Transfer sheet, resin molded product with transfer substrate, and resin molded product

Abstract

To provide a transfer sheet that is excellent in fingerprint resistance and can impart an excellent matte finish design to the surface of resin molded products.SOLUTION: Provided is a transfer sheet in which at least a transfer substrate and a transfer layer are laminated, and on at least a part of the surface of the transfer layer on the transfer substrate side, a surface profile with the ratio of a maximum valley depth Sv to a maximum peak height Sp (Sv / Sp), as defined in ISO25178-2:2012, of 0.60 or more, and an arithmetic mean height Sa of 0.10 or more, is provided.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a transfer sheet, a resin molded article with a transfer substrate, and a resin molded article.

Background Art

[0002] In resin molded articles used for automotive interior and exterior parts, interior building materials, household appliances, etc., and resin molded articles used for organic glass, etc. as an alternative material to inorganic glass, etc., a lamination technique using a decorative sheet is used for the purpose of surface protection and imparting design. Such decorative sheets used in such techniques can be roughly classified into a laminate type decorative sheet and a transfer type decorative sheet (i.e., a transfer sheet).

[0003] The laminate type decorative sheet is laminated so that the protective layer is located on the outermost surface on the support substrate, and the support substrate is incorporated into the resin molded article by laminating the molding resin on the support substrate side. On the other hand, the transfer type decorative sheet (transfer sheet) has a protective layer laminated directly on the support substrate (transfer substrate) or via a release layer provided as necessary. After laminating a molding resin layer on the side opposite to the transfer substrate, the transfer substrate is peeled off so that the transfer substrate does not remain on the resin molded article. These two types of decorative sheets are properly selected according to the shape of the resin molded article and the required functions.

[0004] For decorating a resin molded body having a complex surface shape such as a three-dimensional curved surface, an in-mold decorating method has been used. The in-mold decorating method is a method of integrating a decorative sheet inserted into an in-mold molding die during injection molding with the molten injection resin injected into the cavity to decorate the surface of the resin molded body. Furthermore, depending on the difference in the configuration of the decorative sheet integrated with the resin molded body (the above-mentioned laminate type and transfer type decorative sheets (transfer sheets)), it is generally classified into an in-mold lamination decorating method and an in-mold transfer decorating method.

[0005] In the injection molding simultaneous transfer decoration method, the transfer sheet is arranged with the transfer layer side facing the inside of the mold, heated from the transfer layer side by a hot plate, and molded so that the transfer sheet conforms to the shape inside the mold. Next, molten injection resin is injected into the cavity, and the injection resin is cooled to form a molded resin layer, integrating the transfer sheet and the molded resin layer. Then, after taking out the laminate in which the transfer sheet is integrated with the molded resin layer from the mold, by peeling the transfer base material, a resin molded product including the transfer layer is obtained.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] In order to improve the design quality of the surface of a resin molded product manufactured by a transfer sheet, a technique is known in which at least a part of the surface of the resin molded product is made into a matte finish. As a method of making the surface of the resin molded product into a matte finish, for example, a method of forming a fine uneven shape on the surface of the resin molded product is known.

[0008] However, when touching the surface of a resin molded product having such a matte finish design with a finger, there is a problem that fingerprints are likely to adhere to the surface.

[0009] In addition, when the transfer sheet is used for three-dimensional molding, the transfer sheet is integrated with the molded resin layer in a high-temperature and high-pressure environment to manufacture a resin molded product (decorated resin molded product). When a transfer sheet having a matte finish design on the transfer layer is exposed to a high-temperature and high-pressure environment, the matte finish design on the surface of the transfer layer deteriorates, and there is also a problem that it is difficult to impart an excellent matte finish design to the surface of the resin molded product.

[0010] Under such circumstances, the main object of the present disclosure is to provide a transfer sheet that can impart excellent fingerprint resistance and an excellent matte finish design to the surface of a resin molded article. Further, it is also an object of the present disclosure to provide a resin molded article with a transfer substrate and a resin molded article from which the transfer substrate has been peeled off, using the transfer sheet.

Means for Solving the Problems

[0011] The inventors of the present disclosure have conducted intensive studies to solve the above problems. As a result, at least in a transfer sheet in which a transfer substrate and a transfer layer are laminated in this order, at least a part of the surface shape of the surface of the transfer layer on the transfer substrate side is such that the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO25178-2:2012 is a predetermined value or more. It has been found that a transfer sheet can be obtained that can impart excellent fingerprint resistance and an excellent matte finish design to the surface of a resin molded article. The present disclosure has been completed by further studies based on such findings.

[0012] That is, the present disclosure provides an invention in the following aspects. Item 1. A transfer sheet in which at least a transfer substrate and a transfer layer are laminated, wherein at least a part of the surface of the transfer layer on the transfer substrate side has a surface shape in which the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. Transfer sheet. Item 2. The transfer sheet according to Item 1, wherein the surface shape has a ratio (Sp / Sz) of the maximum peak height Sp to the maximum height Sz defined in ISO25178-2:2012 of 0.30 or more. Item 3. The transfer sheet according to Item 1 or 2, wherein the surface shape has a ratio (Sv / Sz) of the maximum valley depth Sv to the maximum height Sz defined in ISO25178-2:2012 of 0.40 or more. Item 4. The transfer sheet according to any one of Items 1 to 3, wherein the surface shape has a maximum height Sz of 8.00 or more as defined in ISO 25178-2:2012. Item 5. The transfer sheet according to any one of Items 1 to 4, wherein the transfer layer further includes at least one layer selected from the group consisting of a protective layer, a primer layer, a decorative layer, and an adhesive layer. Item 6. The transfer sheet according to any one of Items 1 to 5, wherein the surface of the transfer layer on the side of the transfer substrate is formed by a protective layer. Item 7. The transfer sheet according to any one of Items 1 to 5, wherein a release layer is laminated between the transfer layer and the transfer substrate. Item 8. The transfer sheet according to any one of Items 1 to 7, further comprising an anti-blocking layer on the side of the transfer substrate opposite to the transfer layer. Item 9. A resin molded article with a transfer substrate, in which at least a molded resin layer, a transfer layer, and a transfer substrate are laminated in this order, wherein at least a part of the surface of the transfer layer on the side of the transfer substrate has a surface shape in which the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. Item 10. A resin molded article in which at least a molded resin layer and a transfer layer are laminated, wherein at least a part of the surface of the transfer layer on the side opposite to the molded resin layer has a surface shape in which the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more.

Advantages of the Invention

[0013] According to the present disclosure, it is possible to provide a transfer sheet that is excellent in fingerprint resistance and can impart an excellent matte design to the surface of a resin molded article. Furthermore, according to the present disclosure, it is also possible to provide a resin molded article with a transfer substrate and a resin molded article from which the transfer substrate has been peeled off, using the transfer sheet.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Modes for Carrying Out the Invention

[0015] The transfer sheet of the present disclosure is a transfer sheet in which at least a transfer base material and a transfer layer are laminated, and on at least a part of the surface of the transfer layer on the transfer base material side, the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. The transfer sheet of the present disclosure has such a configuration, so that it can impart excellent fingerprint resistance and an excellent matte design to the surface of the resin molded product. Furthermore, the resin molded product manufactured using the transfer sheet of the present disclosure has excellent fingerprint resistance and an excellent matte design. Note that, as described later, the transfer sheet of the present disclosure may not have a decorative layer or the like, and may be transparent, for example. Hereinafter, the transfer sheet of the present disclosure will be described in detail.

[0016] In this specification, unless otherwise specified as "above" or "below", the numerical range indicated by "~" means "above" and "below". For example, the notation 2~15 mm means 2 mm or more and 15 mm or less. In the numerical ranges described step by step in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other step-by-step descriptions. In addition, the upper limit value and the upper limit value, the upper limit value and the lower limit value, or the lower limit value and the lower limit value described separately may be combined to form a numerical range, respectively. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples. Further, in this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar ones have the same meaning.

[0017] Laminated structure of the transfer sheet The transfer sheet 10 of the present disclosure has at least a transfer base material 1 and a transfer layer 8 in this order. In the transfer sheet 10 of the present disclosure, on at least a part of the surface of the transfer layer 8 on the side of the transfer base material 1, the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. The surface shape may be formed on at least a part of the surface of the transfer layer 8 on the side of the transfer base material 1, and the portion of the transfer layer 8 having the surface shape is excellent in fingerprint resistance and can impart an excellent matte finish design. The ratio of the area of the surface of the transfer layer 8 on the side of the transfer base material 1 having the surface shape is preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 80% or more, and may be 100% (that is, the surface shape is formed on the entire surface).

[0018] The transfer layer 8 can further include at least one layer among the protective layer 2, the adhesive layer 3, the primer layer 4, the decorative layer 5, etc. The transfer layer 8 preferably includes at least the protective layer 2. From the viewpoint of improving the adhesion of the protective layer 2, it is preferable to include the primer layer 4 on the side of the protective layer 2 opposite to the transfer substrate 1 side. Further, the transfer sheet 10 of the present disclosure may include a decorative layer 5 for the purpose of imparting decorativeness to the transfer sheet 10, etc. In the transfer sheet 10 of the present disclosure, the transfer layer 8 is transferred to the molded resin layer 9 to become the resin molded product 20 of the present disclosure. From the viewpoint of strongly adhering the transfer layer 8 of the transfer sheet 10 of the present disclosure to the molded resin layer 9, it is preferable to provide the adhesive layer 3 on the surface of the transfer layer 8 opposite to the transfer substrate 1 side.

[0019] Between the transfer substrate 1 and the transfer layer 8, a release layer 6 may be provided as necessary for the purpose of enhancing the peelability between the transfer substrate 1 and the transfer layer 8, etc. As will be described later, for example, a fine uneven shape is formed on the surface of the release layer opposite to the transfer substrate 1 side by a predetermined method, and further, the transfer layer 8 is laminated on the surface, and the uneven shape is transferred to the surface of the transfer layer 8 on the transfer substrate 1 side, whereby at least a part of the surface of the transfer layer 8 on the transfer substrate side has a surface shape in which the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO25178-2:2012 is 0.60 or more and the arithmetic mean height Sa is 0.10 or more. In this case, since the uneven shape formed on the surface of the release layer and the surface shape (uneven shape) of the transfer layer 8 have an inverted structure (so-called negative-positive relationship), the shapes defined in ISO25178-2:2012 (for example, the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp, the shape such as the arithmetic mean height Sa, etc.) are different.

[0020] Also, in the transfer sheet 10 of the present disclosure, a blocking prevention layer 7 may be provided on the side of the transfer base material 1 opposite to the transfer layer 8 in order to prevent blocking of the transfer sheet. In the transfer sheet 10 of the present disclosure, the transfer base material 1, the release layer 6 provided as necessary, and the blocking prevention layer 7 provided as necessary constitute a support. After integrating the transfer layer 8 of the transfer sheet 10 with the molding resin layer 9, the support is peeled off and removed.

[0021] As the laminated structure of the transfer sheet of the present disclosure, there are a laminated structure in which a base material for transfer / protective layer are laminated in this order; a laminated structure in which a base material for transfer / protective layer / adhesive layer are laminated in this order; a laminated structure in which a base material for transfer / protective layer / primer layer / adhesive layer are laminated in this order; a laminated structure in which a base material for transfer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order; a laminated structure in which a base material for transfer / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order; a laminated structure in which an anti-blocking layer / base material for transfer / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order, and the like. In FIG. 1, as one aspect of the laminated structure of the transfer sheet of the present disclosure, a schematic diagram of a cross-sectional structure of one form of the transfer sheet in which a base material for transfer / protective layer are laminated in this order is shown. Further, in FIG. 2, as one aspect of the laminated structure of the transfer sheet of the present disclosure, a schematic diagram of a cross-sectional structure of one form of the transfer sheet in which a base material for transfer / protective layer / adhesive layer are laminated in this order is shown. Further, in FIG. 3, as one aspect of the laminated structure of the transfer sheet of the present disclosure, a schematic diagram of a cross-sectional structure of one form of the transfer sheet in which a base material for transfer / protective layer / primer layer / adhesive layer are laminated in this order is shown. Further, in FIG. 4, as one aspect of the laminated structure of the transfer sheet of the present disclosure, a schematic diagram of a cross-sectional structure of one form of the transfer sheet in which a base material for transfer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order is shown. Further, in FIG. 5, as one aspect of the laminated structure of the transfer sheet of the present disclosure, a schematic diagram of a cross-sectional structure of one form of the transfer sheet in which a base material for transfer / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order is shown. Further, in FIG. 6, as one aspect of the laminated structure of the transfer sheet of the present disclosure, a schematic diagram of a cross-sectional structure of one form of the transfer sheet in which an anti-blocking layer / base material for transfer / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order is shown. Note that " / " means the separation between layers.

[0022] Each layer forming the transfer sheet [Support] The transfer sheet of the present disclosure has a transfer base material 1 as a support. The support may further have a release layer 6 and an antiblocking layer 7 as required. At least one layer such as a protective layer 2, an adhesive layer 3, a primer layer 4, and a decorative layer 5 formed on the transfer base material 1 constitutes a transfer layer 8. In the present disclosure, after integrally molding the transfer sheet and the molding resin, the interface between the support and the transfer layer 8 is peeled off to obtain a resin molded product.

[0023] (Transfer base material 1) In the present disclosure, the transfer base material 1 is used as a support that serves as a support member in the transfer sheet. The transfer base material 1 used in the present disclosure is selected in consideration of vacuum molding suitability, and typically a resin sheet made of a thermoplastic resin is used. Examples of the thermoplastic resin include polyester resins; acrylic resins; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; acrylonitrile-butadiene-styrene resins (ABS resins); vinyl chloride resins and the like.

[0024] From the viewpoint of suitably forming a recess on the surface of the transfer layer 8 to be transferred to the molding resin layer 9 by the transfer of the transfer sheet 10, in the present disclosure, it is preferable to use a polyester sheet as the transfer base material 1. The polyester resin constituting the polyester sheet refers to a polymer containing an ester group obtained by polycondensation from a polyvalent carboxylic acid and a polyhydric alcohol, and preferably includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. Polyethylene terephthalate (PET) is particularly preferable in terms of heat resistance and dimensional stability.

[0025] The polyester sheet suitably used as the base material 1 for transfer in the present disclosure is manufactured, for example, as follows. First, the above polyester resin and other raw materials are supplied to a well-known melt extrusion apparatus such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester resin to be melted. Next, while extruding the molten polymer, it is rapidly cooled and solidified on a rotating cooling drum to a temperature equal to or lower than the glass transition temperature to obtain a substantially amorphous and unoriented sheet. This sheet is obtained by stretching it in a biaxial direction to form a sheet and then performing heat setting. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Further, if necessary, it may be stretched again in the longitudinal and / or transverse directions before or after heat setting. In the present disclosure, in order to obtain sufficient dimensional stability, the stretching ratio is preferably 7 times or less, more preferably 5 times or less, and even more preferably 3 times or less, based on the area ratio. Within this range, when the obtained polyester sheet is used as a transfer sheet, the transfer sheet does not shrink again in the temperature range when injecting the molding resin, and the required sheet strength in this temperature range can be obtained. Note that the polyester sheet may be manufactured as described above or a commercially available product may be used.

[0026] Further, when providing the release layer 6 described later on the base material 1 for transfer, for the purpose of improving the adhesion to the release layer 6, if desired, physical or chemical surface treatments such as an oxidation method or a roughening method can be performed on one or both sides. Examples of the above oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method, etc., and examples of the roughening method include sandblasting method, solvent treatment method, etc. These surface treatments are appropriately selected according to the type of the base material 1 for transfer, but generally, the corona discharge treatment method is preferably used in terms of effect and operability, etc. Further, the base material 1 for transfer may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of strengthening the interlayer adhesion between the base material 1 for transfer and the layer provided thereon. Note that when using a commercially available polyester sheet, commercially available products that have been previously subjected to the above-described surface treatment or those provided with an easy-adhesion layer can also be used.

[0027] The thickness of the substrate 1 for transfer is preferably 50 μm or more, more preferably 60 μm or more, and is preferably 100 μm or less, more preferably 60 μm or less. The preferable range of the thickness of the substrate 1 for transfer is about 50 μm or more and 100 μm or less, and more preferably about 60 μm or more and 75 μm or less. As the substrate 1 for transfer, a single-layer sheet of these resins or a multi-layer sheet made of the same or different resins can be used.

[0028] (Release layer 6) The release layer 6 is provided, if necessary, on the surface of the substrate 1 for transfer on the side where the transfer layer 8 is laminated, for the purpose of enhancing the peelability between the substrate 1 for transfer and the transfer layer 8.

[0029] Further, the release layer 6 can also be suitably used to form a surface shape in which the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more and the arithmetic mean height Sa is 0.10 or more, with respect to at least a part of the surface of the transfer layer 8 on the side of the transfer substrate 1. Specifically, an uncured radiation-curable resin composition for forming the release layer 6 is laminated on the surface of the transfer substrate 1, and the layer of the uncured radiation-curable resin composition is irradiated with short-wavelength ultraviolet rays from an excimer lamp or the like to cure the radiation-curable resin composition, thereby forming the release layer 6 and forming a minute uneven shape on the surface. By adjusting the composition of the radiation-curable resin composition, the irradiation conditions of the short-wavelength ultraviolet rays, etc., the minute uneven shape formed on the surface of the release layer can be adjusted. Specific examples of the composition of the radiation-curable resin composition and the irradiation conditions of the short-wavelength ultraviolet rays will be described later. By laminating an uncured resin composition (for example, the uncured resin composition for forming the protective layer 2) for forming the transfer layer 8 on the minute uneven shape of the release layer 6, a surface shape in which the uneven shape of the release layer 6 is inverted is formed on the surface of the transfer layer 8 on the side of the transfer substrate 1. By adjusting the uneven shape of the release layer 6, it is possible to adjust the surface of the transfer layer 8 on the side of the transfer substrate 1 to a desired shape. As described above, since the uneven shape formed on the surface of the release layer 6 and the surface shape (uneven shape) of the transfer layer 8 have an inverted structure (so-called negative-positive relationship), the shapes defined in ISO 25178-2:2012 (for example, the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp, the arithmetic mean height Sa, etc.) are different.

[0030] In addition, when the release layer 6 is not provided on the support, a minute uneven shape may be formed on the surface of the transfer substrate 1 described above, and the surface of the transfer layer 8 on the side of the transfer substrate 1 may be adjusted to a desired shape.

[0031] The release layer 6 may be a solid release layer that covers the entire surface (solid state), or may be provided in part. Usually, considering the peelability, a solid release layer is preferable.

[0032] The release layer 6 can be formed using a resin composition that is a single resin or a mixture of multiple resins selected from silicone resins, fluorine resins, acrylic resins (e.g., including acrylic-melamine resins), polyester resins, polyolefin resins, polystyrene resins, polyurethane resins, cellulose resins, thermoplastic resins such as vinyl chloride-vinyl acetate copolymer resins and nitrocellulose, copolymers of the monomers forming these thermoplastic resins, radiation curable resins, or those obtained by modifying these resins with (meth)acrylic acid or urethane. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of the monomers forming these resins, and those obtained by urethane-modifying these are preferred. More specifically, examples include an acrylic-melamine resin alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and a resin composition obtained by mixing an emulsion of a copolymer of an acrylic resin, styrene, and acrylic acid. Among these, it is particularly preferable to configure the release layer 6 with an acrylic-melamine resin alone or a composition containing 50% by mass or more of an acrylic-melamine resin.

[0033] (Radiation curable resin) The radiation curable resin used for forming the release layer 6 is a resin that crosslinks and cures upon irradiation with radiation. Specifically, examples include those obtained by appropriately mixing at least one of prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or an epoxy group in the molecule. Here, the radiation is as described in the column of [Protective layer 2] below.

[0034] As the monomer used as the radiation-curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is more preferable. As the polyfunctional (meth)acrylate monomer, a (meth)acrylate monomer having two or more (difunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule may be used. Specific examples of the polyfunctional (meth)acrylate monomer include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified diphosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. These monomers may be used alone or in combination of two or more.

[0035] Further, as the oligomer used as the radiation-curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate oligomer having two or more polymerizable unsaturated bonds (bifunctional or higher) in the molecule is more preferable. Examples of the polyfunctional (meth)acrylate oligomer include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, and an oligomer having a cationically polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). Here, the polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth)acrylate group at the terminal or side chain, and can be obtained, for example, by esterifying a polycarbonate polyol with (meth)acrylic acid. The polycarbonate (meth)acrylate may be, for example, a urethane (meth)acrylate having a polycarbonate skeleton. The urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth)acrylate. The acrylic silicone (meth)acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth)acrylate monomer. The urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol, a polyester polyol, or a caprolactone-based polyol and a polyisocyanate compound with (meth)acrylic acid. The epoxy (meth)acrylate can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac type epoxy resin to effect esterification.In addition, a carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. The polyester (meth)acrylate can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, which is obtained by the condensation of a polyvalent carboxylic acid and a polyhydric alcohol, with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid. The polyether (meth)acrylate can be obtained by esterifying the hydroxyl groups of a polyether polyol with (meth)acrylic acid. The polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer. The silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in the main chain. Among these, as the polyfunctional (meth)acrylate oligomer, polycarbonate (meth)acrylate, urethane (meth)acrylate, etc. are particularly preferable. These oligomers may be used alone or in combination of two or more.

[0036] Preferable compositions of the radiation-curable resin composition for forming the release layer 6 include, for example, a radiation-curable resin composition containing a polyfunctional (meth)acrylate monomer (preferably a difunctional (meth)acrylate monomer, a trifunctional (meth)acrylate monomer, etc.), a polyfunctional urethane (meth)acrylate oligomer (preferably a difunctional urethane (meth)acrylate oligomer, a trifunctional urethane (meth)acrylate oligomer, etc.), silicone, fine particles (such as silica particles), and a photopolymerization initiator.

[0037] When forming the release layer 6 using a radiation-curable resin, the formation of the release layer 6 is performed, for example, by preparing a radiation-curable resin composition containing a radiation-curable resin, applying this, and curing it. Note that the viscosity of the radiation-curable resin composition may be any viscosity that can form an uncured resin layer depending on the coating method described later.

[0038] In the present disclosure, the prepared coating solution is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., preferably by gravure coating, so as to have the above thickness, to form an uncured resin layer.

[0039] By irradiating a layer of an uncured radiation-curable resin composition (uncured resin layer) for forming the release layer 6 with short-wavelength ultraviolet rays (light having a wavelength of at least 100 nm or more and 280 nm or less), a fine uneven shape can be formed on the surface of the release layer 6. When the surface of the uncured resin layer for forming the release layer 6 is irradiated with short-wavelength ultraviolet rays, the energy of the ultraviolet rays penetrates only the surface portion of the uncured resin layer, and it is difficult for the energy to reach the portion below. As a result, only the surface portion of the uncured resin layer starts to cure and undergoes curing shrinkage, thereby forming a fine uneven shape (wrinkles). Thus, it is considered that the formation of the fine uneven shape occurs in a state where only a certain thickness direction from the surface of the uncured resin layer for forming the release layer 6 is cured by irradiation with short-wavelength ultraviolet rays.

[0040] Specific examples of the irradiation conditions of the short-wavelength ultraviolet rays when forming the fine uneven shape on the surface of the release layer 6 are as follows.

[0041] As short-wavelength ultraviolet light (light with a wavelength of at least 100 nm and at most 380 nm), for example, "excimer light" including light in the ultraviolet wavelength range from excited dimers, i.e., excimers, formed by the discharge of noble gases such as Ar, Kr, Xe, Ne, etc., halides of noble gases by halogens such as F, Cl, I, Br, etc., or mixed gases of these is preferable. As the wavelength of the excimer light and the excimer serving as the light source, for example, light with a wavelength of 126 nm radiated from an excimer of Ar2 (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), 351 nm (XeF), etc. can be preferably adopted. As the excimer light, either natural emission light or laser light with high coherence (interferability) by induced emission can be used, but usually natural emission light is sufficient. Note that the discharge lamp that emits the light (ultraviolet light) is also referred to as an "excimer lamp". The excimer light is characterized in that it has a single wavelength peak and a narrower half-value width of the wavelength compared to ordinary ultraviolet light (for example, ultraviolet light radiated from a metal halide lamp, a mercury lamp, etc.). By using such excimer light, a fine uneven shape can be preferably formed on the surface of the release layer 6, and the surface shape of the transfer layer 8 can be preferably adjusted to a desired shape.

[0042] From the viewpoint of suitably forming a fine concavo-convex shape on the surface of the release layer 6, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, even more preferably 155 nm or more, and the upper limit is preferably 320 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, even more preferably less than 200 nm, and most preferably 172 nm (Xe2). Thus, in the present disclosure, from the viewpoint of suitably forming a fine concavo-convex shape on the surface of the release layer 6, it is preferable to use light having a shorter wavelength, and medium wavelength ultraviolet rays (wavelength: 280 to 320 nm), short wavelength ultraviolet rays (wavelength: 280 nm or less) are more preferable, and short wavelength ultraviolet rays are even more preferable. The short wavelength ultraviolet rays preferably have a wavelength region of less than 200 nm.

[0043] In the present disclosure, from the viewpoint of suitably forming a fine concavo-convex shape on the surface of the release layer 6, the integrated light amount of the above wavelength light is preferably 1 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, still more preferably 30 mJ / cm 2 or more, even more preferably 50 mJ / cm 2 or more. Also, there is no particular limitation on the upper limit. From the viewpoint of reducing the number of lamps required for irradiation of the wavelength light and improving productivity such as improving production efficiency, the upper limit is preferably 1,000 mJ / cm 2 or less, more preferably 500 mJ / cm 2 or less, still more preferably 300 mJ / cm 2 or less. From the same viewpoint, the ultraviolet output density is preferably 0.001 W / cm or more, more preferably 0.01 W / cm or more, still more preferably 0.03 W / cm or more, and the upper limit is preferably 10 W / cm or less, more preferably 5 W / cm or less, still more preferably 3 W / cm or less. Further, the oxygen concentration during irradiation of the above wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, still more preferably 500 ppm or less, even more preferably 300 ppm or less.

[0044] When forming the release layer 6, in addition to irradiation with the above-mentioned short-wavelength ultraviolet rays, other treatments that contribute to the curing of the radiation-curable resin composition for forming the release layer 6 may be performed. For example, from the viewpoint of stabilizing the uneven shape due to the difference in the degree of progress of curing between the surface portion and the deep portion away from the surface in the depth direction, and promoting the progress of curing in the deep portion, for example, light having a wavelength exceeding 380 nm, preferably light having a wavelength of about 385 nm or more and 400 nm or less may be used for pre-irradiation to preliminarily cure the resin composition as a whole, and then irradiation with light having a wavelength of 100 nm or more and 380 nm or less may be performed, or after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, post-curing may be performed to further cure the resin composition. Whether to employ pre-curing and post-curing may be appropriately determined according to the desired properties required for the release layer 6 (for example, surface properties such as processing characteristics and stain resistance). In addition, although the above-mentioned wavelength light belongs to ultraviolet rays, it is not limited to ultraviolet rays, and other ionizing radiations such as electron beams can also be used. For example, in post-curing, an electron beam may preferably be used from the viewpoint of improving the surface properties of the matting layer.

[0045] Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin and layer thickness to be used, but usually the acceleration voltage is 70 kV or more and 300 kV or less.

[0046] In the irradiation of the electron beam, since the higher the acceleration voltage, the greater the penetration ability, when a resin that is easily deteriorated by electron beam irradiation is used under the release layer 6, the acceleration voltage is selected so that the penetration depth of the electron beam is substantially equal to the thickness of the release layer 6. Thereby, the irradiation of the excess electron beam to the layer located under the release layer 6 can be suppressed, and the deterioration of each layer due to the excess electron beam can be minimized.

[0047] Also, the irradiation dose is preferably an amount at which the crosslinking density of the release layer 6 saturates, usually 5 kGy or more (0.5 Mrad or more), preferably 10 kGy or more (1 Mrad or more), and usually 300 kGy or less (30 Mrad or less), preferably 50 kGy or less (5 Mrad or less). The irradiation dose is usually selected in the range of 5 kGy or more and 300 kGy or less (0.5 Mrad or more and 30 Mrad or less), preferably 10 kGy or more and 50 kGy or less (1 Mrad or more and 5 Mrad or less).

[0048] Furthermore, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, a linear type, a dynatron type, and a high-frequency type can be used.

[0049] When using ultraviolet rays as the ionizing radiation, light rays including ultraviolet rays with a wavelength of 190 nm or more and 380 nm or less may be emitted. The ultraviolet ray source is not particularly limited, and examples include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an ultraviolet light-emitting diode (LED-UV).

[0050] The thickness of the release layer 6 is preferably 0.01 μm or more, more preferably 0.05 μm or more, and preferably 5 μm or less, more preferably 3 μm or less. The preferable range of the thickness of the release layer 6 is 0.01 μm or more and preferably 5 μm or less, more preferably 0.05 μm or more and 3 μm or less.

[0051] (Blocking prevention layer 7) In the transfer sheet of the present disclosure, the blocking prevention layer 7 is a layer provided on the side opposite to the transfer layer 8 of the transfer base material 1 in order to effectively suppress blocking in the transfer sheet. The blocking prevention layer 7 is preferably formed of a resin composition containing particles and a thermoplastic resin.

[0052] The thermoplastic resin is not particularly limited. For example, acrylic resins such as poly(meth)acrylate methyl; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymers; polyethylene terephthalate (PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic ester resin; and the like can be mentioned. The thermoplastic resin may be used alone or in combination of two or more kinds.

[0053] The particles are not particularly limited, and those known as anti-blocking agents can be used. Examples of the particles include inorganic particles, resin particles, and the like.

[0054] The inorganic particles are not particularly limited as long as they are particles formed of an inorganic compound. For example, silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles can be mentioned. Among these, silica particles are preferably mentioned. The inorganic particles may be used alone or in combination of two or more kinds.

[0055] The resin particles are not particularly limited as long as they are particles formed of a resin. For example, urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, polyethylene beads, and the like can be mentioned. The resin particles may be used alone or in combination of two or more kinds.

[0056] The particle size of the particles is, for example, 0.5 μm or more, preferably 1 μm or more, and preferably 20 μm or less, more preferably 10 μm or less. The preferred range of the particle size of the particles is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less. In the present disclosure, the particle size of the particles is a value measured by an injection-type dry measurement method in which a laser diffraction particle size distribution measuring device is used, compressed air is used to inject the powder to be measured from a nozzle, and it is dispersed in the air and measured.

[0057] The content of the particles in the anti-blocking layer 7 is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less. The preferred range of the content of the particles in the anti-blocking layer 7 is preferably 1% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less.

[0058] Also, the thickness of the anti-blocking layer 7 is not particularly limited, but is, for example, 10 μm or less, preferably 5 μm or less, and preferably 1 μm or more, more preferably 2 μm or more. The preferred range of the thickness of the anti-blocking layer 7 is, for example, 1 μm or more and 10 μm or less, more preferably 2 μm or more and 5 μm or less. In the present disclosure, the thickness of the anti-blocking layer 7 means the thickness at a portion where no convex portion due to particles exists.

[0059] The particle size of the particles is preferably larger than the thickness of the anti-blocking layer 7. For example, the particle size of the particles is preferably 1.1 times or more, more preferably 1.3 times or more, of the thickness of the anti-blocking layer 7, and preferably 5 times or less, more preferably 3 times or less. For example, the particle size of the particles is preferably 1.1 times or more and 5 times or less, more preferably 1.3 times or more and 3 times or less, of the thickness of the anti-blocking layer 7.

[0060] [Transfer layer 8] In the transfer sheet of the present disclosure, at least one layer among the protective layer 2, the adhesive layer 3, the primer layer 4, the decorative layer, etc. formed on the support constitutes the transfer layer 8. In the transfer sheet of the present disclosure, the transfer layer 8 preferably contains at least one layer among the adhesive layer 3, the primer layer 4, the decorative layer 5, etc. in addition to the protective layer 2.

[0061] In the present disclosure, after integrally molding the transfer sheet and the molded resin, the interface between the support and the transfer layer 8 is peeled off, and a resin molded product in which the transfer layer 8 of the transfer sheet is transferred to the molded resin layer 9 is obtained. At this time, in the resin molded product of the present disclosure, the surface shape of the transfer layer 8, which is excellent in fingerprint resistance and has an excellent matte finish design, is exposed.

[0062] In the transfer sheet 10 of the present disclosure, on at least a part of the surface of the transfer layer 8 on the side of the transfer base material 1, the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. The decorative sheet of the present disclosure adjusts the balance between the peaks and valleys of the surface shape, so that the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp and the arithmetic mean height Sa are each a predetermined value or more, and it is considered that it is difficult for fingerprints (sebum) to enter the groove portion of the unevenness. Also, even if fingerprints (sebum) enter the groove portion of the unevenness, it is considered that the unevenness is not filled. For this reason, it is considered that there is little visual change before and after touching the surface of the decorative sheet by hand, and the fingerprint resistance is enhanced. In addition, the decorative sheet of the present disclosure makes the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp and the arithmetic mean height Sa each a predetermined value or more, so that when the surface of the decorative sheet is observed from various angles (front direction, diagonal direction), the unevenness is easy to visually recognize, and it is considered that it exhibits an excellent matte finish design. The method for measuring the surface shape of the transfer layer 8 on the side of the transfer base material 1 is as described below.

[0063] From the perspective of more preferably exerting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 is such that the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO25178-2:2012 is preferably 0.80 or more, more preferably 1.00 or more, and preferably 2.40 or less, more preferably 2.20 or less, still more preferably 2.00 or less. Preferred ranges include 0.60 to 2.40, 0.60 to 2.20, 0.60 to 2.00, 0.80 to 2.40, 0.80 to 2.20, 0.80 to 2.00, 1.00 to 2.40, 1.00 to 2.20, 1.00 to 2.00, etc.

[0064] From the perspective of more preferably exerting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 is such that the arithmetic mean height Sa is preferably 0.10 or more, more preferably 0.50 or more, still more preferably 0.70 or more, still more preferably 1.00 or more, and preferably 2.00 or less, more preferably 1.70 or less, still more preferably 1.50 or less. Preferred ranges include 0.10 to 2.00, 0.10 to 1.70, 0.10 to 1.50, 0.50 to 2.00, 0.50 to 1.70, 0.50 to 1.50, 0.70 to 2.00, 0.70 to 1.70, 0.70 to 1.50, 1.00 to 2.00, 1.00 to 1.70, 1.00 to 1.50, etc.

[0065] Also, from the perspective of more preferably exerting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 is such that the ratio (Sp / Sz) of the maximum peak height Sp to the maximum height Sz defined in ISO25178-2:2012 is preferably 0.30 or more, more preferably 0.35 or more, still more preferably 0.40 or more, and preferably 0.60 or less, more preferably 0.55 or less, still more preferably 0.50 or less. Preferred ranges include 0.30 to 0.60, 0.30 to 0.55, 0.30 to 0.50, 0.35 to 0.60, 0.35 to 0.55, 0.35 to 0.50, 0.40 to 0.60, 0.40 to 0.55, 0.40 to 0.50, etc.

[0066] Further, from the viewpoint of more suitably exhibiting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 has a ratio (Sv / Sz) of the maximum valley depth Sv to the maximum height Sz, as defined in ISO 25178-2:2012, preferably of 0.40 or more, more preferably 0.45 or more, still more preferably 0.50 or more, and preferably 0.70 or less, more preferably 0.65 or less, still more preferably 0.60 or less. The preferred range is 0.40 to 0.70, 0.40 to 0.65, 0.40 to 0.60, 0.45 to 0.70, 0.45 to 0.65, 0.45 to 0.60, 0.50 to 0.70, 0.50 to 0.65, 0.50 to 0.60, and the like.

[0067] Further, from the viewpoint of more suitably exhibiting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 has a maximum height Sz (the distance from the highest point to the lowest point on the surface, corresponding to Sp + Sv) as defined in ISO 25178-2:2012, preferably of 8.00 or more, more preferably 8.50 or more, still more preferably 9.00 or more, and preferably 16.00 or less, more preferably 15.00 or less, still more preferably 10.00 or less. The preferred range is 8.00 to 16.00, 8.00 to 15.00, 8.00 to 10.00, 8.50 to 16.00, 8.50 to 15.00, 8.50 to 10.00, 9.00 to 16.00, 9.00 to 15.00, 9.00 to 10.00, and the like.

[0068] Further, from the viewpoint of more suitably exhibiting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 has a maximum peak height Sp as defined in ISO 25178-2:2012, preferably of 2.00 or more, more preferably 3.00 or more, still more preferably 4.00 or more, and preferably 10.00 or less, more preferably 8.00 or less, still more preferably 6.00 or less. The preferred range is 2.00 to 10.00, 2.00 to 8.00, 2.00 to 6.00, 3.00 to 10.00, 3.00 to 8.00, 3.00 to 6.00, 4.00 to 10.00, 4.00 to 8.00, 4.00 to 6.00, and the like.

[0069] Also, from the viewpoint of more preferably exerting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 has a maximum valley depth Sv defined in ISO25178-2:2012, preferably 5.20 or more, more preferably 6.00 or more, still more preferably 6.50 or more, and preferably 10.00 or less, more preferably 9.00 or less, still more preferably 8.00 or less. Preferred ranges include 5.20 to 10.00, 5.20 to 9.00, 5.20 to 8.00, 6.00 to 10.00, 6.00 to 9.00, 6.00 to 8.00, 6.50 to 10.00, 6.50 to 9.00, 6.50 to 8.00, etc.

[0070] Also, from the viewpoint of more preferably exerting the effects of the invention of the present disclosure, the surface shape of the transfer layer 8 has a root mean square height Sq defined in ISO25178-2:2012, preferably 0.50 or more, more preferably 0.75 or more, still more preferably 1.00 or more, and preferably 2.00 or less, more preferably 1.75 or less, still more preferably 1.50 or less. Preferred ranges include 0.50 to 2.00, 0.50 to 1.75, 0.50 to 1.50, 0.75 to 2.00, 0.75 to 1.75, 0.75 to 1.50, 1.00 to 2.00, 1.00 to 1.75, 1.00 to 1.50, etc.

[0071] <Measurement of surface shape> For the surface of the transfer sheet and the surface of the protective layer on the surface of the resin molded product, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the root mean square height Sq, and the arithmetic mean height Sa defined in ISO 25178-2:2012 are measured respectively. The measurement area shall be a rectangular area (1024 μm × 768 μm) at any location on the surface of the protective layer. For the transfer sheet, after peeling off and removing the support (such as the anti-blocking layer, the transfer base material, and the release layer, etc.) from the transfer layer, the surface shape of the transfer layer surface (for example, the surface of the protective layer) is measured. The measuring device uses a shape analysis laser microscope, with an objective lens: 50 times, a laser wavelength: 658 nm, a measurement mode: surface shape mode, a measurement pitch: 0.13 μm, and a measurement quality: high-speed mode. The cut-off value of the arithmetic mean roughness Ra is 0.8 mm.

[0072] (Protective layer 2) The protective layer 2 is a layer provided on the transfer layer 8 so as to be located on the surface of the resin molded product as needed to enhance the scratch resistance, chemical resistance, etc. of the resin molded product. The surface of the transfer layer 8 on the side of the transfer base material 1 is preferably formed by the protective layer 2. That is, in the present disclosure, at least a part of the surface of the protective layer 2 on the side of the transfer base material 1 preferably has the above-mentioned surface shape defined in ISO 25178-2:2012.

[0073] The resin for forming the protective layer 2 is not particularly limited, and examples include thermosetting resins, thermoplastic resins, and radiation-curable resins. Among these, from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability, radiation-curable resins are preferred.

[0074] The thermosetting resin for forming the protective layer 2 is not particularly limited, and examples thereof include polyol resins such as acrylic polyol; polyester polyol; urethane polyols such as polyester urethane polyol and acrylic-urethane polyol; polyolefin polyols such as polyethylene polyol, polypropylene polyol, polybutadiene polyol, and polyisoprene polyol; and resins containing such polyol resins and curing agents. The thermosetting resin may be used alone or in combination of two or more.

[0075] The thermoplastic resin for forming the protective layer 2 is not particularly limited, and examples thereof include acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride-based resin; polyethylene terephthalate (PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic ester resin; and the like. The thermoplastic resin may be used alone or in combination of two or more.

[0076] (Ionizing radiation curable resin) The ionizing radiation curable resin used for forming the protective layer 2 is a resin that crosslinks and cures by irradiation with ionizing radiation. Specifically, it includes at least one of prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or an epoxy group in the molecule, appropriately mixed. Here, ionizing radiation means electromagnetic waves or charged particle beams having energy quanta capable of polymerizing or crosslinking molecules. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams. Among the ionizing radiation curable resins, electron beam curable resins are preferably used in the formation of the protective layer 2 because they can be solvent-free, do not require a photoinitiator for photopolymerization, and stable curing characteristics can be obtained.

[0077] In the laminate of the present disclosure, when an ionizing radiation curable resin is used for forming the protective layer 2, the protective layer 2 in the state of the laminate may be cured, or may be uncured or semi-cured. When the protective layer 2 in the state of the laminate is uncured or semi-cured, after forming the laminate, the protective layer 2 is cured.

[0078] As the monomer used as the radiation-curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is more preferable. As the polyfunctional (meth)acrylate monomer, any (meth)acrylate monomer having two or more (difunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule may be used. Specific examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. These monomers may be used alone or in combination of two or more.

[0079] In addition, as the above oligomer used as a radiation-curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate oligomer having two or more polymerizable unsaturated bonds (bifunctional or higher) in the molecule is more preferable. Examples of the polyfunctional (meth)acrylate oligomer include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, and an oligomer having a cationically polymerizable functional group in the molecule (for example, novolak-type epoxy resin, bisphenol-type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). Here, the polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth)acrylate group at the terminal or side chain, and can be obtained, for example, by esterifying a polycarbonate polyol with (meth)acrylic acid. The polycarbonate (meth)acrylate may be, for example, a polycarbonate-based urethane (meth)acrylate which is a urethane (meth)acrylate having a polycarbonate skeleton. The urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth)acrylate. The acrylic silicone (meth)acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth)acrylate monomer. The urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol, a polyester polyol, or a caprolactone-based polyol with a polyisocyanate compound with (meth)acrylic acid. The epoxy (meth)acrylate can be obtained, for example, by reacting and esterifying (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin.In addition, a carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic anhydride can also be used. The polyester (meth)acrylate can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid. The polyether (meth)acrylate can be obtained by esterifying the hydroxyl groups of a polyether polyol with (meth)acrylic acid. The polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer. The silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in the main chain. Among these, as the polyfunctional (meth)acrylate oligomer, polycarbonate (meth)acrylate (such as polycarbonate-based urethane (meth)acrylate), urethane (meth)acrylate, etc. are particularly preferred. These oligomers may be used alone or in combination of two or more.

[0080] Among the above-described radiation-curable resins, from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability, it is preferable to use polycarbonate (meth)acrylate (such as polycarbonate-based urethane (meth)acrylate), and it is particularly preferable to use polycarbonate (meth)acrylate (such as polycarbonate-based urethane (meth)acrylate) in combination with a polyfunctional (meth)acrylate other than the polycarbonate (meth)acrylate.

[0081] The polycarbonate (meth)acrylate can be obtained, for example, by converting some or all of the hydroxyl groups of a polycarbonate polyol into (meth)acrylate (acrylate or methacrylate). This esterification reaction can be carried out by a normal esterification reaction. For example, 1) a method of condensing a polycarbonate polyol with an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol with acrylic anhydride or methacrylic anhydride in the presence of a catalyst, or 3) a method of condensing a polycarbonate polyol with acrylic acid or methacrylic acid in the presence of an acid catalyst, etc. can be mentioned.

[0082] The above polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having two or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups at the terminal or side chain. A typical production method of this polycarbonate polyol is a method by polycondensation reaction from a diol compound (A), a polyhydric alcohol (B) having a trivalent or higher valence, and a compound (C) serving as a carbonyl component. The diol compound (A) used as a raw material is represented by the general formula HO-R 1 -OH. Here, R 1 is a divalent hydrocarbon group having 2 to 20 carbon atoms, and may contain an ether bond in the group. For example, it is a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

[0083] Specific examples of the diol compound (A) include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc. These diols may be used alone or in combination of two or more.

[0084] Examples of the polyhydric alcohol (B) having a valency of 3 or more include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, sorbitol, etc. Further, alcohols having a hydroxyl group obtained by adding 1 equivalent or more and 5 equivalents or less of ethylene oxide, propylene oxide, or other alkylene oxides to the hydroxyl groups of these polyhydric alcohols may also be used. The polyhydric alcohols may be used alone or in combination of two or more.

[0085] The compound (C) serving as the carbonyl component is any compound selected from diesters of carbonic acid, phosgene, or their equivalents. Specific examples thereof include diesters of carbonic acid such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, phosgene, or halogenated formic acid esters such as methyl chloroformate, ethyl chloroformate, phenyl chloroformate, etc. These may be used alone or in combination of two or more.

[0086] The polycarbonate polyol is synthesized by subjecting the above-described diol compound (A), a polyhydric alcohol (B) having a valence of 3 or higher, and a compound (C) serving as a carbonyl component to a polycondensation reaction under general conditions. For example, the charged molar ratio (B / A) of the diol compound (A) to the polyhydric alcohol (B) is preferably in the range of 50 / 50 or more and 99 / 1 or less. Also, the charged molar ratio of the compound (C) serving as the carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is preferably 0.2 equivalents or more and 2 equivalents or less with respect to the hydroxyl groups of the diol compound and the polyhydric alcohol.

[0087] The number of equivalents (eq. / mol) of the hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above-described charged ratio is 3 or more, preferably 50 or less, more preferably 20 or less, on average per molecule. When it is within this range, the required amount of (meth)acrylate groups is formed by the esterification reaction described below, and appropriate flexibility is imparted to the polycarbonate (meth)acrylate resin. Note that the terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

[0088] The method for producing the polycarbonate polyol described above is described, for example, in JP-A-64-1726. Also, as described in JP-A-3-181517, this polycarbonate polyol can also be produced by a transesterification reaction between a polycarbonate diol and a polyhydric alcohol having a valence of 3 or higher.

[0089] The weight average molecular weight of the polycarbonate (meth)acrylate used in the present disclosure is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth)acrylate is not particularly limited, but from the viewpoint of controlling so that the viscosity does not become too high, it is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. The preferable range of the weight average molecular weight of the polycarbonate (meth)acrylate is 500 or more and 100,000 or less, more preferably 1,000 or more and 50,000 or less, and particularly preferably 2,000 or more and 30,000 or less. Note that the weight average molecular weight of the polycarbonate (meth)acrylate in the present disclosure is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

[0090] In the radiation curable resin composition, the polycarbonate (meth)acrylate is preferably used together with a polyfunctional (meth)acrylate other than the polycarbonate (meth)acrylate. The mass ratio of the polycarbonate (meth)acrylate to the polyfunctional (meth)acrylate (polycarbonate (meth)acrylate / polyfunctional (meth)acrylate) is more preferably 50 / 50 or more and 98 / 2 or less. When the mass ratio of the polycarbonate (meth)acrylate to the polyfunctional (meth)acrylate is less than 98 / 2 (that is, when the amount of the polycarbonate (meth)acrylate is 98% by mass or less based on the total amount of the two components), the above-mentioned durability and chemical resistance are further improved. On the other hand, when the mass ratio of the polycarbonate (meth)acrylate to the polyfunctional (meth)acrylate is greater than 50 / 50 (that is, when the amount of the polycarbonate (meth)acrylate is 50% by mass or more based on the total amount of the two components), the three-dimensional moldability is further improved. Preferably, the mass ratio of the polycarbonate (meth)acrylate to the polyfunctional (meth)acrylate is 60 / 40 or more and 95 / 5 or less.

[0091] In the present disclosure, the polyfunctional (meth)acrylate other than the polycarbonate (meth)acrylate used in combination with the polycarbonate (meth)acrylate may be any (meth)acrylate having two or more functional groups, and there is no particular limitation. Here, bifunctional means having two ethylenically unsaturated bonds {(meth)acryloyl groups} in the molecule. The number of functional groups is preferably 2 or more, or preferably 6 or less.

[0092] Further, the polyfunctional (meth)acrylate used in combination with the polycarbonate (meth)acrylate may be either an oligomer or a monomer, but from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability, a polyfunctional (meth)acrylate oligomer is preferred.

[0093] Examples of the above-mentioned polyfunctional (meth)acrylate oligomers used in combination with polycarbonate (meth)acrylate include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and the like. Here, the urethane (meth)acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate with (meth)acrylic acid. The epoxy (meth)acrylate oligomer can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin for esterification. In addition, a carboxyl-modified epoxy (meth)acrylate oligomer obtained by partially modifying this epoxy (meth)acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The polyester (meth)acrylate oligomer can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by the condensation of a polyvalent carboxylic acid and a polyvalent alcohol with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid. The polyether (meth)acrylate oligomer can be obtained by esterifying the hydroxyl groups of a polyether polyol with (meth)acrylic acid.

[0094] Furthermore, examples of other polyfunctional (meth)acrylate oligomers used in combination with polycarbonate (meth)acrylate include hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and the like.

[0095] In addition, specific examples of the above polyfunctional (meth)acrylate monomers used in combination with polycarbonate (meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified diphosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. The above polyfunctional (meth)acrylate oligomers and polyfunctional (meth)acrylate monomers may be used alone or in combination of two or more.

[0096] In the present disclosure, for the purpose of reducing the viscosity, etc., together with the polyfunctional (meth)acrylate used in combination with the polycarbonate (meth)acrylate, a monofunctional (meth)acrylate can be appropriately used in combination within a range that does not impair the purpose of the present disclosure. Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, and the like. These monofunctional (meth)acrylates may be used alone or in combination of two or more.

[0097] The content of the polycarbonate (meth)acrylate in the radiation-curable resin composition for forming the protective layer 2 is not particularly limited. However, from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability, it is preferably 98% by mass or less, more preferably 90% by mass or less, and preferably 50% by mass or more, more preferably 65% by mass or more. The preferable range of the content of the polycarbonate (meth)acrylate in the radiation-curable resin composition for forming the protective layer 2 is preferably 50% by mass or more and 98% by mass or less, more preferably 65% by mass or more and 90% by mass or less.

[0098] When forming the protective layer 2 using a radiation-curable resin, the formation of the protective layer 2 is performed, for example, by preparing a radiation-curable resin composition, applying it, and subjecting it to crosslinking and curing. Note that the viscosity of the radiation-curable resin composition may be a viscosity capable of forming an uncured resin layer depending on the coating method described later.

[0099] In the present disclosure, the prepared coating solution is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., preferably by gravure coating, so as to have a desired thickness to form an uncured resin layer.

[0100] Irradiate the uncured resin layer thus formed with ionizing radiation such as electron beams or ultraviolet rays to cure the uncured resin layer and form the protective layer 2. Here, when using an electron beam as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but usually the acceleration voltage is 70 kV or more and 300 kV or less.

[0101] In the irradiation of the electron beam, since the higher the acceleration voltage, the greater the penetration ability, when using a resin that is easily deteriorated by electron beam irradiation under the protective layer 2, select the acceleration voltage so that the penetration depth of the electron beam is substantially equal to the thickness of the protective layer 2. Also, when curing with an electron beam together with the release layer 6 formed on the transfer substrate layer and the protective layer 2, select the acceleration voltage so that the penetration depth of the electron beam is substantially equal to the total thickness of the release layer 6 and the protective layer 2. Thereby, it is possible to suppress the irradiation of the excess electron beam to the transfer substrate layer located under the release layer 6 and minimize the deterioration of the transfer substrate layer due to the excess electron beam.

[0102] Also, the irradiation dose is an amount such that the crosslinking density of the protective layer 2 becomes a sufficient value, preferably 30 kGy (3 Mrad) or more, and preferably 300 kGy (30 Mrad) or less, more preferably 100 kGy (10 Mrad) or less. The irradiation dose is preferably 30 kGy (3 Mrad) or more and 300 kGy (30 Mrad) or less, more preferably 30 kGy (3 Mrad) or more and 100 kGy (10 Mrad) or less. By setting the irradiation dose within this range, it is possible to suppress the deterioration of the layer located under the protective layer 2 due to the ionizing radiation that has passed through the protective layer 2. The above example is the case where the number of functional groups of the polyfunctional (meth)acrylate is 2, and an appropriate irradiation dose is required according to the number of functional groups.

[0103] Furthermore, there is no particular limitation on the electron beam source, and for example, various electron beam accelerators such as a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, a linear type, a Dynamitron type, and a high frequency type can be used.

[0104] When using ultraviolet rays as the ionizing radiation, it is sufficient to emit a light ray containing ultraviolet rays with a wavelength of 190 nm or more and 380 nm or less. The ultraviolet ray source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, an ultraviolet light-emitting diode (LED-UV), and the like.

[0105] The thickness of the protective layer 2 is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, and is preferably 20 μm or less, more preferably 15 μm or less. Preferred ranges of the thickness of the protective layer 2 include 1 μm or more and 20 μm or less, more preferably 2 μm or more and 20 μm or less, and still more preferably 3 μm or more and 15 μm or less. When the thickness satisfies such a range, the laminate can effectively exhibit excellent scratch resistance and excellent three-dimensional formability. Further, when the protective layer 2 is formed of an ionizing radiation curable resin, since it is possible to uniformly irradiate the ionizing radiation curable resin composition with ionizing radiation, it becomes possible to cure uniformly, which is also economically advantageous.

[0106] (Adhesive layer 3) The adhesive layer 3 is a layer provided as necessary for the purpose of improving the adhesion between the transfer layer 8 and the molding resin layer 9, and is a layer constituting the surface of the transfer layer 8 on the side opposite to the transfer base material 1 side. Therefore, when laminating the transfer sheet of the present disclosure with the molding resin layer 9, the adhesive layer 3 becomes the layer in contact with the molding resin layer 9.

[0107] It is preferable to use a resin having adhesiveness suitable for the material of the adherend. For example, when the material of the adherend is an acrylic resin, it is preferable to use an acrylic resin. Further, when the material of the adherend is a polyphenylene oxide-polystyrene resin, a polycarbonate resin, or a styrene resin, it is preferable to use an acrylic resin, a polystyrene resin, a polyamide resin, etc. having affinity with these resins. Furthermore, when the material of the adherend is a polypropylene resin, it is preferable to use a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone-indene resin. Additives such as an ultraviolet absorber and an infrared absorber may be blended in the adhesive layer. The thickness of the adhesive layer is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[0108] The adhesive layer can be formed by a known printing method such as a gravure printing method, an offset printing method, a letterpress printing method, or a silk screen printing method.

[0109] (Primer layer 4) The primer layer 4 is a layer provided on the transfer layer 8 as needed for the purpose of improving the adhesion of the protective layer 2, etc. The primer layer 4 is preferably provided so as to be adjacent to the protective layer 2. The primer layer 4 can be formed from a resin composition for forming a primer layer.

[0110] The resin used in the resin composition for forming the primer layer is not particularly limited, and examples thereof include polyol and / or its cured product, urethane resin, acrylic resin, (meth)acrylic-urethane copolymer resin, polyester resin, butyral resin, etc. Among these resins, preferably, polyol and / or its cured product, urethane resin, acrylic resin, and acrylic urethane resin are mentioned. These resins may be used alone or in combination of two or more.

[0111] In the present disclosure, the primer layer 4 is preferably formed of a resin composition containing a polyol and a urethane resin. The polyol may be a compound having two or more hydroxyl groups in the molecule. Specifically, examples thereof include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, etc., and preferably acrylic polyol.

[0112] When a polyol and a urethane resin are used for forming the primer layer 4, the mass ratio thereof (polyol / urethane resin) is preferably 5 / 5 or more, preferably 7 / 3 or more, or preferably 9.5 / 0.5 or less, more preferably 9 / 1 or less. The preferable range of the mass ratio (polyol / urethane resin) is 5 / 5 or more and 9.5 / 0.5 or less, more preferably 7 / 3 or more and 9 / 1 or less.

[0113] Examples of the cured product of the polyol include urethane resin. As the urethane resin, a polyurethane having a polyol (polyhydric alcohol) as the main agent and an isocyanate as a crosslinking agent (curing agent) can be used.

[0114] As the isocyanate, specifically, polyvalent isocyanates having two or more isocyanate groups in the molecule; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. are mentioned. When using isocyanate as a curing agent, the content of isocyanate in the primer layer-forming resin composition is not particularly limited, but from the viewpoint of adhesion and printability when laminating the decorative layer 5 etc. described later, it is preferably 3 parts by mass or more, and preferably 45 parts by mass or less, more preferably 25 parts by mass or less with respect to 100 parts by mass of the above polyol. The content of isocyanate in the primer layer-forming resin composition is preferably 3 parts by mass or more and 45 parts by mass or less, more preferably 3 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the above polyol.

[0115] Among the above urethane resins, from the viewpoint of improving adhesion after crosslinking etc., preferably, a combination of an acrylic polyol or a polyester polyol as the polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as the crosslinking agent; more preferably, a combination of an acrylic polyol and hexamethylene diisocyanate is mentioned.

[0116] The above acrylic resin is not particularly limited, and examples thereof include homopolymers of (meth)acrylic acid esters, copolymers of two or more different (meth)acrylic acid ester monomers, or copolymers of (meth)acrylic acid esters and other monomers. More specifically, as the (meth)acrylic resin, (meth)acrylic acid esters such as poly(meth)acrylic acid methyl, poly(meth)acrylic acid ethyl, poly(meth)acrylic acid propyl, poly(meth)acrylic acid butyl, (meth)acrylic acid methyl-(meth)acrylic acid butyl copolymer, (meth)acrylic acid ethyl-(meth)acrylic acid butyl copolymer, ethylene-(meth)acrylic acid methyl copolymer, styrene-(meth)acrylic acid methyl copolymer, etc. are mentioned.

[0117] The acrylic urethane resin is not particularly limited, and examples thereof include acrylic-urethane block copolymers, and specifically, for example, acrylic-polyester urethane block copolymers. Regarding the ratio of acrylic to urethane in the acrylic-urethane block copolymer, there is no particular limitation, but for example, as the acrylic / urethane ratio (mass ratio), it is preferably 9 / 1 or less, more preferably 8 / 2 or less, and also preferably 1 / 9 or more, more preferably 2 / 8 or more. The preferable range of the acrylic / urethane ratio (mass ratio) is 1 / 9 or more and 9 / 1 or less, more preferably 2 / 8 or more and 8 / 2 or less.

[0118] The thickness of the primer layer 4 is not particularly limited, but for example, it is 0.1 μm or more, more preferably 1 μm or more, and also preferably 10 μm or less. That is, the coating amount is, for example, 0.1 g / m 2 or more, preferably 1 g / m 2 or more, and also preferably 10 g / m 2 or less. The preferable range of the thickness of the primer layer 4 is 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 10 μm or less. By the primer layer 4 satisfying such a thickness, the adhesion of the protective layer 2 can be effectively enhanced.

[0119] Various additives can be blended in the composition for forming the primer layer 4 according to the desired physical properties to be provided. Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, defoaming agents, fillers, solvents, colorants, matting agents, etc. These additives can be appropriately selected from commonly used ones and used. For example, as the matting agent, silica particles, aluminum hydroxide particles, etc. can be mentioned. Also, as the ultraviolet absorber and light stabilizer, a reactive ultraviolet absorber and light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

[0120] The primer layer 4 is formed by an ordinary coating method such as gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, whirler coating, dip coating, solid coating by silk screen, wire bar coating, flow coating, comma coating, pour coating, brush coating, spray coating, etc. or a transfer coating method using a resin composition for forming the primer layer. Here, the transfer coating method is a method of forming a coating film of the primer layer 4 or the adhesive layer on a thin sheet (film base material layer) and then coating the surface of the target layer in the laminate.

[0121] When forming the primer layer 4 on the surface of the protective layer 2 during the production of the transfer sheet, it may be formed on the cured protective layer 2. Also, after laminating a layer composed of the primer layer forming composition on the layer of the radiation curable resin composition for forming the protective layer 2 to form the primer layer 4, the layer composed of the radiation curable resin may be irradiated with radiation to cure the layer composed of the radiation curable resin to form the protective layer 2.

[0122] (Decoration layer 5) The decoration layer 5 is a layer provided as necessary to impart decorativeness to the resin molded product. The decoration layer 5 is composed of, for example, a pattern layer and / or a concealing layer. Here, the pattern layer is a layer provided to express a pattern-like picture such as a pattern, characters, etc. Also, the concealing layer is usually a solid layer provided to conceal the coloring of the molded resin, etc. The concealing layer may be provided inside the pattern layer to enhance the pattern of the pattern layer in the resin molded product, or the decoration layer 5 may be formed by the concealing layer alone.

[0123] The pattern of the pattern layer is not particularly limited, and examples thereof include patterns composed of wood grain, stone grain, cloth grain, sand grain, geometric patterns, characters, etc.

[0124] The decoration layer 5 is formed using printing ink containing a colorant, a binder resin, and a solvent or dispersion medium.

[0125] The colorant of the printing ink used for forming the decorative layer 5 is not particularly limited. For example, metallic pigments composed of flaky foil powder of metals, alloys, or metal compounds such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass, etc.; pearlescent (pearl) pigments composed of foil powder such as mica iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, basic lead carbonate, etc.; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide, etc.; white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide, etc.; inorganic pigments such as zinc white, red lead, vermilion, ultramarine, cobalt blue, titanium yellow, lead yellow, carbon black, etc.; organic pigments (including dyes) such as isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, aniline black, etc. These colorants may be used alone or in combination of two or more.

[0126] Also, the binder resin of the printing ink used for forming the decorative layer 5 is not particularly limited. For example, acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins, etc. These binder resins may be used alone or in combination of two or more.

[0127] In addition, the solvent or dispersion medium of the printing ink used for forming the decorative layer 5 is not particularly limited. For example, petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; water, etc. may be mentioned. These solvents or dispersion media may be used alone or in combination of two or more.

[0128] In addition, the printing ink used for forming the decorative layer 5 may contain, if necessary, a sedimentation inhibitor, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant, etc.

[0129] The decorative layer 5 can be formed, for example, on an adjacent layer such as on the protective layer 2 or the primer layer 4 by a known printing method such as gravure printing, flexographic printing, silk screen printing, offset printing, etc. Further, when the decorative layer 5 is a combination of a pattern layer and a concealing layer, one layer may be laminated and dried, and then the other layer may be laminated and dried.

[0130] The thickness of the decorative layer 5 is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and is preferably 40 μm or less, more preferably 30 μm or less. The preferred range of the thickness of the decorative layer 5 is 1 μm or more and 40 μm or less, more preferably 3 μm or more and 30 μm or less.

[0131] The decorative layer 5 may be a metal thin film layer. Examples of the metal for forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. The method for forming the metal thin film layer is not particularly limited, and examples include vapor deposition methods such as vacuum vapor deposition using the above metals, sputtering methods, and ion plating methods. Further, in order to improve the adhesion to an adjacent layer, a primer layer using a known resin may be provided on the front or back surface of the metal thin film layer.

[0132] 2. Resin molded product and method for manufacturing the same The resin molded article of the present disclosure is formed by integrating the transfer layer and the molding resin layer of the transfer sheet of the present disclosure. Specifically, by laminating the molding resin layer 9 on the side opposite to the support of the transfer sheet, a resin molded article 21 with a transfer substrate having at least the molding resin layer 9, the transfer layer 8, and the transfer substrate laminated in this order is obtained (see, for example, FIG. 7). Next, by peeling the support from the resin molded article 21 with a transfer substrate, the resin molded article of the present disclosure in which at least the molding resin layer 9 and the transfer layer 8 are laminated is obtained (see, for example, FIG. 8).

[0133] The resin molded article with a transfer substrate of the present disclosure is a resin molded article with a transfer substrate in which at least a molding resin layer, a transfer layer, and a transfer substrate are laminated in this order. Similar to the transfer sheet 10 of the present disclosure, on at least a part of the surface on the transfer substrate side of the transfer layer 8, the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. Further, the resin molded article of the present disclosure is a resin molded article in which at least a molding resin layer and a transfer layer are laminated. Similar to the transfer sheet 10 of the present disclosure, on at least a part of the surface on the transfer substrate side of the transfer layer, the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more.

[0134] In the resin molded article with a transfer substrate and the resin molded article of the present disclosure, regarding the preferable surface shape (each of the above-described surface shapes defined in ISO25178-2:2012) on the side of the transfer substrate 1 of the transfer layer 8, it is the same as the transfer sheet 10 of the present disclosure described above, and the description thereof is omitted.

[0135] Further, from the viewpoint of more preferably exerting the effects of the invention of the present disclosure, the surface (transfer layer 8) of the resin molded article of the present disclosure has a 60-degree specular glossiness measured by the method described in the following <Evaluation of the design property of a matte finish>, preferably 9 or less, more preferably 5 or less, still more preferably 4 or less. Regarding the lower limit, for example, it is 1 or more, and preferable ranges include 1 to 9, 1 to 5, 1 to 4, etc.

[0136] Further, from the viewpoint of more preferably exerting the effects of the invention of the present disclosure, the surface (transfer layer 8) of the resin molded article of the present disclosure has an 85-degree specular glossiness measured by the method described in the following <Evaluation of the design property of a matte finish>, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less. Regarding the lower limit, for example, it is 9 or more, and preferable ranges include 9 to 40, 9 to 30, 9 to 20, etc.

[0137] <Evaluation of the design property of a matte finish> Regarding the surface of the protective layer on the surface of the resin molded article, a three-angle surface gloss meter is used to evaluate the design property of a matte finish from the viewpoints of 60-degree specular glossiness and 85-degree specular glossiness. The smaller the 60-degree specular glossiness and 85-degree specular glossiness are, the more excellent the design property of a matte finish is evaluated.

[0138] The resin molded article of the present disclosure can be manufactured by a manufacturing method including the following steps. A step of disposing the transfer sheet 10 in a mold, injecting a resin in a fluid state into the mold from the side of the transfer layer 8, solidifying the injected resin, and integrating the transfer sheet 10 with the outer surface of the molded resin layer 9 simultaneously with injection molding. A step of obtaining a resin molded article provided with a transfer layer 8 on the surface by peeling the transfer base material 1 from the resin molded article 21 with the transfer base material obtained in the above step (when having a release layer 6 and an antiblocking layer 7, these layers are also peeled).

[0139] When applying the transfer sheet to, for example, the injection molding simultaneous transfer decoration method, examples of the method for manufacturing the resin molded article of the present disclosure include a method including the following steps (1) to (5). (1) First, a step of heating the transfer sheet from the transfer layer 8 side with a hot plate with the transfer layer 8 side of the above transfer sheet facing into the mold. (2) A step of preforming (vacuum forming) the transfer sheet along the shape of the mold inner surface, bringing it into close contact with the mold inner surface, and closing the mold. (3) A step of injecting resin into the mold. (4) A step of taking out the resin molded article (resin molded article with a transfer base material) from the mold after cooling the injected resin, and (5) A step of peeling the transfer base material (including the support) from the resin molded article.

[0140] In both of the above steps (1) and (2), the temperature for heating the transfer sheet is preferably in the range of not less than near the glass transition temperature of the transfer base material 1 and less than the melting temperature (or melting point). Usually, it is more preferable to perform at a temperature near the glass transition temperature. Note that the vicinity of the above glass transition temperature refers to a range of about glass transition temperature ± 5°C. When using a polyester film suitable as the transfer base material 1, it is generally about 70 to 130°C. When using a mold with a not overly complex shape, the step of heating the transfer sheet and the step of preforming the transfer sheet may be omitted, and in the step (3) described later, the transfer sheet may be formed into the shape of the mold by the heat and pressure of the injected resin.

[0141] In the above two steps (3), the resin for molding described below is melted, injected into the cavity, and the transfer sheet and the resin for molding are integrated. When the resin for molding is a thermoplastic resin, it is made into a fluid state by heating and melting. When the resin for molding is a thermosetting resin, an uncured liquid composition is heated at room temperature or appropriately to be in a fluid state and injected, and then cooled and solidified. As a result, the transfer sheet is integrated and adhered to the formed resin molded body, becoming a resin molded product with a transfer substrate. The heating temperature of the resin for molding depends on the type of the resin for molding, but is generally 180°C or higher and 320°C or lower.

[0142] The resin molded product with a transfer substrate thus obtained is taken out of the mold after being cooled in step (4), and then the support is peeled off from the protective layer 2 in step (5) to obtain a resin molded product. Also, the step of peeling the support from the protective layer 2 may be performed simultaneously with the step of taking out the decorated resin molded product from the mold. That is, step (5) may be included in step (4).

[0143] In the resin molded product of the present disclosure, the molding resin layer 9 may be formed by selecting a resin according to the application. The resin for molding for forming the molding resin layer 9 may be a thermoplastic resin or a thermosetting resin.

[0144] Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, vinyl chloride-based resin, etc. These thermoplastic resins may be used alone or in combination of two or more.

[0145] Examples of the thermosetting resin include urethane resin, epoxy resin, etc. These thermosetting resins may be used alone or in combination of two or more.

[0146] In the resin molded article with a transfer substrate, since the transfer substrate serves as a protective sheet for the resin molded article, it may be stored as it is without being peeled off after the production of the resin molded article with a transfer substrate, and the support may be peeled off at the time of use. By using it in such a manner, it is possible to prevent the resin molded article from being damaged by rubbing or the like during transportation.

[0147] The resin molded article of the present disclosure can be used, for example, as an interior material or an exterior material of a vehicle such as an automobile; a fitting such as a window frame or a door frame; an interior material of a building such as a wall, a floor, or a ceiling; a housing of a household electrical appliance such as a television receiver or an air conditioner; a container or the like.

Example

[0148] Hereinafter, the present disclosure will be described in detail by showing examples and comparative examples. However, the present disclosure is not limited to the examples.

[0149] <Manufacture of transfer sheet> [Example 1] As the transfer substrate, a polyethylene terephthalate film (thickness: 75 μm) having an easy-adhesive layer formed on one surface was used. A blocking prevention layer (acrylic resin containing 1% silica particles, thickness: 1.5 μm) was applied to the surface of the polyethylene terephthalate film opposite to the surface on which the easy-adhesive layer was formed. A coating liquid of resin A1 (Table 1) described later was printed on the surface of the easy-adhesive layer of the polyethylene terephthalate film by gravure printing to form a release layer (thickness: 1 μm).

[0150] Next, ultraviolet rays were irradiated using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet ray amount: 6 W / cm 2 ), then ultraviolet rays were irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe2), ultraviolet ray output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm 2 , nitrogen atmosphere (oxygen concentration: 200 ppm or less)), and then further ultraviolet rays were irradiated using a high-pressure mercury lamp (ultraviolet ray output density: 200 W / cm) to form a fine uneven shape on the surface of the release layer.

[0151] Next, an ionizing radiation curable resin composition was applied onto the release layer having a fine concavo-convex shape by a bar coater so that the dry coating amount was 3.0 g / m 2 to form a coating film for forming a protective layer. The ionizing radiation curable resin composition is a urethane acrylate. An electron beam with an accelerating voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated from above this coating film to cure the coating film for forming a protective layer and form a protective layer. The surface shape on the release layer side of the protective layer has a shape in which the fine concavo-convex shape of the release layer is transferred (negative-positive relationship).

[0152] Next, a resin composition (acrylic polyol) for forming a primer layer was applied onto this protective layer by gravure printing to form a primer layer (thickness: 1.5 μm). Further, a black decorative layer forming ink composition containing a binder resin (50% by mass of an acrylic resin and 50% by mass of a vinyl chloride-vinyl acetate copolymer resin) was used to form a solid black decorative layer (thickness: 5 μm) by gravure printing on the primer layer. Further, an adhesive layer (thickness: 1.5 μm) was formed by gravure printing using a resin composition for forming an adhesive layer on the decorative layer, thereby obtaining a transfer sheet composed of a laminate in which an anti-blocking layer / transfer substrate / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order.

[0153] [Example 2] A transfer sheet composed of a laminate in which an anti-blocking layer / transfer substrate / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order was obtained in the same manner as in Example 1, except that resin A2 was used instead of resin A1 in the formation of the release layer.

[0154] [Example 3] A transfer sheet composed of a laminate in which an anti-blocking layer / transfer substrate / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order was obtained in the same manner as in Example 1, except that resin A3 was used instead of resin A1 in the formation of the release layer.

[0155] [Example 4] In the formation of the release layer, a transfer sheet comprising a laminate in which an antiblocking layer / a transfer substrate / a release layer / a protective layer / a primer layer / a decorative layer / an adhesive layer are laminated in this order was obtained in the same manner as in Example 1, except that resin B was used instead of resin A1.

[0156] [Example 5] In the formation of the release layer, a transfer sheet comprising a laminate in which an antiblocking layer / a transfer substrate / a release layer / a protective layer / a primer layer / a decorative layer / an adhesive layer are laminated in this order was obtained in the same manner as in Example 1, except that resin C was used instead of resin A1.

[0157] [Example 6] In the formation of the release layer, a transfer sheet comprising a laminate in which an antiblocking layer / a transfer substrate / a release layer / a protective layer / a primer layer / a decorative layer / an adhesive layer are laminated in this order was obtained in the same manner as in Example 1, except that resin D1 was used instead of resin A1.

[0158] [Example 7] In the formation of the release layer, a transfer sheet comprising a laminate in which an antiblocking layer / a transfer substrate / a release layer / a protective layer / a primer layer / a decorative layer / an adhesive layer are laminated in this order was obtained in the same manner as in Example 1, except that resin D2 was used instead of resin A1.

[0159] [Example 8] In the formation of the release layer, a transfer sheet comprising a laminate in which an antiblocking layer / a transfer substrate / a release layer / a protective layer / a primer layer / a decorative layer / an adhesive layer are laminated in this order was obtained in the same manner as in Example 1, except that resin D3 was used instead of resin A1.

[0160] [Example 9] In the formation of the protective layer, a transfer sheet comprising a laminate in which an antiblocking layer / a transfer substrate / a release layer / a protective layer / a primer layer / a decorative layer / an adhesive layer are laminated in this order was obtained in the same manner as in Example 8, except that a coating film for forming the protective layer was formed by coating with a bar coater so that the dry coating amount of the ionizing radiation curable resin composition was 5.0 g / m 2 And thus obtained.

[0161] [Example 10] In the formation of the protective layer, except that the dry coating amount of the radiation-curable resin composition was applied by a bar coater so as to be 2.4 g / m 2 and a coating film for forming a protective layer was formed, in the same manner as in Example 8, a transfer sheet composed of a laminate in which an antiblocking layer / transfer substrate / release layer / protective layer / primer layer / decorative layer / adhesive layer were laminated in this order was obtained.

[0162] [Comparative Example 1] As the transfer substrate, a polyethylene terephthalate film (thickness: 75 μm) having an easy-adhesive layer formed on one surface was used. An antiblocking layer (acrylic resin containing 1% silica particles, thickness: 1.5 μm) was applied to the surface of the polyethylene terephthalate film opposite to the surface on which the easy-adhesive layer was formed. A coating solution of resin E (Table 1) described later was printed by gravure printing on the surface of the easy-adhesive layer of the polyethylene terephthalate film to form a release layer (thickness: 1 μm).

[0163] Next, on the release layer, a radiation-curable resin composition was applied by a bar coater so as to have a dry coating amount of 3.0 g / m 2 and a coating film for forming a protective layer was formed. The radiation-curable resin composition is a urethane acrylate. An electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated from above this coating film to cure the coating film for forming a protective layer and form a protective layer. On the surface shape of the protective layer on the release layer side, a fine uneven shape due to the presence of silica particles was formed.

[0164] Next, a resin composition for forming a primer layer (acrylic polyol) was coated on this protective layer by gravure printing to form a primer layer (thickness 1.5 μm). Further, on the primer layer, a black decorative layer forming ink composition containing a binder resin (50% by mass of acrylic resin, 50% by mass of vinyl chloride-vinyl acetate copolymer resin) was used to form a full-surface black single-color decorative layer (thickness 5 μm) by gravure printing. Further, an adhesive layer (thickness 1.5 μm) was formed by gravure printing using a resin composition for forming an adhesive layer on the decorative layer, thereby obtaining a transfer sheet composed of a laminate in which a blocking prevention layer / transfer substrate / release layer / protective layer / primer layer / decorative layer / adhesive layer were laminated in order.

[0165] [Comparative Example 2] A transfer sheet composed of a laminate in which a blocking prevention layer / transfer substrate / release layer / protective layer / primer layer / decorative layer / adhesive layer were laminated in order was obtained in the same manner as in Comparative Example 1, except that the amount of silica particles contained in Resin E was reduced.

[0166] <Resin composition for forming a release layer> Resin A1: An ionizing radiation curable resin composition obtained by adding 0.1% by mass of silicone, 6% by mass of silica particles, and a photopolymerization initiator to 40.0 parts by mass of a bifunctional acrylate monomer, 30.0 parts by mass of a trifunctional acrylate monomer, and 30.0 parts by mass of a trifunctional urethane acrylate oligomer having a weight average molecular weight of about 5,000 Resin A2: An ionizing radiation curable resin composition obtained by adding 0.5% by mass of silicone, 6% by mass of silica particles, and a photopolymerization initiator to 40.0 parts by mass of a bifunctional acrylate monomer, 30.0 parts by mass of a trifunctional acrylate monomer, and 30.0 parts by mass of a trifunctional urethane acrylate oligomer having a weight average molecular weight of about 5,000 Resin A3: An ionizing radiation curable resin composition obtained by adding 1.0% by mass of silicone, 6% by mass of silica particles, and a photopolymerization initiator to 40.0 parts by mass of a bifunctional acrylate monomer, 30.0 parts by mass of a trifunctional acrylate monomer, and 30.0 parts by mass of a trifunctional urethane acrylate oligomer having a weight average molecular weight of about 5,000 Resin B: An ionizing radiation curable resin composition obtained by adding 0.5% by mass of silicone, silica particles, and a photopolymerization initiator to 70.0 parts by mass of a bifunctional acrylate monomer and 30.0 parts by mass of a trifunctional urethane acrylate oligomer having a weight average molecular weight of about 2,500 Resin C: An ionizing radiation curable resin composition obtained by adding 0.5% by mass of silicone, 6% by mass of silica particles, and a photopolymerization initiator to 70.0 parts by mass of a bifunctional acrylate monomer and 30.0 parts by mass of a trifunctional acrylate monomer Resin D1: An ionizing radiation curable resin composition obtained by adding 0.1% by mass of silicone, 6% by mass of silica particles, and a photopolymerization initiator to 55.0 parts by mass of a bifunctional acrylate monomer, 15.0 parts by mass of a trifunctional acrylate monomer, and 30.0 parts by mass of a trifunctional urethane acrylate oligomer having a weight average molecular weight of about 2,500 Resin D2: An ionizing radiation curable resin composition obtained by adding 0.5% by mass of silicone, 6% by mass of silica particles, and a photopolymerization initiator to 55.0 parts by mass of a bifunctional acrylate monomer, 15.0 parts by mass of a trifunctional acrylate monomer, and 30.0 parts by mass of a trifunctional urethane acrylate oligomer having a weight average molecular weight of about 2,500 Resin D3: An ionizing radiation curable resin composition obtained by adding 1.0% by mass of silicone, 6% by mass of silica particles, and a photopolymerization initiator to 55.0 parts by mass of a bifunctional acrylate monomer, 15.0 parts by mass of a trifunctional acrylate monomer, and 30.0 parts by mass of a trifunctional urethane acrylate oligomer having a weight average molecular weight of about 2,500 Resin E: An ionizing radiation curable resin composition obtained by adding 1.0% by mass of silicone and 4.4% by mass of silica particles to 85.0 parts by mass of a bifunctional acrylate oligomer and 15.0 parts by mass of a trifunctional monomer

[0167] <Manufacture of Resin Molded Article> Each obtained transfer sheet was placed in a mold and heated at 350 °C for 7 seconds with an infrared heater, preformed along the shape (plate shape) in the mold by vacuum forming, and then mold-clamped (maximum draw ratio 50%). Thereafter, an injection resin was injected into the cavity of the mold, and the transfer sheet and the injection resin were integrally molded to obtain a resin molded product with a transfer substrate. The molding resin temperature was 240 °C, and an ABS resin was used as the injection resin. When the resin molded product with the transfer substrate was taken out of the mold, the support (blocking prevention layer, transfer substrate, and release layer) was peeled off and removed from the transfer layer to obtain a resin molded product.

[0168] <Measurement of surface shape> Regarding the surfaces of the protective layers on the surfaces of the transfer sheet and the resin molded product, the maximum peak height Sp, the maximum valley depth Sv, the maximum height Sz, the root mean square height Sq, and the arithmetic mean height Sa defined in ISO25178-2:2012 were measured, respectively. The measurement area was a rectangular (1024 μm × 768 μm) area at an arbitrary location on the surface of the protective layer. For the transfer sheet, after the support (blocking prevention layer, transfer substrate, and release layer) was peeled off and removed from the transfer layer, the surface shape of the protective layer surface was measured. The measuring device used was a shape analysis laser microscope ("Stand: VK-D1 Measurement unit: VK-X1050", manufactured by Keyence Corporation), with an objective lens: 50 times, laser wavelength: 658 nm, measurement mode: surface shape mode, measurement pitch: 0.13 μm, and measurement quality: measured in high-speed mode. The cut-off value of the arithmetic mean roughness Ra was 0.8 mm. The results are shown in Tables 1 and 2.

[0169] <Evaluation of fingerprint resistance> The fingerprint resistance of the surface of the protective layer on the surface of the resin molded product was evaluated according to the following procedure. The evaluation criteria for fingerprint resistance are as follows. The results are shown in Table 2. (i) Put a finger on a non-woven fabric wipe (Bencot) impregnated with oleic acid. (ii) Press the finger on an unused non-woven fabric wipe 10 times to remove excess oleic acid. (iii) Press the finger on the surface of the resin molded product to attach oleic acid. (iv) Fold the unused non-woven fabric waistband four times around a cylinder with a diameter of 2.5 cm, fix it with a rubber band, and wipe it 10 times back and forth under a load of 300 g. (v) Visually check the wiped area on the surface of the resin molded product under a fluorescent lamp.

[0170] (Evaluation criteria for fingerprint resistance) A+: After wiping the fingerprint, no trace of the fingerprint can be seen at all. A: After wiping the fingerprint, when the viewing angle is arbitrarily changed, it can be seen slightly (the trace is less than 10%). B: After wiping the fingerprint, the trace remains, exceeding 10% and less than or equal to 30%. C: After wiping the fingerprint, the trace remains, exceeding 30% and less than or equal to 50%. D: After wiping the fingerprint, the trace remains, exceeding 50%.

[0171] <Measurement of the peel strength of the release layer> The ease of peeling when manually peeling the support from the surface of the resin molded product with the transfer substrate obtained above was measured by the following method. The evaluation criteria are as follows. The results are shown in Table 2.

[0172] (Evaluation criteria for peel strength) A: It peels off easily. B: It is difficult to peel off, but no release layer remains on the transfer layer side. C: It is even more difficult to peel off, and no release layer exists on the transfer layer side. D: It is difficult to peel off, and the remaining release layer can be recognized on the transfer layer side. E: It does not peel off or the substrate breaks.

[0173] <Evaluation of the design property of the matte finish> Regarding the surface of the protective layer on the surface of the resin molded product, the design property of the matte finish was evaluated from the viewpoints of 60-degree specular glossiness and 85-degree specular glossiness using a BYK micro-trigloss 3-angle surface gloss meter. The smaller the 60-degree specular glossiness and 85-degree specular glossiness, the better the design property of the matte finish is evaluated. The results are shown in Table 2.

[0174] <Evaluation of end adhesion> Regarding the end part of the resin molded product, the adhesion was evaluated by the following method. Using Nichiban cellophane tape (registered trademark) (No. 405), a 90-degree peel test was repeated 10 times at the same location at the end of the molded product to confirm the adhesion. When peeling was observed, the distance of peeling from the end of the molded product was measured with a ruler and evaluated. The evaluation criteria are as follows. The results are shown in Table 2.

[0175] (Evaluation Criteria for End Adhesion) A: No peeling at all B: Peeling is observed and less than 3 mm C: Peeling is observed and 3 - 5 mm D: Peeling is observed and greater than 5 mm

[0176]

Table 1

[0177]

Table 2

Explanation of Symbols

[0178] 1 Substrate for transfer 2 Protective layer 3 Adhesive layer 4 Primer layer 5 Decorative layer 6 Release layer 7 Anti-blocking layer 8 Transfer layer 9 Molded resin layer 10 Transfer sheet 20 Resin molded product 21 Resin molded product with transfer substrate

Claims

1. A transfer sheet in which at least a base material for transfer and a transfer layer are laminated, wherein at least a part of the surface of the transfer layer on the side of the base material for transfer has a surface shape in which the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. A transfer sheet.

2. The transfer sheet according to claim 1, wherein the surface shape has a ratio (Sp / Sz) of the maximum peak height Sp to the maximum height Sz defined in ISO 25178-2:2012 of 0.30 or more.

3. The transfer sheet according to claim 1 or 2, wherein the surface shape has a ratio (Sv / Sz) of the maximum valley depth Sv to the maximum height Sz defined in ISO 25178-2:2012 of 0.40 or more.

4. The transfer sheet according to claim 1 or 2, wherein the surface shape has a maximum height Sz defined in ISO 25178-2:2012 of 8.00 or more.

5. The transfer sheet according to claim 1 or 2, wherein the transfer layer further includes at least one layer selected from the group consisting of a protective layer, a primer layer, a decorative layer, and an adhesive layer.

6. The transfer sheet according to claim 1 or 2, wherein the surface of the transfer layer on the side of the base material for transfer is formed by a protective layer.

7. The transfer sheet according to claim 1 or 2, wherein a release layer is laminated between the transfer layer and the base material for transfer.

8. The transfer sheet according to claim 1 or 2, further comprising an anti-blocking layer on the side of the base material for transfer opposite to the transfer layer.

9. A resin molded article with a base material for transfer, in which at least a molded resin layer, a transfer layer, and a base material for transfer are laminated in this order, wherein at least a part of the surface of the transfer layer on the side of the base material for transfer has a surface shape in which the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more. A resin molded article with a base material for transfer.

10. A resin molded article in which at least a molded resin layer and a transfer layer are laminated, A resin molded product having a surface shape on at least a part of the surface of the transfer layer on the side opposite to the molded resin layer side, wherein the ratio (Sv / Sp) of the maximum valley depth Sv to the maximum peak height Sp defined in ISO 25178-2:2012 is 0.60 or more, and the arithmetic mean height Sa is 0.10 or more.

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