternatively, an intermediate transfer medium may be used in which a thermal transfer image has already been formed on the receiving layer.

[0110] In the integration step, the intermediate transfer medium and the transferee are integrated so that the receiving layer on which the thermally transferred image is formed contacts the transfer area of ​​the transferee. In this step, a laminate is obtained that includes the transferee, the transfer layer, the protective substrate, and the release member in this order in the thickness direction.

[0111] The transfer process is a process in which a transfer layer including a receiving layer on which a thermal transfer image is formed is transferred together with a protective substrate to a transfer area of ​​a transferee. Here, by using the intermediate transfer medium of the present disclosure, during transfer, peeling occurs at the interface between the transfer sheet (protective substrate) and the release member (release layer) in the patch area, and peeling occurs at the interface between the receiving layer and the intermediate layer outside the patch. Therefore, in this process, the patch is transferred to the transfer area of ​​the transferee, and a printed product is obtained in which the receiving layer is transferred to the transfer area outside the patch.

[0112] FIGS. 2 to 4 show an outline of a method for producing a print according to one embodiment. As shown in FIG. 2, the intermediate transfer medium 1 and the receiver P are overlapped, aligning them so that the receptor layer 24 of the intermediate transfer medium 1 contacts one surface of the receiver P that will become the transfer area. As shown in FIG. 3, when viewed from above in the direction of stacking the intermediate transfer medium 1 and the receiver P, it is preferable to align the intermediate transfer medium 1 and the receiver P so that a patch made of a transfer sheet defined by a slit S in the intermediate transfer medium fits inside one surface (transfer area) of the receiver P. This alignment can be performed using a conventionally known method. Next, the intermediate transfer medium 1 is heated from the liner substrate side, and then the intermediate transfer medium 1 is peeled off from the receiver P. As shown in FIG. 4, a patch made of a transfer sheet 20 is transferred to one surface (transfer area) of the receiver P, and the receptor layer 24 is transferred to the transfer area outside the patch. In this manner, the print 100 is obtained.

[0113] [Printed Product] The printed product of the present disclosure includes a transferee and a patch laminated on the transfer area of ​​the transferee. The patch has, from the transferee side, a transfer layer and a protective substrate, in this order. From the transferee side, the transfer layer has at least a receiving layer on which a thermal transfer image is formed, and an intermediate layer in contact with the receiving layer. The receiving layer is laminated on the transfer area outside the patch.

[0114] An example of the configuration of a printed matter according to one embodiment is shown in Figure 4. As shown in Figure 4, the printed matter 100 of the present disclosure has a patch made of a transfer sheet laminated on one surface (transfer area) of a recipient P, and a receiving layer 24 laminated in the transfer area outside the patch. The printed matter 100 of the present disclosure has excellent adhesion between the recipient P and the patch, and the transfer area of ​​the recipient P is appropriately covered by the patch and the receiving layer 24 transferred to the outer edge of the patch.

[0115] The present disclosure relates to, for example, the following items [1] to [8]: [1] An intermediate transfer medium comprising a release member and a transfer sheet laminated on the release member, wherein the transfer sheet has a protective substrate and a transfer layer in this order from the release member side, and a slit is provided in the transfer sheet from the surface opposite the release member side, penetrating the transfer sheet to the release member, and wherein an area of ​​the transfer sheet defined by the slit as an outer periphery can be transferred as a patch to a transfer-receiving body, wherein the transfer layer has at least a receiving layer located on the surface opposite the protective substrate and an intermediate layer in contact with the receiving layer, wherein the receiving layer contains a vinyl chloride-vinyl acetate copolymer, and the intermediate layer contains a (meth)acrylic resin, wherein the (meth)acrylic resin has a glass transition temperature of 120°C or higher, and the (meth)acrylic resin has an acid value of 15 mgKOH / g or higher. [2] The intermediate transfer medium according to [1] above, wherein at least one of the receiving layer and the intermediate layer contains a release agent. [3] The intermediate transfer medium according to [1] or [2] above, wherein the peel force at 50°C when the intermediate layer and the receiving layer are peeled from each other is 10 gf / cm or less. [4] The intermediate transfer medium according to any one of [1] to [3] above, wherein, when the intermediate layer and the receiving layer are peeled from each other, the average value of the water contact angle on the surface of the intermediate layer and the water contact angle on the surface of the receiving layer is 65° or more and 95° or less. [5] The intermediate transfer medium according to any one of [1] to [4] above, wherein the release member has, from the transfer sheet side, a release layer, an adhesive layer, and a liner substrate in this order. [6] The intermediate transfer medium according to any one of [1] to [5] above, wherein the glass transition temperature of the (meth)acrylic resin is 180°C or less. [7] The intermediate transfer medium according to any one of the above [1] to [6], wherein the (meth)acrylic resin has an acid value of 60 mgKOH / g or less.[8] An intermediate transfer medium comprising a release member and a transfer sheet laminated on the release member, wherein the transfer sheet has, from the release member side, a protective substrate and a transfer layer in this order, and a slit is provided on the surface of the transfer sheet opposite the release member side, penetrating the transfer sheet to the release member, and wherein an area of ​​the transfer sheet defined by the slit as an outer periphery can be transferred as a patch to a transferee, wherein the transfer layer has at least a receiving layer located on the surface opposite the protective substrate and an intermediate layer in contact with the receiving layer, wherein the receiving layer contains a vinyl chloride-vinyl acetate copolymer, and the intermediate layer contains a (meth)acrylic resin, and the peel force at 50°C when the intermediate layer and the receiving layer are peeled off is 10 gf / cm or less, and when the intermediate layer and the receiving layer are peeled off, the average of the water contact angle on the surface of the intermediate layer and the water contact angle on the surface of the receiving layer is 65° or more and 95° or less. [9] A printed product comprising: a recipient; and a patch laminated in a transfer area of ​​the recipient, wherein the patch has, from the recipient side, a transfer layer and a protective substrate, in this order, wherein the transfer layer has, from the recipient side, at least a receiving layer on which a thermal transfer image is formed, and an intermediate layer in contact with the receiving layer, wherein the receiving layer is laminated in the transfer area outside the patch.

[10] A method for producing a printed product using the intermediate transfer medium described in any one of [1] to [8] above, comprising: forming a thermal transfer image on the receiving layer of the intermediate transfer medium; integrating the intermediate transfer medium and the recipient so that the receiving layer is in contact with the transfer area of ​​the recipient, and then transferring the patch to the transfer area and transferring the receiving layer to the transfer area outside the patch.

[11] The method for producing a printed matter according to the above

[10] , wherein the thermal transfer image is formed using a thermal transfer sheet having at least one colorant layer.

[0116] Next, the intermediate transfer medium, printed matter, and method for producing a printed matter of the present disclosure will be described in more detail using examples, but the intermediate transfer medium, printed matter, and method for producing a printed matter of the present disclosure are not limited to these examples. In the following description, "parts" means "parts by mass." The blending amounts shown in the following description and Table 1 are values ​​converted into solids, excluding water and organic solvents.

[0117] [Preparation Example] <Thermal Transfer Sheet> A 5 ​​μm thick polyethylene terephthalate film was used as the substrate. A dye primer layer coating liquid having the following composition was applied to a portion of one surface of the substrate to a dry thickness of 0.15 μm and dried to form a dye primer layer. Yellow, magenta, and cyan colorant layer coating liquids having the following compositions were applied to this dye primer layer in surface order to a dry thickness of 0.7 μm and dried to form a yellow colorant layer, a magenta colorant layer, and a cyan colorant layer. Furthermore, a melt-ink layer having the following composition was applied to a region of one surface of the substrate where the dye primer layer was not formed to a dry thickness of 0.7 μm and dried to form a melt-ink layer. Furthermore, a back layer coating liquid having the following composition was applied to the other surface of the substrate to a dry thickness of 1 μm and dried to form a back layer, thereby obtaining a thermal transfer sheet.

[0118] <Coating liquid for back layer> Polyvinyl butyral 1.8 parts (S-LEC (registered trademark) BX-1, Sekisui Chemical Co., Ltd.) Polyisocyanate 5.5 parts (Burnoc (registered trademark) D750, DIC Corporation) Phosphate ester surfactant 1.6 parts (Plysurf (registered trademark) A208N, Dai-ichi Kogyo Seiyaku Co., Ltd.) Talc 0.35 parts (Micro Ace (registered trademark) P-3, Nippon Talc Industrial Co., Ltd.) Toluene 18.5 parts Methyl ethyl ketone 18.5 parts

[0119] <Coating liquid for dye primer layer> Colloidal alumina (solid content 10.5%) 3.5 parts (Aluminasol 200, Nissan Chemical Industries, Ltd.) Vinyl acetate-vinylpyrrolidone copolymer 1.5 parts (PVP / VA E-335, ISP Japan Co., Ltd.) Water 47.5 parts Isopropyl alcohol 47.5 parts

[0120] <Coating liquid for yellow colorant layer> Solvent Yellow 93 2.5 parts Disperse Yellow 201 2.5 parts Polyvinyl acetal 4 parts (S-LEC (registered trademark) KS-5, Sekisui Chemical Co., Ltd.) Organically modified silicone oil 0.04 parts Toluene 50 parts Methyl ethyl ketone 50 parts

[0121] <Coating liquid for magenta colorant layer> Disperse Red 60 3 parts Disperse Violet 26 3 parts Polyvinyl acetal 5 parts (S-LEC (registered trademark) KS-5, Sekisui Chemical Co., Ltd.) Organically modified silicone oil 0.05 parts Toluene 50 parts Methyl ethyl ketone 50 parts

[0122] <Coating liquid for cyan colorant layer> Solvent Blue 63 3 parts Disperse Blue 354 4 parts Polyvinyl acetal 5 parts (S-LEC (registered trademark) KS-5, Sekisui Chemical Co., Ltd.) Organically modified silicone oil 0.05 parts Toluene 50 parts Methyl ethyl ketone 50 parts

[0123] <Coating liquid for melt ink layer> Carbon black 4 parts Vinyl chloride-vinyl acetate copolymer 6 parts (Solvine (registered trademark) CNL, Nissin Chemical Industry Co., Ltd.) Toluene 50 parts Methyl ethyl ketone 50 parts

[0124] <Intermediate transfer medium> (Example 1) A polyethylene terephthalate film (PET E5102, Toyobo Co., Ltd.) having a thickness of 25 μm was used as the liner substrate of the release member, and a coating liquid for adhesive layer having the following composition was applied to the liner substrate so that the thickness when dried was 3 μm, and then dried to obtain a laminate 1 having an adhesive layer provided on the liner substrate.

[0125] <Coating liquid for adhesive layer> Polyester polyol solution (solid content 50%) 54 parts (Seikabond E-295NTL-D50 Dainichiseika Color & Chemicals Mfg. Co., Ltd.) Polyisocyanate (solid content 100%) 6 parts (Seikabond C-55 Dainichiseika Color & Chemicals Mfg. Co., Ltd.) Ethyl acetate 30 parts

[0126] Furthermore, a 16 μm-thick polyethylene terephthalate film (transparent PET E-5102, Toyobo Co., Ltd.) was used as the protective substrate, and a primer layer coating liquid having the following composition was applied to one surface of the protective substrate so as to have a dry thickness of 1.0 μm, followed by drying, to provide a primer layer on the protective substrate.

[0127] <Primer layer coating liquid 1> Vinyl chloride-vinyl acetate copolymer 42 parts (Solvine (registered trademark) A, Nissin Chemical Industry Co., Ltd.) Polyester (Vylon (registered trademark) 200, Toyobo Co., Ltd.) 42 parts Isocyanate compound 16 parts (Takenate (registered trademark) D110N, manufactured by Mitsui Chemicals, Inc., solid content 75%) Toluene 200 parts Methyl ethyl ketone 200 parts

[0128] Next, an intermediate layer coating solution having the following composition was applied onto the primer layer so as to have a dry thickness of 3.0 μm, and then dried to provide an intermediate layer.

[0129] <Coating liquid 1 for forming intermediate layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948, Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°, acid value: 21 mgKOH / g) Methyl ethyl ketone 300 parts

[0130] Furthermore, a receiving layer was formed by applying a coating liquid for a receiving layer having the following composition onto the intermediate layer so that the thickness when dried would be 3.0 μm, and then drying. The primer layer, intermediate layer, and receiving layer constitute a transfer layer.

[0131] <Coating Solution 1 for Receiving Layer> Vinyl chloride-vinyl acetate copolymer 100 parts (Solvine (registered trademark) CNL, Nissin Chemical Industry Co., Ltd., Mn: 16,000) Epoxy-modified silicone oil 5 parts (Shin-Etsu Chemical Co., Ltd., trade name: KP-1800U) Methyl ethyl ketone 315 parts

[0132] Next, a release layer coating solution having the following composition was applied to the other surface of the protective substrate so as to have a dry thickness of 0.5 μm, and then dried to form a release layer, thereby obtaining Laminate 2, in which the release layer, protective substrate, and transfer layer (primer layer, intermediate layer, and receptor layer) were laminated in this order.

[0133] <Coating liquid for release layer> Cellulose acetate propionate 40 parts (CAP-482-20 manufactured by Eastman Chemical Co.) Cellulose acetate butyrate 40 parts (CAP-551-0.01 manufactured by Eastman Chemical Co.) Vinyl chloride-vinyl acetate copolymer 20 parts (Solvine (registered trademark) CNL, Nissin Chemical Industry Co., Ltd.) Methyl ethyl ketone 340 parts Toluene 340 parts

[0134] Subsequently, the laminate 1 and the laminate 2 were bonded together so that the adhesive layer of the laminate 1 and the release layer of the laminate 2 faced each other, thereby obtaining an intermediate transfer medium in which the release member and the transfer sheet were integrated.

[0135] Next, continuous half-cut notches, slightly smaller in size than the card (specifications will be described later) that was the transfer target, were formed on the surface of the transfer sheet opposite the release member, extending to the surface on the release member side, thereby obtaining the intermediate transfer medium of Example 1.

[0136] Example 2 An intermediate transfer medium of Example 2 was obtained in the same manner as in Example 1, except that the receiving layer coating liquid 1 was changed to the receiving layer coating liquid 2 having the following composition.

[0137] <Receptor layer coating liquid 2> Vinyl chloride-vinyl acetate copolymer 100 parts (Solvine (registered trademark) CNL, Nissin Chemical Industry Co., Ltd., Mn: 16,000) Epoxy-modified silicone oil 10 parts (Shin-Etsu Chemical Co., Ltd., trade name: KP-1800U) Methyl ethyl ketone 330 parts

[0138] Example 3 An intermediate transfer medium of Example 3 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 2 having the following composition.

[0139] <Coating liquid 2 for intermediate layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948, Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Epoxy-modified silicone oil 10 parts (Shin-Etsu Chemical Co., Ltd., trade name: KP-1800U) Methyl ethyl ketone 330 parts

[0140] (Example 4) The intermediate transfer medium of Example 4 was obtained in the same manner as in Example 1, except that the intermediate layer coating liquid 1 was changed to the intermediate layer coating liquid 2 and the receiving layer coating liquid 1 was changed to the receiving layer coating liquid 2.

[0141] Example 5 An intermediate transfer medium of Example 5 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 3 having the following composition.

[0142] <Coating liquid 3 for intermediate layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948, Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Epoxy-modified silicone oil 20 parts (Shin-Etsu Chemical Co., Ltd., trade name: KP-1800U) Methyl ethyl ketone 360 ​​parts

[0143] Example 6 An intermediate transfer medium of Example 6 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 4 having the following composition.

[0144] <Coating liquid 4 for intermediate layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948 Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Silicone oil (X-22-1660B-3 Shin-Etsu Chemical Co., Ltd.) 10 parts Methyl ethyl ketone 330 parts

[0145] Example 7 An intermediate transfer medium of Example 7 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 5 having the following composition.

[0146] <Coating liquid 5 for intermediate layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948 Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Silicone-fluorine copolymer 10 parts (Dialomer SP-2420 Dainichiseika Color & Chemicals Mfg. Co., Ltd.) Methyl ethyl ketone 330 parts

[0147] Example 8 An intermediate transfer medium of Example 8 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 6 having the following composition.

[0148] <Coating liquid 6 for intermediate layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948, Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Silicone resin fine particles 10 parts (Tospearl (registered trademark) 120, Momentive Japan) Methyl ethyl ketone 330 parts

[0149] Example 9 An intermediate transfer medium of Example 9 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 7 having the following composition.

[0150] <Coating Solution 7 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948, Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Acrylic-modified silicone 10 parts (Polyalloy NSA-X55, Natoco Corporation) Methyl ethyl ketone 330 parts

[0151] Example 10 An intermediate transfer medium of Example 10 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 8 having the following composition.

[0152] <Coating liquid 8 for intermediate layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948 Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Silica, silicon-modified nanoparticle dispersion 10 parts (NANOBYK3650 BYK-Chemie Japan Co., Ltd.) Methyl ethyl ketone 330 parts

[0153] Example 11 An intermediate transfer medium of Example 11 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 9 having the following composition.

[0154] <Coating Solution 9 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948 Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Silicone surface conditioner for solvent-based paint 10 parts (BYK-SILCLEAN 3700 BYK) Methyl ethyl ketone 330 parts

[0155] (Comparative Example 1) The intermediate transfer medium of Comparative Example 1 was obtained in the same manner as in Example 1, except that primer layer coating liquid 1 was changed to primer layer coating liquid 2 having the following composition, intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 10 having the following composition, and receiving layer coating liquid 1 was changed to receiving layer coating liquid 3 having the following composition.

[0156] <Primer layer coating liquid 2> Acrylic resin (Dianal (registered trademark) BR-87, Mitsubishi Chemical Corporation) 29 parts Polyester (Vylon (registered trademark) 200, Toyobo Co., Ltd.) 1 part Methyl ethyl ketone 35 parts Toluene 35 parts

[0157] <Coating Solution 10 for Forming Intermediate Layer> (Meth)acrylic polyol resin 100 parts (manufactured by Taisei Fine Chemical Co., Ltd., 6KW-700, solid content 36.5%, Tg 102°C, Mw 55,000, hydroxyl value 30.1 mgKOH / g) Isocyanate compound 3.6 parts (manufactured by Mitsui Chemicals, Inc., Takenate (registered trademark) D110N, solid content 75%) MEK 92 parts

[0158] <Receptor layer coating liquid 3> Vinyl chloride-vinyl acetate copolymer 17.6 parts (Solvine (registered trademark) CNL, Nissin Chemical Industry Co., Ltd., Mn: 16,000) Silicone oil (X-22-3000T, Shin-Etsu Chemical Co., Ltd.) 2.4 parts Methyl ethyl ketone 40 parts Toluene 40 parts

[0159] Comparative Example 2 An intermediate transfer medium of Comparative Example 2 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 11 having the following composition.

[0160] <Coating Solution 11 for Intermediate Layer> Cellulose ester resin 100 parts (CAP-482-0.5, Tomoe Engineering Co., Ltd., Mn 25,000, Tg: 142° C.) Methyl ethyl ketone 640 parts

[0161] Comparative Example 3 An intermediate transfer medium of Comparative Example 3 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 12 having the following composition.

[0162] <Coating Solution 12 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) BR87, Mitsubishi Chemical Corporation, Mw 25,000, Tg: 106°C, acid value: 9.8 mgKOH / g) Methyl ethyl ketone 300 parts

[0163] Comparative Example 4 An intermediate transfer medium of Comparative Example 4 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 13 having the following composition.

[0164] <Coating Solution 13 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) BR1022, Mitsubishi Chemical Corporation, Mw 180,000, Tg: 20°C, acid value: 0 mgKOH / g) Methyl ethyl ketone 300 parts

[0165] Comparative Example 5 An intermediate transfer medium of Comparative Example 5 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 14 having the following composition.

[0166] <Coating Solution 14 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) BR105, Mitsubishi Chemical Corporation, Mw 45,000, Tg: 48°C, acid value: 0 mgKOH / g) Methyl ethyl ketone 300 parts

[0167] Comparative Example 6 An intermediate transfer medium of Comparative Example 6 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 15 having the following composition.

[0168] <Coating Solution 15 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) BR64, Mitsubishi Chemical Corporation, Mw 65,000, Tg: 55°C, acid value: 0 mgKOH / g) Methyl ethyl ketone 300 parts

[0169] Comparative Example 7 An intermediate transfer medium of Comparative Example 7 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 16 having the following composition.

[0170] <Coating Solution 16 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7973, Mitsubishi Chemical Corporation, Mw 19,000, Tg: 48°C, acid value: 1.8 mgKOH / g) Methyl ethyl ketone 300 parts

[0171] Comparative Example 8 An intermediate transfer medium of Comparative Example 8 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 17 having the following composition.

[0172] <Coating Solution 17 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) BR119, Mitsubishi Chemical Corporation, Mw 15,000, Tg: 83°C, acid value: 3.9 mgKOH / g) Methyl ethyl ketone 300 parts

[0173] Comparative Example 9 An intermediate transfer medium of Comparative Example 9 was obtained in the same manner as in Example 1, except that the receiving layer coating liquid 1 was changed to the receiving layer coating liquid 4 having the following composition.

[0174] <Receptor layer coating liquid 4> Vinyl chloride-vinyl acetate copolymer 100 parts (Solvine (registered trademark) CNL, Nissin Chemical Industry Co., Ltd., Mn: 16,000) Methyl ethyl ketone 300 parts

[0175] Comparative Example 10 An intermediate transfer medium of Comparative Example 10 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 18 having the following composition.

[0176] <Coating Solution 18 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948, Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Silicone / acrylic graft polymer 10 parts (Simac (registered trademark) US-380, Toagosei Co., Ltd.) Methyl ethyl ketone 330 parts

[0177] Comparative Example 11 An intermediate transfer medium of Comparative Example 11 was obtained in the same manner as in Example 1, except that intermediate layer coating liquid 1 was changed to intermediate layer coating liquid 19 having the following composition.

[0178] <Coating Solution 19 for Intermediate Layer> Acrylic resin 100 parts (Dianal (registered trademark) MB7948 Mitsubishi Chemical Corporation, Mw 25,000, Tg: 126°C, acid value: 21 mgKOH / g) Polyethylene wax 10 parts (average particle diameter 1 μm or less, particle melting point: 90 to 95°C) Methyl ethyl ketone 330 parts

[0179] [Evaluation] <Image formation> The intermediate transfer media of Examples 1 to 11 and Comparative Examples 1 to 9 obtained above were combined with the thermal transfer sheets obtained above, and a black image (image gradation: 0 / 255) was formed on the receiving layer of each intermediate transfer medium using the following test printer.

[0180] (Test printer) Thermal head: KEE-57-12GAN2-STA (Kyocera Corporation) Heating element average resistance: 3303 (Ω) Print density in main scanning direction: 300 (dpi) Print density in sub-scanning direction: 300 (dpi) Print voltage: 18 (V) Line cycle: 1.5 (msec. / line) Print start temperature: 35 (°C) Pulse duty ratio: 85 (%)

[0181] (Evaluation 1) Edge-to-Edge Printing Performance Using an experimental heat roller, the transfer sheets (transfer layer and protective substrate) of the intermediate transfer media of the Examples and Comparative Examples on which the above-described images had been formed were transferred onto a polyvinyl chloride card (approximately 54 mm long x approximately 86 mm wide x approximately 0.8 mm thick, Dai Nippon Printing Co., Ltd.) as a transfer recipient conforming to the dimensions of the JIS X 6301:2005 standard under transfer conditions of 202°C and 20 mm / sec., to produce printed images, and the "coverage of the outer edge of the patch" of the intermediate transfer medium was evaluated. Here, the coverage of the outer edge of the patch was evaluated by evaluating edge-to-edge printing performance based on the following evaluation criteria. The evaluation results of edge-to-edge printing performance are also shown in Table 1.

[0182] (Experimental conditions) Rubber hardness of heat roller: 60° Rubber hardness of nip roller: 70° Roller gap between heat roller and nip roller during heating: 0 mm

[0183] (Evaluation Criteria) ◯: The receptor layer is transferred (edge-to-edge printing) to the transfer area outside the patch frame. ×: The receptor layer is not transferred to the transfer area outside the patch frame.

[0184] (Evaluation 2) Adhesion between patch and transferee For each of the printed materials of the Examples and Comparative Examples used in the evaluation of edge-to-edge printing performance, the patch was peeled off from the polyvinyl chloride card at an angle of 90°, the load required to peel the patch was measured, and the adhesion between the patch and the transferee was evaluated based on the following evaluation criteria. The evaluation results are also shown in Table 1.

[0185] (Conditions for measuring adhesion force) Measuring instrument: Precision universal testing machine Autograph AGS-100B (Shimadzu Corporation) Measuring temperature: 23° C. Peeling angle: 90° Speed: 300 mm / min.

[0186] (Evaluation criteria) ⊚: Break... The patch adheres strongly to the card and breaks when peeled off. ◯: Adhesion strength of 70 gf / cm or more... The patch adheres strongly to the card and cannot be easily peeled off. ×: Adhesion strength of less than 70 gf / cm... The patch adheres weakly to the card and can be easily peeled off.

[0187] (Evaluation 3) Contact angle of the intermediate layer and receiving layer surfaces after transfer For each of the printed materials of the Examples and Comparative Examples used in the evaluation of the edge-to-edge printing performance described above, the contact angle of the intermediate layer surface exposed on the release member side after patch transfer and the contact angle of the receiving layer surface transferred to the outer periphery of the patch on the card side were measured at three points each, and the average of each measurement value was calculated. The contact angle measurement results are also shown in Table 1. Note that for the level in Evaluation 1 above where edge-to-edge printing was not performed, contact angle measurements were not performed. For this reason, "-" is entered instead of a numerical value for the contact angle of the surface after transfer in Table 1. (Measurement conditions) Measuring device: DropMaster series DM-300 (manufactured by Kyowa Interface Science Co., Ltd.) Measurement temperature: 23°C Measurement method: Water (approximately 2 μL / drop) was dropped using the sessile drop method, and the contact angle was measured 1 second after the drop

[0188] (Evaluation 4) Peeling force between intermediate layer and receiving layer For each of the printed materials of the Examples and Comparative Examples used in the evaluation of edge-to-edge printing performance, the patch was peeled at an angle of 90° from a polyvinyl chloride card heated to 50° C., and the peeling force between the intermediate layer and receiving layer was measured. The results of the peeling force measurements are also shown in Table 1.

[0189] (Measuring conditions for peel force) Measuring device: Peel analysis device VPA-3 (manufactured by Kyowa Interface Science Co., Ltd.) Stage temperature: 50° C. Peel angle: 90° Speed: 300 mm / min.

[0190]

[0191] 1: Intermediate transfer medium 10: Release member 11: Liner substrate 12: Adhesion layer 13: Peel layer 20: Transfer sheet 21: Protective substrate 22: Primer layer 23: Intermediate layer 24: Receptor layer 100: Printed object S: Slit P: Transfer recipient

Claims

1. An intermediate transfer medium comprising a release member and a transfer sheet laminated on the release member, wherein the transfer sheet has, from the release member side, a protective substrate and a transfer layer in this order, and a slit is provided on the surface of the transfer sheet opposite the release member side, penetrating the transfer sheet to the release member, and wherein an area of ​​the transfer sheet defined by the slit as an outer periphery can be transferred as a patch to a transferee, wherein the transfer layer has at least a receiving layer located on the surface opposite the protective substrate and an intermediate layer in contact with the receiving layer, wherein the receiving layer contains a vinyl chloride-vinyl acetate copolymer, and the intermediate layer contains a (meth)acrylic resin, the glass transition temperature of the (meth)acrylic resin is 120°C or higher, and the acid value of the (meth)acrylic resin is 15 mgKOH / g or higher.

2. The intermediate transfer medium of claim 1, wherein at least one of the receptor layer and the intermediate layer contains a release agent.

3. The intermediate transfer medium according to claim 1, wherein the peeling force at 50° C. when the intermediate layer and the receiving layer are peeled off is 10 gf / cm or less.

4. An intermediate transfer medium according to claim 1, wherein when the intermediate layer and the receiving layer are peeled off, the average value of the water contact angle on the surface of the intermediate layer and the water contact angle on the surface of the receiving layer is 65° or more and 95° or less.

5. The intermediate transfer medium according to claim 1, wherein the release member has, from the transfer sheet side, a release layer, an adhesive layer, and a liner substrate in this order.

6. The intermediate transfer medium according to claim 1, wherein the (meth)acrylic resin has a glass transition temperature of 180° C. or lower.

7. The intermediate transfer medium according to claim 1, wherein the (meth)acrylic resin has an acid value of 60 mgKOH / g or less.

8. An intermediate transfer medium comprising a release member and a transfer sheet laminated on the release member, the transfer sheet having, from the release member side, a protective substrate and a transfer layer in this order, and a slit is provided on the surface of the transfer sheet opposite the release member side, penetrating the transfer sheet to the release member, and an area of ​​the transfer sheet defined by the slit as an outer periphery can be transferred as a patch to a transferee, the transfer layer having at least a receiving layer located on the surface opposite the protective substrate and an intermediate layer in contact with the receiving layer, the receiving layer comprising a vinyl chloride-vinyl acetate copolymer, and a (meth)acrylic resin, the peel force at 50°C when the intermediate layer and the receiving layer are peeled off is 10 gf / cm or less, and when the intermediate layer and the receiving layer are peeled off, the average value of the contact angle of water on the surface of the intermediate layer and the contact angle of water on the surface of the receiving layer is 65° or more and 95° or less.

9. A printed matter comprising: a transfer object; and a patch laminated on a transfer area of ​​the transfer object, wherein the patch has, from the transfer object side, a transfer layer and a protective substrate in this order, wherein the transfer layer has, from the transfer object side, at least a receiving layer on which a thermal transfer image is formed and an intermediate layer in contact with the receiving layer, and wherein the receiving layer is laminated on the transfer area outside the patch.

10. A method for producing a printed matter using the intermediate transfer medium according to any one of claims 1 to 8, comprising forming a thermal transfer image on the receiving layer of the intermediate transfer medium, integrating the intermediate transfer medium and the object to be transferred so that the receiving layer is in contact with the area to be transferred of the object to be transferred, and then transferring the patch to the area to be transferred and the receiving layer to the area to be transferred outside the patch.

11. The method for producing a print according to claim 10, wherein the thermal transfer image is formed using a thermal transfer sheet having at least one colorant layer.

Images