Thermal transfer sheet, combination of thermal transfer sheet and intermediate transfer medium, decorative sheet, method for manufacturing decorated product, and decorated product

Abstract

To provide a thermal transfer sheet that can transfer an adhesive layer having high adhesion to a glass member even after a heat-water resistance test onto a decorative body not having high adhesion to the glass member.SOLUTION: A thermal transfer sheet has a first substrate layer and a first transfer layer. The first transfer layer has an adhesive layer. The adhesive layer contains a first polyester having a glass transition temperature (Tg) of 30°C or lower and a number average molecular weight (Mn) of 15,000 or more. The adhesive layer constitutes the surface of the first transfer layer on the first substrate layer side.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a thermal transfer sheet, a combination of a thermal transfer sheet and an intermediate transfer medium, a decorative sheet, a method for manufacturing a decorated product, and a decorated product. [Background technology]

[0002] A thermal transfer method is widely used as a method for producing a print. According to this thermal transfer method, a thermal transfer sheet having a colorant layer on one side of a base layer is combined with a thermal transfer image receiving sheet having a receiving layer on one side of another base layer, and a thermal transfer image is formed on the receiving layer of the thermal transfer image receiving sheet, thereby obtaining a print.

[0003] Known thermal transfer methods include dye-sublimation thermal transfer and melting thermal transfer. The dye-sublimation thermal transfer method is a method in which a sublimable dye contained in a colorant layer of a thermal transfer sheet is transferred to a receiving layer of a thermal transfer image-receiving sheet by a heating means such as a thermal head. The melting thermal transfer method is a method in which a colorant layer of a thermal transfer sheet is melted or softened by a heating means such as a thermal head, and the colorant layer is transferred onto a receiving layer of a thermal transfer image-receiving sheet.

[0004] With the diversification of printed products, there is a demand for decorated products in which a thermally transferred image is formed on a transferee such as a glass member, rather than a printed product in which a thermally transferred image is formed on the receiving layer of a thermal transfer image receiving sheet. To meet this demand, a method has been proposed that uses an intermediate transfer medium in which a transfer layer having a receiving layer as a surface layer is provided on one side of a base layer (see, for example, Patent Document 1). In this method, a thermally transferred image is formed on the receiving layer, which is the surface layer of the intermediate transfer medium, using a thermal transfer sheet, and then the transfer layer having the receiving layer on which the thermally transferred image is formed is transferred onto the transferee, thereby obtaining a decorated product in which the transfer layer is provided on the transferee. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-351656 Summary of the Invention [Problem to be solved by the invention]

[0006] The intermediate transfer medium has a receiving layer as a surface layer on one side. Therefore, when a transfer layer having a receiving layer is transferred onto a transferee, the receiving layer becomes the layer that contacts the transferee. However, according to the study by the present inventors, when the transferee is a glass member, it has been found that conventional receiving layers do not have high adhesion to the glass member. Furthermore, decorative bodies are sometimes used to impart design or decorativeness to glass members, not limited to intermediate transfer media. However, there are decorative bodies that are desired to be integrated with the glass member but do not have high adhesion to the glass member. In particular, from the viewpoint of the durability of the resulting decorated product, it is desirable that the above-mentioned decrease in adhesion be suppressed, for example, after a hot water resistance test.

[0007] One objective of the present disclosure is to provide a thermal transfer sheet that can transfer an adhesive layer that has high adhesion to glass components even after a hot water resistance test to a decorative body that does not have high adhesion to such glass components. [Means for solving the problem]

[0008] The thermal transfer sheet of the present disclosure comprises a first substrate layer and a first transfer layer, the first transfer layer comprising an adhesive layer, the adhesive layer containing a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more, and the adhesive layer constituting the surface of the first transfer layer facing the first substrate layer. [Effects of the Invention]

[0009] According to the present disclosure, a thermal transfer sheet can be provided that can transfer an adhesive layer that has high adhesion to glass members even after a hot water resistance test to a decorative body that does not have high adhesion to glass members. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the thermal transfer sheet of the present disclosure. [Figure 2] FIG. 2 is a schematic cross-sectional view showing an example of the thermal transfer sheet of the present disclosure. [Figure 3] FIG. 3 is a schematic cross-sectional view showing an example of the thermal transfer sheet of the present disclosure. [Figure 4] FIG. 4 is a schematic cross-sectional view showing an example of the intermediate transfer medium. [Figure 5] FIG. 5 is a schematic cross-sectional view showing an example of the decorative sheet of the present disclosure. [Figure 6] FIG. 6 is a process diagram showing an example of a method for manufacturing a decorative article according to the present disclosure. [Figure 7] FIG. 7 is a process diagram showing an example of a method for manufacturing a decorative article according to the present disclosure. [Figure 8] FIG. 8 is a schematic cross-sectional view showing an example of the decorative article of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings and the like. The present disclosure can be implemented in many different forms and should not be construed as being limited to the contents of the embodiments described below. Furthermore, to clarify the explanation, the drawings may schematically depict the width, thickness, shape, etc. of each part compared to the actual embodiment, but these are merely examples and are not intended to limit the interpretation of the present disclosure. In this specification and each drawing, elements similar to those described with reference to the previous drawings will be designated by the same reference numerals, and detailed descriptions may be omitted as appropriate.

[0012] In this disclosure, "primary transfer" refers to transferring a first transfer layer from a thermal transfer sheet onto a transfer layer such as a second transfer layer provided on an intermediate transfer medium, and "primary transfer material" refers to the transfer material obtained by this primary transfer. "secondary transfer" refers to transferring a transfer layer such as the second transfer layer provided on the primary transfer material together with the first transfer layer onto a transfer recipient, and "secondary transfer material" refers to the transfer material obtained by this secondary transfer.

[0013] [Thermal transfer sheet] The thermal transfer sheet of the present disclosure includes a first substrate layer and a first transfer layer. More specifically, the thermal transfer sheet includes the first substrate layer and the first transfer layer provided on at least a portion of one surface of the first substrate layer.

[0014] The first transfer layer includes an adhesive layer that forms the surface of the first transfer layer facing the first base layer, and the adhesive layer contains a first polyester having a glass transition temperature (Tg) of 30°C or lower and a number average molecular weight (Mn) of 15,000 or higher.

[0015] Figure 1 is a cross-sectional view showing one embodiment of a thermal transfer sheet according to the present disclosure. In Figure 1, the thermal transfer sheet 1 comprises a first substrate layer 10 and a first transfer layer 20 provided on the first substrate layer 10. In this embodiment, the first transfer layer 20 consists of only an adhesive layer 22.

[0016] 2 is a cross-sectional view showing another embodiment of the thermal transfer sheet of the present disclosure. In Fig. 2, the first transfer layer 20 includes an adhesive layer 22 and an anti-blocking layer 24 in this order in the thickness direction of the thermal transfer sheet 1 from the first base layer 10 side.

[0017] 3 is a cross-sectional view showing another embodiment of the thermal transfer sheet of the present disclosure. In FIG. 3, the thermal transfer sheet 1 includes a release layer 30 between a first base layer 10 and a first transfer layer 20. The thermal transfer sheet 1 of the embodiment shown in FIGS. 1 to 3 includes a back layer 40 on the surface of the first base layer 10 opposite to the first transfer layer 20.

[0018] By using the thermal transfer sheet of the present disclosure, an adhesive layer with high adhesion to glass members can be transferred to a decorative body that does not have high adhesion to glass members. For example, after using this thermal transfer sheet to transfer an adhesive layer onto the decorative body, a portion of the decorative body (e.g., a second transfer layer in an intermediate transfer medium, a protective layer in a protective layer transfer sheet) or all of the decorative body (e.g., a thermal transfer image receiving sheet) can be integrated with the glass member via the adhesive layer. In the decorated product obtained in this manner, the decorative body (part or all) is well adhered to the glass member via the adhesive layer, and therefore peeling of the decorative body is suppressed even in a hot water resistance test.

[0019] In the present disclosure, a glass member refers to a member made of a glass material, preferably an inorganic glass material. Examples of glass members include glass back covers (back covers) included in mobile phones (smartphones, etc.) or tablet devices, display members (cathode ray tube displays, liquid crystal displays, organic electroluminescence displays, plasma displays, etc.) included in image display devices, glass parts included in home appliances, glass tableware (cups, plates, etc.), glass bottles, glass vases, and glass plates. The display members may be any display members included in mobile phones, tablet devices, televisions, personal computers, refrigerators, washing machines, in-vehicle devices, etc. Examples of glass plates include windows, doors, walls, and show windows included in buildings and vehicles, etc. Among these, glass back covers included in mobile phones or tablet devices are preferred.

[0020] <First base layer> The first base layer can be made of any material without particular limitations as long as it has heat resistance to the thermal energy applied during thermal transfer and has the mechanical strength to support the transfer layer and the like provided on the base layer.

[0021] Examples of the first substrate layer include films made of resin materials (hereinafter also referred to as "resin films"). Examples of resin materials include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, 1,4-polycyclohexylene dimethylene terephthalate, and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymers; polyamides; polyimides; polycarbonates; polyolefins such as polyethylene, polypropylene, and polymethylpentene; polystyrenes; vinyl resins such as polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, 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 ionomer resins. The resin film can contain one or more resin materials.

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

[0023] 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.

[0024] The first substrate layer may be a laminate of resin films, which can be produced by, for example, dry lamination, wet lamination, or extrusion.

[0025] The resin film may be a stretched film or an unstretched film. From the viewpoint of strength, a stretched film that is uniaxially or biaxially stretched is preferred.

[0026] When an intermediate layer such as a release layer is provided between the first base layer and the first transfer layer, the surface of the first base layer facing the first transfer layer may be subjected to a surface treatment in order to improve adhesion between the first base layer and the intermediate 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.

[0027] The thickness of the first base layer is preferably from 1 μm to 100 μm, more preferably from 2 μm to 50 μm, and even more preferably from 3 μm to 25 μm, which can improve, for example, the mechanical strength of the first base layer and the transferability of thermal energy during thermal transfer.

[0028] <First transfer layer> The first transfer layer is a layer that can be peeled from the first substrate layer by thermal transfer. The first transfer layer includes an adhesive layer. The first transfer layer may have a single-layer structure consisting of an adhesive layer, or may have a multilayer structure including an adhesive layer and other layers. When the first transfer layer has a multilayer structure, the adhesive layer constitutes the surface layer of the first transfer layer on the side of the first substrate layer.

[0029] ≪Adhesive layer≫ When the first transfer layer of the thermal transfer sheet of the present disclosure is transferred onto a decorative body such as an intermediate transfer medium (more specifically, the second transfer layer of the intermediate transfer medium), the adhesive layer constitutes one surface layer of the resulting transfer. When the decorative body is an intermediate transfer medium, when the second transfer layer of the intermediate transfer medium is transferred onto a glass member via the transferred first transfer layer, the glass member and the adhesive layer come into contact. In one embodiment, the adhesive layer functions as a heat seal layer during secondary transfer to the glass member or integration.

[0030] The adhesive layer contains a first polyester (hereinafter also referred to as "polyester (1)"). The polyester (1) has a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more. When the adhesive layer contains polyester (1), for example, thermal transfer onto a glass member can be performed satisfactorily, and the adhesiveness between the adhesive layer and the glass member in the resulting transferred product can be improved.

[0031] The Tg of the polyester (1) is 30° C. or lower, preferably −20° C. or higher and 26° C. or lower, and more preferably −10° C. or higher and 20° C. or lower. This can improve the adhesion and suppress whitening after a hot water resistance test, for example.

[0032] The Mn of the polyester (1) is 15,000 or more, preferably 18,000 or more and 50,000 or less, and more preferably 20,000 or more and 30,000 or less. When the molecular weight is 15,000 or more, the decrease in adhesion after a hot water resistance test can be suppressed, for example.

[0033] In this disclosure, the glass transition temperature (Tg) is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121 (2012). In this disclosure, the number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight determined by gel permeation chromatography (GPC) in accordance with JIS K7252-1 (2008). The adhesive layer may contain one or more types of polyester (1).

[0034] In one embodiment, the adhesive layer further contains a second polyester (hereinafter also referred to as "polyester (2)"). The polyester (2) has a glass transition temperature (Tg) of 50°C or higher and a number average molecular weight (Mn) of 10,000 or lower. By containing polyester (2) in addition to polyester (1), the adhesive layer can further improve the primary transferability, for example by reducing the peeling noise when peeling the thermal transfer sheet from the intermediate transfer medium. This reduces the roughness of the surface of the primary transfer product, i.e., the adhesive layer surface, and therefore further improves the adhesion between the adhesive layer and the glass member in the secondary transfer product.

[0035] The Tg of the polyester (2) is 50° C. or higher, preferably 53° C. or higher and 100° C. or lower, and more preferably 55° C. or higher and 80° C. or lower, which can improve, for example, the primary transferability.

[0036] The Mn of the polyester (2) is 10,000 or less, preferably 3,000 or more and 10,000 or less, and more preferably 6,000 or more and 10,000 or less, which can suppress the decrease in adhesion after a hot water resistance test, for example. The adhesive layer may contain one or more types of polyester (2).

[0037] In the present disclosure, examples of polyester include copolymers of monomer components containing a dicarboxylic acid compound and a diol compound.

[0038] Examples of dicarboxylic acid compounds include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, adamantanedicarboxylic acid, norbornenedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sodiumsulfoisophthalic acid, phenylendanedicarboxylic acid, anthracenedicarboxylic acid, phenanthrenedicarboxylic acid, 9,9'-bis(4-carboxyphenyl)fluorene acid, and ester derivatives thereof. Dicarboxylic acid compounds can be used alone or in combination.

[0039] Examples of diol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalenedimethanol, decahydronaphthalenediethanol, norbornanedimethanol, norbornanediethanol, tricyclodecanedimethanol, tricyclodecaneethanol, tetracyclododecanedimethanol, tetracyclododecanediethanol, decalindimethanol, and decalindiethanol. , 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane, cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis(4-hydroxycyclohexylpropane), 2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene-1,3-diol, adamantanediol, paraxylene glycol, bisphenol A, bisphenol S, styrene glycol, trimethylolpropane, and pentaerythritol. Diol compounds can be used alone or in combination.

[0040] The monomer components forming the polyester may contain other compounds as copolymerization components in addition to the dicarboxylic acid compound and the diol compound. The proportion of structural units derived from other compounds in the polyester is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0041] The content of polyester (1) in the adhesive layer is preferably 50% by mass or more, more preferably 70% by mass to 99% by mass, and even more preferably 80% by mass to 95% by mass, which allows, for example, the above-mentioned effects of polyester (1) to be more effectively exhibited.

[0042] The content of polyester (2) in the adhesive layer is preferably 1 part by mass or more and 80 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of polyester (1). This allows, for example, the effects of polyester (1) and polyester (2) to be exerted in a well-balanced manner, and improves transferability, adhesion, and whitening resistance.

[0043] The total content of polyester (1) and polyester (2) in the adhesive layer is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more.

[0044] The adhesive layer may contain a resin material other than polyester. Examples of the resin material include vinyl resins such as polyvinyl chloride, polyvinyl acetate, and vinyl chloride-vinyl acetate copolymers, (meth)acrylic resins, vinyl acetal resins, polycarbonates, polyamides, and polyimides. The adhesive layer may contain one or more of the resin materials.

[0045] The adhesive layer preferably contains at least one selected from a silane coupling agent and a metal chelating agent. These components are thought to crosslink the glass constituting the glass member with the resin material in the adhesive layer, thereby further improving the adhesion between the glass member and the adhesive layer. Therefore, the adhesion after a hot water resistance test can be further improved.

[0046] The silane coupling agent is preferably a silane coupling agent having a reactive functional group, such as a group reactive with a carboxy group or a hydroxy group, specifically an epoxy group, an amino group, or a vinyl group.

[0047] Examples of silane coupling agents having a reactive functional group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 2-(2,3-epoxycyclohexyl)ethyltriethoxysilane, 2-(2,3-epoxycyclohexyl)ethylmethyldimeth- oxysilane Examples of the silane coupling agents include epoxy group-containing silane coupling agents (epoxy group-containing organoalkoxysilanes) such as 2-(2,3-epoxycyclohexyl)ethylmethyldiethoxysilane and 2-(2,3-epoxycyclohexyl)ethylmethyldiethoxysilane; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; vinyl group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and 3-(meth)acryloxypropyltrimethoxysilane; and partial hydrolysis condensates of one or more of these. The adhesive layer may contain one or more silane coupling agents.

[0048] Examples of metal chelating agents include polyvalent metal chelating agents such as titanium chelating compounds and aluminum chelating compounds, with titanium chelating compounds being preferred. Examples of titanium chelating compounds include titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetoacetate), titanium di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxide), titanium lactate, titanium lactate ammonium salt, titanium diisopropoxybis(triethanolamine), titanium isostearate, titanium aminoethylaminoethanolate, and titanium triethanolamine. Examples of aluminum chelating compounds include aluminum acetylacetonate and aluminum ethylacetoacetate diisopropylate. The adhesive layer may contain one or more metal chelating agents.

[0049] The total content of the silane coupling agent and the metal chelating agent in the adhesive layer is preferably 10% by mass or less, more preferably 0.1% by mass to 5% by mass, and even more preferably 0.5% by mass to 3% by mass, which can further improve the adhesion between the glass member and the adhesive layer, for example.

[0050] In one embodiment, the adhesive layer contains a colorant. For example, when the first transfer layer has a single-layer structure consisting of an adhesive layer, the adhesive layer can contain a colorant to impart design properties to the first transfer layer.

[0051] Examples of colorants include inorganic and organic pigments, as well as dyes. Specific examples include carbon black, calcium carbonate, silica, titanium oxide, zinc oxide, iron oxide, yellow iron, ultramarine, hologram powder, aluminum powder, fluorescent pigments, metallic pigments, and pearl pigments. The adhesive layer can contain one or more colorants.

[0052] In one embodiment, the adhesive layer contains an additive. Examples of the additive include a plasticizer, an ultraviolet absorber, inorganic particles, organic particles, and a dispersant. The adhesive layer can contain one or more additives.

[0053] The adhesive layer can be formed, for example, by applying a coating liquid containing the above-mentioned components to the first substrate layer or intermediate layer and drying it. Each layer described below other than the adhesive layer can also be formed, for example, by applying a coating liquid containing the components contained in each layer to the desired surface, drying it, and crosslinking or curing it as necessary. Examples of coating methods include roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, and rod coating.

[0054] The thickness of the adhesive layer is preferably 0.2 μm or more and 10 μm or less, more preferably 0.5 μm or more and 2.5 μm or less, which can improve the stability of film formation when forming the adhesive layer, for example.

[0055] <Anti-blocking layer> The first transfer layer may further include an anti-blocking layer. In one embodiment, the anti-blocking layer is provided on the adhesive layer and constitutes the surface of the first transfer layer opposite the first substrate layer. By providing the anti-blocking layer, for example, blocking can be suppressed during storage of the thermal transfer sheet.

[0056] As described above, the adhesive layer contains polyester (1) having a Tg of 30° C. or less. Therefore, by providing an anti-blocking layer as a surface layer on the side of the first transfer layer opposite to the first base layer, blocking by the adhesive layer can be effectively suppressed.

[0057] In one embodiment, the anti-blocking layer contains a resin material. Examples of resin materials include vinyl resins such as polyvinyl chloride, polyvinyl acetate, and vinyl chloride-vinyl acetate copolymers, (meth)acrylic resins, polyurethanes, polyesters, polyamides, and polyimides. Among these, (meth)acrylic resins and vinyl resins are preferred, and (meth)acrylic resins and vinyl chloride-vinyl acetate copolymers are more preferred.

[0058] The glass transition temperature (Tg) of the resin material is preferably 55° C. or higher, more preferably 60° C. or higher and 120° C. or lower, and even more preferably 70° C. or higher and 110° C. or lower. This makes it possible to effectively suppress, for example, the above-mentioned blocking.

[0059] The number average molecular weight (Mn) of the resin material is preferably 30,000 or less, more preferably 8,000 or more and 28,000 or less, and even more preferably 10,000 or more and 26,000 or less, which can improve the foil-cutting properties of the transfer layer during transfer, for example.

[0060] The anti-blocking layer can contain one or more resin materials. The content of the resin material in the anti-blocking layer is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, which can effectively suppress, for example, the above-mentioned blocking.

[0061] In one embodiment, the anti-blocking layer contains a colorant. By using a thermal transfer sheet having a first transfer layer including an anti-blocking layer containing a colorant, decorated products with various designs can be produced. Alternatively, the first transfer layer may further include a colorant layer containing a colorant.

[0062] Examples of colorants include pigments such as inorganic pigments and organic pigments, and dyes. Specific examples include carbon black, calcium carbonate, silica, titanium oxide, zinc oxide, iron oxide, yellow iron, ultramarine, hologram powder, aluminum powder, fluorescent pigments, metallic pigments, and pearl pigments.

[0063] For example, metallic pigments or pearlescent pigments can impart a glossy effect to the anti-blocking layer, which can impart a glossy appearance to the thermally transferred image of the resulting decorated article. For example, titanium oxide or carbon black can provide the anti-blocking layer with the functions of a base layer and a concealing layer. An anti-blocking layer that functions as a base layer can improve the visibility of the thermally transferred image when the resulting decorated article is viewed from the thermally transferred image side. An anti-blocking layer that functions as a concealing layer can conceal the texture of the transfer recipient and is suitable for decorated articles manufactured using a transparent transfer recipient such as a glass plate when it is not desired that the thermally transferred image be visible from the transfer recipient side. The anti-blocking layer may contain one or more colorants.

[0064] In one embodiment, the anti-blocking layer contains additives, such as plasticizers, ultraviolet absorbers, inorganic particles, organic particles, and dispersants. The adhesive layer may contain one or more additives.

[0065] The thickness of the anti-blocking layer is preferably 0.1 μm or more and 5 μm or less, more preferably 0.3 μm or more and 1.5 μm or less, which can, for example, more effectively suppress blocking in the thermal transfer sheet.

[0066] <Color layer> In one embodiment, the thermal transfer sheet of the present disclosure further includes a colorant layer on one side of the first substrate layer, in frame sequence with the first transfer layer. In this embodiment, the colorant layer and the first transfer layer are provided in frame sequence on one side of the first substrate layer. By using the thermal transfer sheet of this embodiment, a thermal transfer image can be formed on the receiving layer of the intermediate transfer medium. Therefore, using the thermal transfer sheet of the present disclosure, it is possible to simultaneously form a thermal transfer image on the receiving layer of the intermediate transfer medium and transfer the first transfer layer onto the second transfer layer, without using a separate thermal transfer sheet including a colorant layer.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] The sublimation transfer colorant layer may contain one or more types of 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.

[0072] The sublimation transfer colorant layer may contain one or more release agents. Examples of release agents 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.

[0073] 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.

[0074] The colorant preferably has sufficient color density and does not discolor or fade due to light, heat, or the like. Examples include organic pigments, inorganic pigments, and dyes. The colorant color is not limited to cyan, magenta, yellow, or black, but may be any of a variety of colors. The melt-transfer colorant layer may 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.

[0075] 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.

[0076] The melt transfer colorant layer may further contain a conventionally known wax. The colorant layer may contain one or more of the above additives.

[0077] The thermal transfer sheet of the present disclosure may have one colorant layer on one side of the first substrate layer, or may have multiple colorant layers of different hues, for example, 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.

[0078] <Release layer> The thermal transfer sheet of the present disclosure may further include a release layer between the first substrate layer and the first transfer layer. When the colorant layer provided face-sequentially with the first transfer layer is a melt-transfer colorant layer, the thermal transfer sheet may further include a release layer between the first substrate layer and the melt-transfer colorant layer. This, for example, can further improve the releasability of the first transfer layer or melt-transfer colorant layer from the first substrate layer. The release layer is a layer that does not constitute the first transfer layer or melt-transfer colorant layer, and remains on the first substrate layer side when the first transfer layer or melt-transfer colorant layer is transferred.

[0079] In one embodiment, the release layer contains a resin material. Examples of resin materials include vinyl resins such as polyvinyl alcohol, vinyl acetal resins such as polyvinyl acetal, (meth)acrylic resins, polyesters, polyamides, polyimides, polyurethanes, cellulose resins, silicone resins, and fluororesins. Among these, polyvinyl alcohol is preferred because it can maintain the functionality of the adhesive layer located on the release layer while improving the releasability of the first transfer layer provided with the adhesive layer. The release layer can contain one or more resin materials. The content of the resin material in the release layer is preferably 50% by mass or more.

[0080] The release layer may contain a release agent. 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 release layer may contain one or more types of release agents. The content of the release agent in the release 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. The release layer may contain one or more of the above additives.

[0081] The thickness of the release layer is preferably 0.1 μm or more and 3 μm or less, more preferably 0.1 μm or more and 2 μm or less, which can, for example, further improve the transferability of the first transfer layer.

[0082] <Back layer> The thermal transfer sheet of the present disclosure may have a backing layer on the surface of the first base layer opposite the first transfer layer, which can, for example, prevent sticking and wrinkles caused by heating during thermal transfer.

[0083] In one embodiment, the back layer contains one or more resin materials. Examples of the resin materials include polyolefins, polystyrenes, vinyl resins, (meth)acrylic resins, vinyl acetal resins such as polyvinyl butyral and polyvinyl acetoacetal, silicone resins, polyesters, polyamides, polyimides, polyurethanes, and cellulose resins. The content of the resin material in the back layer is preferably 10% by mass or more, more preferably 15% by mass or more.

[0084] The back layer may be a layer formed by crosslinking a resin material having reactive groups such as hydroxyl groups using a crosslinking agent such as polyisocyanate. Examples of polyisocyanates include xylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. One or more crosslinking agents may be used.

[0085] The back layer may contain one or more types of release agents. Examples of release agents include fluorine compounds, phosphate ester compounds, higher fatty acid amide compounds, metal soaps, silicone oils, and waxes such as polyethylene wax and paraffin wax. This can improve slip properties, for example. The content of the release agent in the back layer is preferably 0.5% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 12% by mass or less.

[0086] The back layer may contain one or more additives. Examples of additives include plasticizers, UV absorbers, inorganic particles, organic particles, and dispersants. The content of the additives relative to 100 parts by mass of the resin material contained in the back layer is preferably 0.1 parts by mass or more and 25 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less.

[0087] The thickness of the back layer is preferably 0.1 μm or more and 5 μm or less, more preferably 0.3 μm or more and 3 μm or less, which can improve the heat resistance of the thermal transfer sheet, for example.

[0088] [How to use the thermal transfer sheet] Hereinafter, several examples of usage of the thermal transfer sheet of the present disclosure will be described. The thermal transfer sheet of the present disclosure can be used, for example, to improve adhesion between an object such as a glass member and a desired medium (part or all of the medium) when integrating part or all of the desired medium, such as a decorative body, onto the object.

[0089] In the present disclosure, examples of the target object include, in addition to glass components, metal plates such as aluminum plates; ceramic plates such as pottery; wood; 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.

[0090] In the present disclosure, a decorative body is a component used to impart a desired design or decorativeness to an object. The decorative body may be one in which a portion thereof is separable or one in which a portion thereof is not separable.

[0091] The decorative body may be, for example, an intermediate transfer medium comprising a second substrate layer and a second transfer layer including a receiving layer. A thermal transfer image may be formed on the receiving layer. The thermal transfer image may be composed of, for example, letters, line drawings, patterns, symbols, or combinations thereof. In this case, the second transfer layer including the receiving layer corresponds to part of the decorative body. Specifically, the first transfer layer of the thermal transfer sheet of the present disclosure is transferred onto the receiving layer of the intermediate transfer medium to obtain a primary transfer product. Next, the second transfer layer and the first transfer layer provided on the primary transfer product are transferred onto an object such as a glass member to obtain a secondary transfer product as a decorated item. The second transfer layer is provided on the object via the first transfer layer.

[0092] An example of the decorative body is a protective layer transfer sheet having a protective layer as a transfer layer. In this case, the protective layer corresponds to part of the decorative body. Specifically, a first transfer layer of the thermal transfer sheet of the present disclosure is transferred onto the protective layer of the protective layer transfer sheet to obtain a primary transfer object. Next, the protective layer and the first transfer layer of the primary transfer object are transferred onto the printed object to obtain a secondary transfer object as a decorated product. The protective layer is provided on the printed object via the first transfer layer.

[0093] The decorative body may be, for example, a sheet bearing an image used to decorate a desired object, such as a thermal transfer image receiving sheet having a thermal transfer image formed on a receiving layer. The image may be, for example, a letter, a line drawing, a pattern, a symbol, or a combination thereof. Specifically, the first transfer layer of the thermal transfer sheet of the present disclosure is transferred onto a sheet bearing the image (e.g., the receiving layer of a thermal transfer image receiving sheet) to obtain a transfer. Next, the transfer is integrated with an object such as a glass member to obtain a decorated product. The sheet bearing the image is placed on the object via the first transfer layer.

[0094] Even if the decorative body has poor adhesion to the glass member, by transferring the first transfer layer onto the decorative body, an adhesive layer with excellent adhesion is interposed between the decorative body and the glass member, thereby obtaining a decorated product in which part or all of the decorative body is well adhered to the glass member.

[0095] [Combination of thermal transfer sheet and intermediate transfer medium] The combination of the present disclosure is a combination of the thermal transfer sheet of the present disclosure and an intermediate transfer medium. Since the thermal transfer sheet has been described above, a description thereof will be omitted here.

[0096] The intermediate transfer medium includes a second substrate layer and a second transfer layer. More specifically, the intermediate transfer medium includes a second substrate layer and a second transfer layer provided on at least a portion of one surface of the second substrate layer.

[0097] Fig. 4 is a cross-sectional view showing one embodiment of an intermediate transfer medium. In Fig. 4, the intermediate transfer medium 100 includes a second substrate layer 110 and a second transfer layer 120 provided on the second substrate layer 110. The second transfer layer 120 includes a release layer 124 and a receiving layer 122, in this order from the second substrate layer 110 side in the thickness direction of the intermediate transfer medium 100.

[0098] <Second base layer> The second base layer may be made of the same resin film as the first base layer.

[0099] <Second transfer layer> The second transfer layer includes a receiving layer. The second transfer layer may have a single-layer structure consisting of a receiving layer, or may have a multilayer structure including a receiving layer and other layers. When the second transfer layer has a multilayer structure, the receiving layer constitutes the surface layer on the side opposite the second substrate layer side of the second transfer layer.

[0100] In one embodiment, the second transfer layer includes a release layer and a receiving layer in this order in the thickness direction from the second base layer side. In one embodiment, the second transfer layer includes a release layer, a protective layer, and a receiving layer in this order in the thickness direction from the second base layer side.

[0101] <Receptor layer> The receptor layer is a layer that constitutes the surface layer on one side of the intermediate transfer medium. In one embodiment, the receiving layer contains a resin material, for example, polyolefins such as polyethylene and polypropylene, vinyl resins such as polyvinyl chloride, polyvinyl acetate, and vinyl chloride-vinyl acetate copolymers, 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 types of resin materials.

[0102] 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.

[0103] In one embodiment, the receptor layer contains a release agent, which can improve the releasability between the receptor layer and the thermal transfer sheet including the sublimation transfer colorant layer, for example.

[0104] 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. Among these, silicone oils are preferred from the viewpoint of the above-mentioned release properties.

[0105] Examples of silicone oils include straight silicone oils such as dimethyl silicone oil and methylphenyl silicone 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 type, double-end type, and side-chain single-end type. The receiving layer may contain one or more types of release agents.

[0106] 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 the releasability, for example.

[0107] The receiving layer may contain an additive. Examples of additives include plasticizers, UV absorbers, inorganic particles, organic particles, and dispersants. The receiving layer may contain one or more additives. 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.

[0108] In one embodiment of the method for manufacturing a decorated article according to the present disclosure, the second transfer layer is not in direct contact with the object to be transferred, but is transferred onto the object to be transferred via the first transfer layer including the adhesive layer described above. Therefore, it is not necessarily necessary to impart a function to the receiving layer to enhance adhesion to the object to be transferred, and the degree of freedom in designing the receiving layer is increased.

[0109] 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 second transfer layer.

[0110] <Release layer> In one embodiment, the second transfer layer of the intermediate transfer medium has a release layer as a surface layer on the second substrate layer side. This, for example, can improve the releasability of the second transfer layer from the second substrate layer when transferring the second transfer layer from the intermediate transfer medium. The release layer is the layer that is transferred from the intermediate transfer medium to the transfer recipient and is the layer that will be located on the outermost surface of the decorated product.

[0111] In one embodiment, the release layer contains one or more resin materials, such as polyolefin, vinyl resin, polystyrene, (meth)acrylic resin, polyester, polyamide, polyimide, polycarbonate, cellulose resin, and ionomer resin.

[0112] The release layer may contain one or more of the above-mentioned release agents. The release layer may contain one or more of the above additives. The thickness of the release layer is preferably 0.1 μm or more and 8 μm or less, and more preferably 0.5 μm or more and 5 μm or less, which can, for example, further improve the durability of the release layer.

[0113] ≪Protective layer≫ In one embodiment, the second transfer layer of the intermediate transfer medium comprises a protective layer on the surface of the receiving layer facing the second substrate layer, or between the release layer and the receiving layer.

[0114] In one embodiment, the protective layer contains one or more resin materials, such as polyester, polyurethane, polystyrene, (meth)acrylic resin, and (meth)acrylic polyol resin. The protective layer may contain one or more of the above additives.

[0115] The thickness of the protective layer is preferably 0.5 μm or more and 7 μm or less, and more preferably 1 μm or more and 5 μm or less, which can, for example, further improve the durability of the protective layer.

[0116] [Decorative sheet] The decorative sheet of the present disclosure comprises a decorative body and an adhesive layer provided on the decorative body. The adhesive layer contains polyester (1). The adhesive layer constitutes a surface layer on one side of the decorative sheet. The decorative sheet preferably comprises a first transfer layer, including an adhesive layer, derived from the thermal transfer sheet of the present disclosure on the decorative body. FIG. 5 is a cross-sectional view showing one embodiment of the decorative sheet of the present disclosure. In FIG. 5, the decorative sheet 200 comprises a decorative body 150 and an adhesive layer 22.

[0117] In one embodiment, the decorative body is an intermediate transfer medium including a second substrate layer and a second transfer layer including a receiving layer on which a thermal transfer image is formed. In this embodiment, a first transfer layer including an adhesive layer derived from the thermal transfer sheet of the present disclosure is transferred onto the receiving layer of the intermediate transfer medium.

[0118] The decorative body may be, for example, a protective layer transfer sheet having a protective layer as a transfer layer. In this embodiment, a first transfer layer including an adhesive layer derived from the thermal transfer sheet of the present disclosure is transferred onto the protective layer of the protective layer transfer sheet.

[0119] The decorative body may be, for example, a sheet having an image used to decorate a desired object, and may be a thermal transfer image receiving sheet having a thermal transfer image formed on a receiving layer. In this embodiment, a first transfer layer including an adhesive layer derived from the thermal transfer sheet of the present disclosure is transferred onto the sheet having the image (for example, the receiving layer of the thermal transfer image receiving sheet). The details of each component of the decorative sheet are as described above.

[0120] [Decorative product manufacturing method and decorative product] The method for manufacturing a decorative article according to the present disclosure includes: A preparation step of preparing the thermal transfer sheet of the present disclosure, a decorative body, and a glass member; a transfer step of transferring a first transfer layer including an adhesive layer provided in the thermal transfer sheet onto a decorated body to obtain a transferred product including the decorated body and the first transfer layer including an adhesive layer; an integration step of integrating a part or all of the decorative body with a glass member via a first transfer layer so that the adhesive layer of the transfer comes into contact with the glass member; Includes. In one embodiment, the decorative body is the intermediate transfer medium described above. In this embodiment, the method for manufacturing a decorative article of the present disclosure includes: A preparation step of preparing an intermediate transfer medium including a thermal transfer sheet of the present disclosure, a second substrate layer, and a second transfer layer including a receiving layer on which a thermal transfer image is formed, and a glass member; a primary transfer step in which a first transfer layer including an adhesive layer provided on the thermal transfer sheet is transferred onto a second transfer layer provided on the intermediate transfer medium to obtain a primary transfer product including the intermediate transfer medium and the first transfer layer; a secondary transfer step in which the second transfer layer of the primary transfer product is transferred onto a glass member together with the first transfer layer to obtain a decorated product that is a secondary transfer product; Includes. 6 and 7 show an embodiment of a method for manufacturing a decorative product.

[0121] <Preparation process> The details of the thermal transfer sheet, decorative body, and glass member of the present disclosure are as described above.

[0122] In the preparation process, an intermediate transfer medium may be used in which a thermal transfer image has already been formed on the receiving layer, or a thermal transfer image may be formed on the receiving layer of an intermediate transfer medium that has a second substrate layer and a second transfer layer including a receiving layer (hereinafter also referred to as the "image forming process").

[0123] 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.

[0124] In the image forming process, a thermal transfer image may be formed on the receiving layer using a thermal transfer sheet of the present disclosure in which a colorant layer and a first transfer layer are arranged in face-sequential order on one side of a first substrate layer, or a thermal transfer image may be formed on the receiving layer using a conventionally known thermal transfer sheet that has a colorant layer.

[0125] <Transfer process (primary transfer process)> The transfer step is a step of transferring the first transfer layer of the thermal transfer sheet onto a decorative body, or in one embodiment, onto a second transfer layer of an intermediate transfer medium, including a receiving layer on which a thermal transfer image is formed. This step results in a transfer product comprising the decorative body and the first transfer layer, and in one embodiment, a primary transfer product comprising an intermediate transfer medium including a second transfer layer and the first transfer layer transferred onto the second transfer layer. These transfer products have the adhesive layer as the surface layer on one side.

[0126] Figure 6 shows an outline of the primary transfer step according to one embodiment. As shown in Figure 6(A), the thermal transfer sheet 1 and the intermediate transfer medium 100 are attached together so that the anti-blocking layer 24 and the receiving layer 122 are in contact with each other. Next, heat is applied to a desired area of the thermal transfer sheet 1, and the first transfer layer 20 in that area is transferred onto the receiving layer 122, as shown in Figure 6(B). In this way, a primary transfer product 200 is obtained.

[0127] Examples of thermal transfer methods for the first transfer layer of the thermal transfer sheet include a method using a heating device such as a thermal head, a method using a hot stamp, and a method using a heat roll. The same applies to the transfer of the second transfer layer in the secondary transfer step described below. For example, a thermal transfer printer may be used in this step, and a laminator may be used in the integration step (secondary transfer step).

[0128] <Integration process (secondary transfer process)> The integration step is a step of integrating a part or all of the decorative body with the glass member via the first transfer layer so that the adhesive layer of the transfer material contacts the glass member. This step results in a decorated product having the glass member, the first transfer layer, and a part or all of the decorative body in this order in the thickness direction. The integration of the decorative body with the glass member may be achieved by using a partially separable decorative body, such as an intermediate transfer medium, and then separating and integrating that part with the glass member, or by integrating the entire decorative body with the glass member.

[0129] The secondary transfer step is a step in which the second transfer layer, which includes a receiving layer on which a thermal transfer image is formed, of the primary transfer product obtained in the primary transfer step is transferred together with the first transfer layer onto a glass member. In this step, a decorated product is obtained which includes, in the thickness direction, a glass member, the first transfer layer, and the second transfer layer including a receiving layer on which a thermal transfer image is formed, in this order.

[0130] Here, the decorative body (part or all) or the second transfer layer is provided on the glass member via the adhesive layer, and therefore peeling of the decorative body or the second transfer layer can be effectively prevented even after the decorated article is subjected to, for example, a hot water resistance test.

[0131] 7 shows an outline of the secondary transfer step according to one embodiment. As shown in FIG. 7(A), the primary transfer object 200 and the glass member 300 are bonded together so that the adhesive layer 22 contacts the glass member 300. Next, heat is applied to a desired region of the primary transfer object 200, and the first transfer layer 20 and the second transfer layer 120 in that region are transferred onto the glass member 300, as shown in FIG. 7(B). In this manner, the secondary transfer object 400 is obtained.

[0132] In one embodiment, the decorated article of the present disclosure comprises a glass member and a decorative body. The decorated article comprises an adhesive layer containing polyester (1) between the glass member and the decorative body, with the adhesive layer being in contact with the glass member. The decorated article preferably comprises a first transfer layer between the glass member and the decorative body, the first transfer layer including an adhesive layer derived from the thermal transfer sheet of the present disclosure. FIG. 8 is a cross-sectional view showing one embodiment of the decorated article of the present disclosure. In FIG. 8, the decorated article 400 comprises a glass member 300, an adhesive layer 22, and a decorative body 150.

[0133] In one embodiment, the decorated article of the present disclosure comprises a glass member and a receiving layer on which a thermal transfer image is formed. The decorated article comprises an adhesive layer containing polyester (1) between the glass member and the receiving layer, with the adhesive layer being in contact with the glass member. The decorated article preferably comprises a glass member, a first transfer layer including an adhesive layer derived from the thermal transfer sheet of the present disclosure, and a second transfer layer including a receiving layer derived from the intermediate transfer medium described above, in this order in the thickness direction (see FIG. 7(B)). The details of each component of the decorative product are as described above.

[0134] The present disclosure relates to, for example, the following [1] to

[14] . [1] A thermal transfer sheet comprising a first base layer and a first transfer layer, wherein the first transfer layer comprises an adhesive layer, the adhesive layer contains a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more, and the adhesive layer constitutes the surface of the first transfer layer facing the first base layer. [2] The thermal transfer sheet according to [1] above, wherein the adhesive layer further contains a second polyester having a Tg of 50°C or higher and an Mn of 10,000 or lower. [3] The thermal transfer sheet according to [2] above, wherein the content of the second polyester in the adhesive layer is 1 part by mass or more and 80 parts by mass or less per 100 parts by mass of the first polyester. [4] The thermal transfer sheet according to any one of the above [1] to [3], wherein the adhesive layer further contains at least one agent selected from the group consisting of a silane coupling agent and a metal chelating agent. [5] The thermal transfer sheet according to the above [4], wherein the total content of the silane coupling agent and the metal chelating agent in the adhesive layer is 0.1% by mass or more and 10% by mass or less. [6] A thermal transfer sheet according to any one of [1] to [5] above, wherein the first transfer layer further comprises an anti-blocking layer, and the anti-blocking layer constitutes the surface of the first transfer layer opposite to the first substrate layer. [7] A combination of a thermal transfer sheet and an intermediate transfer medium, wherein the thermal transfer sheet is a thermal transfer sheet according to any one of [1] to [6] above, and the intermediate transfer medium comprises a second substrate layer and a second transfer layer including a receiving layer. [8] A decorative sheet comprising a decorative body and an adhesive layer provided on the decorative body, wherein the adhesive layer contains a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more, and the adhesive layer constitutes a surface layer on one side of the decorative sheet. [9] The decorative sheet according to [8] above, wherein the decorative body is an intermediate transfer medium comprising a second substrate layer and a second transfer layer including a receiving layer on which a thermal transfer image is formed.

[10] A method for manufacturing a decorated product, comprising: a preparation step of preparing the thermal transfer sheet described in any one of [1] to [6] above, a decorated body, and a glass member; a transfer step of transferring a first transfer layer including an adhesive layer provided on the thermal transfer sheet onto the decorated body to obtain a transferred product including the decorated body and the first transfer layer including the adhesive layer; and an integration step of integrating a part or all of the decorated body with the glass member via the first transfer layer so that the adhesive layer of the transferred product contacts the glass member.

[11] A method for manufacturing a decorated product according to the above

[10] , wherein in the preparation step, the decorated body is an intermediate transfer medium having a second base layer and a second transfer layer including a receiving layer on which a thermal transfer image is formed, the transfer step is a primary transfer step in which a first transfer layer including an adhesive layer provided on a thermal transfer sheet is transferred onto the second transfer layer provided on the intermediate transfer medium to obtain a primary transfer product comprising the intermediate transfer medium and the first transfer layer, and the integration step is a secondary transfer step in which the second transfer layer of the primary transfer product is transferred together with the first transfer layer onto a glass member to obtain a decorated product which is a secondary transfer product.

[12] A method for manufacturing a decorated product according to the above

[11] , wherein in the preparation step, an intermediate transfer medium having a second substrate layer and a second transfer layer including a receiving layer is prepared, and a thermal transfer image is formed on the receiving layer.

[13] A decorative article comprising a glass member and a decorative body, the decorative article comprising an adhesive layer between the glass member and the decorative body, the adhesive layer being in contact with the glass member, and the adhesive layer containing a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more.

[14] A decorated product comprising a glass member and a receiving layer on which a thermal transfer image is formed, the decorated product comprising an adhesive layer between the glass member and the receiving layer, the adhesive layer being in contact with the glass member, and the adhesive layer containing a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more. [Example]

[0135] The thermal transfer sheet of the present disclosure will be described in more detail below based on examples, but the thermal transfer sheet of the present disclosure is not limited to these examples. Unless otherwise specified, "parts" below mean "parts by mass." The blending amounts shown in the following descriptions and Table 1 are values converted into solids, excluding water and organic solvents.

[0136] [Example 1] A 5 μm-thick polyethylene terephthalate (PET) film with an easy-adhesion layer was used as the first base layer. A back layer coating liquid having the following composition was applied to the non-adhesion layer side of the PET film and dried to form a 1 μm-thick back layer. A release layer coating liquid having the following composition was applied to the adhesion layer side of the PET film and dried to form a 0.2 μm-thick release layer. An adhesive layer coating liquid having the following composition was applied to the release layer and dried to form a 1 μm-thick adhesive layer. In this way, a thermal transfer sheet was obtained having a first base layer, a release layer, and an adhesive layer in this order in the thickness direction. The first transfer layer in this thermal transfer sheet consisted of an adhesive layer.

[0137] <Coating liquid for back layer> Polyvinyl butyral 2 parts (S-LEC (registered trademark) BX-1, Sekisui Chemical Co., Ltd.) Polyisocyanate 9.2 parts (Burnoc® D750, DIC Corporation) Phosphate ester surfactant 1.3 parts (Plysurf (registered trademark) A208N, Daiichi Kogyo Seiyaku Co., Ltd.) Talc 0.3 parts (MicroAce (registered trademark) P-3, Nippon Talc Kogyo Co., Ltd.) Toluene 43.6 parts Methyl ethyl ketone 43.6 parts

[0138] <Release layer coating liquid> 10 parts polyvinyl alcohol (PVA-110, Kuraray Co., Ltd.) ·Water 70 parts 20 parts isopropyl alcohol

[0139] <Coating liquid for adhesive layer> Polyester A 20 parts (Vylon (registered trademark) 630, Tg: 7°C, Mn: 23,000, Toyobo Co., Ltd.) 40 parts methyl ethyl ketone 40 parts toluene

[0140] [Examples 2 to 8, Comparative Examples 1 to 11] A thermal transfer sheet was obtained in the same manner as in Example 1, except that the adhesive layer was formed by changing the solid content composition in the coating liquid for the adhesive layer as shown in Table 1.

[0141] [Example 9] A thermal transfer sheet was obtained in the same manner as in Example 1, except that a coating liquid for an anti-blocking layer having the following composition was applied to the adhesive layer and dried to form an anti-blocking layer with a thickness of 0.4 μm. The first transfer layer in this thermal transfer sheet consisted of an adhesive layer and an anti-blocking layer.

[0142] <Coating liquid for anti-blocking layer> (Meth)acrylic resin 10 parts (Dianal (registered trademark) BR-87, Tg: 105°C, Mn: 25,000, Mitsubishi Chemical Corporation) Vinyl chloride-vinyl acetate copolymer 10 parts (Solvine (registered trademark) CNL, Tg: 76°C, Mn: 12,000, Nissin Chemical Industry Co., Ltd. 80 parts methyl ethyl ketone

[0143] The products used in the examples and comparative examples are listed below. <Polyester (both manufactured by Toyobo Co., Ltd.)> Polyester A (Vylon (registered trademark) 630, Tg: 7°C, Mn: 23,000) Polyester B (Vylon (registered trademark) 635, Tg: 25°C, Mn: 21,000) Polyester C (Vylon (registered trademark) GK-180, Tg: 0°C, Mn: 10,000) Polyester D (Vylon (registered trademark) 226, Tg: 65°C, Mn: 8,000) Polyester E (Vylon (registered trademark) 660, Tg: 55°C, Mn: 8,000) Polyester F (Vylon (registered trademark) GK-250, Tg: 60°C, Mn: 10,000) Polyester G (Vylon (registered trademark) 290, Tg: 72°C, Mn: 22,000) Polyester H (Vylon (registered trademark) 600, Tg: 47°C, Mn: 16,000) Polyester I (Vylon (registered trademark) 296, Tg: 71°C, Mn: 14,000)

[0144] <Modified polyolefin> EVA (ethylene-vinyl acetate copolymer, AQUATEX® MC-3800, Japan Coating Resin Co., Ltd. Polypropylene A (Modified polypropylene, Chemipearl (registered trademark) HP-400, Mitsui Chemicals, Inc.) Polypropylene B (Modified polypropylene, Auroren® 353S, Nippon Paper Industries Co., Ltd.)

[0145] <Additives> Silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.) Titanium chelating agent (Orgatix® TC-100, Matsumoto Fine Chemical Co., Ltd.

[0146] [Preparation of intermediate transfer medium] A 16 μm thick PET film was used as the second substrate layer. A release layer coating liquid having the following composition was applied to the PET film and dried to form a 1 μm thick release layer. A protective layer coating liquid having the following composition was applied to the release layer and dried to form a 2 μm thick protective layer. A receiving layer coating liquid having the following composition was applied to the protective layer and dried to form a 1.5 μm thick receiving layer. In this way, an intermediate transfer medium was obtained that had a second substrate layer, a release layer, a protective layer, and a receiving layer in this order in the thickness direction. The second transfer layer of the intermediate transfer medium consisted of a release layer, a protective layer, and a receiving layer.

[0147] <Coating liquid for release layer> (Meth)acrylic resin 29 parts (Dianal (registered trademark) BR-87, Mitsubishi Chemical Corporation) 1 part polyester (Vylon (registered trademark) 200, Toyobo Co., Ltd.) 35 parts methyl ethyl ketone Toluene 35 parts

[0148] <Coating liquid for protective layer> 30 parts polyester (Vylon (registered trademark) 200, Toyobo Co., Ltd.) 35 parts methyl ethyl ketone Toluene 35 parts

[0149] <Coating liquid for receiving layer> Vinyl chloride-vinyl acetate copolymer 20 parts (Solvine (registered trademark) CNL, Nissin Chemical Industry Co., Ltd.) 1 part silicone oil (X-22-3000T, Shin-Etsu Chemical Co., Ltd.) 79 parts methyl ethyl ketone

[0150] [Preparation of thermal transfer sheet with colorant layer] A 5 μm-thick PET film was used as the substrate layer. A back layer coating liquid having the above composition was applied to one side of the PET film and dried to form a 1 μm-thick back layer. A dye primer layer coating liquid having the following composition was applied to the other side of the PET film and dried to form a 0.15 μm-thick dye primer layer. A yellow colorant layer coating liquid, a magenta colorant layer coating liquid, and a cyan colorant layer coating liquid having the following compositions were coated on the dye primer layer in face-sequential order to form a yellow colorant layer, a magenta colorant layer, and a cyan colorant layer, each with a thickness of 0.7 μm. In this way, a thermal transfer sheet having a colorant layer was obtained.

[0151] <Coating liquid for dye primer layer> Colloidal alumina (solid content 10.5% by mass) 3.5 parts (Alumina Sol 200, Nissan Chemical Industries, Ltd.) Vinyl acetate-vinylpyrrolidone copolymer 1.5 parts (PVP / VA E-335, ISP Japan Co., Ltd.) ·Wednesday 47.5 parts 47.5 parts isopropyl alcohol

[0152] <Coating liquid for yellow colorant layer> 2.5 parts Solvent Yellow 93 Disperse Yellow 201 2.5 parts Polyvinyl acetal 4 parts (S-LEC (registered trademark) KS-5, Sekisui Chemical Co., Ltd.) Polyethylene wax 0.1 parts 50 parts toluene 50 parts methyl ethyl ketone

[0153] <Coating liquid for magenta colorant layer> 3 parts Disperse Red 60 3 parts Disperse Violet 26 Polyvinyl acetal 5 parts (S-LEC (registered trademark) KS-5, Sekisui Chemical Co., Ltd.) Polyethylene wax 0.1 parts 50 parts toluene 50 parts methyl ethyl ketone

[0154] <Coating liquid for cyan colorant layer> 3 parts Solvent Blue 63 Disperse Blue 354 4 parts Polyvinyl acetal 5 parts (S-LEC (registered trademark) KS-5, Sekisui Chemical Co., Ltd.) Polyethylene wax 0.1 parts 50 parts toluene 50 parts methyl ethyl ketone

[0155] [Thermal transfer image formation] The thermal transfer sheet having the colorant layer prepared above was combined with the intermediate transfer medium prepared above, and a gray image (image gradation: 128 / 256) was formed on the receiving layer of the intermediate transfer medium using the printer described below.

[0156] (Printer) Thermal head: KEE-57-12GAN2-STA (Kyocera Corporation) Heating element average resistance: 3303 (Ω) Print density in the main scanning direction: 300 (dpi) Sub-scanning direction print density: 300 (dpi) Line period: 3.0 (msec. / line) Printing start temperature: 35(℃) Pulse duty ratio: 85(%) Printing voltage: 18.0 (V)

[0157] [Transfer of the first transfer layer of the thermal transfer sheet to the intermediate transfer medium: primary transfer] Using the printer, energy of 100 / 255 gradation (energy gradation) was applied to the thermal transfer sheets of the Examples and Comparative Examples, and the first transfer layer of the thermal transfer sheets of the Examples and Comparative Examples was transferred onto the second transfer layer of the intermediate transfer medium on which the gray image was formed, thereby obtaining a primary transfer product. The primary transferability at this time was evaluated based on the following criteria.

[0158] A: Transfer is possible without any transfer chipping or peeling noise. B: There is no transfer chipping, but there is a peeling sound. NG: Missing transfer occurs.

[0159] [Decorative product manufacturing: secondary transfer] A 1.3 mm thick glass plate (large slide glass S9224, Matsunami Glass Industry Co., Ltd.) was used as the transfer target. Using a laminator (THS330, Meiko Shokai Co., Ltd.), the second transfer layer of the intermediate transfer medium in the primary transfer product and the first transfer layer of the thermal transfer sheet transferred onto the second transfer layer were transferred onto the transfer target under transfer conditions of a transfer temperature of 140°C and a transfer speed of 60 mm / sec. That is, the second transfer layer on which the image of the intermediate transfer medium was formed was transferred onto the transfer target via the first transfer layer of the thermal transfer sheet of the Examples and Comparative Examples, and a decorated product, which was a secondary transfer product, was obtained.

[0160] [Adhesion test] When the decorated products obtained above were visually inspected, it was confirmed that in all of the decorated products, the second transfer layer on which the image of the intermediate transfer medium was formed had been transferred onto the transfer target object via the first transfer layer of the thermal transfer sheet.

[0161] A tape (Scotch (registered trademark) Tape BK-24, 3M) was applied to the surface of the decorated article obtained above (the surface of the second transfer layer of the intermediate transfer medium), and a 90° peel test was performed. Specifically, the tape was abruptly peeled off from the decorated article at a 90° angle, and the state of the first transfer layer and the second transfer layer was confirmed, and the adhesion was evaluated based on the following evaluation criteria (Adhesion Evaluation 1). In addition, the adhesion of the decorated article after the hot water resistance test described below was similarly evaluated (Adhesion Evaluation 2).

[0162] A: The transfer layer does not peel off. B: The transfer layer peels off slightly. NG: The transfer layer peels off significantly.

[0163] [Hot water resistance test] The decorated product obtained above was left to stand in boiling water at 100°C for 30 minutes. The decorated product was then removed from the boiling water and dried at room temperature for 4 hours. The change in appearance of the decorated product before and after the hot water resistance test was confirmed.

[0164] A: No change in appearance is observed. B: Slight whitening is observed. NG: Changes in appearance such as whitening, cracks, and bleeding are observed.

[0165] [Table 1] [Explanation of symbols]

[0166] 1. Thermal transfer sheet 10... First substrate layer 20 First transfer layer 22...Adhesive layer 24. Anti-blocking layer 30...Release layer 40...Back layer 100···Intermediate transfer medium 110: Second substrate layer 120...Second transfer layer 122...Receptor layer 124....Peeling layer 150···Decorative body 200 Primary transfer or decorative sheet 300: Transferred object (glass member) 400 Secondary transfer or decorative item

Claims

1. A combination of a thermal transfer sheet and an intermediate transfer medium, the thermal transfer sheet comprises a first substrate layer and a first transfer layer; the first transfer layer comprises an adhesive layer; the adhesive layer contains a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more, and the adhesive layer constitutes a surface of the first transfer layer facing the first base material layer; the intermediate transfer medium comprises a second substrate layer and a second transfer layer including a receiving layer; A combination of a thermal transfer sheet and an intermediate transfer medium.

2. 2. The combination of a thermal transfer sheet and an intermediate transfer medium according to claim 1, wherein the adhesive layer further comprises a second polyester having a Tg of 50[deg.] C. or higher and an Mn of 10,000 or lower.

3. 3. The combination of the thermal transfer sheet and the intermediate transfer medium according to claim 2, wherein the content of the second polyester in the adhesive layer is 1 part by weight or more and 80 parts by weight or less per 100 parts by weight of the first polyester.

4. 4. The combination of the thermal transfer sheet and the intermediate transfer medium according to claim 1, wherein the adhesive layer further contains at least one agent selected from the group consisting of a silane coupling agent and a metal chelating agent.

5. 5. The combination of the thermal transfer sheet and the intermediate transfer medium according to claim 4, wherein the total content of the silane coupling agent and the metal chelating agent in the adhesive layer is 0.1% by mass or more and 10% by mass or less.

6. the first transfer layer further comprises an anti-blocking layer; the anti-blocking layer constitutes a surface of the first transfer layer opposite to the first substrate layer; A combination of the thermal transfer sheet according to any one of claims 1 to 5 and an intermediate transfer medium.

7. A decorative sheet comprising a decorative body and an adhesive layer provided on the decorative body, The decorative body includes a second substrate layer and a second transfer layer including a receiving layer on which a thermal transfer image is formed. an intermediate transfer medium comprising: the adhesive layer contains a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more, and the adhesive layer constitutes a surface layer on one side of the decorative sheet; Decorative sheet.

8. A method for manufacturing a decorative product, a preparation step of preparing a combination of the thermal transfer sheet according to any one of claims 1 to 6 and an intermediate transfer medium, and a glass member; a primary transfer step of transferring a first transfer layer, including an adhesive layer, of the thermal transfer sheet onto a second transfer layer of the intermediate transfer medium to obtain a primary transfer product including the intermediate transfer medium and the first transfer layer; a secondary transfer step in which the second transfer layer of the primary transfer product is transferred onto the glass member together with the first transfer layer to obtain a decorated product that is a secondary transfer product; A method for manufacturing a decorated product, comprising:

9. The method for manufacturing a decorated product according to claim 8 , wherein in the preparation step, a thermal transfer image is formed on the receptor layer of the intermediate transfer medium.

10. A decorative article comprising a glass member and a receiving layer on which a thermal transfer image is formed, The decorative article has an adhesive layer between the glass member and the receiving layer, the adhesive layer being in contact with the glass member, and the adhesive layer containing a first polyester having a glass transition temperature (Tg) of 30°C or less and a number average molecular weight (Mn) of 15,000 or more. Decorations.

Images