JP6728569B2 - Transfer sheet and decorative resin molded product using the same - Google Patents

Description

The present invention provides a transfer sheet capable of imparting a texture and a three-dimensional effect to the surface of a decorative resin molded product by a concavo-convex forming resin layer provided on a transfer substrate, a decorative resin molded product using the same, and It relates to a manufacturing method.

2. Description of the Related Art Conventionally, as a method for decorating interior and exterior of vehicles, interior materials for building materials, housings for home appliances, and the like, decoration using a transfer-type decorating sheet (transfer sheet) is known. Such a transfer sheet is produced by laminating a surface protective layer, a pattern layer, an adhesive layer and the like on a film serving as a transfer base material. Most of the decorative resin molded products manufactured using such a transfer sheet are pressed by the resin in the mold and have a flat surface shape.

In recent years, the texture and the three-dimensional effect are very important. Therefore, a decorative method called an overlay method, in which a decorative sheet is laminated later on a resin molded product that has been molded in advance, has been increasingly used. In these methods, there is no need for a process that receives a large amount of heat or pressure while the surface of the decorative sheet is pressed against the mold, such as the injection molding simultaneous decoration method in which decoration and molding are performed simultaneously in the mold. Therefore, there is an advantage that a decorative resin molded product can be produced without impairing the texture and the three-dimensional appearance of the surface of the decorative sheet.

However, in the post-decoration in these construction methods, since the undecorated resin molded product is decorated with the decorating sheet, it is compared with the method of simultaneously decorating and molding in the mold using the transfer sheet. Then, there is a drawback that the number of steps is increased. Therefore, it is required to develop a method for imparting a texture or a three-dimensional effect to the surface of the decorative resin molded product in the decorative resin molded product using the transfer sheet.

Conventionally, a method of forming a raised printing layer on a base material of a transfer sheet is known as a technique for forming a concavo-convex shape on the surface of a decorative resin molded article using a transfer sheet (for example, patents References 1-4). However, in the raised printing, fine patterning is difficult, and fine uneven shapes cannot be formed. For this reason, it is difficult to form an excellent texture or three-dimensional effect on the surface of the decorative resin molded product by the method using these transfer sheets. There is also a method (Patent Document 5) in which unevenness is formed on the surface of the molded product by forming hairline-shaped unevenness by embossing on the back surface of the transfer substrate. However, it is preferable to use a PET film or the like having high heat resistance as the transfer base material from the viewpoint of dimensional stability and suppression of generation of wrinkles, since a high heat resistance film is unsuitable for embossing, it is sufficient. It is not possible to obtain an uneven design.

JP-A-60-264213 JP-A-60-264214 JP, 2006-239967, A Japanese Patent Publication No. 2008-510638 Special table 2003-326552 gazette

The main object of the present invention is to provide a transfer sheet capable of imparting excellent texture and three-dimensional effect to the surface of a decorative resin molded product. Furthermore, the present invention relates to a method for manufacturing the transfer sheet, a decorative resin molded product using the transfer sheet, and a method for manufacturing the decorative resin molded product.

The present inventors diligently studied to solve the above problems. As a result, a transfer substrate having a first surface and a second surface, a surface protection layer laminated on the first surface side of the transfer substrate, and the second surface side of the transfer substrate. According to the transfer sheet having the embossed unevenness shape and the unevenness forming resin layer formed on the surface opposite to the transfer substrate, the embossed uneven shape has an excellent texture or It was found that a three-dimensional effect can be given. The present invention has been completed by further studies based on such findings.

That is, the present invention provides the inventions of the following modes.
Item 1. A transfer substrate having a first surface and a second surface;
A surface protective layer laminated on the first surface side of the transfer substrate,
A concavo-convex forming resin layer which is laminated on the second surface side of the transfer substrate and has an embossed concavo-convex shape formed on the surface opposite to the transfer substrate;
A transfer sheet including.
Item 2. Item 2. The transfer sheet according to Item 1, wherein the unevenness forming resin layer is formed of a cured product of an ionizing radiation curable resin or a thermoplastic resin.
Item 3. Item 3. The transfer sheet according to Item 1 or 2, wherein the unevenness-forming resin layer has a thickness in the range of 10 to 100 µm.
Item 4. Item 4. The transfer sheet according to any one of Items 1 to 3, wherein the height difference between the embossed uneven shapes is in the range of 10 to 100 µm.
Item 5. Item 5. The transfer sheet according to any one of Items 1 to 4, wherein the embossed concavo-convex concave portion does not reach the transfer substrate.
Item 6. Item 6. The transfer sheet according to any one of Items 1 to 5, wherein a primer layer is laminated on the side of the surface protective layer opposite to the transfer substrate.
Item 7. Item 7. The transfer sheet according to any one of Items 1 to 6, wherein a pattern layer is laminated on a side of the surface protective layer opposite to the transfer substrate.
Item 8. Item 8. The transfer sheet according to any one of Items 1 to 7, wherein an adhesive layer is laminated on a surface of the surface protective layer opposite to the transfer substrate.
Item 9. Item 9. The transfer sheet according to any one of Items 1 to 8, wherein the transfer substrate has a release layer and a substrate film layer in this order from the first surface side.
Item 10. Item 10. The transfer sheet according to any one of Items 1 to 9, wherein only one base film layer is laminated on the transfer sheet.
Item 11. Item 11. A method for producing a decorated resin molded product, comprising a step of laminating the transfer sheet according to any one of items 1 to 10 on a resin molded product and peeling the transfer base material and the concavo-convex forming resin layer.
Item 12. Item 10. A method for manufacturing a transfer sheet according to any one of Items 1 to 10,
A transfer substrate having a first surface and a second surface, a surface protective layer laminated on the first surface side of the transfer substrate, and a second surface side of the transfer substrate. And a step of preparing a laminated sheet including a resin layer,
Embossing is performed from the resin layer side of the laminated sheet to form a concavo-convex forming resin layer having an embossed concavo-convex shape on the surface of the resin layer,
A method of manufacturing a transfer sheet, comprising:

According to the present invention, a transfer base material having a first surface and a second surface, a surface protective layer laminated on the first surface side of the transfer base material, and the second transfer base material of the transfer base material. On the surface side of the decorative resin molded article by forming a transfer sheet that is laminated on the surface side and has an embossed unevenness forming resin layer formed on the surface opposite to the transfer base material. Excellent texture and three-dimensional effect can be added. Further, according to the present invention, it is possible to provide a method for producing the transfer sheet, a decorative resin molded article using the transfer sheet, and a method for producing the decorative resin molded article.

It is a schematic diagram of a cross-sectional structure of one form of the transfer sheet of the present invention. It is a schematic diagram of a cross-sectional structure of one form of the transfer sheet of the present invention. It is a schematic diagram for demonstrating the manufacturing process of the decorative resin molded product of this invention. It is a schematic diagram for demonstrating the manufacturing process of the decorative resin molded product of this invention. It is a schematic diagram for demonstrating the manufacturing process of the decorative resin molded product of this invention. It is a schematic diagram of a cross-sectional structure of one embodiment of the decorative resin molded product of the present invention.

1. Transfer sheet The transfer sheet of the present invention comprises a transfer base material having a first surface and a second surface, a surface protection layer laminated on the first surface side of the transfer base material, and a transfer base material of the transfer base material. An unevenness-forming resin layer, which is laminated on the second surface side and has an embossed uneven shape formed on the surface opposite to the transfer substrate. The transfer sheet of the present invention having such a configuration can impart excellent texture and three-dimensional effect to the surface of the decorative resin molded product.

The transfer sheet of the present invention is a transfer sheet that is used by separating the transfer base material and the concavo-convex forming resin layer from the final product. Specifically, the transfer sheet of the present invention is laminated on various objects to be transferred, for example, a resin molded product, and the transfer base material and the concavo-convex forming resin layer are separated from the surface protective layer to give a decorative resin molded product. can get. Such a decorative resin molded product has excellent scratch resistance and designability (texture and three-dimensional effect) because the surface protective layer is formed on the surface and at the same time, an uneven shape is also formed.

In the present specification, unless otherwise specified, “(meth)acrylic acid” means “acrylic acid or methacrylic acid”, and other similar notations have the same meaning. Further, the transfer sheet of the present invention does not have to have a layer having a pattern or the like, and may be, for example, transparent or may be composed of a single color.

Laminated structure of transfer sheet The transfer sheet of the present invention comprises a transfer base material 10 having a first surface 10a and a second surface 10b, and a surface protective layer 4 laminated on the first surface 10a side of the transfer base material 10. And a concavo-convex forming resin layer 1 laminated on the second surface 10b side of the transfer base material 10 have a laminated structure.

A primer layer 5 is laminated on the side of the surface protective layer 4 opposite to the transfer substrate 10 as needed for the purpose of enhancing the adhesion between the surface protective layer 4 and a layer adjacent thereto. May be. In addition, a pattern layer 6 may be laminated on the side of the surface protective layer 4 opposite to the transfer substrate 10, if necessary, for the purpose of imparting decorative properties. Further, an adhesive layer 7 may be laminated on the surface of the surface protective layer 4 opposite to the transfer substrate 10, if necessary. In the transfer sheet of the present invention, the layer on the surface protective layer 4 side of the transfer substrate 10 (that is, the surface protective layer 4, the primer layer 5, the pattern layer 6, the adhesive layer 7, etc., which are provided as necessary) is provided. The transfer layer 11 is formed integrally with the decorative resin molded product.

The transfer substrate 10 is provided adjacent to the surface protective layer 4 and can be peeled from the surface protective layer 4. The transfer substrate 10 may be a single layer or a plurality of layers. When the transfer substrate 10 is formed of a single layer, the transfer substrate 10 is usually formed of the substrate film layer 2. The base film layer 2 is a layer that can function as a support in the transfer base 10. When the transfer base material 10 is formed of a plurality of layers, examples of the layer included in the transfer base material 10 include the release layer 3 in addition to the base material film layer 2. The release layer 3 is provided between the base film layer 2 and the surface protective layer 4 as needed for the purpose of enhancing the releasability between these layers.

The concavo-convex forming resin layer 1 is laminated on the second surface 10b side of the transfer substrate 10. In the unevenness forming resin layer 1, an embossed uneven shape is formed on the surface opposite to the transfer substrate 10.

As the laminate structure of the transfer sheet of the present invention, a laminate structure in which a concavo-convex forming resin layer/base film layer/surface protective layer is laminated in this order; a concavo-convex forming resin layer/base film layer/release layer/surface protective layer Laminated structure laminated in this order; Laminated structure resin layer/base film layer/surface protection layer/pattern layer laminated structure in this order; Concavo-convex formation resin layer/base film layer/surface protection layer/primer layer/ Laminated structure in which picture layers are laminated in this order; Laminated structure in which concavo-convex forming resin layer/base film layer/surface protective layer/adhesive layer are laminated in this order; concavo-convex forming resin layer/base film layer/surface protective layer/ Laminated structure in which primer layer/adhesive layer is laminated in this order; concavo-convex forming resin layer/base film layer/surface protection layer/picture layer/adhesive layer laminated in this order; concavo-convex forming resin layer/base film Layer/surface protective layer/primer layer/pattern layer/adhesive layer laminated in this order; unevenness-forming resin layer/base film layer/release layer/surface protective layer/primer layer/pattern layer/adhesive layer Examples thereof include a laminated structure in which the layers are laminated in this order. FIG. 1 shows a schematic view of a cross-sectional structure of one embodiment of a transfer sheet in which an unevenness-forming resin layer/base film layer/surface protection layer are laminated in this order as one embodiment of the laminated structure of the transfer sheet of the present invention. In addition, in FIG. 2, as one embodiment of the laminated structure of the transfer sheet of the present invention, a concavo-convex forming resin layer/base film layer/release layer/surface protection layer/primer layer/pattern layer/adhesive layer are laminated in this order. The schematic diagram of the cross-sectional structure of one form of the transfer sheet is shown.

Composition of each layer forming the transfer sheet [transfer substrate 10]
The transfer base material 10 is provided adjacent to the surface protection layer 4, and is a base material that can be peeled from the surface protection layer 4. The surface protection layer 4 is laminated on the first surface 10a side of the transfer substrate 10. As described above, when the transfer base material 10 is formed of a single layer, the transfer base material 10 is usually formed of the base material film layer 2. When the transfer base material 10 is formed of a plurality of layers, as the layers included in the transfer base material 10, the release layer 3 and the like are formed in addition to the base material film layer 2.

[Base film layer 2]
The base material film layer 2 is a layer that can function as a support in the transfer base material 10 (further, the transfer sheet). The base film layer 2 used in the present invention is selected in consideration of vacuum forming suitability, and a resin sheet made of a thermoplastic resin is typically used. Examples of the thermoplastic resin include polyester resin; acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; acrylonitrile-butadiene-styrene resin (ABS resin); vinyl chloride resin and the like.

In the present invention, it is preferable to use a polyester sheet as the base film layer 2 in terms of heat resistance, dimensional stability, moldability, and versatility. 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 includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate. (PEN) can be preferably mentioned, and polyethylene terephthalate (PET) is particularly preferable in terms of heat resistance and dimensional stability.

In the present invention, from the viewpoint of heat resistance and dimensional stability, the base film layer 2 preferably has a thermal shrinkage of 3.0% or less when heated at 180° C. for 5 minutes, and preferably 2% or less. Is more preferable. By using such a base film layer 2, it is possible to suppress heat shrinkage of the base film layer 2 when embossing the unevenness forming resin layer.

Further, the base film layer 2 may contain fine particles for the purpose of improving workability. As the fine particles, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide, inorganic particles such as kaolin, organic particles made of acrylic resin, internally deposited particles And so on. The average particle diameter of the fine particles is preferably 0.01 to 5.0 μm, more preferably 0.05 to 3.0 μm. The content of the fine particles in the polyester resin is preferably 0.01 to 5.0% by mass, more preferably 0.1 to 1.0% by mass. In addition, various stabilizers, lubricants, antioxidants, antistatic agents, defoamers, optical brighteners and the like can be added as required.

The polyester sheet used in the present invention is manufactured, for example, as follows. First, the above polyester resin and other raw materials are supplied to a known melt extrusion device such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester resin to melt. Then, while extruding the molten polymer, it is rapidly cooled and solidified on the rotating cooling drum to a temperature not higher than the glass transition temperature to obtain a substantially amorphous unoriented sheet. This sheet is obtained by stretching the sheet biaxially to form a sheet, and heat-setting the sheet. 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 machine direction and/or the transverse direction before or after the heat setting. In the present invention, the stretching ratio is preferably 7 times or less, more preferably 5 times or less, still more preferably 3 times or less, in order to obtain sufficient dimensional stability. Within this range, when the obtained polyester sheet is used for the transfer sheet of the present invention and used in the injection molding simultaneous transfer method, the transfer sheet does not shrink again in the temperature range at the time of injecting the injection resin, The required sheet strength can be obtained in the temperature range. The polyester sheet may be manufactured as described above or a commercially available product may be used.

In addition, the base film layer 2 has a physical or chemical property such as an oxidation method or a textured method on one or both sides, if desired, for the purpose of improving the adhesion to the unevenness-forming resin layer 1 and the release layer 3 described later. Surface treatment can be applied. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone treatment method and the like, and examples of the roughening method include sand blast method and solvent treatment method. These surface treatments are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effect and operability. Further, the base film may be subjected to a treatment such as formation of an easy-adhesion layer for the purpose of enhancing interlayer adhesion between the base film and the layer provided thereon. When a commercially available polyester sheet is used, the commercially available polyester sheet which has been subjected to the above-mentioned surface treatment in advance or which is provided with an easily adhesive layer can be used.

The thickness of the base film layer 2 is usually 10 to 150 μm, preferably 10 to 125 μm, and more preferably 10 to 80 μm. As the base film layer 2, a single layer sheet of these resins or a multi-layer sheet of the same or different resins can be used.

[Release layer 3]
The release layer 3 is a layer provided on the first surface side 10a side of the transfer substrate 10 as needed for the purpose of enhancing the releasability between the substrate film layer 2 and the surface protective layer 4. .. That is, when the transfer substrate 10 includes the release layer 3, the transfer substrate 10 includes the release layer 3 and the base film layer 2 in order from the first surface 10a side.

The release layer 3 may be a solid release layer which covers the entire surface (solid surface), or may be partially provided. Usually, a solid release layer is preferable in consideration of releasability.

The release layer 3 includes a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin is included), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, a cellulose resin. , Vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrification cotton, copolymers of monomers that form the thermoplastic resins, or those resins modified with (meth)acrylic acid or urethane. The resin composition can be formed by using a single resin composition or a mixture of a plurality of resin compositions. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. -Based resin alone, acrylic-melamine-based resin-containing composition, resin composition obtained by mixing polyester-based resin and urethane-modified copolymer of ethylene and acrylic acid, copolymer of acrylic-based resin and styrene and acrylic The resin composition and the like mixed with the emulsion of Of these, it is particularly preferable that the release layer 3 is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

The thickness of the release layer 3 is usually about 0.01 to 5 μm, preferably about 0.05 to 3 μm.

[Transfer layer 11]
In the present invention, the transfer layer 11 constitutes a transfer sheet together with the transfer base material 10, and is transferred to a transfer target (molding resin layer 8 or the like). After being transferred to the transferred material, the transfer base material 10 is peeled off to form a decorative resin molded product in which the transfer layer 11 and the transferred material are laminated.

The transfer layer 11 includes at least the surface protective layer 4, and the surface protective layer 4 is in contact with the transfer base material 10. As described above, the transfer layer 11 can be provided with the primer layer 5, the pattern layer 6, the adhesive layer 7, and the like, if necessary.

[Surface protection layer 4]
In the transfer sheet of the present invention, the surface protective layer 4 is used to enhance the chemical resistance and scratch resistance of the decorative resin molded product, and at the same time, to improve the texture and three-dimensional appearance of the decorative resin molded product. It is a layer provided on the transfer sheet so as to be located on the surface.

In the present invention, the resin forming the surface protective layer 4 is not particularly limited, and examples thereof include a thermosetting resin, a thermoplastic resin, an ionizing radiation curable resin, etc., which may be appropriately selected according to the application of the transfer sheet. You can Among these, the ionizing radiation curable resin is preferable from the viewpoint of enhancing the scratch resistance of the transfer sheet and imparting excellent texture and three-dimensional effect to the surface of the decorative resin molded product. The surface protective layer 4 may be formed of one layer, or may be formed of two or more layers.

When the surface protective layer 4 is formed of a curable resin such as a thermosetting resin or an ionizing radiation curable resin, the surface protective layer 4 may be cured at the time of manufacturing the transfer sheet, or may be uncured in the transfer sheet state or It may be semi-cured, and may be cured after transferring the surface protective layer 4 onto the resin molded product.

The thermosetting resin is not particularly limited, and examples thereof include epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, and carboxyl functional acrylic. Resins, amide functional copolymers, urethane resins and the like.

The thermoplastic resin is not particularly limited, and acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; polyethylene terephthalate (PET). ), polyester resins such as polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic ester resin; and the like.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface protective layer 4 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group is contained in the molecule. And a mixture of at least one of a prepolymer, an oligomer, a monomer, and the like. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays are also included. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the surface protective layer 4 because it can be solvent-free, does not require a photopolymerization initiator, and has stable curing characteristics. Used for.

As the above-mentioned monomer used as the ionizing radiation-curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more (two or more functional) polymerizable unsaturated bonds, preferably three or more (three or more functional) polymerizable unsaturated bonds in the molecule. As the polyfunctional (meth)acrylate, specifically, 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, hydroxypivalic acid neopentyl glycol 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.

Further, as the above-mentioned oligomer used as the ionizing radiation curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds are contained in the molecule. A polyfunctional (meth)acrylate oligomer having (bifunctional or more) is 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, oligomers 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.) and the like. .. 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 for example, polycarbonate polyol (meth) It can be obtained by esterification with acrylic acid. The polycarbonate (meth)acrylate may be, for example, a polycarbonate urethane (meth)acrylate that is a urethane (meth)acrylate having a polycarbonate skeleton. The urethane (meth)acrylate having a polycarbonate skeleton is obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth)acrylate. Acrylic silicone (meth)acrylate can be obtained by radically 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 reacting a polyether polyol, a polyester polyol, a caprolactone-based polyol, or a polycarbonate polyol with a polyisocyanate compound with (meth)acrylic acid. it can. Epoxy (meth)acrylate can be obtained by, for example, reacting (meth)acrylic acid with the oxirane ring of a bisphenol type epoxy resin or novolac type epoxy resin having a relatively low molecular weight to esterify. A carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate is obtained by, for example, esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acid and polyhydric alcohol with (meth)acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding alkylene oxide with (meth)acrylic acid. The polyether (meth)acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer. Silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. Among these, polycarbonate (meth)acrylate and urethane (meth)acrylate are particularly preferable as the polyfunctional (meth)acrylate oligomer. These oligomers may be used alone or in combination of two or more.

When the transfer sheet of the present invention is used for three-dimensional molding, it is preferable to use polycarbonate (meth)acrylate among the above-mentioned ionizing radiation curable resins from the viewpoint of obtaining excellent three-dimensional molding. From the viewpoint of achieving both three-dimensional moldability and scratch resistance, it is more preferable to use a combination of polycarbonate (meth)acrylate and urethane (meth)acrylate. When a polyfunctional (meth)acrylate monomer is used as the ionizing radiation curable resin, it is preferable to use it in combination with a thermoplastic resin such as an acrylic resin from the viewpoint of obtaining excellent three-dimensional moldability. From the viewpoint of achieving both moldability and scratch resistance, the mass ratio of the polyfunctional (meth)acrylate monomer and the thermoplastic resin in the ionizing radiation curable resin composition may be 25:75 to 75:25. More preferable. When urethane (meth)acrylate is used as the ionizing radiation-curable resin, a polyurethane oligomer obtained by reacting a caprolactone-based polyol and a polyisocyanate compound (meth) is used from the viewpoint of achieving both three-dimensional moldability and scratch resistance. ) It is preferable to use a caprolactone-based urethane (meth)acrylate obtained by esterification with acrylic acid or the above-mentioned polycarbonate-based urethane (meth)acrylate. In particular, when the surface protective layer 4 is cured during the production of the transfer sheet, the surface protective layer 4 is likely to crack during three-dimensional molding. Therefore, it is preferable to use an ionizing radiation curable resin having excellent three-dimensional moldability.

(Additional ingredients)
Inorganic particles, organic particles, and various additives can be added to the surface protective layer 4 as other additive components depending on desired physical properties to be provided in the surface protective layer 4.

The inorganic particles are not particularly limited, for example, silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, metal oxide particles such as zinc oxide particles are preferably mentioned. , Silica particles and alumina particles are preferable, and silica particles are particularly preferable. The inorganic particles may be used alone or in combination of two or more.

The organic particles are not particularly limited, and examples thereof include urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, polyethylene beads and the like. Among these, urethane beads, nylon beads, and acrylic beads are preferable. The organic particles may be used alone or in combination of two or more.

Other additives include, for example, weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents. , A thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant and the like. These additives can be appropriately selected and used from commonly used additives. Further, as the ultraviolet absorber or the light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can be used.

(Thickness of the surface protective layer 4)
The thickness of the surface protective layer 4 (thickness after drying or curing) is not particularly limited, but from the viewpoint of imparting a texture and a three-dimensional effect to the surface of the decorative resin molded product, for example, 1 to 1000 μm, preferably 1 ˜50 μm, and more preferably 1 to 30 μm. Further, when the thickness in such a range is satisfied, sufficient physical properties as a protective layer such as scratch resistance and weather resistance can be obtained, and when the surface protective layer 4 is formed using an ionizing radiation curable resin. Since it can be uniformly irradiated with ionizing radiation, it can be uniformly cured, which is economically advantageous. Further, when the thickness of the surface protective layer 4 satisfies the above range, the three-dimensional formability of the transfer sheet is improved, so that it is possible to obtain high conformability to a complicated three-dimensional shape such as an automobile interior application.

(Formation of surface protection layer 4 when using ionizing radiation curable resin)
The surface protective layer 4 is formed, for example, by preparing an ionizing radiation-curable resin composition containing an ionizing radiation-curable resin, applying the composition, and crosslinking-curing the composition. The cross-linking and curing of the surface protective layer 4 may be performed during the production of the transfer sheet as described above, or after the transfer onto the resin molded product. The viscosity of the ionizing radiation curable resin composition is such that an uncured resin layer can be formed on a layer (for example, the transfer substrate 10) located under the surface protective layer 4 by a coating method described later. Good.

In the present invention, the prepared coating solution is applied onto the layer located under the surface protective layer 4 such that the thickness becomes the above-mentioned, such as gravure coat, bar coat, roll coat, reverse roll coat and comma coat. A known method, preferably gravure coating is applied to form an uncured resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam or ultraviolet ray to cure the uncured resin layer to form the surface protective layer 4. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage thereof can be appropriately selected according to the resin used and the thickness of the layer, but usually the accelerating voltage is about 70 to 300 kV.

In the irradiation of electron beams, the higher the accelerating voltage is, the higher the transmissivity is. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protection layer 4, the penetration depth of the electron beams and the surface protection are reduced. The accelerating voltage is selected so that the thicknesses of the layers 4 are substantially equal. Thereby, the irradiation of the extra electron beam to the layer located under the surface protective layer 4 can be suppressed, and the deterioration of each layer due to the excess electron beam can be minimized.

The irradiation dose is preferably such that the crosslink density of the surface protective layer 4 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as Cockloft-Walton type, Van de Graft type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. Can be used.

When ultraviolet rays are used as the ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, but examples thereof 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).

By adding various additives to the surface protective layer 4 thus formed, a hard coat function, an antifogging coat function, an antifouling coat function, an antiglare coat function, an antireflection coat function, an ultraviolet shielding coat function, You may perform the process of giving functions, such as an infrared shielding coat function.

[Primer layer 5]
The primer layer 5 is a layer provided as needed for the purpose of enhancing the adhesiveness between the surface protective layer 4 and the layer located thereunder (on the side opposite to the transfer substrate 10 ). The primer layer 5 can be formed of resin.

The resin forming the primer layer 5 is not particularly limited, but examples thereof include urethane resin, acrylic resin, (meth)acrylic-urethane copolymer resin, polyester resin, butyral resin, and the like. Among these resins, urethane resin, acrylic resin, and (meth)acrylic-urethane copolymer resin are preferable. These resins may be used alone or in combination of two or more.

As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main agent and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like. Specific examples of the above-mentioned isocyanates include polyvalent isocyanates having two or more isocyanate groups in the molecule; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, Aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate may be mentioned.

Among the urethane resins, from the viewpoint of improving adhesion after cross-linking, etc., preferably a combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking agent; more preferably Examples include a combination of acrylic polyol and hexamethylene diisocyanate.

The acrylic resin is not particularly limited, but includes, for example, (meth)acrylic acid ester homopolymer, two or more different (meth)acrylic acid ester monomer copolymers, or (meth)acrylic acid ester and other And a copolymer with the above monomer. Specific examples of the (meth)acrylic resin include methyl poly(meth)acrylate, ethyl poly(meth)acrylate, propyl poly(meth)acrylate, butyl poly(meth)acrylate, and (meth)acrylic acid. Methyl-(meth)butyl acrylate copolymer, ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-(meth)acrylic acid methyl copolymer, styrene-(meth)acrylic acid methyl copolymer Examples thereof include (meth)acrylic acid esters such as polymers. These acrylic resins may be used alone or in combination of two or more.

The (meth)acrylic-urethane copolymer resin is not particularly limited, and examples thereof include an acrylic-urethane (polyester urethane) block copolymer resin. Further, the above-mentioned various isocyanates are used as the curing agent. The ratio of acrylic to urethane in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited, but for example, the acrylic/urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 /2 to 2/8 is included.

The thickness of the primer layer 5 is not particularly limited, but is, for example, about 0.1 to 10 μm, preferably about 1 to 10 μm. By satisfying such a thickness of the primer layer, the weather resistance of the transfer sheet can be further enhanced, and cracking, breakage, whitening, etc. of the surface protective layer 4 can be effectively suppressed.

The primer layer 5 uses a resin for forming the primer layer 5, and is gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, It is formed by a usual coating method such as a wire bar coat, a flow coat, a comma coat, a pouring coat, a brush coat, a spray coat or a transfer coating method. Here, the transfer coating method is a method of forming a coating film of a primer layer 5 and an adhesive layer 7 described later on a thin sheet (film base material) and then coating the surface of a target layer in the transfer sheet. ..

[Pattern layer 6]
The pattern layer 6 is a layer provided as necessary in order to give the resin molded article a decorative property. The pattern layer 6 is formed by printing various patterns using ink and a printing machine. The pattern formed by the pattern layer 6 is not particularly limited, and for example, a wood grain pattern, a marble pattern (for example, a travertine marble pattern), a stone pattern that imitates the surface of rock, or a cloth that imitates a texture or cloth-like pattern. Examples include patterns, tile pasting patterns, brickwork patterns, etc., and also composite patterns such as parquet and patchwork. These patterns are formed by multicolor printing using ordinary process colors of yellow, red, blue, and black, and also by multicolor printing using special colors prepared by preparing individual color plates that make up the pattern. It is formed.

As the pattern ink used for the pattern layer 6, a binder in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent is appropriately mixed is used. The binder is not particularly limited and includes, for example, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, Examples thereof include polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins. These resins may be used alone or in combination of two or more.

The colorant is not particularly limited, and examples thereof include inorganic pigments such as carbon black (black ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, rouge, cadmium red, ultramarine blue, cobalt blue, and quinacridone red. , Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metallic pigments consisting of scale-like foil pieces such as aluminum and brass, titanium dioxide coated mica, pearlescent gloss consisting of scale-like foil pieces such as basic lead carbonate (pearl) ) Pigments and the like.

The thickness of the pattern layer 6 is not particularly limited, but is, for example, about 1 to 30 μm, preferably about 1 to 20 μm.

[Adhesive layer 7]
The adhesive layer 7 is provided under the surface protective layer 4, the pattern layer 6 and the like (on the side of the molding resin layer 8) for the purpose of improving the adhesion between the transfer sheet and the transfer target (molding resin layer 8 etc.). It is a layer provided as necessary. The resin forming the adhesive layer 7 is not particularly limited as long as it can improve the adhesion and adhesiveness between these layers, and for example, a thermoplastic resin or a thermosetting resin is used. Examples of the thermoplastic resin include acrylic resin, acryl-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber resin. .. The thermoplastic resins may be used alone or in combination of two or more. Further, examples of the thermosetting resin include urethane resin and epoxy resin. The thermosetting resin may be used alone or in combination of two or more.

Although the adhesive layer 7 is not always a necessary layer, when it is assumed that the transfer sheet of the present invention is applied to a decorating method by sticking it onto a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Is preferably provided. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 7 by using one of the above-mentioned various resins that is commonly used as a resin that exhibits adhesiveness when pressed or heated.

The thickness of the adhesive layer 7 is not particularly limited, but is, for example, about 0.1 to 30 μm, preferably about 0.5 to 20 μm, and more preferably about 1 to 8 μm.

[Concavo-convex forming resin layer 1]
The concavo-convex forming resin layer 1 is laminated on the second surface 10b side of the transfer substrate 10, and has an embossed concavo-convex shape provided by embossing on the surface opposite to the transfer substrate. The concavo-convex forming resin layer 1 is a layer provided to form a concavo-convex shape corresponding to the embossed concavo-convex shape of the concavo-convex forming resin layer 1 on the surface protective layer 4 when the transfer sheet is transferred.

The material for forming the concavo-convex forming resin layer 1 is not particularly limited as long as it can impart the concavo-convex shape to the surface protective layer 4 during transfer, and examples thereof include a cured product of an ionizing radiation curable resin or a thermoplastic resin. To be As the ionizing radiation curable resin and the thermoplastic resin, the same ones as those exemplified in the item of the above-mentioned [surface protective layer 4] can be exemplified.

In the present invention, from the viewpoint of imparting a more excellent texture and three-dimensional effect to the surface of the decorative resin molded product, it is preferable that the unevenness forming resin layer 1 is made of a thermoplastic resin or an ionizing radiation curable resin. Since the concavo-convex forming resin layer 1 is made of a thermoplastic resin or an ionizing radiation curable resin, a desired concavo-convex shape can be easily obtained by embossing, and the fine embossed concavo-convex shape formed on the surface of the concavo-convex forming resin layer 1 can be obtained. Is reflected in the surface protective layer 4 with high accuracy, and it becomes possible to impart more excellent texture and three-dimensional effect to the surface of the decorative resin molded product.

As the thermoplastic resin forming the unevenness forming resin layer 1, acrylic resin is more preferable, and acrylic polyol is particularly preferable.

As the ionizing radiation curable resin for forming the concavo-convex forming resin layer 1, the same resins as those used for the surface protective layer can be used.

The concavo-convex forming resin layer 1 may contain a filler. By including the filler in the unevenness forming resin layer 1, it is possible to prevent the unevenness forming resin layer 1 from adhering to the mold side and peeling from the surface protective layer 4 when the decorative resin molded product is taken out after molding. it can. The filler is not particularly limited, and inorganic particles such as silica particles (colloidal silica, fumed silica, precipitated silica, reactive silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles; urethane beads, nylon Examples thereof include organic particles such as beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene beads. The filler may be used alone or in combination of two or more. When the irregularity-forming resin layer 1 contains a filler, the content thereof is not particularly limited and may be, for example, 1 to 10 mass %.

The thickness of the concavo-convex forming resin layer 1 is not particularly limited, but is, for example, preferably about 5 to 100 μm, more preferably about 5 to 60 μm, and further preferably about 10 to 40 μm. The thickness of the unevenness forming resin layer 1 means the distance in the stacking direction from the back surface (the surface on the surface protective layer 4 side) of the unevenness forming resin layer 1 to the convex portion.

In the transfer sheet of the present invention, the embossed uneven shape of the unevenness forming resin layer 1 can be formed as follows. First, the transfer substrate 10 having the first surface 10a and the second surface 10b, the surface protective layer 4 laminated on the first surface 10a side of the transfer substrate 10, and the second surface of the transfer substrate 10 A laminated sheet including a resin layer laminated on the surface side 10b is prepared. The resin layer is a layer before the unevenness forming resin layer 1 is provided with an uneven shape, and is formed of the same material as the unevenness forming resin layer 1. Next, embossing is performed from the resin layer side of the laminated sheet to form the concavo-convex forming resin layer 1 in which embossed concavo-convex shapes are provided on the surface of the resin layer. Specific examples of embossing conditions are as follows.

As a method of performing embossing, an embossing method using heat and pressure is usually used. The embossing method by heating and pressing is a method of heating and softening the surface of the resin layer of the above-mentioned laminated sheet, applying pressure with an embossing plate to form an uneven pattern on the embossing plate, and cooling and fixing. The shape of the embossing plate used for embossing corresponds to the embossed uneven shape given to the unevenness forming resin layer. For the embossing, for example, a known single-wafer type or rotary type embossing machine can be used.

The height difference of the embossed concavo-convex shape provided by embossing is preferably about 5 to 100 μm, more preferably about 5 to 60 μm, from the viewpoint of imparting excellent texture and three-dimensional effect to the surface of the decorative resin molded product. Preferably, it is about 10 to 40 μm. In the transfer sheet of the present invention, the height difference of the embossed concavo-convex shape means the distance in the laminating direction from the back surface (surface on the surface protective layer 4 side) of the concavo-convex forming resin layer 1 to the convex portion, and the laminating direction to the concave portion. Means the difference from the distance.

From the viewpoint of imparting excellent texture and three-dimensional effect to the surface of the decorative resin molded product, in the transfer sheet of the present invention, the embossed concavo-convex concave portion of the concave-convex forming resin layer 1 does not reach the transfer substrate 10. However, it may reach the transfer substrate 10.

The heating temperature in embossing is not particularly limited, but is preferably about 180°C to 220°C.

Since the transfer sheet of the present invention includes the unevenness-forming resin layer 1 having the embossed shape as described above and the transfer base material 10, the transfer sheet has high dimensional stability, and a desired uneven shape can be decorated with a resin. It can be applied to a molded product.

2. Transfer Sheet Manufacturing Method The transfer sheet of the present invention can be manufactured by a method including the following steps.
A transfer substrate 10 having a first surface 10a and a second surface 10b, a surface protective layer 4 laminated on the first surface 10a side of the transfer substrate 10, and a second surface 10b of the transfer substrate 10. A step of preparing a laminated sheet including a resin layer laminated on the side,
A step of performing embossing from the resin layer side of the laminated sheet to form a concavo-convex forming resin layer 1 having embossed concavo-convex shapes on the surface of the resin layer.

The resin layer and embossing are as described above. When the transfer layer 11 is provided with the primer layer 5, the pattern layer 6, the adhesive layer 7, and the like, after the surface protective layer 4 is formed on the transfer substrate 10, the surface protective layer 4 is formed. Then, these layers may be laminated. The composition of each layer constituting the transfer sheet, the laminated structure, and the like are as described in detail in the above item “1. Transfer sheet”.

Further, in the present invention, the transfer sheet of the present invention can be configured by laminating only one base film layer by adopting the above manufacturing method. By using the transfer sheet, it is possible to manufacture a decorative resin molded product having an excellent texture and a three-dimensional effect on the surface.

3. Decorative Resin Molded Product and Method of Manufacturing the Same The transfer sheet of the present invention described above was formed on the second surface 10b side of the transfer substrate 10 when transferring to various transferred bodies (for example, resin molded products). The unevenness-forming resin layer 1 can form an uneven shape on the surface of the decorative resin molded product, and by peeling the transfer substrate 10 and the unevenness-forming resin layer 1 from the resin molded product, an excellent texture can be obtained on the surface. It can be used for the purpose of producing a decorated resin molded product having a three-dimensional effect.

The decorative resin molded product of the present invention is manufactured by laminating the molding resin layer 8 on the transfer sheet of the present invention. The decorative resin molded product of the present invention can be manufactured by a method including a step of laminating the transfer sheet of the present invention on the resin molded product and peeling the transfer substrate 10 and the unevenness forming resin layer 1. More specifically, for example, the transfer sheet of the present invention is used as a sheet for simultaneous injection molding transfer, and the transfer sheet and the resin molded product (molding resin layer 8) are laminated to form the concavo-convex forming resin layer 1, A transfer base material and a decorative resin molded product with a concavo-convex forming resin layer are obtained by stacking a transfer base material 10, a transfer layer 11 including the surface protective layer 4, and a molding resin layer 8 in this order (see FIG. 5). ).

Next, the transfer base material 10 and the concavo-convex formation resin layer 1 are peeled from the transfer base material and the decorative resin molded article with the concavo-convex formation resin layer, thereby forming at least the transfer layer 11 including the surface protective layer 4 and the molding resin. A decorative resin molded product in which the layers 8 and 8 are laminated is obtained (for example, see FIG. 6 ).

When the surface protective layer 4 is formed of an uncured or semi-cured curable resin, the surface protective layer 4 is further irradiated with ionizing radiation or heated for the obtained decorative resin molded product. Can be cured.

Further, as described above, when the transfer layer 11 of the present invention has the primer layer 5, the pattern layer 6, the adhesive layer 7 and the like in addition to the surface protective layer 4, the decorative resin molded article contains these Layers are included.

The specific production of the decorative resin molded product of the present invention can be performed, for example, in the order of the following steps (1) to (5).
(1) A step of heating the transfer sheet from the surface protective layer 4 side by a heating plate with the surface protective layer 4 side (opposite the concavo-convex forming resin layer 1) of the transfer sheet facing the inside of the mold (2) The transfer sheet (3) Molding resin (resin forming the molding resin layer 8) is preformed (vacuum forming) so as to conform to the shape of the inside of the mold, and brought into close contact with the inner surface 20 of the mold to close the mold. Step (4) of injecting into the mold (4) Step of removing the decorative resin molded article (the decorative resin molded article with the transfer base material and the concavo-convex forming resin layer) from the mold after the molding resin is cooled (5) The decorative resin molding A step of peeling the transfer substrate 10 and the concavo-convex forming resin layer 1 from the surface protection layer 4 of the product.

In both the steps (1) and (2), the temperature for heating the transfer sheet is preferably in the range of the glass transition temperature of the transfer substrate 10 or higher and lower than the melting temperature (or melting point). Usually, it is more preferable to carry out at a temperature near the glass transition temperature. In addition, the above-mentioned glass transition temperature vicinity refers to a range of glass transition temperature ±5° C., and when a polyester film suitable as the transfer substrate 10 is used, it is generally about 70 to 130° C. When using a mold having a shape that is not so complicated, the step of heating the transfer sheet and the step of preforming the transfer sheet are omitted, and the transfer sheet is heated by the heat and pressure of the molding resin in step (3) described later. You may shape in a mold shape.

In the above step (2), since the unevenness forming resin layer 1 is pressed against the inner surface 20 of the mold, the transfer sheet is deformed as a result, and the transfer base material 10 and at least the surface of the surface protection layer 4 of the transfer layer 11 are removed. It is formed into an uneven shape (see FIGS. 3 to 4).

In the step (3), a resin (a resin forming the molding resin layer 8) described later is melted and injected into the cavity to integrate the transfer sheet and the molding resin. At this time, in the step (2), since the transfer layer 11 having the uneven shape and the molding resin layer 8 are laminated, usually, the molding resin layer 8 also has an uneven shape corresponding to the uneven shape of the transfer layer 11. It is formed. When the molding resin is a thermoplastic resin, it is made into a fluid state by heating and melting, and when the molding resin is a thermosetting resin, the uncured liquid composition is heated at room temperature or appropriately and injected in a fluid state. Then, it is cooled and solidified. As a result, the transfer sheet is attached integrally with the molding resin layer 8 to form a decorative resin molded product with a transfer base material and an unevenness forming resin layer (see FIGS. 4 and 5). The heating temperature of the molding resin depends on the type of resin forming the molding resin layer 8, but is generally about 180 to 320°C.

The transfer base material and the decorative resin molded product with the concavo-convex forming resin layer thus obtained are taken out from the mold after being cooled in the step (4), and then the transfer base material 10 and the concavo-convex formation in the step (5). By peeling the resin layer 1 from the surface protective layer 4, a decorative resin molded product having the surface protective layer 4 provided with an uneven shape is obtained. The step of peeling the transfer base material 10 and the concavo-convex forming resin layer 1 from the surface protective layer 4 may be performed at the same time as the step of taking out the decorative resin molded product from the mold. That is, the step (5) may be included in the step (4). Thus, the decorated resin molded product of the present invention is obtained.

In the decorative resin molded product of the present invention, the molding resin layer 8 may be formed by selecting a resin according to the application. The molding resin forming the molding resin layer 8 may be a thermoplastic resin or a thermosetting resin.

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

Further, examples of the thermosetting resin include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

Since the decorative resin molded product of the present invention has excellent scratch resistance and excellent designability, for example, interior materials or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames It can be used as an interior material for buildings such as walls, floors and ceilings; a housing for home electric appliances such as a television receiver and an air conditioner; a container and the like.

The present invention will be described in detail below with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
On one side of the PET film (thickness 75 μm, thermal shrinkage rate at 180° C. for 5 minutes 1.8%), a resin layer formed by acrylic polyol (thickness about 20 μm, silica particles as an additive, film reinforcing material) , Including polyethylene wax). After curing the ionizing radiation curable resin composition (acrylic polymer/3-functional acrylate monomer (mass ratio 7/3) and UVA, HALS, leveling agent, coupling agent as additives) on the other surface of the PET film Was coated with a bar coater to have a thickness of 3 μm to form a coating film for forming a surface protective layer. An electron beam having an accelerating voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) was applied onto the coating film to cure the surface protective layer-forming coating film to form a surface protective layer. Further, on the surface protective layer, a primer layer (material composition: acrylic polyol, thickness 1.5 μm), a pattern layer (material composition: vinyl chloride-vinyl acetate copolymer/acrylic polymer, thickness 2 μm), an adhesive layer (material Composition: acrylic polymer, thickness 2 μm) were laminated in this order by gravure printing to obtain a laminated sheet in which a resin layer/PET film/surface protection layer/primer layer/pattern layer/adhesive layer were laminated in order.

Next, embossing (stripe shape) was applied from the resin layer side to form a resin layer for forming irregularities. The embossing plate depth of the embossing plate used for embossing (the height from the bottom of the concave portion to the top surface of the convex portion) was 20 μm. Thus, a transfer sheet was obtained in which the concavo-convex forming resin layer/PET film/surface protective layer/primer layer/pattern layer/adhesive layer were laminated in this order.

Example 2
A transfer sheet was obtained in the same manner as in Example 1 except that the thickness of the resin layer was 10 μm.

Example 3
Ionizing radiation curable resin composition (acrylic polymer/3-functional acrylate monomer (mass ratio 7/3) was used for forming the resin layer, and transfer was performed in the same manner as in Example 1 except that the thickness of the resin layer was 30 μm. Got the sheet.

Example 4
A transfer sheet was obtained in the same manner as in Example 3 except that the thickness of the resin layer was 10 μm.

Comparative Example 1
A transfer sheet was obtained in the same manner as in Example 1 except that the transfer substrate was directly embossed without providing the resin layer.

Next, the transfer sheet was placed in a mold, preformed by vacuum forming so as to conform to the shape inside the mold, and clamped (maximum stretching ratio 100%). Then, the molding resin was injected into the cavity of the mold, and the transfer sheet and the molding resin were integrally molded to obtain a decorative resin molded product with a transfer base material and a concavo-convex forming resin layer. Next, the decorative resin molded product was obtained by peeling and removing the transfer base material and the uneven resin film with the concavo-convex forming resin layer.

<Evaluation of uneven shape of decorative resin molded product>
The unevenness of the surface of the decorative resin molded product manufactured from each decorative sheet was evaluated visually and by touch. The evaluation criteria are as follows. The results are shown in Table 1.
◯: The unevenness is strongly felt.
Δ: Feeling of unevenness is felt.
X: No unevenness is felt.

DESCRIPTION OF SYMBOLS 1 Unevenness forming resin layer 2 Base film layer 3 Release layer 4 Surface protection layer 5 Primer layer 6 Picture layer 7 Adhesive layer 8 Molding resin layer 10 Transfer base material 11 Transfer layer 20 Inner surface of mold

Claims (13)

A transfer substrate having a first surface and a second surface;
A surface protective layer laminated on the first surface side of the transfer substrate,
A concavo-convex forming resin layer which is laminated on the second surface side of the transfer substrate and has an embossed concavo-convex shape formed on the surface opposite to the transfer substrate;
Equipped with
The unevenness forming resin layer is formed of a thermoplastic resin containing a filler ,
The uneven amount of the filler of forming the resin layer is 1 to 10% by mass Ru transfer sheet. The transfer sheet according to claim 1, wherein the unevenness-forming resin layer has a thickness of 10 to 100 μm. The transfer sheet according to claim 1, wherein the height difference between the embossed uneven shapes is in the range of 10 to 100 μm. The transfer sheet according to claim 1, wherein the embossed concave-convex concave portion does not reach the transfer base material. The transfer sheet according to claim 1, wherein a primer layer is laminated on the side of the surface protective layer opposite to the transfer substrate. The transfer sheet according to claim 1, wherein a pattern layer is laminated on the side of the surface protective layer opposite to the transfer substrate. The transfer sheet according to claim 1, wherein the unevenness forming resin layer, the transfer base material, the surface protection layer, a primer layer, and a pattern layer are laminated in this order. The transfer sheet according to claim 1, wherein an adhesive layer is laminated on a surface of the surface protective layer opposite to the transfer substrate. The transfer sheet according to claim 1, wherein the transfer base material has a release layer and a base material film layer in this order from the first surface side. The transfer sheet according to claim 9, wherein the transfer sheet has only one base film layer. The step of laminating the transfer sheet according to any one of claims 1 to 10 on a resin molded article and peeling off the transfer base material and the concavo-convex forming resin layer , wherein the surface coating layer of the transfer sheet is the resin. A method for manufacturing a decorative resin molded product laminated on a molded product,
A step of bringing the transfer sheet into close contact with the inner surface of the mold so as to follow the inner shape of the mold, and
Toward the surface protective layer side of the transfer sheet in the mold, the molding resin is injected toward the surface protective layer side of the transfer sheet in the mold, the unevenness formed on the surface protective layer A step of forming an uneven shape corresponding to the uneven shape of the resin layer,
A step of taking out the decorative resin molded article with the transfer base material and the concavo-convex forming resin layer from the mold after the molding resin has cooled;
A step of peeling the transfer base material and the concavo-convex forming resin layer from the surface protective layer of the decorative resin molded article with the transfer base material and the concavo-convex forming resin layer,
A method for producing a decorated resin molded product, which comprises: The uneven shape corresponding to the uneven shape of the unevenness forming resin layer is formed in the resin molded product in the step of forming the uneven shape corresponding to the uneven shape of the uneven forming resin layer on the surface protection layer. A method for producing a decorated resin molded article according to. A method for manufacturing the transfer sheet according to claim 1, wherein
A transfer substrate having a first surface and a second surface, a surface protection layer laminated on the first surface side of the transfer substrate, and a second surface side of the transfer substrate. And a step of preparing a laminated sheet including a resin layer,
Embossing is performed from the resin layer side of the laminated sheet to form a concavo-convex forming resin layer having an embossed concavo-convex shape provided on the surface of the resin layer,
A method of manufacturing a transfer sheet, comprising: