Heat transfer film, combination of heat transfer film and intermediate transfer medium, and method for manufacturing printed materials

Abstract

This invention relates to heat transfer sheets, combinations of heat transfer sheets and intermediate transfer media, and methods for manufacturing printed materials. The heat transfer sheet of this invention is characterized by comprising a first substrate and a metallic gloss layer containing metallic pigments, wherein the 45-degree specular gloss of the metallic gloss layer is 30% to 80%.

Description

[0001] This application is a divisional application. The original application has the application number 202080063292.7, the application date is September 11, 2020, and the invention title is "Heat transfer sheet, combination of heat transfer sheet and intermediate transfer medium, and method for manufacturing printed matter". Technical Field

[0002] This invention relates to heat transfer sheets, combinations of heat transfer sheets and intermediate transfer media, and methods for manufacturing printed materials. Background Technology

[0003] Various thermal transfer recording methods are known in the past. In recent years, the following sublimation thermal transfer method has been widely used: a thermal transfer sheet containing a coloring layer with sublimable dye is combined with the object to be transferred. Then, the thermal head of a thermal transfer printer heats the thermal transfer sheet, thereby transferring the sublimable dye in the coloring layer to the object to be transferred, forming an image and obtaining a printed object.

[0004] Depending on the surface shape of the object to be transferred, it is sometimes difficult to form an image using a sublimation-type heat transfer method. In such cases, an image is formed using an intermediate transfer medium having a transfer layer including a receiving layer. For example, the heat transfer sheet is heated, causing the sublimable dye in the coloring layer of the heat transfer sheet to transfer to the receiving layer of the intermediate transfer medium. After the image is formed, the intermediate transfer medium is heated, causing the transfer layer to transfer onto the object to be transferred, thereby forming the image.

[0005] In recent years, there have been various requirements for the aesthetics of printed materials obtained by the above methods. For example, printed materials are required to have a high gloss.

[0006] In Patent Document 1, a metallic luster layer is transferred from a heat transfer sheet having a metallic luster layer onto a substrate, and then a coloring layer is melted and transferred onto the metallic luster layer, thereby creating a printed object. This enhances the gloss of the printed object, giving it a premium feel.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 9-39399 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] The inventors have discovered the following new problem: In existing heat transfer sheets with metallic luster layers disclosed in Patent Document 1, etc., when the heat energy applied to the metallic luster layer during transfer is insufficient, cohesive destruction will occur in the metallic luster layer, which may prevent the transfer from being performed well.

[0012] The transfer of the metallic luster layer onto the transfer layer of the intermediate transfer medium, and the transfer of the transfer layer and the metallic luster layer onto the substrate, involves heating the substrate and the transfer layer of the intermediate transfer medium from side to side to make them thermally bonded. Sometimes the substrate is removed (peeled off when cold) after the temperature of the substrate of the intermediate transfer medium decreases. This is a particularly problematic issue.

[0013] Hereinafter, the transferability of a material with low heat applied during transfer or when peeled off at cold will be referred to as transferability.

[0014] Therefore, the problem to be solved by the present invention is to provide a heat transfer sheet having a metallic luster layer with high transferability, which can produce printed materials with high gloss.

[0015] Furthermore, the problem to be solved by the present invention is to provide a combination of the heat transfer sheet and the intermediate transfer medium, and a method for manufacturing a printed product using the combination.

[0016] Methods for solving problems

[0017] The inventors conducted in-depth research on methods to solve the aforementioned problems. As a result, the inventors discovered that by setting the 45-degree specular gloss of the metallic layer to a specific numerical range, it is possible to significantly improve the transferability while maintaining the high gloss of the metallic layer.

[0018] The heat transfer film of the present invention is characterized in that it comprises a first substrate and a metallic luster layer containing metallic pigment, wherein the 45-degree mirror gloss of the metallic luster layer is 30% or more and 80% or less.

[0019] The combination of the heat transfer sheet and the intermediate transfer medium of the present invention is characterized in that it has the above-described heat transfer sheet and the intermediate transfer medium having a second substrate and a transfer layer.

[0020] The method for manufacturing the printed matter of the present invention is characterized by comprising: a step of preparing the combination of the heat transfer sheet and the intermediate transfer medium and the object to be transferred; a step of transferring a metallic luster layer from the heat transfer sheet to a transfer layer provided in the intermediate transfer medium; and a step of transferring the transfer layer provided in the intermediate transfer medium and the metallic luster layer on the transfer layer to the object to be transferred.

[0021] The effects of the invention

[0022] According to the present invention, a heat transfer sheet is provided having a metallic luster layer with high transferability, which can produce printed materials with high gloss.

[0023] In addition, according to the present invention, a combination of the heat transfer sheet and the intermediate transfer medium, and a method for manufacturing a printed material using the combination can be provided. Attached Figure Description

[0024] Figure 1 This is a schematic cross-sectional view illustrating one embodiment of the thermal transfer sheet of the present invention.

[0025] Figure 2 This is a schematic cross-sectional view illustrating one embodiment of the thermal transfer sheet of the present invention.

[0026] Figure 3 This is a schematic cross-sectional view illustrating one embodiment of an intermediate transfer medium constituting the combination of the heat transfer sheet and the intermediate transfer medium of the present invention.

[0027] Figure 4 This is a schematic cross-sectional view illustrating one embodiment of an intermediate transfer medium constituting the combination of the heat transfer sheet and the intermediate transfer medium of the present invention.

[0028] Figure 5 This is a schematic cross-sectional view showing one embodiment of a print manufactured by the print manufacturing method of the present invention.

[0029] Symbol Explanation

[0030] 10: Heat transfer film

[0031] 11: First substrate

[0032] 12: Metallic luster layer

[0033] 13: Coloring layer

[0034] 14: Back layer

[0035] 20: Intermediate transfer medium

[0036] 21: Second substrate

[0037] 22: Transfer layer

[0038] 23: Reception Layer

[0039] 24: Peel-off layer

[0040] 30: Prints

[0041] 31: Transferred Entity Detailed Implementation

[0042] (Heat transfer film)

[0043] like Figure 1 As shown, the heat transfer sheet 10 of the present invention includes a first substrate 11 and a metallic luster layer 12.

[0044] In one implementation, such as Figure 2 As shown, the heat transfer sheet 10 further comprises a coloring layer 13 on the first substrate 11 in a manner that is sequential with the metallic luster layer 12. Figure 2 As shown, the heat transfer film 10 may have multiple coloring layers 13.

[0045] In one implementation, such as Figure 1 and Figure 2 As shown, the heat transfer sheet 10 has a back layer 14 on the side of the first substrate 11 opposite to the side where the metallic luster layer 12 is provided.

[0046] The layers of the heat transfer film of the present invention will be described below.

[0047] (First substrate)

[0048] As a first substrate, it can be used without particular restrictions as long as it has heat resistance that can withstand the heat energy applied during heat transfer, mechanical strength that can support the metallic luster layer and the like provided on the first substrate.

[0049] Examples of first substrates include films made of resin (hereinafter referred to as "resin films"). Examples of resin materials include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), poly(1,4-cyclohexanedimethyl terephthalate), and terephthalic acid-cyclohexanediethanol-ethylene glycol copolymer; polyamides such as nylon 6 and nylon 6,6; polyolefins such as polyethylene (PE), polypropylene (PP), and polymethylpentene; vinyl resins such as polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and polyvinylpyrrolidone (PVP); (meth)acrylic resins such as poly(meth)acrylate and poly(meth)acrylate; imide resins such as polyimide and polyetherimide; cellulose resins such as celluloid, cellulose acetate, cellulose nitrate, cellulose acetate-propionate (CAP), and cellulose acetate-butyrate (CAB); styrene resins such as polystyrene (PS); polycarbonate; and ionomer resins.

[0050] Among the above resins, polyesters such as PET and PEN are preferred in terms of heat resistance and mechanical strength, with PET being particularly preferred.

[0051] In this invention, "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". "(meth)acrylate" includes both "acrylate" and "methacrylate".

[0052] The laminate of the above-mentioned resin film can also be used as the first substrate. The laminate of the resin film can be manufactured by using dry lamination, wet lamination, extrusion, etc.

[0053] When the first substrate is a resin film, the resin film can be a stretched film or an unstretched film. From the perspective of strength, a stretched film that has been stretched in a uniaxial or biaxial direction is preferred as the resin film.

[0054] The thickness of the first substrate is preferably 2 μm to 25 μm, more preferably 3 μm to 16 μm. This improves the mechanical strength of the first substrate and the heat transfer during heat transfer.

[0055] (Metallic luster layer)

[0056] The metallic gloss of the heat transfer sheet of the present invention has a 45-degree specular gloss level of 30% to 80%. This improves the transferability of the metallic gloss layer of the heat transfer sheet and the gloss of the printed matter produced using the heat transfer sheet.

[0057] The 45-degree specular gloss of the metallic luster layer is preferably 30% to 75%, more preferably 31% to 75%, and even more preferably 32% to 75%.

[0058] In this invention, the 45-degree specular gloss of the metallic layer is measured using a gloss meter according to the 45-degree specular gloss measurement method described in JIS Z8741.

[0059] A 45-degree specular gloss level can be adjusted, for example, by the content of metallic pigments, average particle size and surface smoothness, as well as the thickness of the metallic gloss layer. Specifically, there is a tendency for higher metallic pigment content in the metallic gloss layer to result in higher gloss; a tendency for higher average particle size of metallic pigments to result in higher gloss; a tendency for higher surface smoothness of metallic pigments to result in higher gloss; and a tendency for greater thickness of the metallic gloss layer to result in lower gloss.

[0060] In one embodiment, the metallic luster layer comprises one or more metallic pigments. Examples of metallic pigments include aluminum, nickel, chromium, brass, tin, bronze, zinc, silver, platinum, gold and their oxides, as well as particles of glass subjected to metal vapor deposition. Among these, aluminum pigments are particularly preferred from the perspective of further improving the transferability of the metallic luster layer and the gloss of the produced print.

[0061] Aluminum pigments can be either floating or non-floating. From the perspective of further improving the transferability of the metallic gloss layer and the gloss of the produced prints, non-floating aluminum pigments are preferred.

[0062] The average particle size of the metallic pigment is preferably 4 μm to 10 μm, more preferably 6.5 μm to 9.5 μm. This improves the fine-line printability of the heat transfer film. Average particle size refers to the median particle size (D50).

[0063] In this invention, the average particle size of the metallic pigment was determined according to JIS Z8825:2013.

[0064] The hiding power of the metallic pigment is preferably 2 or more, more preferably 2.5 or more, and particularly preferably 4 or more. This effectively covers the tones of the transferred material, preventing the image formed on the printed material from affecting the tones. The hiding power of the metallic pigment is preferably 6 or less, more preferably 5.5 or less.

[0065] In this invention, the hiding power of the metallic pigments is measured according to JIS K5600-4-1.

[0066] The content of metallic pigment in the metallic luster layer is preferably 23% by mass or more and 83% by mass or less, more preferably 33% by mass or more and 67% by mass or less. This further improves the transferability of the metallic luster layer and the gloss of the printed material produced using the heat transfer sheet.

[0067] In one embodiment, the metallic layer comprises one or more resin materials. Examples of resin materials include polyesters, polyamides, polyolefins, vinyl resins, (meth)acrylic resins, cellulose resins, styrene resins, polycarbonates, and ionomer resins. Among these, polyesters, vinyl resins (especially vinyl chloride-vinyl acetate copolymers), and (meth)acrylic resins are preferred from the viewpoint of further improving the transferability and fine-line printability of the metallic layer; vinyl resins and (meth)acrylic resins are even more preferred.

[0068] The resin content in the metallic luster layer is preferably 17% to 77% by mass, more preferably 33% to 67% by mass. This further improves the transferability of the metallic luster layer.

[0069] The ratio of the metallic pigment content to the resin material content in the metallic gloss layer (PV ratio = metallic pigment content / resin material content) is preferably 0.3 to 5 by mass, more preferably 0.5 to 2 by mass. This further improves the transferability of the metallic gloss layer and the gloss of the printed material produced using the heat transfer sheet.

[0070] In one embodiment, the metallic layer comprises one or more additives. Examples of additives include fillers, plasticizers, antistatic materials, UV-absorbing materials, inorganic particles, organic particles, release agents, and dispersants.

[0071] The thickness of the metallic luster layer is preferably 0.1 μm to 7 μm, more preferably 0.2 μm to 4.5 μm. This improves the printability of fine lines in the metallic luster layer.

[0072] A metallic finish layer can be formed, for example, by dispersing or dissolving the aforementioned material in water or a suitable organic solvent, applying the resulting coating solution onto a first substrate using known methods to form a coating film, and then drying it, thereby forming a metallic finish layer. Examples of the known methods mentioned above include roller coating, reverse roller coating, gravure coating, reverse gravure coating, bar coating, and rod coating.

[0073] (Coloring layer)

[0074] In one embodiment, the heat transfer sheet further comprises coloring layers on the first substrate in sequence with respect to the metallic finish layer. The heat transfer sheet may comprise multiple coloring layers.

[0075] The coloring layer can be a sublimation transfer type coloring layer in which only the sublimation dye contained in the coloring layer is transferred, or a melt transfer type coloring layer in which the coloring layer itself is transferred.

[0076] In one embodiment, the heat transfer sheet has, in a facet-to-face manner, a sublimation transfer type coloring layer, a white layer containing white pigment, and a metallic luster layer on the first substrate.

[0077] The coloring layer contains one or more coloring materials. The coloring materials can be pigments or dyes. Additionally, the dyes can be sublimable dyes.

[0078] Examples of coloring materials include carbon black, acetylene black, lampblack, soot, iron black, aniline black, silica, calcium carbonate, titanium dioxide, cadmium red, cadmium red, chrome red, vermilion, iron oxide red, azo pigments, alizarin lake, quinacridone, carmine red lake, yellow iron oxide, cobalt yellow, cadmium yellow, cadmium orange, chrome yellow, zinc yellow, Neapolitan yellow, nickel yellow, azo pigments, onion yellow, cyan, verdigris, cobalt, phthalocyanine, anthraquinone, indigo, vermilion green, and cadmium green. Chrome green, phthalocyanine, azo dyes, perylene, aluminum pigments, as well as diarylmethane dyes, triarylmethane dyes, thiazole dyes, cyanide dyes, pyrazolone dyes, methine dyes, indigo dyes, acetophenone azo dyes, pyrazoloazo dyes, xanthan dyes, oxazine dyes, thiazine dyes, azazine dyes, acridine dyes, azo dyes, spiropyran dyes, indolespiropyran dyes, fluorane dyes, naphthoquinone dyes, anthraquinone dyes, and quinoline dyes, etc., are all sublimable dyes.

[0079] In one embodiment, the coloring layer comprises one or more resin materials. Examples of resin materials include polyester, polyamide, polyolefin, vinyl resin, (meth)acrylic resin, cellulose resin, styrene resin, polycarbonate, butyral resin, phenoxy resin, and ionomer resin.

[0080] The coloring layer may contain one or more of the above-mentioned additives.

[0081] The thickness of the coloring layer is preferably 0.1 μm or more and 3 μm or less.

[0082] The coloring layer can be formed, for example, by dispersing or dissolving the above-mentioned material in water or a suitable organic solvent, applying the resulting coating liquid onto a first substrate by the above-mentioned known means to form a coating film, and drying it, thereby forming the coloring layer.

[0083] (Back layer)

[0084] In one embodiment, the heat transfer sheet has a back layer on the side of the first substrate opposite to the side where the metallic luster layer is provided. This improves the heat transfer sheet's resistance to sticking.

[0085] In one embodiment, the back layer comprises one or more resin materials. Examples of resin materials include cellulose resins, styrene resins, vinyl resins, polyesters, polyurethanes, silicone-modified polyurethanes, fluorinated polyurethanes, and (meth)acrylic resins.

[0086] In one embodiment, the back layer contains one or more types of inorganic or organic particles. This further prevents adhesion and wrinkling caused by heating during heat transfer.

[0087] Examples of inorganic particles include: clay minerals such as talc and kaolin; carbonates such as calcium carbonate and magnesium carbonate; hydroxides such as aluminum hydroxide and magnesium hydroxide; sulfates such as calcium sulfate; oxides such as silicon dioxide; and inorganic particles such as graphite, nitrate, and boron nitride.

[0088] Examples of organic particles include: organic resin particles composed of (meth)acrylic resins, Teflon (registered trademark) resins, silicone resins, lauroyl resins, phenolic resins, acetal resins, styrene resins, and polyamides; or cross-linked resin particles formed by reacting them with cross-linking materials.

[0089] The back layer may contain one or more of the above-mentioned additives.

[0090] The thickness of the back layer is preferably 0.1 μm or more and 2 μm or less.

[0091] The back layer can be formed, for example, by dispersing or dissolving the above-mentioned material in water or a suitable organic solvent, applying the resulting coating liquid onto a first substrate by the above-mentioned known means to form a coating film, and drying it, thereby forming the back layer.

[0092] (Combination of heat transfer film and intermediate transfer medium)

[0093] The combination of the heat transfer sheet and the intermediate transfer medium of the present invention consists of the heat transfer sheet described above and the intermediate transfer medium having a second substrate and a transfer layer.

[0094] The heat transfer sheets constituting the combination of the present invention have been described above, and therefore will not be described here.

[0095] (Intermediate transfer medium)

[0096] like Figure 3 As shown, the intermediate transfer medium 20 constituting the combination of the present invention includes a second substrate 21 and a transfer layer 22.

[0097] In one implementation, such as Figure 3 As shown, the transfer layer 22 includes a receiving layer 23. In one embodiment, as... Figure 4 As shown, the transfer layer 22 has a release layer 24 between the second substrate 21 and the receiving layer 23.

[0098] In one embodiment, the transfer layer 22 of the intermediate transfer medium 20 may have a protective layer (not shown) between the receiving layer 23 and the release layer 24. It should be noted that the intermediate transfer medium 20 may be configured to not have a release layer 24 and have a protective layer under the receiving layer 23.

[0099] (Second substrate)

[0100] As the second substrate, a resin film can be used, for example. Examples of resins constituting the resin film include: polyesters such as PET, PBT, PEN, poly(1,4-cyclohexanedimethyl terephthalate), and terephthalic acid-cyclohexanediethanol-ethylene glycol copolymer; polyamides such as nylon 6 and nylon 6,6; polyolefins such as PE, PP, and polymethylpentene; vinyl resins such as polyvinyl chloride, PVA, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and PVP; (meth)acrylic resins such as poly(meth)acrylate and poly(meth)methyl acrylate; imide resins such as polyimide and polyetherimide; cellulose resins such as celluloid, cellulose acetate, cellulose nitrate, CAP, and CAB; styrene resins such as PS; polycarbonate; and ionomer resins.

[0101] In one embodiment, a substrate with a roughened surface of the resin film (hereinafter referred to as a roughened second substrate, depending on the circumstances) can be used as the second substrate.

[0102] The transfer layer is created by casting and peeling off the rough surface of the substrate, thus giving the resulting print a matte finish. This matte finish, which suppresses surface reflection, emphasizes the luster of the metallic layer located on the inner side of the transfer layer, further enhancing the print's aesthetic appeal.

[0103] The haze value of the roughened second substrate is preferably 15% to 50%. This allows for the maintenance of the clarity of the manufactured print while imparting a good matte finish, further enhancing the aesthetics of the print.

[0104] In this invention, the haze value of the roughened second substrate is measured according to JIS K 7136.

[0105] In one embodiment, by containing one or more filler materials in the resin film, the second substrate can be roughened. Examples of filler materials include inorganic particles such as SYLOID, Aerosil, zeolite, talc, and silica; and organic particles such as dicarboxylic acid ester amide and polyethylene.

[0106] The content of filler material in the resin film is preferably 5% by mass or more and 30% by mass or less. This allows the haze value of the roughened second substrate to be of a favorable value.

[0107] The roughening of the second substrate can be achieved using commercially available materials, such as preferably EMBLET (registered trademark) PTH-12 (haze value: 20%) and EMBLET (registered trademark) PTHZ-12 (haze value: 50%) manufactured by Unitika Co., Ltd.

[0108] The thickness of the second substrate is preferably 1 μm or more and 50 μm or less, more preferably 6 μm or more and 25 μm or less.

[0109] (Acceptance layer)

[0110] In one embodiment, the receiving layer comprises one or more resin materials. Examples of resin materials include: vinyl resins such as polyolefins, polyvinyl chloride and vinyl chloride-vinyl acetate copolymers; (meth)acrylic resins, cellulose resins, polyesters, polyamides, polycarbonates, styrene resins, epoxy resins, polyurethanes, epoxy resins, and ionomer resins.

[0111] Among these, vinyl chloride-vinyl acetate copolymer and epoxy resin are preferred from the perspective of further improving the adhesion between the receiving layer and the metallic luster layer of the heat transfer film.

[0112] The content of the above-mentioned resin material in the acceptor layer is preferably 80% by mass or more and 98% by mass or less.

[0113] In one embodiment, the receiving layer comprises one or more release materials. This improves the release properties from the heat transfer sheet.

[0114] As release materials, examples include solid waxes such as polyethylene wax, polyamide wax, and Teflon (registered trademark) powder; fluorinated or phosphate ester surfactants; various modified silicone oils such as silicone oil, reactive silicone oil, and curing silicone oil; and organosilicon resins.

[0115] As the aforementioned silicone oil, an oily substance can be used, with modified silicone oil being preferred. Among the modified silicone oils, amino-modified silicone, epoxy-modified silicone, aralkyl-modified silicone, epoxy-aralkyl-modified silicone, alcohol-modified silicone, vinyl-modified silicone, and urethane-modified silicone are preferred, with epoxy-modified silicone, aralkyl-modified silicone, and epoxy-aralkyl-modified silicone being particularly preferred.

[0116] The content of the release material in the receiving layer is preferably 0.5% to 20% by mass, more preferably 0.5% to 10% by mass. This further improves the release properties between the receiving layer and the heat transfer sheet.

[0117] The receiving layer may contain the aforementioned additives.

[0118] The thickness of the receiving layer is preferably 0.5 μm to 20 μm, more preferably 1 μm to 10 μm. This increases the density of the image formed on the receiving layer.

[0119] The receiving layer can be formed, for example, by dispersing or dissolving the above-mentioned material in water or a suitable organic solvent, applying the resulting coating liquid onto a second substrate or any layer on the second substrate by the above-mentioned known means to form a coating film, and drying it, thereby forming the receiving layer.

[0120] (Peel-off layer)

[0121] In one embodiment, the transfer layer of the intermediate transfer medium has a release layer below the receiving layer. This improves the transferability of the transfer layer.

[0122] In one embodiment, the release layer comprises one or more resin materials. Examples of resin materials include (meth)acrylic resins, cellulose resins, vinyl resins, polyurethanes, silicone resins, polyesters, and fluoropolymers.

[0123] In one embodiment, the release layer comprises one or more types of wax. Examples of waxes include: natural waxes such as beeswax, whale wax, wood wax, rice bran wax, carnauba wax, candelilla wax, and lignite wax; synthetic waxes such as paraffin wax, microcrystalline wax, oxidized wax, ceresin wax, pure white ceresin wax, ester wax, and polyethylene wax; higher saturated fatty acids such as heptadecanoic acid, lauric acid, tetradecanoic acid, palmitic acid, stearic acid, furoic acid, and behenic acid; higher saturated monohydric alcohols such as stearyl alcohol and behenyl alcohol; higher esters such as fatty acid esters of sorbitan anhydride; and higher fatty amides such as stearamide and oleamide.

[0124] The release layer may contain both the aforementioned resin material and wax, and may contain more than two of these substances.

[0125] The thickness of the release layer is preferably 0.5 μm to 3 μm, more preferably 0.7 μm to 2 μm. This further improves the transferability of the transfer layer.

[0126] The release layer can be formed, for example, by dispersing or dissolving the above-mentioned material in water or a suitable organic solvent, applying the resulting coating liquid onto a second substrate by the above-mentioned known means to form a coating film, and drying it, thereby forming a release layer.

[0127] (protective layer)

[0128] In one embodiment, the intermediate transfer medium has a protective layer beneath the receiving layer.

[0129] In one embodiment, the protective layer comprises one or more resin materials. Examples of resin materials include polyester, (meth)acrylic resins, epoxy resins, styrene resins, (meth)acrylic polyol resins, polyurethanes, ionizing radiation curable resins, and ultraviolet-absorbing resins.

[0130] In one embodiment, the protective layer comprises one or more isocyanate compounds. Examples of isocyanate compounds include xylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

[0131] The protective layer may contain one or more of the above-mentioned additives.

[0132] The thickness of the protective layer is preferably 0.5 μm to 7 μm, more preferably 1 μm to 5 μm. This further improves the durability of the protective layer.

[0133] The protective layer can be formed, for example, by dispersing or dissolving the above-mentioned material in water or a suitable organic solvent, applying the resulting coating liquid onto a second substrate or any layer on the second substrate by the above-mentioned known means to form a coating film, and drying it, thereby forming a protective layer.

[0134] (Method for manufacturing printed materials)

[0135] The method for manufacturing the printed material of the present invention comprises:

[0136] The process of preparing the combination of the above-mentioned heat transfer film and intermediate transfer medium, as well as the transfer object;

[0137] The process of transferring a metallic luster layer from a heat transfer sheet to a transfer layer on an intermediate transfer medium; and

[0138] The process of transferring the transfer layer and the metallic sheen layer of the intermediate transfer medium onto the object to be transferred.

[0139] In one embodiment, the method for manufacturing the printed image of the present invention includes the following step: before transferring the metallic luster layer, forming an image on the receiving layer of the transfer layer of the intermediate transfer medium using a heat transfer sheet.

[0140] like Figure 5 As shown, the print 30 manufactured by the print manufacturing method of the present invention comprises a transfer body 31, a metallic luster layer 12 and a transfer layer 22.

[0141] In the printed material 30, the metallic luster layer 12 and the transfer layer 22 can be disposed on the entire surface of the transferred material 31 or on a portion thereof.

[0142] As the transfer substrate for the printed material, the following can be used: high-grade paper, art printing paper, coated paper, resin coated paper, high-gloss printing paper, cardboard, synthetic paper and impregnated paper, etc.; and resin film of the same type as the first substrate mentioned above.

[0143] As the substrate, their laminates can be used.

[0144] The thickness of the substrate to be transferred is preferably between 50 μm and 2000 μm.

[0145] The present invention relates, for example, to the following [1] to

[11] .

[0146] [1] A heat transfer film having a first substrate and a metallic gloss layer containing metallic pigment, wherein the 45-degree mirror gloss of the metallic gloss layer is 30% or more and 80% or less.

[0147] [2] As described in [1] above, the heat transfer film has an average particle size of 4 μm or more and 10 μm or less for the metallic pigment.

[0148] [3] As described in [1] or [2] above, the heat transfer film, wherein the metallic luster layer comprises a resin material, and the ratio of the content of metallic pigment in the metallic luster layer to the content of resin material (content of metallic pigment / content of resin material) is 0.3 to 5.0 by mass.

[0149] [4] As described in [3] above, the heat transfer film is made of one or more resin materials selected from polyester, vinyl resin and (meth)acrylic resin.

[0150] [5] The heat transfer sheet as described in any one of [1] to [4] above, wherein the thickness of the metallic luster layer is 0.1 μm or more and 7 μm or less.

[0151] [6] The heat transfer film as described in any one of [1] to [5] above, wherein the metallic pigment is an aluminum pigment.

[0152] [7] As described in [6] above, the heat transfer film contains aluminum pigment that is non-floating.

[0153] [8] The heat transfer film as described in any one of [1] to [7] above, wherein the hiding power of the metallic pigment is 2.5 or more.

[0154] [9] The heat transfer sheet as described in any one of [1] to [8] above, wherein a coloring layer is further provided on the first substrate in a manner that is in the same order as the metallic luster layer.

[0155]

[10] A combination of a heat transfer sheet and an intermediate transfer medium, which is any one of the above [1] to [9] heat transfer sheet and intermediate transfer medium, wherein the intermediate transfer medium has a second substrate and a transfer layer.

[0156]

[11] A method for manufacturing a printed image, comprising: a step of preparing the combination of the heat transfer sheet and the intermediate transfer medium described above

[10] and a transfer object; a step of transferring a metallic luster layer from the heat transfer sheet to a transfer layer provided by the intermediate transfer medium; and a step of transferring the transfer layer provided by the intermediate transfer medium and the metallic luster layer on the transfer layer to the transfer object.

[0157] Example

[0158] Next, examples will be given to illustrate the invention in more detail, but the invention is not limited to these examples. Furthermore, unless otherwise stated, the content, mixing ratio, etc., are based on quality.

[0159] (Production of heat transfer film)

[0160] Example 1

[0161] As the first substrate, a PET film (manufactured by Toray Industries, Inc., Lumiror (registered trademark)) with a thickness of 4.5 μm was prepared. Coating solutions A, B, C and D, which consist of the following components, were sequentially applied to one side of the PET film and then dried to form color layers A to D with a thickness of 0.7 μm, respectively.

[0162] <Coating solution A for forming coloring layer>

[0163] · 5 parts by weight of yellow sublimation dye

[0164] ·5 parts by weight of polyvinyl alcohol acetal

[0165] ·Methyl ethyl ketone (MEK) 90 parts by weight

[0166] <Coating solution B for forming coloring layer>

[0167] · 5 parts by weight of magenta sublimation dye

[0168] ·5 parts by weight of polyvinyl alcohol acetal

[0169] MEK 90 parts by weight

[0170] <Coating solution C for forming coloring layer>

[0171] · 5 parts by weight of cyan sublimation dye

[0172] ·5 parts by weight of polyvinyl alcohol acetal

[0173] MEK 90 parts by weight

[0174] <Coating solution D for forming coloring layer>

[0175] · 5 parts by weight of carbon black

[0176] 5 parts by weight of vinyl chloride-vinyl acetate copolymer

[0177] MEK 90 parts by weight

[0178] The metallic luster layer forming liquid with the following composition was applied in sequence with the coloring layer and then dried to form a metallic luster layer with a thickness of 2 μm. The 45-degree specular gloss was measured using a gloss meter (manufactured by Nippon Denshoku Co., Ltd., VG 7000) according to the 45-degree specular gloss measurement method described in JIS Z8741, and the result was 46.6%.

[0179] In the following examples and comparative examples, the 45-degree specular gloss of the metallic layer was measured in the same manner as in Example 1. The measurement results are shown in Tables 1 and 2.

[0180] <Coating solution for forming metallic luster>

[0181] ·Aluminum pigment A 20 parts by weight

[0182] (Manufactured by Asahi Kasei Corporation, FD-5060, average particle size 6μm, hiding power 3.4, non-floating type)

[0183] 20 parts by weight of vinyl chloride-vinyl acetate copolymer

[0184] (Manufactured by Nissin Chemical Industry Co., Ltd., SOLBIN (registered trademark) CNL)

[0185] MEK 30 parts by weight

[0186] 30 parts by weight of toluene

[0187] A back-side layer forming liquid with the following composition is coated on the other side of the first substrate and dried to form a back-side layer with a thickness of 0.1 μm, thereby obtaining a heat transfer sheet.

[0188] <Coating liquid for back layer formation>

[0189] · 2 parts by weight of polyvinyl butyral

[0190] (Manufactured by Sekisui Chemicals Co., Ltd., S-LEC (registered trademark) BX-1)

[0191] 9.2 parts by weight of polyisocyanate

[0192] (Manufactured by DIC Corporation, BURNOCK (registered trademark) D750)

[0193] • 1.3 parts by weight of phosphate ester surfactant

[0194] (Daiichi Kogyo Pharmaceutical Co., Ltd., Plysurf (registered trademark) A208N)

[0195] 0.3 parts by weight of talc

[0196] (Nippon Talc Industries, Ltd., Micro Ace (registered trademark) P-3)

[0197] 43.6 parts by weight of toluene

[0198] MEK 43.6 parts by weight

[0199] Examples 2-16 and Comparative Examples 1-11

[0200] The composition of the metallic luster layer was changed as shown in Tables 1 and 2, and the heat transfer film was made in the same manner as in Example 1.

[0201] The details of each component in Tables 1 and 2 are as follows. In Tables 1 and 2, aluminum pigment is referred to as "Al pigment".

[0202] • Aluminum Pigment A: Manufactured by Asahi Kasei Corporation, FD-5060

[0203] Average particle size 6μm, hiding power 3.4

[0204] non-floating

[0205] • Aluminum Pigment B: Manufactured by Asahi Kasei Corporation, AM-1501

[0206] Average particle size 8μm, hiding power 5.0,

[0207] non-floating

[0208] • Aluminum Pigment C: Manufactured by Asahi Kasei Corporation, S-8801T

[0209] Average particle size 15μm, hiding power 2.4,

[0210] non-floating

[0211] • Aluminum Pigment D: Manufactured by Asahi Kasei Corporation, BS-120

[0212] Average particle size 13μm, hiding power 3.7

[0213] non-floating

[0214] • Aluminum Pigment E: Manufactured by Asahi Kasei Corporation, FD-508H

[0215] Average particle size 8μm, hiding power 4.8

[0216] non-floating

[0217] • Aluminum Pigment F: Manufactured by Asahi Kasei Corporation, 8NL-S

[0218] Average particle size 8μm, hiding power 2.3,

[0219] non-floating

[0220] • Aluminum Pigment G: Manufactured by Toyo Aluminium Co., Ltd., 2173

[0221] Average particle size 11 μm

[0222] non-floating

[0223] Vinyl chloride-vinyl acetate copolymer: manufactured by Nissin Chemical Industry Co., Ltd.

[0224] SOLBIN (registered trademark) CNL

[0225] • (Meth)acrylic resins: Manufactured by Mitsubishi Chemical Corporation

[0226] DIANAL (registered trademark) BR-87

[0227] • Polyester: Manufactured by Unitika Co., Ltd.

[0228] elitel (registered trademark) UE3200

[0229] (Preparation of intermediate transfer medium A)

[0230] As the second substrate, a 12 μm thick PET film (manufactured by Toray Industries, Inc., Lumiror (registered trademark)) is prepared. A release layer forming coating solution with the following composition is coated on one side of the PET film and dried to form a release layer with a thickness of 1 μm.

[0231] <Coating solution for forming release layer>

[0232] 9.5 parts by weight of (meth)acrylic resin

[0233] (Manufactured by Mitsubishi Chemical Corporation, DIANAAL (registered trademark) BR-87)

[0234] · 0.5 parts by weight of polyester

[0235] (Manufactured by Toyobo Co., Ltd., Vylon (registered trademark) 200)

[0236] · Toluene 20 parts by weight

[0237] MEK 20 parts by weight

[0238] A protective layer forming liquid with the following composition is applied to the release layer formed as described above and then dried to form a protective layer with a thickness of 2 μm.

[0239] <Coating liquid for forming protective layer>

[0240] 100 parts by weight of (meth)acrylic acid polyol resin

[0241] (Manufactured by Taisei Fine Chemical Co., Ltd., 6KW-700, solids content 36.5%, Tg 102℃, Mw 55000, hydroxyl value 30.1)

[0242] · 3.6 parts by weight of isocyanate compound

[0243] (Manufactured by Mitsui Chemicals, Ltd., Takenate (registered trademark) D110N, 75% solids)

[0244] MEK 92 parts by weight

[0245] A receiving layer forming liquid with the following composition is applied to the protective layer formed as described above and dried to form a receiving layer with a thickness of 2 μm, thus obtaining intermediate transfer medium A.

[0246] <Coating solution for forming the acceptor layer>

[0247] 95 parts by weight of vinyl chloride-vinyl acetate copolymer

[0248] (Manufactured by Nissin Chemical Industry Co., Ltd., SOLBIN (registered trademark) CNL)

[0249] · 5 parts by weight of epoxy modified silicone oil

[0250] (Manufactured by Shin-Etsu Chemical Industry Co., Ltd., KP-1800U)

[0251] ·Toluene 200 parts by weight

[0252] ·MEK 200 parts by weight

[0253] (Preparation of intermediate transfer medium B)

[0254] The second substrate was changed to a roughened second substrate (manufactured by Unitika Co., Ltd., EMBLET (registered trademark) PTH-12), and the intermediate transfer medium B was made in the same manner as described above.

[0255] <Transferability Evaluation>

[0256] Using the printer described below, at an energy grayscale of 128 / 255, the sublimation dye is sublimated and transferred from the coloring layers A to C of the heat transfer sheets of each embodiment and comparative example to the receiving layers of the intermediate transfer media A and B (hereinafter collectively referred to as intermediate transfer media) prepared as described above, and after forming a grayscale image, the metallic luster layer is transferred to the receiving layer on which the image is formed.

[0257] (printer)

[0258] HDP5000 (manufactured by FARGO)

[0259] Re-transfer temperature: 175℃

[0260] Re-transfer speed: 2.3 seconds / inch

[0261] Prepare a vinyl chloride card as the substrate. On one side of the card, use the printer described above to transfer the release layer, protective layer, receiving layer and metallic sheen layer, which are laminated from the intermediate transfer medium, to the entire surface of the substrate to obtain a printed image.

[0262] The above transfer is performed as follows: after the vinyl chloride card is thermally bonded to the intermediate transfer medium, the temperature of the intermediate transfer medium is reduced, and then the second substrate is peeled off, thereby performing the transfer.

[0263] The transfer area of ​​the metallic layer, acceptor layer, protective layer, and release layer was visually confirmed, and the transferability of the metallic layer on vinyl chloride card was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 1 and 2.

[0264] (Evaluation Criteria)

[0265] A: The transfer area of ​​the metallic luster layer, receiving layer, protective layer, and release layer is more than 95% of the area of ​​the vinyl chloride card.

[0266] B: The transfer area of ​​the metallic luster layer, receiving layer, protective layer, and release layer is more than 70% and less than 95% of the area of ​​the vinyl chloride card.

[0267] NG: The transfer area of ​​the metallic layer, acceptor layer, protective layer and release layer is less than 70% of the area of ​​the vinyl chloride card, and cohesive failure is confirmed in the metallic layer.

[0268] <Aesthetic Appeal (Glossiness) Evaluation>

[0269] The prints produced in the above transferability evaluation were visually observed, and the evaluation was conducted based on the following evaluation criteria. The evaluation results are shown in Tables 1 and 2.

[0270] (Evaluation Criteria)

[0271] A: It has been confirmed that the printed material has a very high gloss and is highly aesthetically pleasing.

[0272] B: The printed material has a high gloss.

[0273] C: The printed material has a glossy appearance.

[0274] NG: The printed material lacks luster, and there is room for improvement in its aesthetics.

[0275] <Evaluation of Printability of Fine Lines>

[0276] The metallic luster layer is transferred onto the receiving layer with an image formed on the intermediate transfer medium in the above-mentioned transferability evaluation, in the manner of forming a thin line at a point.

[0277] The above transfer is performed using thin lines that form 2 points and thin lines that form 3 points.

[0278] The metallic finish after transfer was visually inspected, and evaluated based on the following criteria. The evaluation results are shown in Tables 1 and 2.

[0279] (Evaluation Criteria)

[0280] A: No deformation or blurring was observed in the thin lines at points 1, 2, and 3.

[0281] B: No distortion or blurring was observed in the thin lines at points 2 and 3, but it was observed in the thin line at point 1.

[0282] C: No distortion or blurring was observed in the thin line at point 3, but distortion and blurring were observed in the thin lines at points 1 and 2.

[0283] D: Deformation and blurring were observed in the thin lines at points 1, 2, and 3.

[0284]

[0285]

[0286] As those skilled in the art will understand, the thermal transfer film and the like of the present invention are not limited to the embodiments described above. The embodiments and description are only for illustrating the principles of the present invention. Various changes or improvements can be made without departing from the spirit and scope of the present invention, and all such changes or improvements are included within the scope of the present invention as claimed. Furthermore, the scope of protection of the present invention includes not only the claims but also their equivalents.

Claims

1. A combination of a thermal transfer sheet and an intermediate transfer medium, wherein the thermal transfer sheet comprises: a first substrate, and a metallic luster layer comprising a metallic pigment and a resin material selected from one or more of a polyester, a vinyl resin, and a (meth)acrylic resin, a 45-degree specular glossiness of the metallic luster layer is 30% or more and 80% or less, the 45-degree specular glossiness of the metallic luster layer is measured in accordance with the 45-degree specular glossiness measurement method described in JIS Z8741 using a gloss meter, the intermediate transfer medium comprises: a second substrate, and a transfer layer comprising a receiving layer comprising one or more resin materials selected from a chlorovinyl-vinyl acetate copolymer and an epoxy resin, a haze value of the second substrate measured in accordance with JIS K 7136 is 15% or more and 50% or less.

2. The combination of a heat transfer sheet and an intermediate transfer medium of claim 1, wherein, an average particle diameter of the metallic pigment is 4 μm or more and 10 μm or less.

3. The combination of a heat transfer sheet and an intermediate transfer medium according to claim 1 or 2, wherein, a ratio of a content of the metallic pigment to a content of the resin material in the metallic luster layer, i.e., the content of the metallic pigment / content of the resin material, is 0.3 or more and 5.0 or less on a mass basis.

4. The combination of a heat transfer sheet and an intermediate transfer medium according to claim 1 or 2, wherein a thickness of the metallic luster layer is 0.1 μm or more and 7 μm or less.

5. The combination of a heat transfer sheet and an intermediate transfer medium according to claim 1 or 2, wherein the metallic pigment is an aluminum pigment.

6. The combination of a heat transfer sheet and an intermediate transfer medium of claim 5, wherein, the aluminum pigment is a non-floating type.

7. The combination of a heat transfer sheet and an intermediate transfer medium of claim 1 or 2, wherein, a hiding power of the metallic pigment is 2.5 or more.

8. The combination of a heat transfer sheet and an intermediate transfer medium of claim 1 or 2, wherein, the thermal transfer sheet further comprises a coloring layer on the first substrate in a manner that the metallic luster layer is on the coloring layer.

9. A method for producing a printed matter, comprising: a step of preparing a combination of the thermal transfer sheet according to any one of claims 1 to 8 and the intermediate transfer medium, and a transfer target; a step of transferring the metallic luster layer from the thermal transfer sheet to the transfer layer comprised by the intermediate transfer medium; and a step of transferring the transfer layer comprised by the intermediate transfer medium and the metallic luster layer on the transfer layer to the transfer target.

Images