Method for manufacturing transfer sheet, transfer sheet

Abstract

To provide a method for producing a transfer sheet that can produce a transfer sheet that has excellent blocking resistance and excellent friction resistance of the transferred product after transfer. Also provided is a transfer sheet that has excellent blocking resistance and excellent friction resistance of the transferred product after transfer. The method includes a step 1 of forming a decorative layer on a temporary support, and a step 2 of applying a composition containing a (meth)acrylate compound onto the decorative layer to form a coating film. Step 3 of forming a hot melt adhesive layer on the coating film; and step 4 of subjecting the coating film to a curing treatment to form an image layer containing a (meth)acrylate resin, A method for producing a transfer sheet, wherein the intensity ratio P1 calculated by the formula (X1) is 0.005 to 0.300.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a transfer sheet and a transfer sheet. [Background technology]

[0002] In recent years, various methods for textile printing on fabrics have been investigated. In addition, prints obtained by textile printing are required to have a wide variety of designs, for example, high gloss.

[0003] For example, Patent Document 1 discloses a metallic-finish thin film sheet for pressure-sensitive transfer that can be transferred to any surface, whether flat or curved, by pressure-sensitive operation. The metallic-finish thin film sheet has a layer structure in the following order: base film (1) having releasability or provided with a release layer (1a) / protective layer (2) / metal vapor deposition layer (3) / adhesive layer (4) / elastic resin layer (5) / pressure-sensitive adhesive layer (6) / release sheet (7), and the elastic resin layer (5) is formed from a resin whose elongation at break in a tensile strength / elongation test of a 25 mm sheet is 2 to 300%. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 63-302087 Summary of the Invention [Problem to be solved by the invention]

[0005] The inventors have studied the method for manufacturing a transfer sheet described in Patent Document 1 and have found that, depending on the manufacturing method, when multiple transfer sheets are stacked on top of each other, the transfer sheets may adhere too tightly to each other, which may result in chipping of the image layer when the transfer sheets are peeled off (poor blocking resistance), and the abrasion resistance of the transferred product may be poor after transfer.

[0006] Therefore, an object of the present invention is to provide a method for producing a transfer sheet that is capable of producing a transfer sheet that has excellent blocking resistance and that provides a transferred product with excellent friction resistance after transfer. Another object of the present invention is to provide a transfer sheet that has excellent blocking resistance and provides a transferred product that is excellent in abrasion resistance after transfer. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by the following configuration.

[0008] [1] Step 1 of forming a decorative layer on a temporary support; Step 2 of applying a composition containing one or more compounds selected from the group consisting of acrylate compounds and methacrylate compounds onto the decorative layer to form a coating film; Step 3 of forming a hot melt adhesive layer on the coating film; and step 4 of subjecting the coating film to a curing treatment to form an image layer containing one or more resins selected from the group consisting of acrylate resins and methacrylate resins, A method for producing a transfer sheet, wherein the intensity ratio P1 calculated by the following formula (X1) is 0.005 to 0.300. Formula (X1) P1=Z 12 / Z 11 In formula (X1), P1 represents the intensity ratio. 11 represents the normalized carbon-double bond peak intensity of the coating film obtained by the formula (X2). 12 represents the normalized carbon-double bond peak intensity obtained by the formula (X3) on the surface of the image layer facing the hot-melt adhesive layer. Formula (X2) Z 11 =Y 11 / X 11 In formula (X2), X 11 represents the peak intensity derived from C=O of the ester group, as determined by infrared absorption spectroscopy of the coating film. 11represents the peak intensity derived from the carbon-carbon double bond C=C determined by infrared absorption spectroscopy of the coating film. 11 represents the normalized carbon-carbon double bond peak intensity. Formula (X3) Z 12 =Y 12 / X 12 In formula (X3), X 12 Y represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 12 represents the peak intensity derived from the carbon double bond C=C, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 12 represents the normalized carbon-carbon double bond peak intensity. [2] In the step 2, the coating film is formed on at least a part of the decorative layer, The method for producing a transfer sheet described in [1], wherein in step 3, powdered hot melt adhesive is sprayed from the coating film side to remove the hot melt adhesive other than on the coating film, thereby forming the hot melt adhesive layer on the coating film. [3] The composition contains one or more compounds selected from the group consisting of a monofunctional acrylate compound, a monofunctional methacrylate compound, a bifunctional acrylate compound, and a bifunctional methacrylate compound, The method for producing a transfer sheet according to [1] or [2], wherein the total content of the monofunctional acrylate compound, the monofunctional methacrylate compound, the bifunctional acrylate compound, and the bifunctional methacrylate compound is 50% by mass or more relative to the total solid content of the composition. [4] The method for producing a transfer sheet according to any one of [1] to [3], wherein the weight average molecular weight of the acrylate resin and the methacrylate resin in the image layer is 200,000 or more. [5] The method for producing a transfer sheet according to any one of [1] to [4], wherein the composition contains a compound represented by formula (1) described below. [6] The method for producing a transfer sheet according to [5], wherein both R3 and R4 are each independently a linear or branched alkylene group. [7] The decorative layer is a metal layer or a cholesteric liquid crystal layer, The method for producing a transfer sheet according to any one of [1] to [6], wherein the metal layer is a metal foil or a metal vapor deposition layer. [8] The method for producing a transfer sheet according to any one of [1] to [7], wherein, when the transfer sheet is viewed in plan, the hot melt adhesive layer is disposed only on the image layer, and the ratio of the area of ​​the hot melt adhesive layer to the area of ​​the image layer is 60 to 100%. [9] A transfer sheet manufactured by the manufacturing method of [1], A transfer sheet having a temporary support, a decorative layer, an image layer, and a hot-melt adhesive layer in this order, the image layer contains one or more resins selected from the group consisting of acrylate resins and methacrylate resins, A transfer sheet having an intensity ratio P2 calculated by the following formula (Y1) of 1.25 to 50.0. Formula (Y1) P2=Z 22 / Z 21 In formula (Y1), P2 represents the intensity ratio. 21 represents the normalized carbon-double bond peak intensity of the surface of the image layer facing the decorative layer, which is determined by the formula (Y2). 22 represents the normalized carbon-double bond peak intensity obtained by the formula (Y3) on the surface of the image layer facing the hot-melt adhesive layer. Formula (Y2) Z 21 =Y 21 / X 21 In formula (Y2), X 21 Y represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the decorative layer. 21 represents the peak intensity derived from the carbon double bond C=C, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the decorative layer. 21 represents the normalized carbon-carbon double bond peak intensity. Formula (Y3) Z 22 =Y 22 / X 22 In formula (Y3), X 22 Y represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 22 represents the peak intensity derived from the carbon double bond C=C, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 22 represents the normalized carbon-carbon double bond peak intensity.

[10] The image layer is a cured layer derived from a composition containing one or more compounds selected from the group consisting of acrylate compounds and methacrylate compounds, the composition contains one or more compounds selected from the group consisting of a monofunctional acrylate compound, a monofunctional methacrylate compound, a bifunctional acrylate compound, and a bifunctional methacrylate compound; The transfer sheet according to [9], wherein the total content of the monofunctional acrylate compound, the monofunctional methacrylate compound, the bifunctional acrylate compound, and the bifunctional methacrylate compound is 50% by mass or more based on the total solid content of the composition.

[11] The transfer sheet according to [9] or

[10] , wherein the weight average molecular weight of the acrylate resin and the methacrylate resin in the image layer is 200,000 or more.

[12] The transfer sheet according to any one of [9] to

[11] , wherein the composition contains a compound represented by formula (1) described below.

[13] The transfer sheet according to

[12] , wherein both R3 and R4 are each independently a linear or branched alkylene group.

[14] The decorative layer is a metal layer or a cholesteric liquid crystal layer, The transfer sheet according to any one of [9] to

[13] , wherein the metal layer is a metal foil or a metal vapor deposition layer.

[15] The transfer sheet according to any one of [9] to

[14] , wherein, when the transfer sheet is viewed in plan, the hot melt adhesive layer is disposed only on the image layer, and the ratio of the area of ​​the hot melt adhesive layer to the area of ​​the image layer is 60 to 100%. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing a transfer sheet that is excellent in blocking resistance and in which the transferred product has excellent friction resistance after transfer. Furthermore, according to the present invention, it is possible to provide a transfer sheet that has excellent blocking resistance and provides a transferred product that is excellent in abrasion resistance after transfer. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic diagram showing an example of an embodiment of a transfer sheet obtained by the production method of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. Furthermore, in the numerical ranges described in stages in this specification, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0012] Furthermore, the term "process" in this specification does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0013] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, the temperature when performing each of the above steps may be 25° C. unless otherwise specified.

[0014] In this specification, unless otherwise specified, when there is a molecular weight distribution, the molecular weight is a weight average molecular weight. In this specification, the weight average molecular weight means a value measured by gel permeation chromatography (GPC). The GPC is performed using an HLC-8020GPC (manufactured by Tosoh Corporation) with three TSKgel (registered trademark) Super Multipore HZ-H columns (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) and THF (tetrahydrofuran) as the eluent. GPC is performed using a refractive index (RI) detector at a sample concentration of 0.45% by mass, a flow rate of 0.35 ml / min, a sample injection volume of 10 μl, and a measurement temperature of 40° C. Calibration curves are prepared from eight samples of "Standard Sample TSK Standard, Polystyrene" manufactured by Tosoh Corporation: "F-40," "F-20," "F-4," "F-1," "A-5000," "A-2500," "A-1000," and "n-propylbenzene."

[0015] In this specification, "(meth)acrylate compound" is a general term for compounds selected from the group consisting of acrylate compounds and methacrylate compounds, "(meth)acrylate resin" is a general term for compounds selected from the group consisting of acrylate resins and methacrylate resins, and "(meth)acryloyl" is a concept that encompasses both acryloyl and methacryloyl.

[0016] The "solid content" of a composition refers to components that form a composition layer (e.g., a coating film obtained in step 2 described below) formed using the composition, and when the composition contains a solvent (e.g., an organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0017] Unless otherwise specified, the layer thickness (film thickness) in this specification is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0018] [Transfer sheet manufacturing method] The method for producing the transfer sheet of the present invention (hereinafter also referred to as the "production method of the present invention") is as follows: Step 1 of forming a decorative layer on a temporary support; Step 2 of applying a composition containing one or more compounds selected from the group consisting of acrylate compounds and methacrylate compounds onto the decorative layer to form a coating film; Step 3 of forming a hot melt adhesive layer on the coating film; and step 4 of subjecting the coating film to a curing treatment to form an image layer containing one or more resins selected from the group consisting of acrylate resins and methacrylate resins, The method for producing a transfer sheet is such that the intensity ratio P1 calculated by the following formula (X1) is 0.005 to 0.300. Formula (X1) P1=Z 12 / Z 11 In formula (X1), P1 represents the intensity ratio. 11 represents the normalized carbon-double bond peak intensity of the coating film obtained by the formula (X2). 12 represents the normalized carbon-double bond peak intensity obtained by the formula (X3) on the surface of the image layer facing the hot-melt adhesive layer. Formula (X2) Z 11 =Y 11 / X 11 In formula (X2), X 11 represents the peak intensity derived from C=O of the ester group, as determined by infrared absorption spectroscopy of the coating film. 11represents the peak intensity derived from the carbon-carbon double bond C=C determined by infrared absorption spectroscopy of the coating film. 11 represents the normalized carbon double bond peak intensity. Formula (X3) Z 12 =Y 12 / X 12 In formula (X3), X 12 Y represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 12 represents the peak intensity derived from the carbon double bond C=C, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 12 represents the normalized carbon double bond peak intensity.

[0019] The transfer sheet obtained by the production method of the present invention has excellent blocking resistance, and the transferred product has excellent resistance to rubbing after transfer. The main features of the manufacturing method of the present invention include forming a hot melt adhesive layer on the coating film formed on the decorative layer without subjecting the coating film to a curing treatment, and then curing the coating film after the hot melt adhesive layer is formed to form an image layer, and adjusting the residual carbon double bonds on the surface of the image layer facing the hot melt adhesive layer to fall within a predetermined range (the intensity ratio P1 calculated by the above formula (X1) is 0.005 to 0.300). In the manufacturing method of the present invention having the above-mentioned features, the intensity ratio P1 calculated by the formula (X1) of the surface of the image layer formed in step 4 facing the hot-melt adhesive layer is 0.005 or more. This allows the resulting transfer sheet to exhibit the flexibility required for transfer during transfer and to be easily transferred while conforming to the unevenness of the transfer target object. Furthermore, by subjecting the image layer in the transfer target object to a curing treatment such as light irradiation after transfer to polymerize the remaining carbon double bonds, the image layer in the transfer target object is hardened, resulting in stronger adhesion of the transfer target object. As a result, it is believed that the transferred object has excellent friction resistance. Typically, when attempting to transfer a transfer layer having a decorative layer with excellent smoothness, such as a metal foil or a metal vapor deposition layer (the transfer layer refers to a layer formed on a temporary support and transferred to the transfer target object; the transfer layer includes the decorative layer, image layer, and hot-melt adhesive layer), to an uneven substrate such as fabric, the transfer layer has difficulty conforming to the uneven substrate, resulting in no physical anchoring effect between the transfer layer and the uneven substrate, and the resulting transfer target object tends to have poor friction resistance. In contrast, the transfer sheet obtained by the manufacturing method of the present invention, due to the above-mentioned mechanism of action, easily follows the unevenness of the transferred object even if it has a decorative layer such as a metal foil or a metal vapor deposition layer, and a physical anchor effect easily works between the transfer layer and the uneven substrate. Furthermore, by subjecting the image layer in the transferred object to a curing treatment such as light irradiation after transfer to polymerize the remaining carbon double bonds, the transferred object can be more firmly adhered to the uneven substrate. Furthermore, since the intensity ratio P1 calculated by formula (X1) of the surface of the image layer formed in step 4 on the side of the hot melt adhesive layer is 0.300 or less, the image layer does not become too flexible, and it is presumed that the resulting transfer sheet has excellent blocking resistance. Furthermore, since the image layer is formed by carrying out a curing treatment of the coating film after the formation of the hot-melt adhesive layer, the adhesion between the hot-melt adhesive layer and the image layer is excellent, and this is also presumably one of the factors that contribute to the excellent friction resistance of the transferred product after transfer.

[0020] Hereinafter, the better blocking resistance of the transfer sheet obtained by the manufacturing method of the present invention and / or the better friction fastness of the transferred product after transfer will also be referred to as "the better effect of the present invention."

[0021] [Configuration of transfer sheet] First, the structure of the transfer sheet obtainable by the production method of the present invention will be described below.

[0022] FIG. 1 is a cross-sectional view showing an example of an embodiment of a transfer sheet. The transfer sheet 10 shown in FIG. 1 has a configuration in which a temporary support 12 is laminated on the temporary support 12 with a transfer layer 20 made up of a decorative layer 14, an image layer 16, and a hot-melt adhesive layer 18 laminated in this order. Although the transfer sheet 10 shown in FIG. 1 has the decorative layer 14 disposed over the entire main surface of the temporary support 12, the decorative layer 14 may be disposed over only a portion of the main surface of the temporary support 12. Furthermore, the transfer sheet 10 shown in FIG. 1 has the image layer 16 partially disposed on the decorative layer 14, but the image layer 16 may be disposed over the entire surface of the decorative layer 14. In addition, the transfer sheet 10 shown in Figure 1 is in a form in which the hot melt adhesive layer 18 is arranged over the entire surface of the image layer 16, but the hot melt adhesive layer 18 may be arranged on only a part of the image layer 16, or may be arranged so as to cover the image layer 16.

[0023] Each step of the production method of the present invention will be described below.

[0024] [Process 1] Step 1 is a step of forming a decorative layer on a temporary support. <Temporary support> The temporary support is a member that supports a transfer layer, such as an image layer, that is disposed on the temporary support. As will be described later, when the transfer sheet is used, the transfer layer is transferred to an object to be transferred, and then the temporary support is peeled off from the transfer sheet. Examples of the temporary support include paper, leather, cloth, and resin film, and among these, resin film is more preferred. Examples of resins that can be used to make the resin film include cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, acrylic resin, chlorinated polyolefin resin, polyethersulfone resin, polyester (e.g., polyethylene terephthalate (PET) and polyethylene naphthalate), nylon, polyethylene, polystyrene, polypropylene, polycycloolefin resin, polyvinyl chloride, polyamide, polyimide, polycarbonate, polyethersulfone, polyetheretherketone, polyvinyl acetal, and polyurethane. The resin film may contain only one of these resins, or may be a mixture of two or more of them.

[0025] The temporary support may have a configuration including a resin film and other layers, such as an easy-adhesion layer, an antistatic layer, and an antifouling layer, disposed on the resin film. Furthermore, in order to improve adhesion between the temporary support and the transfer layer formed on the temporary support, the surface of the temporary support that comes into contact with the transfer layer may be surface-modified by UV (ultraviolet) irradiation, corona discharge, plasma, or the like. The temporary support may also contain various additives such as UV (ultraviolet) absorbers, matting agent particles, plasticizers, deterioration inhibitors, and release agents.

[0026] The thickness of the temporary support is not particularly limited, and is, for example, from 1 μm to 10 mm. From the viewpoint of thinning and ease of handling, the thickness of the temporary support is preferably from 10 to 200 μm, more preferably from 20 to 200 μm.

[0027] <Decorative layer> The decorative layer is a layer for further improving the design of the image layer, and is preferably a layer having excellent gloss. As the decorative layer, a layer (reflective layer) having the function of reflecting at least a portion of incident light, such as a metal layer, a cholesteric liquid crystal layer, or a dielectric multilayer film, is preferred, with a metal layer or a cholesteric liquid crystal layer being preferred, and a metal foil or a metal vapor deposition layer being more preferred.

[0028] (metal layer) Examples of the metal layer include thin metal films formed by foil transfer, vapor deposition, sputtering, or other techniques using metals such as aluminum, indium, brass, chromium, gold, silver, and copper, and coatings formed from coating compositions containing metal pigments consisting of scaly foil pieces of aluminum flakes, indium flakes, brass, etc. Among these, metal layers are preferably metal foils or metal vapor deposition layers.

[0029] (cholesteric liquid crystal layer) The cholesteric liquid crystal layer means a layer in which a cholesteric liquid crystal phase is fixed. The cholesteric liquid crystal layer may be any layer in which the orientation of a liquid crystal compound in a cholesteric liquid crystal phase is maintained. For example, the cholesteric liquid crystal layer is preferably a layer obtained by aligning a polymerizable liquid crystal compound in a cholesteric liquid crystal phase, polymerizing it by ultraviolet irradiation, heating, or the like, and curing it. The cholesteric liquid crystal layer is preferably a layer that has no fluidity and has been changed to a state in which the orientation state does not change due to an external field or external force. Note that it is sufficient for the cholesteric liquid crystal layer to maintain the optical properties of the cholesteric liquid crystal phase within the layer, and the liquid crystal compound in the layer may no longer exhibit liquid crystallinity. For example, the polymerizable liquid crystal compound may be polymerized by a curing reaction and no longer have liquid crystallinity.

[0030] Cholesteric liquid crystal phases are known to exhibit selective reflectivity at specific wavelengths. In a typical cholesteric liquid crystal phase, the central wavelength of selective reflection (selective reflection central wavelength) λ depends on the helical pitch P in the cholesteric liquid crystal phase and follows the relationship between the average refractive index n of the cholesteric liquid crystal phase and λ = n × P. Therefore, the selective reflection central wavelength can be adjusted by adjusting this helical pitch. The longer the helical pitch, the longer the selective reflection central wavelength of the cholesteric liquid crystal phase becomes. The helical pitch is one pitch (helical period) of the helical structure of the cholesteric liquid crystal phase, or in other words, one turn of the helix. In other words, the helical pitch is the length of the helical axis direction in which the director (the long axis direction in the case of rod-shaped liquid crystals) of the liquid crystal compound that constitutes the cholesteric liquid crystal phase rotates 360°.

[0031] The helical pitch of the cholesteric liquid crystal phase depends on the type and concentration of the chiral dopant used together with the liquid crystal compound when forming the cholesteric liquid crystal layer. Therefore, by adjusting these factors, a desired helical pitch can be obtained. The adjustment of the pitch is described in detail in Fujifilm Research Report No. 50 (2005), pp. 60-63. The helical sense and pitch can be measured using the methods described in "Introduction to Liquid Crystal Chemistry Experiments" edited by the Japanese Liquid Crystal Society, published by Sigma Publishing in 2007, p. 46, and "Liquid Crystal Handbook" edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen, p. 196.

[0032] Cholesteric liquid crystal phases also exhibit selective reflection for either left- or right-handed circularly polarized light at specific wavelengths. Whether the reflected light is right-handed or left-handed circularly polarized depends on the helical twist (sense) of the cholesteric liquid crystal phase. When the helical twist direction of the cholesteric liquid crystal layer is right-handed, right-handed circularly polarized light is reflected, and when the helical twist direction is left-handed, left-handed circularly polarized light is reflected. The direction of rotation of the cholesteric liquid crystal phase can be adjusted by the type of liquid crystal compound forming the cholesteric liquid crystal layer and / or the type of chiral agent added.

[0033] The color of the cholesteric liquid crystal layer and the degree of change in color of the cholesteric liquid crystal layer depending on the observation angle can be appropriately adjusted by the length of the helical pitch in the thickness direction of the cholesteric liquid crystal layer, the refractive index of the cholesteric liquid crystal layer, the thickness of the cholesteric liquid crystal layer, etc. The decorative layer may have a configuration including a plurality of cholesteric liquid crystal layers. When the transfer sheet has a plurality of cholesteric liquid crystal layers, the helical pitches of the cholesteric liquid crystal layers may be different from each other. Furthermore, the helical pitch of the cholesteric liquid crystal layers may be configured to change in a gradational manner.

[0034] The method for forming the cholesteric liquid crystal layer is not particularly limited, and any known method can be used. For example, the cholesteric liquid crystal layer can be formed using a liquid crystal composition containing a liquid crystal compound and a chiral agent. As the cholesteric liquid crystal layer as the decorative layer, for example, the cholesteric liquid crystal layers described in International Publication No. 2020 / 203318 and Japanese Patent Application Laid-Open No. 2024-063719 can be referred to.

[0035] The decorative layer may have either a single layer structure or a multi-layer structure. The thickness of the decorative layer is not particularly limited, and the lower limit is, for example, 0.001 μm or more. The lower limit is preferably 0.01 μm or more, and more preferably 0.1 μm or more. The upper limit is, for example, 300 μm or less, and more preferably 100 μm or less.

[0036] <Method for forming decorative layer> The decorative layer can be formed by any known method depending on the type of decorative layer to be formed.

[0037] [Process 2] Step 2 is a step of applying a composition containing a (meth)acrylate compound (hereinafter also referred to as "ink") onto the decorative layer to form a coating film. In the following, first, the composition used in step 2 will be explained, and then the procedure for step 2 will be explained.

[0038] <Composition> The composition contains one or more compounds ((meth)acrylate compounds) selected from the group consisting of acrylate compounds and methacrylate compounds. The composition is preferably an ink composition containing a (meth)acrylate compound, a photopolymerization initiator, and an organic solvent, and more preferably a composition containing a (meth)acrylate compound, a photopolymerization initiator, an organic solvent, and a colorant. Components that may be contained in the composition are described in detail below.

[0039] ((Meth)acrylate compounds) The composition includes a (meth)acrylate compound. In the (meth)acrylate compound, the number of (meth)acryloyloxy groups is not particularly limited and may be, for example, 1 to 6, and from the viewpoint of providing the image layer with better flexibility and alcohol resistance, 2 to 6 is preferred, 2 to 4 is more preferred, and 2 to 3 is even more preferred. The (meth)acrylate compound may be a monomer, an oligomer, or a mixture thereof.

[0040] Examples of the monofunctional (meth)acrylate compound (a compound selected from the group consisting of a monofunctional acrylate compound and a monofunctional methacrylate compound) include phenoxyethyl acrylate (PEA), cyclic TMP formal acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), 2-(2-ethoxyethoxy)ethyl acrylate, octadecyl acrylate (ODA), tridecyl acrylate (TDA), isodecyl acrylate (IDA), and lauryl acrylate, with PEA being preferred.

[0041] Examples of polyfunctional (meth)acrylate compounds (compounds selected from the group consisting of polyfunctional acrylate compounds and polyfunctional methacrylate compounds) include hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate (e.g., tetraethylene glycol diacrylate), dipropylene glycol diacrylate, tri(propylene glycol) triacrylate, neopentyl glycol diacrylate, bis(pentaerythritol)hexaacrylate, and acrylate esters of ethoxylated or propoxylated glycols and polyols (e.g., propoxylated neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, and mixtures thereof). Specific examples of polyfunctional (meth)acrylate compounds include hexanediol dimethacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, and 1,4-butanediol dimethacrylate.

[0042] The (meth)acrylate compound is preferably an oligomer, since this provides better adhesion and flexibility to the image. Examples of the (meth)acrylate compound include urethane (meth)acrylate, bisphenol A epoxy (meth)acrylate, and epoxy novolac (meth)acrylate, and among these, urethane (meth)acrylate is preferred.

[0043] Examples of urethane (meth)acrylates include polyether-based urethane (meth)acrylates having a polyether skeleton, polyester-based urethane (meth)acrylates having a polyester skeleton, and polycarbonate-based (meth)urethane acrylate oligomers having a polycarbonate skeleton, with polyether-based urethane (meth)acrylates being preferred. Moreover, the urethane (meth)acrylate is preferably an aliphatic (meth)urethane acrylate.

[0044] The urethane (meth)acrylate is preferably a polyether-based urethane (meth)acrylate, as it provides better effects for the present invention, and more preferably a compound represented by the following formula (1).

[0045] [ka]

[0046] In formula (1), R a represents a hydrogen atom or a methyl group. R1 to R4 each independently represent a divalent linking group. Examples of the divalent linking group represented by R1 to R4 include hydrocarbon groups in which at least one -CH2- group may be substituted with -CO- and -O-. Examples of hydrocarbon groups in which at least one -CH2- group may be substituted with -CO- and -O- include alkylene groups in which at least one -CH2- group may be substituted with -CO- and -O-, and arylene groups. In terms of achieving better effects of the present invention, alkylene groups (e.g., hexamethylene groups) are preferred. The alkylene group may be linear, branched, or cyclic, but is preferably linear or branched, as this makes it easier to achieve the effects of the present invention. The number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 4 to 8. Examples of the arylene group include a phenylene group. The hydrocarbon group may further have a substituent. n represents an integer of 1 to 10,000, preferably 5 to 2,000, and more preferably 10 to 200. However, in formula (1), it is preferable that at least one of R3 and R4 each independently represents an alkylene group (preferably a linear or branched alkylene group), and that both R3 and R4 each independently represent an alkylene group (preferably a linear or branched alkylene group).

[0047] The weight average molecular weight (Mw) of the (meth)acrylate compound is preferably 1,000 to 30,000, more preferably 1,500 to 15,000, even more preferably 2,000 to 10,000, and particularly preferably 2,000 to 7,000, from the viewpoints of optimizing the viscosity of the composition and improving the ejection stability when the composition is applied to inkjet printing. The number average molecular weight (Mn) of the (meth)acrylate compound is preferably 1,000 to 30,000, more preferably 1,500 to 15,000, even more preferably 2,000 to 10,000, and particularly preferably 2,000 to 7,000, from the viewpoints of optimizing the viscosity of the composition and improving the ejection stability when the composition is applied to inkjet printing.

[0048] Commercially available (meth)acrylate compounds include oligomers such as CN996 (difunctional oligomer, urethane acrylate, weight average molecular weight (Mw)=2850) from Sartomer Corporation, UA-122P (difunctional oligomer, urethane acrylate, Mw=1100) from Shin-Nakamura Chemical Co., Ltd., and Shikoh (registered trademark) UV-6630B (difunctional oligomer, urethane acrylate, Mw=3000), Shikoh (registered trademark) UV-3310B (difunctional oligomer, urethane acrylate, Mw=5000), and Shikoh (registered trademark) UV-7630B (hexafunctional oligomer, urethane acrylate, Mw=2200) from The Nippon Synthetic Chemical Industry Co., Ltd.

[0049] The composition preferably contains an oligomeric (meth)acrylate compound, since this provides better image flexibility, alcohol resistance, and adhesion of the image layer. When the composition contains an oligomeric (meth)acrylate compound, the content of the oligomeric (meth)acrylate compound is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total solid content of the composition. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less.

[0050] In addition, the total content of monofunctional (meth)acrylate compounds and bifunctional (meth)acrylate compounds (compounds selected from the group consisting of bifunctional acrylate compounds and bifunctional methacrylate compounds) in the composition is preferably 35% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the composition, in order to obtain a superior texture of the transferred product obtained by transferring the transfer sheet. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less.

[0051] The composition preferably contains one or more monofunctional (meth)acrylate compounds and one or more bifunctional (meth)acrylate compounds, and the total content of the monofunctional (meth)acrylate compounds and the bifunctional (meth)acrylate compounds is 50% by mass or more relative to the total mass of the (meth)acrylate compounds, in order to prevent the network structure of the image layer from becoming too dense and to achieve better image flexibility and image adhesion.

[0052] The content of (meth)acrylate compounds having a weight-average molecular weight of less than 1000 in the composition is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total mass of the (meth)acrylate compounds.

[0053] (Polymerizable compounds other than (meth)acrylate compounds) The composition may contain a polymerizable compound other than the (meth)acrylate compound (hereinafter also referred to as "other polymerizable compound"). Other polymerizable compounds include vinyl ether monomers such as triethylene glycol divinyl ether, diethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and ethylene glycol monovinyl ether; N-vinyl amides such as N-vinylcaprolactam (NVC) and N-vinylpyrrolidone (NVP); and N-(meth)acryloylamines such as N-acryloylmorpholine (ACMO).

[0054] The content of the (meth)acrylate compound in the composition is preferably from 80 to 100% by mass, more preferably from 90 to 100% by mass, and even more preferably from 95 to 100% by mass, based on the total mass of the polymerizable compounds.

[0055] The content of the polymerizable compound in the composition is preferably 50 to 95 mass %, more preferably 50 to 90 mass %, and even more preferably 60 to 90 mass %, based on the total solid content of the composition. The content of the (meth)acrylate compound in the composition is preferably 50 to 95 mass %, more preferably 50 to 90 mass %, and even more preferably 60 to 90 mass %, based on the total solid content of the composition.

[0056] (coloring agent) The composition preferably includes a colorant. The colorant is not particularly limited and may be either a pigment or a dye, but from the viewpoint of light resistance, a pigment is preferred. The pigment is not particularly limited and can be appropriately selected depending on the purpose. The pigment is preferably dispersed in the liquid medium of the composition.

[0057] The pigment may be either an organic pigment or an inorganic pigment, or an organic pigment and an inorganic pigment may be used in combination. Examples of organic pigments include polycyclic pigments such as azo lakes, azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye lakes such as basic dye lakes and acid dye lakes; nitro pigments, nitroso pigments, aniline black; and daylight fluorescent pigments. Examples of inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. As the colorant, for example, organic or inorganic pigments having the following numbers as listed in the Color Index can be used. Examples of blue or cyan pigments include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60, Green pigments include, for example, Pigment Green 7, 26, 36, 50, Examples of red or magenta pigments include Pigment Red 3, 5, 9, 19, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, and 257; Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; and Pigment Orange. 13, 16, 20, 36, Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, Examples of black pigments include Pigment Black 7, 28, 26, Examples of white pigments include Pigment White 6, 18, and 21.

[0058] Pigments not listed in the Color Index can also be used appropriately depending on the purpose. For example, pigments whose surfaces have been treated with surfactants or polymer dispersants, and grafted carbon can also be used.

[0059] Examples of polymer dispersants include polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, and polyether esters. The polymer dispersant may be a commercially available product, such as DisperBYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-164, DisperBYK-166, DisperBYK-167, DisperBYK-168, DisperBYK-169, DisperBYK-200, DisperBYK-201, DisperBYK-202, DisperBYK-203, DisperBYK-204, DisperBYK-205, DisperBYK-206, DisperBYK-207, DisperBYK-208, DisperBYK-209, DisperBYK-210, DisperBYK-211, DisperBYK-212, DisperBYK-213, DisperBYK-214, DisperBYK-215, DisperBYK-216, DisperBYK-217, DisperBYK-218, DisperBYK-219, DisperBYK-220, DisperBYK-221, DisperBYK-222, DisperBYK-223, DisperBYK-224, DisperBYK-225, DisperBYK-226, DisperBYK-227, DisperBYK-228, DisperBYK-229, DisperBYK-230, DisperBYK-231, DisperBYK-232, DisperBYK-233, DisperBYK-234, DisperBYK-235, DisperBYK-236, DisperBYK-237, DisperBYK-238, DisperBYK-239, DisperBYK-240, DisperBYK-241, Disper YK-170, DisperBYK-171, DisperBYK-174, and DisperBYK-182 (all manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA4080, EFKA5010, EFKA5207, EFKA5244, EFKA6745, EFKA6750, EFKA7414, EFKA745, EFKA7462, EFKA7500, EFKA7570, EFKA7575 and EFKA7580 (all manufactured by EFKA Additive Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, and Disperse Aid 9100 (manufactured by San Nopco Ltd.), and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, and 36000 , 39000, 41000, and 71000, and other various Solsperse dispersants (manufactured by Avecia); ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, and P-123 (manufactured by ADEKA Corporation), IONET (registered trademark) S-20 (manufactured by Sanyo Chemical Industries, Ltd.), and "DISPARLON KS-860, 873SN, 874 (polymer dispersant), #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester type)" manufactured by Kusumoto Chemicals Co., Ltd. In the pigment surface-treated with a polymer dispersant, the content ratio of the polymer dispersant to the pigment (polymer dispersant:pigment) is preferably 1:1 to 1:10, more preferably 1:1 to 1:5, and even more preferably 1:2 to 1:3.

[0060] Commercially available colorants may be used, such as Paliotol (BASF), Cinquasia and Irgalite (both Ciba Speciality Chemicals), and Hostaperm (Clariant UK).

[0061] Among the above colorants, preferred cyan pigments include phthalocyanine pigments such as Phthalocyanine Blue 15:4; preferred yellow pigments include azo pigments such as Pigment Yellow 120, Pigment Yellow 151, and Pigment Yellow 155; preferred magenta pigments include quinacridone pigments such as Pigment Violet 19 and mixed crystal quinacridones such as Cinquasia MAGENTA L4540; and preferred black pigments include carbon black pigments such as Pigment Black 7.

[0062] The volume average particle diameter of the colorant is not particularly limited, but is preferably less than 8 μm, more preferably less than 5 μm, even more preferably less than 1 μm, and particularly preferably less than 0.5 μm, in order to provide superior jetting properties for the composition. The lower limit of the volume average particle diameter of the colorant is not particularly limited, but is preferably 0.001 μm or more, more preferably 0.01 μm or more, in order to provide superior coloring properties and lightfastness. The volume average particle diameter can be measured using a laser diffraction particle size analyzer (e.g., a Mastersizer 2000 manufactured by Malvern or a laser diffraction / scattering particle size analyzer LA-920 manufactured by Horiba, Ltd.).

[0063] The lower limit of the colorant content is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 12% by mass or less, based on the total solid content of the composition.

[0064] (Photopolymerization initiator) The composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include radical photopolymerization initiators such as benzophenone, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, isopropyl thioxanthone, benzyl dimethyl ketal, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide. Commercially available radical photopolymerization initiators include IRGACURE (registered trademark), Darocur (registered trademark), and LUCIRIN (registered trademark) (all manufactured by BASF). The content of the photopolymerization initiator in the composition is preferably from 1 to 20% by mass, more preferably from 1 to 15% by mass, based on the total solid content of the composition.

[0065] (organic solvent) The composition preferably contains an organic solvent. The organic solvent is liquid at ambient temperature and functions as a dispersion medium or solvent for the components contained in the composition. The organic solvent is not particularly limited and can be selected from any organic solvent commonly used in the printing industry.

[0066] The boiling point of the organic solvent is preferably 75 to 300°C, more preferably 90 to 280°C, even more preferably 100 to 260°C, and particularly preferably 120 to 260°C. The boiling point of the organic solvent can be measured using a known method. For example, it can be measured in accordance with JIS K2254. When the composition contains multiple organic solvents, the boiling points of the organic solvents are calculated by averaging the products of the proportion of each organic solvent in the total organic solvent content (% by mass / 100) and the boiling points of each organic solvent.

[0067] Organic solvents include, for example, glycol ethers, glycol ether esters, alcohols, ketones, esters, and pyrrolidones. Glycol ethers include, for example, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, and triethylene glycol monobutyl ether. An example of the ketone is methyl ethyl ketone. Esters include, for example, 3-methoxybutyl acetate and γ-butyrolactone.

[0068] Of these, the organic solvent is preferably diethylene glycol diethyl ether, ethylene glycol monomethyl ether, 3-methoxybutyl acetate, or γ-butyrolactone.

[0069] The content of the organic solvent in the composition is preferably from 20 to 90% by mass, more preferably from 30 to 85% by mass, and even more preferably from 40 to 80% by mass, based on the total mass of the composition.

[0070] (Other additives) The composition may further contain other ingredients in addition to the above ingredients. Examples of other components include surfactants, polymers, acrylic-modified polyorganosiloxanes, polymerization inhibitors, sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and basic compounds.

[0071] <Surfactants> The composition preferably contains a surfactant to provide stable ejection properties for a long period of time. Examples of surfactants include those described in JP-A-62-173463 and JP-A-62-183457. Specific examples of surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene-polyoxypropylene block copolymers; and cationic surfactants such as alkylamine salts and quaternary ammonium salts. The content of the surfactant in the composition is appropriately selected depending on the purpose of use, but is preferably 0.0001 to 1% by mass based on the total solid content of the composition.

[0072] "polymer" The composition may include a polymer. When the composition contains a polymer, the polymer functions as a binder that holds the components contained in the composition together. Preferably, the polymer does not contain a polymerizable group. Specific examples of polymers include epoxy resins, polyesters, vinyl resins, acrylic resins, and methacrylic resins. Examples of vinyl resins include vinyl chloride, vinyl acetate, and copolymers of vinyl chloride and vinyl acetate. Examples of acrylic resins and methacrylic resins include copolymers of methyl methacrylate and n-butyl methacrylate. Commercially available polymers may be used. Examples of commercially available polymers include VINNOL (registered trademark) E15 / 45 (a copolymer of vinyl chloride and vinyl acetate, weight average molecular weight (Mw) = 50,000) from Wacker Chemie AG, and Elvacite 2013 (a copolymer of methyl methacrylate and n-butyl methacrylate, Mw = 34,000), Elvacite 2014 (a copolymer of methyl methacrylate and n-butyl methacrylate, Mw = 119,000), and Elvacite 4099 (a copolymer of methyl methacrylate and n-butyl methacrylate, Mw = 15,000) from Lucite International.

[0073] The weight average molecular weight of the polymer is preferably from 10,000 to 150,000, more preferably from 15,000 to 120,000, and even more preferably from 20,000 to 100,000, in that it satisfactorily exhibits a binder function and provides excellent discharge stability.

[0074] When the composition contains a polymer, the content of the polymer in the composition is preferably 2% by mass or more, more preferably 2 to 10% by mass, and even more preferably 5 to 7% by mass, relative to the total mass of the composition, in order to favorably exhibit the binder function and achieve better discharge stability.

[0075] Acrylic-modified polyorganosiloxane The composition also preferably contains an acrylic-modified polyorganosiloxane having a weight average molecular weight of 20,000 or more and 400,000 or less. Preferred aspects and specific examples of the acrylic-modified polyorganosiloxane are the same as those described in WO 2017 / 104845 (paragraphs 0122 to 0124).

[0076] (Physical properties of the composition) The surface tension of the composition is preferably 20 to 40 mN / m, more preferably 22 to 30 mN / m, and even more preferably 25 to 30 mN / m at 25° C. The surface tension can be measured in an environment at a temperature of 25° C. using an Automatic Surface Tensiometer CBVP-Z (Kyowa Interface Science Co., Ltd.).

[0077] The viscosity of the composition at 25°C is preferably 200 mPa·s or less, more preferably 100 mPa·s or less, even more preferably 25 mPa·s or less, and particularly preferably 10 mPa·s or less. The viscosity of the composition at 25°C is preferably 2 mPa·s or more, more preferably 4 mPa·s or more, and even more preferably 5 mPa·s or more. The viscosity of the composition is a value measured under conditions of 25°C (±1°C) using a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO., LTD.).

[0078] <Coating film formation method> (Method of applying composition (ink)) The composition can be applied to the decorative layer to form a coating film by known methods such as coating, inkjet recording, and dipping. Examples of the coating method include a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, and a reverse roll coater.

[0079] There are no particular limitations on the ink ejection method used in inkjet recording, and any of the well-known methods may be used, such as a charge control method that uses electrostatic attraction to eject ink, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezoelectric element, an acoustic inkjet method that converts an electric signal into an acoustic beam and irradiates the ink with it, thereby ejecting the ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method that heats the ink to form bubbles and uses the resulting pressure.

[0080] As the inkjet recording method, the method described in JP-A-54-059936 is particularly suitable, in which ink subjected to the action of thermal energy undergoes a sudden change in volume, and the ink is ejected from the nozzles by the force caused by this state change. As the inkjet recording method, the method described in paragraphs

[0093] to

[0105] of JP-A-2003-306623 can also be applied.

[0081] When applying a composition (ink) onto the decorative layer, it is preferable to use an inkjet recording method in which ink is ejected from the nozzles of an inkjet head.

[0082] Inkjet head methods include the shuttle method, in which a short serial head is scanned across the width of the recording medium to perform recording, and the line method, which uses a line head in which recording elements are arranged to cover the entire area of ​​one side of the recording medium.

[0083] The line method makes it possible to record an image over the entire surface of a recording medium by scanning the recording medium in a direction intersecting the arrangement direction of the recording elements. The line method does not require a transport system such as a carriage that scans a short head, as in the shuttle method. Furthermore, compared to the shuttle method, the line method does not require complex scanning control of the carriage movement and the recording medium, and only the recording medium moves. Therefore, the line method achieves faster image recording than the shuttle method.

[0084] The composition (ink) is preferably applied using an inkjet head with a resolution of 300 dpi or higher. Here, dpi stands for dots per inch, and 1 inch is 2.54 cm. The resolution is more preferably 600 dpi or higher, and even more preferably 800 dpi or higher.

[0085] The amount of droplets of the composition (ink) ejected from the nozzles of the inkjet head is preferably 1 to 10 pL (picoliters), more preferably 1.5 to 6 pL, from the viewpoint of obtaining a high-resolution image. Also, from the viewpoint of improving image unevenness and continuous gradation, it is effective to eject droplets of different amounts in combination.

[0086] The thickness of the coating film is not particularly limited, but is preferably 1 to 20 μm, more preferably 1 to 15 μm, and even more preferably 1 to 10 μm.

[0087] The amount of ink applied per unit area is 0.1 to 30 g / m 2 is preferred, and 1 to 30 g / m 2 More preferably, 3 to 25 g / m 2 More preferably, 3 to 20 g / m 2 is more preferred. The amount of ink applied is calculated using the following method. The desired dot ratio (the ratio of the area where the image is recorded to the total area calculated as a percentage) is applied to the substrate. 2An image is recorded with an area of ​​. The mass of the recording medium before and after image recording is measured, and the amount of ink applied is calculated from the mass difference. The amount of ink applied can be changed as desired by setting the dot ratio and adjusting the ink ejection amount of the device.

[0088] (heat treatment) When forming the coating film, the composition (ink) applied to the decorative layer may be heated. By heating the ink, the solvent component in the ink volatilizes, accelerating the drying of the ink. The drying method is not particularly limited, but examples include a method of heating the ink applied to the decorative layer using a heating device (e.g., a hairdryer, a hot plate, an infrared irradiation device, etc.), and a method of heating the ink by preheating the recording medium (temporary support with a decorative layer) onto which the ink will be applied, and then applying the ink onto the heated recording medium.

[0089] Examples of the means for heating the ink and / or the recording medium include a heat drum, hot air, an infrared lamp, an oven, a heat plate, and a hot plate. The heating temperature of the ink and / or recording medium is preferably 45°C or higher, more preferably 45 to 100°C, and even more preferably 45 to 80°C. The heating time is preferably, for example, 10 seconds or more and 60 minutes or less.

[0090] [Step 3] Step 3 is a step of forming a hot melt adhesive layer on the coating film obtained in step 2. As a specific example of step 3, it is preferable to have a step of applying a hot melt adhesive onto the coating film, and a step of heating and melting the hot melt adhesive applied onto the coating film, and then cooling the molten hot melt adhesive to form a hot melt adhesive layer. Below, we will first explain the hot melt adhesive, and then explain the procedure for step 3.

[0091] <Hot melt adhesive> A hot melt adhesive is typically an adhesive that is solid at room temperature, liquefies when heated and melted, wets and spreads over the adherend, and bonds when cooled and solidifies. Hot melt adhesives typically contain thermoplastic resins or thermoplastic elastomers, such as polyurethane resins, polyester resins, polyester polyurethane resins, polyamide resins, synthetic rubbers, and polyolefin resins. The properties of the hot melt adhesive are not particularly limited, and examples include powdered hot melt adhesives, water-based hot melt adhesives in which a thermoplastic resin is dissolved or dispersed in water, and organic solvent-based hot melt adhesives in which a thermoplastic resin is dissolved or dispersed in an organic solvent.Of these, powdered hot melt adhesives are preferred because the transfer product obtained by transferring the transfer sheet has better friction resistance. As the hot melt adhesive, a known hot melt adhesive can be used. A suitable form of the resin constituting the hot melt adhesive is, for example, a polyester polyurethane resin made from hexamethylene diisocyanate (HDI), adipic acid (APA), and 1,4-butanediol (1,4-BD).

[0092] The weight average molecular weight of the resin constituting the hot melt adhesive is preferably 30,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more, in order to provide a transfer sheet with better blocking resistance. From the viewpoint of heat melting during transfer, the upper limit is preferably 350,000 or less, more preferably 300,000 or less, and even more preferably 250,000 or less. The melting temperature of the resin constituting the hot melt adhesive is, for example, preferably 200° C. or lower, more preferably 150° C. or lower, and even more preferably 90° C. or lower, from the viewpoint of improving workability during heat transfer. The lower limit of the melting temperature is, for example, preferably 40° C. or higher, more preferably 45° C. or higher, and even more preferably 50° C. or higher, from the viewpoint of improving the heat resistance of the transferred product. The recrystallization temperature (solidification temperature) of the resin constituting the hot melt adhesive is, for example, preferably 45°C or higher, more preferably 50°C or higher, in order to provide a transfer sheet with better blocking resistance. The upper limit of the recrystallization temperature is, for example, 200°C or lower. The glass transition temperature of the resin constituting the hot melt adhesive is preferably, for example, 25°C or lower, more preferably 0°C or lower, and even more preferably -10°C or lower, in order to provide a better texture for the transfer sheet. The upper limit of the glass transition temperature is, for example, 45°C. The glass transition temperature is measured as the peak temperature of tanδ (loss tangent) measured by a dynamic viscoelasticity measuring device for the resin constituting the hot melt adhesive.

[0093] <Hot melt adhesive application process> The step of applying a hot melt adhesive to the coating film can be appropriately set depending on the properties of the hot melt adhesive. For example, when the hot melt adhesive is a water-based hot melt adhesive or an organic solvent-based hot melt adhesive, the inkjet coating method is preferred. When the hot melt adhesive is a powdered hot melt adhesive, the step of applying the hot melt adhesive onto the coating film is preferably a step of spraying the hot melt adhesive from the coating film side, removing the hot melt adhesive other than on the coating film, and forming a hot melt adhesive layer on the coating film. When powdered hot melt adhesive is sprayed from the coating film side, the tackiness of the coating film makes it easy for the powdered hot melt adhesive to adhere firmly to the coating film in areas where the coating film is present. On the other hand, powdered hot melt adhesive sprayed in areas where no coating film is present (i.e., sprayed on areas other than the coating film) can be easily removed. By using the above method, a hot melt adhesive layer can be placed only on the image layer obtained by curing the coating film in step 4. Note that, as shown in Figure 1 above, if a coating film is formed on part of the decorative layer, the hot melt adhesive will be removed in areas where the coating film is not present on the decorative layer, and no hot melt adhesive layer will be formed. In order to ensure excellent friction resistance of the transferred product after transfer, the hot melt adhesive layer is preferably formed so that the area ratio of the hot melt adhesive layer to the area of ​​the image layer is 60 to 100% when the transfer sheet obtained through step 4 is viewed in plan. When the area ratio of the hot melt adhesive layer to the area of ​​the image layer is 60% or more, the transferred product obtained by transferring the transfer sheet has better friction resistance. When the area ratio of the hot melt adhesive layer to the area of ​​the image layer is 100% or less, the transferred product obtained by transferring the transfer sheet has better releasability of the image edge.

[0094] <Hot melt adhesive layer forming process> After applying the hot melt adhesive onto the coating film, the hot melt adhesive applied onto the coating film is heated and melted, and the melted hot melt adhesive is then cooled to form a hot melt adhesive layer.

[0095] Examples of means for heating the hot melt adhesive include a heat drum, hot air, an infrared lamp, an oven, a heat plate, and a hot plate. The heating temperature of the hot melt adhesive is preferably at least +3°C above the melting point of the hot melt adhesive, more preferably +5°C, and even more preferably +10°C, and the upper limit is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 90°C or lower. The heating time is preferably, for example, 5 seconds to 5 minutes. The means for cooling the molten hot melt adhesive is not particularly limited as long as it can be cooled to a temperature at which the resin constituting the hot melt adhesive recrystallizes, and examples thereof include air cooling.

[0096] [Step 4] Step 4 is a step of forming an image layer containing a (meth)acrylate resin by subjecting the coating film in the laminate obtained through step 3 to a curing treatment. By carrying out step 4, a polymerization reaction of the (meth)acrylate compound contained in the coating film progresses, and an image layer containing a (meth)acrylate resin is formed.

[0097] The curing treatment is preferably a curing treatment that allows the polymerization reaction of the (meth)acrylate compound contained in the coating film to proceed, and light irradiation treatment is more preferred. The light source used in the light irradiation treatment may be any light source capable of irradiating light at least in a wavelength range sufficient to cure the coating film, and examples of such light sources include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The peak wavelength of the irradiation light is preferably from 200 to 405 nm, more preferably from 220 to 395 nm, and even more preferably from 260 to 395 nm. The exposure dose was 300 mJ / cm 2 Super 1000mJ / cm 2 Less than 350-800mJ / cm is preferable. 2 is more preferred.

[0098] The light irradiation treatment is preferably carried out in an atmosphere with an oxygen concentration of 180,000 ppm by volume or more, since this tends to keep the remaining amount of carbon-carbon double bonds C=C in the coating film within a predetermined range. The oxygen concentration is more preferably 200,000 ppm by volume or more, and even more preferably 210,000 ppm by volume or more. The upper limit is, for example, 400,000 ppm by volume or less. The light irradiation treatment is particularly preferably carried out in the atmosphere.

[0099] When the curing treatment in step 4 is a light irradiation treatment, the amount of carbon-carbon double bonds C=C remaining in the coating film can be adjusted by appropriately setting conditions such as oxygen concentration, illuminance, irradiation time, and exposure dose. The weight average molecular weight of the (meth)acrylate resin in the image layer formed through step 4 is preferably 150,000 or more, more preferably 200,000 or more, in terms of achieving better effects of the present invention. There is no particular upper limit, and a preferable upper limit is, for example, 500,000.

[0100] When the curing treatment in step 4 is a light irradiation treatment, it is preferable to perform the light irradiation from the hot-melt adhesive layer side of the laminate. That is, it is preferable to irradiate the coating film with light through the hot-melt adhesive layer. Furthermore, it is preferable that the light irradiation treatment is performed on the entire surface of the side of the laminate on which the hot-melt adhesive layer is formed.

[0101] On the surface of the image layer formed in step 4 on the side of the hot-melt adhesive layer, the remaining carbon-carbon double bonds are adjusted so that the intensity ratio P1 calculated by the above-mentioned formula (X1) is 0.005 to 0.300. The intensity ratio P1 calculated by the above-mentioned formula (X1) is preferably 0.100 to 0.300, since the effects of the present invention are more likely to be excellent. The method for measuring the intensity ratio P1 will be described below.

[0102] (Measurement of infrared absorption spectra of coating film and image layer) The infrared absorption spectrum of the coating film in the transfer sheet having the uncured image layer (coating film) obtained in step 3 is measured, and the peak intensity due to the C=O of the ester group and the peak intensity due to the carbon-carbon double bond C=C are determined. First, the transfer sheet with the uncured image layer (coating) obtained in step 3 is irradiated with an ion beam from the hot-melt adhesive layer side toward the depth direction, and the components of the transfer sheet in the depth direction are analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS). This analysis is performed until the film region of the uncured image layer (coating) is reached. (Specifically, the analysis is performed until the depth where the secondary ion intensity originating from the components of the uncured image layer (coating) begins to be observed and the secondary ion intensity originating from the components of the hot-melt adhesive layer is essentially no longer observed. Here, the secondary ion intensity originating from the components of the uncured image layer (coating) refers to the intensity of fragment ions originating from the components of the uncured image layer (coating), and the secondary ion intensity originating from the components of the hot-melt adhesive layer refers to the intensity of fragment ions originating from the components of the hot-melt adhesive layer.) The depth direction refers to the thickness direction of the coating. TOF-SIMS is specifically described in "Surface Analysis Technology Selection: Secondary Ion Mass Spectrometry" edited by the Japan Surface Science Society, published by Maruzen Co., Ltd. (1999). When analyzing the components of the transfer sheet in the depth direction using TOF-SIMS while ion sputtering, the following series of operations is repeated: first, component analysis is performed in a depth region of 1 to 2 nm, then digging further in the depth direction by 20 nm, and component analysis is performed in the next depth region of 1 to 2 nm.

[0103] The TOF-SIMS measurement is preferably carried out under the following measurement conditions. Equipment used: TRIFT V nanoTOF manufactured by ULVAC-PHI Charge compensation: Use of low-speed electron gun Primary ion: Bi3+ Measurement mode: bunching mode (high mass resolution mode) Ion beam: Ar-GCIB gun (Ar 2500 +, 20kV, 2nA, sputtering range 3mm□)

[0104] Next, the uncured image layer (coating film) excavated by the etching is subjected to infrared absorption spectroscopy to determine the peak intensity due to C═O of the ester group and the peak intensity due to the carbon-carbon double bond C═C. The infrared absorption spectrum of the uncured image layer (coating film) is measured by the single-reflection ATR method of Fourier transform infrared spectroscopy (FT-IR). Specifically, it is preferable to use an "iS5" (germanium crystal) manufactured by Thermo Fisher Scientific, with 32 accumulations and a TGS detector. In the infrared absorption spectrum of the uncured image layer (coating film) obtained under the above measurement conditions, -1 The absorbance of the peak maximum value that appears at the wavelength of 1640 cm -1 and wavelength 1780 cm -1 The straight line connecting the absorbances at wavelengths 800 to 830 cm is taken as the baseline. -1 The absorbance of the peak maximum value that appears at the wavelength of 800 cm -1 and wavelength 830 cm -1 The straight line connecting the absorbances at points 1 and 2 is taken as the baseline. ) is taken as the peak intensity derived from the carbon double bond C=C. The peak intensity derived from the C=O of the ester group and the peak intensity derived from the carbon-carbon double bond C=C, which were determined by measuring the infrared absorption spectrum of the uncured image layer (coating), were introduced into the above formula (X2) to obtain the normalized carbon-carbon double bond peak intensity Z of the uncured image layer (coating). 11 The normalized carbon-carbon double bond peak intensity Z of the uncured image layer (coating film) calculated by the formula (X2) is calculated as follows: 11 indicates the amount of carbon double bonds present in the coating film before the curing reaction is carried out.

[0105] The infrared absorption spectrum measurement of the coating film may be carried out on the coating film formed in step 2.

[0106] (Measurement of infrared absorption spectrum on the surface of the image layer facing the hot melt adhesive layer) The components in the depth direction of the transfer sheet obtained in step 4 are analyzed using TOF-SIMS while irradiating the transfer sheet from the hot-melt adhesive layer side in the depth direction, and the region of the film surface on the hot-melt adhesive layer side of the image layer is excavated (specifically, the region is excavated to a depth where the secondary ion intensity originating from the components of the image layer begins to be observed and the secondary ion intensity originating from the components of the hot-melt adhesive layer is no longer observed. Here, the secondary ion intensity originating from the components of the image layer means the intensity of fragment ions originating from the components of the image layer, and the secondary ion intensity originating from the components of the hot-melt adhesive layer means the intensity of fragment ions originating from the components of the hot-melt adhesive layer). The depth direction refers to the thickness direction of the image layer. When analyzing the components of the transfer sheet in the depth direction using TOF-SIMS while ion sputtering, the following series of operations is repeated: first, component analysis is performed in a depth region of 1 to 2 nm, then digging further in the depth direction by 20 nm, and component analysis is performed in the next depth region of 1 to 2 nm.

[0107] The TOF-SIMS measurement is preferably carried out under the following measurement conditions. Equipment used: TRIFT V nanoTOF manufactured by ULVAC-PHI Charge compensation: Use of low-speed electron gun Primary ion: Bi3+ Measurement mode: bunching mode (high mass resolution mode) Ion beam: Ar-GCIB gun (Ar 2500 +, 20kV, 2nA, sputtering range 3mm□)

[0108] Next, infrared absorption spectroscopy is performed on the surface of the image layer on the hot melt adhesive side that has been excavated by the above-mentioned etching, and the peak intensity due to the C=O of the ester group and the peak intensity due to the carbon double bond C=C are determined. The infrared absorption spectrum of the hot melt adhesive side of the image layer is measured by the single reflection ATR method of Fourier transform infrared spectroscopy (FT-IR). Specifically, it is preferable to use an "iS5" (germanium crystal) manufactured by Thermo Fisher Scientific, with 32 accumulations and a TGS detector. In the infrared absorption spectrum obtained under the above measurement conditions, the wavelength ranges from 1640 to 1780 cm -1 The absorbance of the peak maximum value that appears at the wavelength of 1640 cm -1 and wavelength 1780 cm -1 The straight line connecting the absorbances at wavelengths 800 to 830 cm is taken as the baseline. -1 The absorbance of the peak maximum value that appears at the wavelength of 800 cm -1 and wavelength 830 cm -1 The straight line connecting the absorbances at points 1 and 2 is taken as the baseline. ) is taken as the peak intensity derived from the carbon double bond C=C. The peak intensity due to C=O of the ester group and the peak intensity due to C=C of the carbon double bond, which were obtained by infrared absorption spectroscopy of the surface of the image layer facing the hot melt adhesive, were introduced into the above formula (X3) to obtain the normalized carbon double bond peak intensity Z of the surface of the image layer facing the hot melt adhesive. 12 The normalized carbon-double bond peak intensity Z of the surface of the image layer formed in step 4 on the side of the hot-melt adhesive layer is calculated by the above-mentioned formula (X3). 12 indicates the content of carbon double bonds in the image layer.

[0109] The normalized carbon-double bond peak intensity Z of the uncured image layer (coating film) formed in step 3 obtained by the above method 11 , and the normalized carbon-double bond peak intensity Z of the surface of the image layer formed in step 4 on the side of the hot-melt adhesive layer. 12 The value of is introduced into the formula (X1) to obtain the peak intensity ratio P1.

[0110] [Transfer Method] The transfer sheet obtained by the production method of the present invention can be suitably used for textile printing of fabrics. Examples of fiber types in the fabric include synthetic fibers such as nylon, polyester, and acrylonitrile; semi-synthetic fibers such as acetate and rayon; natural fibers such as cotton, silk, and wool; and mixed fibers consisting of two or more types selected from the group consisting of synthetic fibers, semi-synthetic fibers, and natural fibers.

[0111] The type of fiber in the fabric is preferably cellulose fiber, more preferably cotton. Examples of the fabric include woven fabric, knitted fabric, nonwoven fabric, etc. The fabric may be a fabric for fabric products.

[0112] Examples of fabric products include clothing (for example, T-shirts, sweatshirts, jerseys, pants, sweatsuits, dresses, blouses, etc.), bedding, and handkerchiefs.

[0113] <Transfer process> Below, an example of an embodiment of the process for transferring the transfer layer of the transfer sheet obtained by the manufacturing method of the present invention to fabric will be explained, taking the process for transferring the transfer layer 20 of the transfer sheet 10 shown in Figure 1 described above to fabric as an example. First, the transfer sheet 10 and the fabric are overlapped so that the surface of the transfer sheet 10 facing the hot melt adhesive layer 18 contacts the fabric to which the transfer is to be made, and the laminate of the transfer layer 20 of the transfer sheet 10 and the fabric is heated (thermocompression bonded). Next, the temporary support 12 is peeled off from the decorative layer 14 in the portion where the image layer 14 is not formed (the decorative layer 14 located at the opening of the image layer 14 in FIG. 1). Then, by subjecting the transferred product after peeling the temporary support 12 and the decorative layer 14 to a curing treatment, the remaining carbon-carbon double bonds in the image layer 14 are polymerized, completely curing the image layer 14, and obtaining a transferred product. The specific steps will be explained below.

[0114] (Thermocompression bonding process) As a method for transferring the transfer layer of the transfer sheet to the fabric, for example, a method in which the transfer sheet and the fabric are superimposed with the transfer layer and the fabric in contact with each other, and then heated, can be mentioned. The heating temperature is preferably, for example, 100 to 200°C. The heating time is preferably, for example, 20 seconds to 5 minutes.

[0115] A commercially available heat press can be used for the transfer, such as the AF-54TEN automatic tabletop flat press (manufactured by Asahi Textile Machinery Co., Ltd.) and the Zeus PZ-130110D (manufactured by Europort).

[0116] (hardening process) Next, it is preferable to subject the transferred product after the heat treatment to a curing treatment, which promotes a polymerization reaction of the remaining carbon-carbon double bonds in the image layer, further improving the strength of the image layer and the adhesion between the transfer target and the transfer layer, resulting in excellent abrasion resistance of the resulting transferred product.

[0117] The curing treatment is preferably a curing treatment that can cause a polymerization reaction of the residual carbon-carbon double bonds contained in the image layer, and is more preferably a light irradiation treatment. Examples of light sources for the light irradiation treatment include various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The peak wavelength of the irradiation light is preferably from 200 to 405 nm, more preferably from 220 to 395 nm, and even more preferably from 260 to 395 nm. The exposure dose is 500 to 5,000 mJ / cm 2 is preferred, and 1,000 to 1,500 mJ / cm 2 is more preferable

[0118] The light irradiation treatment is preferably carried out in a low-oxygen atmosphere with an oxygen concentration of 1,000 ppm by volume or less so as not to inhibit polymerization. The oxygen concentration is more preferably 500 ppm by volume or less, and even more preferably 100 ppm by volume or less. The lower limit is, for example, 10 ppm by volume or more.

[0119] [Transfer sheet] The transfer sheet of the present invention is A transfer sheet obtained by the manufacturing method of the present invention, A transfer sheet having a temporary support, a decorative layer, an image layer, and a hot-melt adhesive layer in this order, the image layer contains one or more resins selected from the group consisting of acrylate resins and methacrylate resins, The transfer sheet has an intensity ratio P2 calculated by the following formula (Y1) of 1.25 to 50.0. Formula (Y1) P2=Z 22 / Z 21 In formula (Y1), P2 represents the intensity ratio. 21 represents the normalized carbon-double bond peak intensity of the surface of the image layer facing the decorative layer, which is determined by the formula (Y2). 22 represents the normalized carbon-double bond peak intensity obtained by the formula (Y3) on the surface of the image layer facing the hot-melt adhesive layer. Formula (Y2) Z 21 =Y 21 / X 21 In formula (Y2), X 21 Y represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the decorative layer. 21represents the peak intensity derived from the carbon double bond C=C, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the decorative layer. 21 represents the normalized carbon-carbon double bond peak intensity. Formula (Y3) Z 22 =Y 22 / X 22 In formula (Y3), X 22 Y represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 22 represents the peak intensity derived from the carbon double bond C=C, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. 22 represents the normalized carbon-carbon double bond peak intensity.

[0120] The transfer sheet of the present invention has excellent blocking resistance, and the transferred product has excellent abrasion resistance after transfer. The main feature of the transfer sheet of the present invention is that the residual carbon-carbon double bonds on the surface of the image layer facing the hot-melt adhesive layer are adjusted to a predetermined range (the intensity ratio P2 calculated by the above formula (Y1) is 1.25 to 50.0). As described below, the method of transferring the image to a target object using the transfer sheet of the present invention is preferably a method in which the transfer sheet and the target object are superimposed on each other so that the hot-melt adhesive layer side of the transfer sheet contacts the target object, and then heated (thermocompression bonded) to form a laminate, and then the temporary support is peeled off, and the transferred object after the temporary support has been peeled off is subjected to a curing treatment to polymerize the remaining carbon double bonds in the image layer and completely harden the image layer. The transfer sheet of the present invention having the above-mentioned characteristics exhibits the flexibility required for transfer during transfer, and is easily transferred while conforming to the unevenness of the substrate. Furthermore, after transfer, the image layer in the transferred product can be cured by, for example, irradiating it with light to polymerize the remaining carbon-carbon double bonds, thereby hardening the image layer in the transferred product and resulting in stronger adhesion of the transferred product. As a result, it is believed that the transferred product has excellent friction resistance. Typically, when attempting to transfer a transfer layer having a smooth decorative layer such as a metal foil or a metal vapor deposition layer (the transfer layer refers to a layer formed on a temporary support and transferred to the substrate; the transfer layer includes the decorative layer, the image layer, and a hot-melt adhesive layer) to a substrate with unevenness such as fabric, the transfer layer has difficulty conforming to the substrate with unevenness, resulting in no physical anchoring effect between the transfer layer and the substrate with unevenness, and the resulting transferred product tends to have poor friction resistance. In contrast, the transfer sheet of the present invention, due to the above-mentioned mechanism of action, easily conforms to the unevenness of the transferred object even if it has a decorative layer such as a metal foil or a metal vapor deposition layer, and a physical anchor effect is easily achieved between the transfer layer and the uneven substrate. Furthermore, by subjecting the image layer in the transferred object to a curing treatment such as light irradiation after transfer to polymerize the remaining carbon double bonds, it is possible to more firmly adhere the transferred object to the uneven substrate. Furthermore, it is presumed that when the intensity ratio P2 calculated by the above formula (Y1) is 50.0 or less, the image layer does not become too flexible, and the transfer sheet has excellent blocking resistance.

[0121] Hereinafter, the fact that the transfer sheet of the present invention has better blocking resistance and / or that the transferred product has better friction fastness will also be referred to as "the effect of the present invention is better."

[0122] The construction of the transfer sheet of the present invention will be described below. The transfer sheet of the present invention can be formed by the above-mentioned method for producing a transfer sheet of the present invention. One example of an embodiment of the transfer sheet of the present invention is the transfer sheet 10 shown in Figure 1, which was explained as a transfer sheet that can be formed by the above-mentioned method for producing a transfer sheet of the present invention. Although the transfer sheet 10 shown in FIG. 1 has the decorative layer 14 disposed over the entire main surface of the temporary support 12, the decorative layer 14 may be disposed over only a portion of the main surface of the temporary support 12. Furthermore, the transfer sheet 10 shown in FIG. 1 has the image layer 16 partially disposed on the decorative layer 14, but the image layer 16 may be disposed over the entire surface of the decorative layer 14. In addition, the transfer sheet 10 shown in Figure 1 is in a form in which the hot melt adhesive layer 18 is arranged over the entire surface of the image layer 16, but the hot melt adhesive layer 18 may be arranged on only a part of the image layer 16, or may be arranged so as to cover the image layer 16.

[0123] Each component of the transfer sheet of the present invention will be described below. [Temporary support] The transfer sheet of the present invention has a temporary support. The temporary support is a member that supports a transfer layer, such as an image layer, that is placed on the temporary support. When the transfer sheet is used, the transfer layer is transferred to a transfer target, and then the temporary support is peeled off from the transfer sheet. The specific form of the temporary support is the same as the above-mentioned temporary support used in step 1 of the transfer sheet manufacturing method of the present invention, and the preferred embodiments thereof are also the same.

[0124] [Decorative layer] The transfer sheet of the present invention has a decorative layer. The decorative layer is a layer for further improving the design of the image layer, and is preferably a layer having excellent gloss. The specific form of the decorative layer is the same as that of the decorative layer used in step 1 of the method for producing a transfer sheet of the present invention, and the preferred embodiments thereof are also the same.

[0125] [Image Layer] The transfer sheet of the present invention has an image layer. The image layer contains one or more resins selected from the group consisting of (meth)acrylate resins. In the image layer, the weight average molecular weight of the (meth)acrylate resin is preferably 150,000 or more, more preferably 200,000 or more, in terms of achieving better effects of the present invention. There is no particular upper limit, and a preferable upper limit is, for example, 500,000.

[0126] The image layer is preferably a cured layer derived from a composition containing a (meth)acrylate compound (preferably a cured layer obtained by curing (photocuring) a composition containing a (meth)acrylate compound). Specific examples of the composition containing a (meth)acrylate compound include the composition (ink) containing a (meth)acrylate compound described in step 2 of the method for producing a transfer sheet of the present invention, and preferred embodiments thereof are also the same.

[0127] The image layer has an intensity ratio P2 calculated by the above formula (Y1) of 1.25 to 50.0. The image layer has the remaining carbon-carbon double bonds on the surface on the hot-melt adhesive layer side adjusted so that the intensity ratio P2 calculated by the above formula (Y1) is 1.25 to 50.0. The intensity ratio P2 calculated by the above formula (Y1) is advantageous in that it makes the effects of the present invention more likely to be excellent. It is preferably 5.00 to 50.0, and more preferably 15.0 to 48.0. The method for measuring the intensity ratio P2 will be described below.

[0128] <Measurement of infrared absorption spectrum on the surface of the image layer facing the hot melt adhesive layer> The components in the depth direction of the transfer sheet are analyzed using TOF-SIMS while irradiating the transfer sheet with an ion beam in the depth direction from the hot melt adhesive layer side, and the region of the film surface on the hot melt adhesive layer side of the image layer is excavated (specifically, the region is excavated to a depth where the secondary ion intensity derived from the components of the image layer begins to be observed and the secondary ion intensity derived from the components of the hot melt adhesive layer is no longer observed. Here, the secondary ion intensity derived from the components of the image layer means the intensity of fragment ions derived from the components of the image layer, and the secondary ion intensity derived from the components of the hot melt adhesive layer means the intensity of fragment ions derived from the components of the hot melt adhesive layer). The depth direction above refers to the thickness direction of the image layer. When analyzing the components of the transfer sheet in the depth direction using TOF-SIMS while ion sputtering, the following series of operations is repeated: first, component analysis is performed in a depth region of 1 to 2 nm, then digging further in the depth direction by 20 nm, and component analysis is performed in the next depth region of 1 to 2 nm.

[0129] The TOF-SIMS measurement is preferably carried out under the following measurement conditions. Equipment used: TRIFT V nanoTOF manufactured by ULVAC-PHI Charge compensation: Use of low-speed electron gun Primary ion: Bi3+ Measurement mode: bunching mode (high mass resolution mode) Ion beam: Ar-GCIB gun (Ar 2500 +, 20kV, 2nA, sputtering range 3mm□)

[0130] Next, infrared absorption spectroscopy is performed on the surface of the image layer on the hot melt adhesive side that has been excavated by the above-mentioned etching, and the peak intensity due to the C=O of the ester group and the peak intensity due to the carbon double bond C=C are determined. The infrared absorption spectrum of the hot melt adhesive side of the image layer is measured by the single reflection ATR method of Fourier transform infrared spectroscopy (FT-IR). Specifically, it is preferable to use an "iS5" (germanium crystal) manufactured by Thermo Fisher Scientific, with 32 accumulations and a TGS detector. In the infrared absorption spectrum obtained under the above measurement conditions, the wavelength ranges from 1640 to 1780 cm -1 The absorbance of the peak maximum value that appears at the wavelength of 1640 cm -1 and wavelength 1780 cm -1 The straight line connecting the absorbances at wavelengths 800 to 830 cm is taken as the baseline. -1 The absorbance of the peak maximum value that appears at the wavelength of 800 cm -1 and wavelength 830 cm -1 The straight line connecting the absorbances at points 1 and 2 is taken as the baseline. ) is taken as the peak intensity derived from the carbon double bond C=C. The peak intensity due to C=O of the ester group and the peak intensity due to the carbon-carbon double bond C=C, which were determined by infrared absorption spectroscopy of the surface of the image layer facing the hot melt adhesive, were introduced into the above formula (Y3) to obtain the normalized carbon-carbon double bond peak intensity Z 22 The normalized carbon-double bond peak intensity Z of the surface of the image layer on the side of the hot-melt adhesive layer, which is calculated by the above-mentioned formula (Y3), is calculated. 22 indicates the carbon-carbon double bond content on the surface of the image layer facing the hot melt adhesive.

[0131] <Measurement of infrared absorption spectrum on the surface of the image layer facing the decorative layer> The infrared absorption spectrum measurement on the surface of the image layer facing the decorative layer is also carried out in the same manner as the infrared absorption spectrum measurement on the surface of the image layer facing the hot melt adhesive layer. When measuring the infrared absorption spectrum of the surface of the image layer facing the decorative layer, the above-mentioned procedure is followed: an ion beam is irradiated in the depth direction from the hot-melt adhesive layer side of the transfer sheet while analyzing the components of the image layer in the depth direction using TOF-SIMS, and the area is excavated up to the film surface area on the decorative layer side of the image layer (specifically, the depth area just before the secondary ion intensity derived from the components of the decorative layer begins to be observed is preferred; for example, excavation is performed to a depth of 2 nm from the interface of the image layer on the decorative layer side).

[0132] Next, the infrared absorption spectrum of the surface of the image layer on the decorative layer side excavated by the above-mentioned etching is measured to determine the peak intensity due to C=O of the ester group and the peak intensity due to the carbon-carbon double bond C=C. The infrared absorption spectrum of the image layer on the decorative layer side is measured using the single-reflection ATR method of Fourier transform infrared spectroscopy (FT-IR). Specifically, it is preferable to use an "iS5" (germanium crystal) manufactured by Thermo Fisher Scientific, with 32 accumulations and a TGS detector. In the infrared absorption spectrum obtained under the above measurement conditions, the wavelength ranges from 1640 to 1780 cm -1 The absorbance of the peak maximum value that appears at the wavelength of 1640 cm -1 and wavelength 1780 cm -1 The straight line connecting the absorbances at wavelengths 800 to 830 cm is taken as the baseline. -1 The absorbance of the peak maximum value that appears at the wavelength of 800 cm -1 and wavelength 830 cm -1 The straight line connecting the absorbances at points 1 and 2 is taken as the baseline. ) is taken as the peak intensity derived from the carbon double bond C=C. The peak intensity derived from the C=O of the ester group and the peak intensity derived from the C=C carbon double bond were determined by infrared absorption spectroscopy of the surface of the image layer facing the decorative layer, and the normalized carbon double bond peak intensity Z of the surface of the image layer facing the decorative layer was calculated by inserting the peak intensity Z of the C=C carbon double bond of the ester group into the above formula (Y2). 21 The normalized carbon-double bond peak intensity Z obtained by the above-mentioned formula (Y2) on the surface of the image layer facing the decorative layer is calculated. 21indicates the carbon-carbon double bond content on the surface of the image layer facing the decorative layer. Typically, the carbon-carbon double bond content on the decorative layer side of the image layer is significantly low. The reason for this is that when a composition layer formed from a composition containing a (meth)acrylate compound is photocured to form an image layer, the oxygen concentration becomes lower in the deeper regions of the composition layer, making it difficult for radical polymerization inhibition to occur and facilitating the polymerization reaction. In other words, the polymerization reaction described above has progressed sufficiently on the decorative layer side of the image layer, resulting in a significantly low content of residual carbon-carbon double bonds.

[0133] Next, the normalized carbon-double bond peak intensity Z obtained by the above-mentioned formula (Y2) on the surface of the image layer facing the decorative layer 21 , and the normalized carbon-double bond peak intensity Z obtained by the above-mentioned formula (Y3) on the surface of the image layer facing the hot-melt adhesive layer. 22 The value of is introduced into formula (Y1) to determine the peak intensity ratio P2. The transfer sheet of the present invention is one in which the content of residual carbon-carbon double bonds on the surface of the image layer facing the hot-melt adhesive layer is adjusted based on the content of carbon-carbon double bonds on the surface of the image layer facing the decorative layer. When the intensity ratio P2 of the image layer determined by the above formula (Y1) satisfies the range of 1.25 to 50.0, the image layer has excellent blocking resistance and the transferred product has excellent abrasion fastness.

[0134] [Hot melt adhesive layer] The transfer sheet of the present invention has a hot melt adhesive layer. The hot melt adhesive layer is a layer formed from a hot melt adhesive. The hot melt adhesive layer is typically a layer formed by heating and melting a composition layer of the hot melt adhesive and then cooling the molten hot melt adhesive. Examples of the hot melt adhesive include the same hot melt adhesive as that used in step 3 of the above-described method for producing a transfer sheet of the present invention, and the preferred embodiments are also the same. Typical examples of resins constituting the hot melt adhesive layer include thermoplastic resins and thermoplastic elastomers such as polyurethane resin, polyester resin, polyester polyurethane resin, polyamide resin, synthetic rubber, and polyolefin resin. The weight average molecular weight of the resin constituting the hot melt adhesive is preferably 30,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more, in order to provide a transfer sheet with better blocking resistance. From the viewpoint of heat melting during transfer, the upper limit is preferably 350,000 or less, more preferably 300,000 or less, and even more preferably 250,000 or less.

[0135] The thickness of the hot melt adhesive layer is preferably 1 μm or more, more preferably 3 μm or more, from the viewpoint of further enhancing adhesiveness, and is, for example, 200 μm or less, more preferably 100 μm or less, from the viewpoint of providing a superior texture derived from the transfer target.

[0136] In order to ensure excellent abrasion resistance of the transferred product after transfer, the hot melt adhesive layer is preferably arranged so that the area ratio of the hot melt adhesive layer to the area of ​​the image layer is 60 to 100% when the transfer sheet is viewed from above. When the area ratio of the hot melt adhesive layer to the area of ​​the image layer is 60% or more, the abrasion resistance of the transferred product obtained by transferring the transfer sheet is superior. When the area ratio of the hot melt adhesive layer to the area of ​​the image layer is 100% or less, the peelability of the image edge of the transferred product obtained by transferring the transfer sheet is superior.

[0137] [Transfer Method] The transfer sheet of the present invention can be suitably used for printing fabrics. Examples of the fabric to which the transfer is to be made include the same fabrics as those described as the fabric to which the transfer is to be made in the transfer method using the transfer sheet obtained by the method for producing a transfer sheet of the present invention. The transfer method using the transfer sheet of the present invention is the same as the transfer method using the transfer sheet obtained by the transfer sheet manufacturing method of the present invention, and the preferred embodiments are also the same. [Example]

[0138] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0139] [Production and Evaluation of DTF Sheet of Example 1] [Preparation of pigment dispersion] The components other than the pigment shown in Table 1 below were mixed to obtain the composition shown in Table 1, and the mixture was stirred in a Silverson mixer at 2,000 to 3,000 rpm for 10 to 15 minutes to obtain a uniformly diluted dispersant. To this diluted dispersant was added each pigment in the type and amount shown in Table 1, and the mixture was further stirred in the mixer at 2,000 to 3,000 rpm for 10 to 20 minutes to obtain 500 parts of a uniform preliminary dispersion. Each of the resulting preliminary dispersions was then subjected to a dispersion treatment using a circulating bead mill (Dispermat SL-012C1) to obtain a pigment dispersion of each color. The dispersion treatment conditions were as follows: 200 parts of zirconia beads with a diameter of 0.65 mm were filled into the circulating bead mill, and the peripheral speed was set to 15 m / s. The dispersion time was set to 1 to 6 hours.

[0140] [Table 1]

[0141] Details of the components in Table 1 are as follows: PB15:4 CI Pigment Blue 15:4 (BASF, HELIOGEN BLUE D 7110F) Mixed quinacridone: BASF, CINQUASIA MAGENTA L 4540 PY120: CI Pigment Yellow 120 (Clariant, NOVOPERM YELLOW H2G) Carbon Black ··· CABOT, MOGUL E Sol32000 ··· Lubrizol, SOLSPERSE 32000 DEGDEE: Diethylene glycol diethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd.

[0142] [Ink Preparation] The imaging layer inks were prepared by mixing the components according to the following formula 1 and stirring them in a Silverson mixer at 2,000 to 3,000 rpm for 10 to 15 minutes. Note that the following describes an example in which a black pigment millbase was used as the pigment dispersion, but other color imaging layer inks were also prepared using the same procedure. -Ink composition 1- Pigment dispersion: Pigment mill base Black: 5 parts Organic solvent: Diethylene glycol diethyl ether (Tokyo Chemical Industry Co., Ltd.): 71.9 parts Polymerizable compound: GENOMER 4215 (bifunctional urethane (meth)acrylate oligomer, manufactured by Rahn Corporation): 20 parts Polymerization initiator: IRGACURE 819 (manufactured by BASF Ltd.): 2 parts Polymerization initiator: IRGACURE 2959 (manufactured by BASF Ltd.): 1 part Surfactant: BYK331 (manufactured by BYK-Chemie Co., Ltd.): 0.1 part

[0143] [Image Recording Device] The inkjet recording device used was an inkjet printer (KEGON) manufactured by Affit, equipped with a rubber heater (manufactured by Three High Corporation), a UV exposure device (LED-UV lamp) (LLRG1200FUV, manufactured by ITEC Systems Co., Ltd.), and a low-pressure mercury lamp (germicidal lamp GL15, manufactured by Hitachi Appliances, Inc.). The output of the rubber heater was set so that the temperature of the back surface of the recording medium could be heated to a range of 35°C to 90°C.

[0144] [Method of forming image layer] An image was recorded using the following compositions to form an image layer. Each composition is as shown below. An ink ejection step and an ink heating step were carried out in this order to form an image layer. A PET film with an easy-adhesion layer on one side (Cosmoshine A4100, manufactured by Toyobo Co., Ltd., thickness 50 μm) was prepared as a temporary support. A gold foil sheet was placed on the side of the temporary support without the easy-adhesion layer (i.e., on the PET film side), and this was used as a recording medium. (1) Ink ejection process: K (black) ink was repeatedly ejected in lines onto the recording medium from an inkjet head (Toshiba Tec Corporation, CA4, nozzle diameter 26 μm) heated to 35°C, to achieve an image density of 1200 dpi x 600 dpi (dots per inch). 2 The voltage was adjusted so that the weight was 20 g per unit area. (2) Ink heating process: The recording medium onto which the ink had been ejected was heated with a rubber heater so that the temperature of the backside of the recording medium reached 45°C, forming an image layer. The heating time was set to 10 seconds. The temperature of the backside of the recording medium was measured with an infrared thermometer (AD-5616, manufactured by A&D Co., Ltd.).

[0145] [Method of applying hot melt adhesive] Hot melt powder (product name "O-Powder", manufactured by Celkam Co., Ltd.) was sprinkled onto the recording medium from the image layer side to apply the hot melt powder to the image layer. The hot melt powder adhered to the image layer due to the tackiness of the uncured image layer, forming an image similar to the image layer.

[0146] [Hot melt adhesive baking method] The recording medium was heated at 150°C for 1 minute to heat and melt (baked) the hot-melt adhesive layer, and then air-cooled to room temperature to recrystallize, forming a hot-melt adhesive layer and obtaining an uncured DTF sheet.

[0147] [Image layer curing process] After the hot-melt adhesive layer was formed on the recording medium, ultraviolet light was irradiated onto the entire surface of the side on which the hot-melt adhesive layer was formed. Note that a UV exposure machine (LED-UV lamp, wavelength 385 nm) was used as the light source for irradiating ultraviolet light, and the ultraviolet light was irradiated at 500 mJ / cm. 2 The image layer was cured by irradiation with ultraviolet light in the atmosphere at an exposure dose of 1000 kJ / cm 2 , thereby obtaining a DTF sheet.

[0148] [IR peak measurement] <Calculation of intensity ratio P1> (Measurement of IR peaks of DTF sheet) The surface area of ​​the image layer on the hot-melt adhesive layer side was excavated by etching the DTF sheet using TOF-SIMS according to the following procedure. Note that etching was performed from the hot-melt adhesive layer side. The etching conditions were as follows: Equipment used: TRIFT V nanoTOF manufactured by ULVAC-PHI Charge compensation: Use of low-speed electron gun Primary ion: Bi3+ Measurement mode: bunching mode (high mass resolution mode) Ion beam: Ar-GCIB gun (Ar 2500 +, 20kV, 2nA, sputtering range 3mm□)

[0149] Next, the IR peak of the surface of the image layer excavated by etching, which was on the side of the hot-melt adhesive layer, was measured by FT-IR / single-reflection ATR method (crystal: Ge). Apparatus: iS5 (Thermo Fisher Scientific) Detector: TGS, Number of integrations: 32 (Ge)

[0150] And, the C=O of the ester group is derived from 1640-1780cm -1 The peak maximum at (1640 cm -1 and 1780cm -1 The line connecting the absorbances at x and y is used as the baseline. 12, derived from the carbon-carbon double bond C=C, 800-830 cm -1 Peak maximum at (800cm -1 and 830cm -1 The line connecting the absorbances at 12 The normalized carbon-carbon double bond peak intensity Z 12 asked for.

[0151] <Measurement of IR peaks of uncured DTF sheet> The uncured DTF sheet was etched using TOF-SIMS according to the following procedure to excavate the uncured image layer (coating). Note that etching was performed from the hot-melt adhesive layer side. The etching conditions were as follows: Equipment used: TRIFT V nanoTOF manufactured by ULVAC-PHI Charge compensation: Use of low-speed electron gun Primary ion: Bi3+ Measurement mode: bunching mode (high mass resolution mode) Ion beam: Ar-GCIB gun (Ar 2500 +, 20kV, 2nA, sputtering range 3mm□) Next, the IR peaks of the uncured image layer (coating film) excavated by etching were measured using the FT-IR / single reflection ATR method (crystal: Ge). Apparatus: iS5 (Thermo Fisher Scientific) Detector: TGS, Number of integrations: 32 (Ge)

[0152] And, the C=O of the ester group is derived from 1640-1780cm -1 The peak maximum at (1640 cm -1 and 1780cm -1 The line connecting the absorbances at x and y is used as the baseline. 11 , derived from the carbon-carbon double bond C=C, 800-830 cm -1 Peak maximum at (800cm -1 and 830cm -1The line connecting the absorbances at 11 The normalized carbon-carbon double bond peak intensity Z 11 asked for.

[0153] (Intensity ratio P1) Normalized carbon double bond peak intensity Z of uncured DTF sheet 11 and the normalized carbon double bond peak intensity Z of the cured DTF sheet 12 The numerical value of was introduced into the above formula (X1) to calculate the intensity ratio P1.

[0154] <Calculation of intensity ratio P2> (Measurement of IR peak on the surface of the image layer of the DTF sheet facing the hot melt adhesive layer) The surface area of ​​the image layer on the hot-melt adhesive layer side was excavated by etching the DTF sheet using TOF-SIMS according to the following procedure. Note that etching was performed from the hot-melt adhesive layer side. The etching conditions were as follows: Equipment used: TRIFT V nanoTOF manufactured by ULVAC-PHI Charge compensation: Use of low-speed electron gun Primary ion: Bi3+ Measurement mode: bunching mode (high mass resolution mode) Ion beam: Ar-GCIB gun (Ar 2500 +, 20kV, 2nA, sputtering range 3mm□)

[0155] Next, the IR peak of the surface of the image layer excavated by etching on the side of the hot-melt adhesive layer was measured using the FT-IR / single-reflection ATR method (crystal: Ge). Apparatus: iS5 (Thermo Fisher Scientific) Detector: TGS, Number of integrations: 32 (Ge)

[0156] And, the C=O of the ester group is derived from 1640-1780cm -1The peak maximum at (1640 cm -1 and 1780cm -1 The line connecting the absorbances at x and y is used as the baseline. 22 , derived from the carbon-carbon double bond C=C, 800-830 cm -1 Peak maximum at (800cm -1 and 830cm -1 The line connecting the absorbances at 22 The normalized carbon-carbon double bond peak intensity Z 22 asked for.

[0157] (Measurement of IR peak on the decorative layer side of the image layer of the DTF sheet) The IR peak measurement on the decorative layer side of the image layer was also performed using the same procedure as the measurement of the IR peak on the hot melt adhesive layer side of the image layer. Specifically, the DTF sheet was etched using TOF-SIMS using the procedure described above to excavate the surface area of ​​the decorative layer side of the image layer, and then the IR peak on the decorative layer side of the image layer excavated by etching was measured. The etching conditions and IR peak measurement conditions were as described in the upper part, and etching was performed from the hot melt adhesive layer side. And, the C=O of the ester group is derived from 1640-1780cm -1 The peak maximum at (1640 cm -1 and 1780cm -1 The line connecting the absorbances at x and y is used as the baseline. 21 , derived from the carbon-carbon double bond C=C, 800-830 cm -1 Peak maximum at (800cm -1 and 830cm -1 The line connecting the absorbances at 21 The normalized carbon-carbon double bond peak intensity Z 21 asked for.

[0158] (Intensity ratio P2) Normalized carbon double bond peak intensity Z on the decorative layer side of the image layer of the DTF sheet 21 and the normalized carbon double bond peak intensity Z on the hot melt adhesive layer side of the image layer of the DTF sheet 22 The value of was introduced into the above formula (Y1) to calculate the intensity ratio P2.

[0159] 〔evaluation〕 <Blocking resistance> The DTF sheet was cut to prepare two test pieces. Each test piece measured 5 cm x 4 cm. The two test pieces were stacked so that the hot-melt adhesive layer side of one test piece, test piece A, was in contact with the temporary support side of the other test piece, test piece B, to obtain a laminate. The laminate was sandwiched between a pair of stainless steel plates larger than the laminate. A weight was placed on the stainless steel plates to adjust the load to 0.03 MPa. The laminate with the weight placed on it was left in a thermostatic chamber at 60°C for 24 hours. After 24 hours, the laminate was removed from the thermostatic chamber, and the presence or absence of image defects on test piece A was visually evaluated when the laminate was separated into two test pieces. A: No defects are observed in the image of test piece A D: Image chipping of test piece A is observed.

[0160] <Rubbing resistance> To evaluate the rubbing fastness and texture when the thermal transfer sheet was transferred to fabric, the sheet was transferred to a fabric substrate using the following procedure, and the remaining carbon double bonds were polymerized by light irradiation to increase the film strength, and the rubbing fastness was evaluated. (Transfer to fabric substrate) A cotton fabric was prepared, and the fabric and the thermal transfer sheet were overlapped so that the hot-melt adhesive layer surfaces of the fabric and the thermal transfer sheet were in contact with each other, and then they were heat-pressed together at 150°C for 30 seconds using a heat press. After that, the temporary support and the gold foil on the part where the image layer was not formed were peeled off, and a transfer product was obtained. (light irradiation) The transferred material was exposed to UV light (LED-UV lamp, wavelength 385 nm) at 1000 mJ / cm in a low-oxygen atmosphere (oxygen concentration: 1,000 ppm by volume or less). 2 The image was irradiated with ultraviolet light at an exposure dose of 1000 u / s, thereby polymerizing the remaining carbon-carbon double bonds in the image layer and improving the abrasion resistance of the transferred product. (Rubbing durability evaluation) The transferred product was subjected to a rubbing test based on ISO105X12:2001 (wet), and the rubbing resistance was evaluated based on the area of ​​peeled decorative layer. A: Peeling of the decorative layer is less than 5% B: Peeling of the decorative layer is 5% or more but less than 10% C: Peeling of the decorative layer is 10% or more but less than 15% D: Peeling of the decorative layer is 15% or more

[0161] <Texture of the transfer> The transfer product obtained above was cut into a 10 cm x 4 cm piece (hereinafter also referred to as an evaluation sample). A white cloth of the same size, but before the DTF sheet was attached, was prepared as a reference white cloth sample. A stainless steel plate with a length (long side) of 200 mm, a width (short side) of 100 mm, and a thickness of 1 mm was prepared as an evaluation jig. The evaluation jig was set upright so that the short side direction was vertical and the long side direction was horizontal. Next, the center of the longitudinal direction of the evaluation sample (i.e., the center line) was placed on the long side of the horizontal evaluation jig so that both ends of the evaluation sample in the longitudinal direction (both end sides) hung down. In this state, the linear distance between one end of the evaluation sample in the longitudinal direction and the other end of the evaluation sample in the longitudinal direction was measured and defined as the deflection distance. The deflection distance of the reference white cloth sample was measured in the same manner. The difference between the deflection distance of the evaluation sample and the deflection distance of the reference white cloth sample, Δ deflection distance, was used to evaluate the softness of the texture of the printed product based on the following evaluation criteria. A: Δ Deflection distance is less than 20 mm. B: Δ Deflection distance is 20 mm or more and less than 40 mm. C: Δ Deflection distance is 40 mm or more and less than 60 mm. D: Δ Deflection distance is 60 mm or more.

[0162] <Image edge peelability> The image edges of the transferred product obtained above were observed and evaluated based on the presence or absence of chipping at the edges. A: No defects are visible on the image edges B: There is chipping at the edge of the image

[0163] [Comparative Example 1] A DTF sheet was produced in the same manner as in Example 1, except that the image layer was prepared using the materials shown in Table 4 below, and the same evaluations as in Example 1 were carried out.

[0164] Comparative Example 2 A DTF sheet was prepared in the same manner as in Example 1, except that the image layer curing step was not carried out, and the same evaluations as in Example 1 were carried out.

[0165] Comparative Example 3 In the image layer curing process, the ultraviolet irradiation conditions are 300 mJ / cm 2 A DTF sheet was prepared in the same manner as in Example 1, except that the exposure dose was changed to , and the same evaluation was carried out as in Example 1. The intensity ratio P1 was 0.400.

[0166] Comparative Example 4 In the image layer curing process, the ultraviolet irradiation conditions are set to 1000 mJ / cm in a low-oxygen atmosphere (oxygen concentration: 1,000 ppm or less). 2 A DTF sheet was prepared in the same manner as in Example 1, except that the exposure dose was changed to , and the same evaluation as in Example 1 was carried out. The intensity ratio P1 was 0.002.

[0167] Comparative Example 5 A DTF sheet was produced in the same manner as in Example 1, except that the process order was changed as shown in Table 4 below, and the same evaluations were carried out as in Example 1. The hot melt powder did not adhere to the image layer, and due to lack of adhesiveness, it could not be transferred to the cloth.

[0168] Comparative Example 6 A DTF sheet was prepared in the same manner as in Example 1, except that the ink preparation and image formation methods were changed to the procedures and materials shown below, and the same evaluations were carried out as in Example 1. Because the ink did not contain a (meth)acrylate compound, no peaks derived from carbon-carbon double bonds C=C were detected. Furthermore, transfer was possible, but the rub fastness was rated "D."

[0169] [Ink Preparation] The components shown in Table 4 below were mixed to prepare an ink for forming an image layer (ink for image layer). APD1000 Black (Fujifilm Imaging Colorants Ltd.) (pigment dispersion) Superflex 470 (polyurethane latex aqueous solution, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Surfynol 440 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) Glycerin (organic solvent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0170] [Image Forming Method] As an inkjet recording device, a device equipped with an inkjet head (product name "StarFire SG-1024SA", manufactured by Fujifilm Dimatix) and an ink circulation pump was prepared. A PET film with an easy-adhesion layer on one side (Cosmoshine A4100, manufactured by Toyobo Co., Ltd., thickness 50 μm) was prepared as a temporary support. A gold foil sheet was placed on the side of the temporary support without the easy-adhesion layer (i.e., on the PET film side), and this was used as a recording medium. An ink tank connected to the inkjet head was filled with ink for the image layer. The inkjet heads were arranged in a line with the nozzles aligned in a direction perpendicular to the direction of movement of the stage. The ink ejection conditions were a droplet volume of 49.5 pL, an ejection frequency of 10 kHz, a resolution of 400 dpi x 400 dpi, and an ink application amount per fabric area of ​​12.3 g / m. 2 It was decided. The ink circulation pump was operated so that the ink circulated between the ink tank and the inkjet head. Under the above conditions, the ink was ejected onto the recording medium to form an image layer.

[0171] [Examples 2 to 8, 17 to 19, 22 to 24] A DTF sheet was produced in the same manner as in Example 1, except that the formulation and materials were changed to those shown in Table 4 below, and the same evaluations as in Example 1 were carried out.

[0172] [Example 9] [Preparation of Synthetic Urethane Acrylate Compound 1] A three-neck flask was charged with 333.3 g of polycarbonate diol (product name "Duranol (registered trademark) T5651", manufactured by Asahi Kasei Chemicals Corporation), 148.2 g of isophorone diisocyanate (IPDI), and 77.4 g of methyl ethyl ketone, and heated to 50°C. Duranol (registered trademark) T5651 is a compound (2-18) PC having Rc 1 and Rc 2 are each an alkylene group having 5 or 6 carbon atoms, and Mn is 1000. 0.500 g of an inorganic bismuth catalyst (product name "Neostan U-600" manufactured by Nitto Kasei Co., Ltd.) was diluted with 2.00 g of methyl ethyl ketone and added, followed by stirring at 60°C for 3 hours. 77.4 g of 2-hydroxyethyl acrylate was then added, followed by stirring at 80°C for 5 hours. Subsequently, the methyl ethyl ketone was removed under reduced pressure to obtain synthetic urethane acrylate compound 1.

[0173] [ka]

[0174] A DTF sheet was produced in the same manner as in Example 1, except that synthetic urethane acrylate compound 1 was used and the formulation and materials were changed to those shown in Table 4 below, and evaluations similar to those in Example 1 were carried out.

[0175] [Examples 10 to 12] [Preparation of Synthetic Urethane Acrylate Compounds 2 to 4] Synthetic urethane acrylate compounds 2 to 4 were prepared in accordance with the synthesis procedure for synthetic urethane acrylate compound 1 in Example 9, except that the composition and materials were changed to those shown in Table 2 below. [Preparation of transfer sheet] A DTF sheet was produced in the same manner as in Example 9, except that the formulation and materials were changed to those shown in Table 4 below, and the same evaluations as in Example 1 were carried out.

[0176] Table 2 below shows the compositions of the monomer components that make up the synthetic urethane acrylate compounds 1 to 4. The content of each component in Table 2 is expressed in grams (g). The details of the components are shown in Table 2. Hexanediol (Tokyo Chemical Industry Co., Ltd.) HMDI (Hexamethylene diisocyanate, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0177] [Table 2]

[0178] [Example 13] A DTF sheet was produced in the same manner as in Example 1, except that the metallic ink and undercoat ink were prepared and the recording medium was produced using the following procedure, and the same evaluations as in Example 1 were carried out.

[0179] [Preparation of metallic ink] The components were mixed to obtain the composition shown in Table 3 below (the units of content in the table are "% by mass") The resulting mixture was stirred at 4000 rpm for 30 minutes using a mixer (product name "L4R", manufactured by Silverson) to prepare a metallic ink. [Preparation of Undercoat Ink] The components were mixed to obtain the composition shown in Table 3 below (the units of content in the table are "mass %") The resulting mixture was stirred at 4000 rpm for 30 minutes using a mixer (product name "L4R", manufactured by Silverson) to prepare an undercoat ink.

[0180] [Table 3]

[0181] [Preparation of recording medium] A PET film (Cosmoshine A4100, manufactured by Toyobo Co., Ltd., 50 μm thick) with an easy-adhesion layer on one side was prepared as a temporary support. The temporary support was set in a desktop inkjet printer (UJF-7151 plus, manufactured by Mimaki Engineering Co., Ltd.) equipped with an LED light source so that the side without the easy-adhesion layer (i.e., the PET film side) was the printing surface. The prepared undercoat ink was printed on the temporary support using the Fine 600x900 VD Si gloss mode (20 passes) of the printer's built-in printing conditions. Then, a metallic ink was printed on top of the printed portion of the undercoat ink using the Fine 600x900 VD Si gloss mode (20 passes), producing a recording medium with a metallic image layer as a decorative layer.

[0182] [Example 14] A DTF sheet was prepared in the same manner as in Example 1, except that a cholesteric liquid crystal layer ink was prepared and a recording medium was produced in the following procedure, and the same evaluations as in Example 1 were carried out.

[0183] [Preparation of Cholesteric Liquid Crystal Layer Ink] <Ink Rm1> Ink Rm1 was prepared by heating the components shown below until they were completely dissolved and mixed. The viscosity of Ink Rm1 (at 25°C) was 10.3 mPa·s and the surface tension (at 25°C) was 28 mN / m. Diethylene glycol diethyl ether 61.97 parts by mass 35 parts by mass of a mixture of polymerizable liquid crystal compounds (a mixture of compound (10), compound (11), and compound (12) described below) Futergent 208G (Neos Co., Ltd.) 0.03 parts by weight 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxymethylpropanone (Omnirad 819, manufactured by IGM Resins BV) 1.5 parts by mass Chiral compound A 1.5 parts by mass

[0184] The mixture of polymerizable liquid crystal compounds consisted of 34% by mass of compound (10), 33% by mass of compound (11), and 33% by mass of compound (12). Compound (10), compound (11), and compound (12) are all rod-like liquid crystal compounds. The structures of compound (10), compound (11), compound (12), and chiral compound A are as follows:

[0185] (Compound (10), Compound (11), Compound (12)) [ka]

[0186] (Chiral Compound A) [ka]

[0187] <Preparation of recording medium> FE2000 (product name "Polyester Film", manufactured by Futamura Chemical) was prepared as a temporary support. This support was heated to 55°C, and ink Rm1 was applied using an inkjet method. After printing, the substrate was heated at 70°C for 5 minutes, and then the applied ink was exposed to ultraviolet light to record a cholesteric liquid crystal image layer. This resulted in a recording medium with a cholesteric liquid crystal layer as a decorative layer. In producing the image recording material, the ink was applied using a multi-pass inkjet recording device "UJF3042HG" (manufactured by Mimaki Engineering Co., Ltd.) under conditions of a resolution of 720 dpi x 600 dpi and a recording speed of 32 passes, and exposure was performed using a CSOT-40E (metal halide light source, manufactured by GS Yuasa Corporation).

[0188] [Example 15] A DTF sheet was prepared in the same manner as in Example 1, except that after the hot melt powder was spread, the excess powder was not removed, and the same evaluation as in Example 1 was carried out.

[0189] [Example 16] Hot melt powder spread amount: 10g / m 2 A DTF sheet was prepared in the same manner as in Example 1, except that the thickness was changed to 1 / 2 mm. The DTF sheet was then evaluated in the same manner as in Example 1.

[0190] [Example 20] In the image layer curing process, the ultraviolet irradiation conditions are 280 mJ / cm 2 A DTF sheet was prepared in the same manner as in Example 1, except that the exposure dose was changed to , and the same evaluation was carried out as in Example 1. The intensity ratio P1 was 0.295.

[0191] [Example 21] In the image layer curing process, the ultraviolet irradiation conditions are 2500 mJ / cm 2 A DTF sheet was prepared in the same manner as in Example 1, except that the exposure dose was changed to , and the same evaluation was carried out as in Example 1. The intensity ratio P1 was 0.006.

[0192] [Details of various ingredients shown in Table 4] The various components shown in Table 4 are explained below. Note that the explanations given in the upper part are omitted. UV-6630B: Bifunctional urethane (meth)acrylate compound (Mitsubishi Chemical Corporation) CN996: Difunctional urethane (meth)acrylate compound (Arkema Co., Ltd.) Viscoat #230: Bifunctional (meth)acrylate compound (hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Viscoat #540: Bifunctional (meth)acrylate compound (bisphenol A epoxy (meth)acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) CN1074 NS: Difunctional (meth)acrylate compound (polyester (meth)acrylate, manufactured by Satomer) G4316: Rahn Corporation's "GENOMER 4316" (trifunctional urethane (meth)acrylate compound) UV-7600B: Hexafunctional urethane (meth)acrylate compound (Mitsubishi Chemical Corporation) BR-113: Mitsubishi Chemical Corporation's "Dianal (registered trademark) BR-113" (polymethyl methacrylate) Pigment Millbase Black, Pigment Millbase Cyan, Pigment Millbase Magenta, Pigment Millbase Yellow: The products prepared in the upper section are used.

[0193] Table 4 is shown below. The amounts of each component in Table 4 are expressed in parts by mass. In Table 4, "total mass % of monofunctional and bifunctional compounds" represents the total content (mass %) of the monofunctional (meth)acrylate compound and the bifunctional (meth)acrylate compound relative to the solid content of the composition. In addition, "area ratio of hot melt adhesive layer" in Table 4 represents the ratio (%) of the area of ​​the hot melt adhesive layer to the area of ​​the image layer when the transfer sheet is viewed in plan view. The weight average molecular weight of the acrylate resin and methacrylate resin in the image layer of the DTF sheet of the example was 200,000 to 500,000.

[0194] [Table 4]

[0195] [Table 5]

[0196] [Table 6]

[0197] [Table 7]

[0198] [Table 8]

[0199] [Table 9]

[0200] From the results in Table 1, it is clear that the transfer sheets obtained by the manufacturing methods of the Examples and the transfer sheets of the Examples have excellent blocking resistance and excellent abrasion resistance of the transferred products after transfer. Furthermore, the results of Examples 1 and 2 confirmed that when the hot melt adhesive layer was formed using a powdered hot melt adhesive, the abrasion resistance of the transferred product was superior. Furthermore, a comparison of Example 1 and Examples 3 to 5 confirmed that when the total content of the monofunctional (meth)acrylate compound and the bifunctional (meth)acrylate compound in the composition forming the image layer is 50 mass% or more relative to the total solid content of the composition, the texture of the transferred product after transfer is superior. Furthermore, the results of Examples 1 and 6 to 8 confirmed that when the composition forming the image layer contains a urethane (meth)acrylate compound, the texture of the transferred product after transfer is better or the friction resistance of the transferred product is better. Furthermore, from the results of Examples 1 and 9 to 12, it was confirmed that when the composition forming the image layer contains a compound represented by the above-mentioned formula (1) and at least one (preferably both) of R3 and R4 in the formula represents a linear or branched alkylene group, the texture of the transferred product after transfer is better and the friction resistance of the transferred product after transfer is better. Furthermore, from the results of Examples 1, 15, and 16, it was confirmed that when the ratio of the area of ​​the hot-melt adhesive layer to the area of ​​the image layer was 60% or more, the rub fastness of the transferred product after transfer was superior, and when the ratio of the area of ​​the hot-melt adhesive layer to the area of ​​the image layer was 100% or less, the peelability of the image edge of the transferred product after transfer was superior. [Explanation of symbols]

[0201] 10 Transfer sheet 12 Temporary support 14 Decorative layer 16 Image Layers 18 Hot melt adhesive layer 20 Transfer layer

Claims

1. Step 1 of forming a decorative layer on a temporary support; Step 2: applying a composition containing one or more compounds selected from the group consisting of acrylate compounds and methacrylate compounds onto the decorative layer to form a coating film; Step 3: forming a hot melt adhesive layer on the coating film; and step 4 of subjecting the coating film to a curing treatment to form an image layer containing one or more resins selected from the group consisting of acrylate resins and methacrylate resins, The intensity ratio P calculated by the following formula (X1) １ is 0.005 to 0.

300. Formula (X1) P １ = Z １２ / Z １１ In formula (X1), P １ represents the intensity ratio. １１ represents the normalized carbon-double bond peak intensity of the coating film obtained by the formula (X2). １２ represents the normalized carbon-double bond peak intensity of the surface of the image layer on the side of the hot-melt adhesive layer, which is calculated by the formula (X3). Formula (X2) Z １１ = Y １１ / X １１ In formula (X2), X １１ represents the peak intensity derived from C═O of the ester group, as determined by infrared absorption spectroscopy of the coating film. １１ represents the peak intensity derived from the carbon-carbon double bond C═C determined by infrared absorption spectroscopy of the coating film. １１ represents the normalized carbon-carbon double bond peak intensity. Formula (X3) Z １２ = Y １２ / X １２ In formula (X3), X １２ represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. １２ represents the peak intensity derived from the carbon-carbon double bond C═C determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. １２ represents the normalized carbon-carbon double bond peak intensity.

2. In the step 2, the coating film is formed on at least a part of the decorative layer, 2. The method for producing a transfer sheet according to claim 1, wherein step 3 is a step of spraying a powdered hot melt adhesive from the coating film side to remove the hot melt adhesive other than on the coating film, thereby forming the hot melt adhesive layer on the coating film.

3. the composition contains one or more compounds selected from the group consisting of a monofunctional acrylate compound, a monofunctional methacrylate compound, a bifunctional acrylate compound, and a bifunctional methacrylate compound; 3. The method for producing a transfer sheet according to claim 1, wherein a total content of the monofunctional acrylate compound, the monofunctional methacrylate compound, the bifunctional acrylate compound, and the bifunctional methacrylate compound is 50% by mass or more based on the total solid content of the composition.

4. The method for producing a transfer sheet according to claim 1 or 2, wherein the weight average molecular weight of the acrylate resin and the methacrylate resin in the image layer is 200,000 or more.

5. The method for producing a transfer sheet according to claim 1 or 2, wherein the composition contains a compound represented by the following formula (1): 【Chemistry 1】 In the formula, R ａ represents a hydrogen atom or a methyl group. １ ~R ４ each independently represents a divalent linking group, and n represents an integer of 1 to 10,000. ３ and R ４ At least one of the groups independently represents a linear or branched alkylene group.

6. The R ３ and the R ４ The method for producing a transfer sheet according to claim 5 , wherein both of are independently a linear or branched alkylene group.

7. the decorative layer is a metal layer or a cholesteric liquid crystal layer, The method for producing a transfer sheet according to claim 1 or 2, wherein the metal layer is a metal foil or a metal vapor deposition layer.

8. 3. The method for producing a transfer sheet according to claim 1, wherein, when the transfer sheet is viewed in a plane, the hot melt adhesive layer is disposed only on the image layer, and the ratio of the area of ​​the hot melt adhesive layer to the area of ​​the image layer is 60 to 100%.

9. A transfer sheet manufactured by the manufacturing method of claim 1, A transfer sheet having a temporary support, a decorative layer, an image layer, and a hot-melt adhesive layer in this order, the image layer contains one or more resins selected from the group consisting of acrylate resins and methacrylate resins, The intensity ratio P calculated by the following formula (Y1) ２ A transfer sheet having a viscosity of 1.25 to 50.

0. Formula (Y1) P ２ = Z ２２ / Z ２１ In formula (Y1), P ２ represents the intensity ratio. ２１ represents the normalized carbon-double bond peak intensity of the surface of the image layer facing the decorative layer, which is calculated by the formula (Y2). ２２ represents the normalized carbon-double bond peak intensity of the surface of the image layer on the hot-melt adhesive layer side, which is calculated by the formula (Y3). Formula (Y2) Z ２１ = Y ２１ / X ２１ In formula (Y2), X ２１ represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the decorative layer. ２１ represents the peak intensity derived from the carbon-carbon double bond C═C determined by infrared absorption spectroscopy of the surface of the image layer facing the decorative layer. ２１ represents the normalized carbon-carbon double bond peak intensity. Formula (Y3) Z ２２ = Y ２２ / X ２２ In formula (Y3), X ２２ represents the peak intensity derived from C═O of the ester group, which is determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. ２２ represents the peak intensity derived from the carbon-carbon double bond C═C determined by infrared absorption spectroscopy of the surface of the image layer facing the hot-melt adhesive layer. ２２ represents the normalized carbon-carbon double bond peak intensity.

10. the image layer is a cured layer derived from a composition containing one or more compounds selected from the group consisting of an acrylate compound and a methacrylate compound, the composition contains one or more compounds selected from the group consisting of a monofunctional acrylate compound, a monofunctional methacrylate compound, a bifunctional acrylate compound, and a bifunctional methacrylate compound; The transfer sheet according to claim 9, wherein the total content of the monofunctional acrylate compound, the monofunctional methacrylate compound, the bifunctional acrylate compound, and the bifunctional methacrylate compound is 50% by mass or more based on the total solid content of the composition.

11. 11. The transfer sheet according to claim 9, wherein the acrylate resin and the methacrylate resin in the image layer have a weight average molecular weight of 200,000 or more.

12. The transfer sheet according to claim 9 or 10, wherein the composition contains a compound represented by the following formula (1): 【Chemistry 2】 In the formula, R ａ represents a hydrogen atom or a methyl group. １ ~R ４ each independently represents a divalent linking group, and n represents an integer of 1 to 10,000. ３ and R ４ At least one of the groups independently represents a linear or branched alkylene group.

13. The R ３ and the R ４ The transfer sheet according to claim 12, wherein both of are each independently a linear or branched alkylene group.

14. the decorative layer is a metal layer or a cholesteric liquid crystal layer, The transfer sheet according to claim 9 or 10, wherein the metal layer is a metal foil or a metal vapor deposition layer.

15. 11. The transfer sheet according to claim 9, wherein, when the transfer sheet is viewed in a plane, the hot melt adhesive layer is disposed only on the image layer, and the ratio of the area of ​​the hot melt adhesive layer to the area of ​​the image layer is 60 to 100%.

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