JP2016190332A - Transfer sheet and decorative resin molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet which can give an excellent texture and a three-dimensional feeling to the surface of a decorative resin molding.SOLUTION: A transfer sheet comprises: a transfer base material 10 which has a first surface 10a and a second surface 10b; a surface protection layer 4 which is laminated on the first surface side of the transfer base material 10; and an uneven formation resin layer 1 which is laminated on the second surface side of the transfer base material and in which the embossed uneven shape is formed on the surface opposite to the transfer base material.SELECTED DRAWING: Figure 1

Description

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

  Conventionally, decoration using a transfer type decoration sheet (transfer sheet) is known as a decoration method for interior and exterior of vehicles, building material interior materials, home appliance housings, and the like. Such a transfer sheet is produced by laminating a surface protective layer, a picture layer, an adhesive layer and the like on a film serving as a transfer substrate. Moreover, most of the decorative resin molded products manufactured using such a transfer sheet are pressed by a resin in a mold and have a flat surface shape.

  In recent years, the texture and the three-dimensional effect have been regarded as very important. For this reason, adoption of the decorating method called the overlay method which laminates | stacks a decorating sheet later with respect to the resin molded product shape | molded previously is increasing. In these methods, there is no need for a process of receiving a large amount of heat or pressure while the surface of the decorative sheet is pressed against the mold, such as the simultaneous injection molding method in which the decoration and molding are performed simultaneously in the mold. Therefore, it has the advantage that a decorated resin molded product can be produced without impairing the texture and stereoscopic effect of the surface of the decorative sheet.

  However, post-decoration in these methods involves decorating a resin molded product that has not been decorated with a decorative sheet, so compared with the method of simultaneously decorating and molding in a mold using a transfer sheet Thus, there is a drawback that the number of processes increases. For this reason, in a decorative resin molded product using a transfer sheet, development of a method for imparting a texture or a three-dimensional effect to the surface of the decorative resin molded product is required.

  Conventionally, as a technique for forming a concavo-convex shape on the surface of a decorative resin molded product using a transfer sheet, a method in which a raised printing layer is formed on a substrate of the transfer sheet is known (for example, a patent) References 1-4). However, in the engraving printing, fine patterning is difficult and a fine uneven shape cannot be formed. For this reason, it is difficult to form an excellent texture and three-dimensional effect on the surface of the decorative resin molded product by a method using these transfer sheets. There is also a method of forming irregularities on the surface of a molded article by forming hairline irregularities on the back surface of the transfer substrate by embossing (Patent Document 5). However, it is preferable to use a highly heat-resistant PET film or the like as a substrate for transfer from the viewpoint of dimensional stability and wrinkle generation suppression. Since a film with high heat resistance is not suitable for embossing, it is sufficient. A design with unevenness cannot be obtained.

JP 60-264213 A JP 60-264214 A JP 2006-239967 A Special table 2008-510638 gazette Special table 2003-326552 gazette

  The main object of the present invention is to provide a transfer sheet capable of imparting an excellent texture and stereoscopic effect to the surface of a decorative resin molded product. Furthermore, this invention relates to the manufacturing method of the said transfer sheet, the decorative resin molded product using the said transfer sheet, and the manufacturing method of the said decorative resin molded product.

  The present inventors have intensively studied to solve the above problems. As a result, 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 the second surface side of the transfer substrate According to the transfer sheet provided with the concavo-convex forming resin layer formed on the surface opposite to the transfer substrate, the embossed concavo-convex shape is excellent on the surface of the decorative resin molded product, It has been found that a three-dimensional effect can be imparted. The present invention has been completed by further studies based on this finding.

That is, this invention provides the invention of the aspect hung up below.
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;
An unevenness-forming resin layer that is laminated on the second surface side of the transfer substrate, and an embossed uneven shape is formed on the surface opposite to the transfer substrate;
A transfer sheet comprising:
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 of the embossed uneven shape 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 recesses and recesses do 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 the 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 the 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 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 layer of the base film layer is laminated on the transfer sheet.
Item 11. Item 11. A method for producing a decorative 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 unevenness forming resin layer.
Item 12. The method for producing 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 stacked on the first surface side of the transfer substrate, and a second surface side of the transfer substrate. Preparing a laminated sheet comprising a resin layer,
Embossing from the resin layer side of the laminated sheet, and forming a concavo-convex forming resin layer having an embossed concavo-convex shape on the surface of the resin layer;
A method for producing a transfer sheet.

  According to the present invention, 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 the second of the transfer substrate. Is formed on the surface of the decorative resin molded article by providing a transfer sheet having an uneven embossed uneven shape formed on the surface opposite to the transfer substrate. Excellent texture and stereoscopic effect can be imparted. Moreover, according to this invention, the manufacturing method of the said transfer sheet, the decorative resin molded product using the said transfer sheet, and the manufacturing method of the said decorative resin molded product can be provided.

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

1. The transfer sheet of the present invention comprises 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 the transfer substrate. It is laminated | stacked on the said 2nd surface side, The embossing uneven | corrugated shape is provided with the uneven | corrugated resin layer currently formed in the surface on the opposite side to the said transfer base material. By having such a configuration, the transfer sheet of the present invention can impart an excellent texture and stereoscopic effect to the surface of the decorative resin molded product.

  The transfer sheet of the present invention is a transfer sheet that is used after the transfer substrate and the unevenness-forming resin layer are peeled from the final product. Specifically, a decorative resin molded product is obtained by laminating the transfer sheet of the present invention on various transferred materials, for example, resin molded products, and peeling the transfer substrate and the concavo-convex forming resin layer from the surface protective layer. can get. Such a decorative resin molded product has excellent scratch resistance and design properties (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 need 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 has a transfer substrate 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 substrate 10. And a concavo-convex forming resin layer 1 laminated on the second surface 10b side of the transfer substrate 10.

  On the opposite side of the surface protective layer 4 from the transfer substrate 10, a primer layer 5 is laminated as necessary for the purpose of improving the adhesion between the surface protective layer 4 and a layer adjacent thereto. It may be. Moreover, the pattern layer 6 may be laminated | stacked on the opposite side to the transfer base material 10 of the surface protective layer 4 as needed for the purpose of providing decorating property. Furthermore, the adhesive layer 7 may be laminated | stacked on the surface on the opposite side to the transfer base material 10 of the surface protective layer 4 as needed. 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, a primer layer 5, a pattern layer 6, an adhesive layer 7, etc. provided as necessary). 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 may be formed of 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 substrate film layer 2 is a layer that can function as a support in the transfer substrate 10. When the transfer substrate 10 is formed of a plurality of layers, examples of the layer included in the transfer substrate 10 include the release layer 3 in addition to the substrate film layer 2. The release layer 3 is provided between the base film layer 2 and the surface protective layer 4 as necessary for the purpose of enhancing the peelability between these layers.

  An unevenness forming resin layer 1 is laminated on the second surface 10 b 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 a laminated structure of the transfer sheet of the present invention, a concavo-convex forming resin layer / base film layer / surface protective layer is laminated in this order; concavo-convex resin layer / base film layer / release layer / surface protective layer. Laminated structure laminated in this order; Laminated structure resin layer / base film layer / surface protective layer / pattern layer laminated structure in this order; concavo-convex resin layer / base film layer / surface protective layer / primer layer / Laminated structure in which pattern 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; Laminated structure resin layer / base film layer / surface protective layer / pattern layer / adhesive layer laminated in this order; concavo-convex resin layer / base film Layer / surface protective layer Laminate structure in which primer layer / design layer / adhesive layer are laminated in this order; irregularity-forming resin layer / base film layer / release layer / surface protective layer / primer layer / design layer / adhesive layer in this order Examples include the structure. FIG. 1 shows a schematic diagram of a cross-sectional structure of one form of a transfer sheet in which an unevenness-forming resin layer / base film layer / surface protective layer are laminated in this order as an embodiment of the transfer sheet laminated structure of the present invention. Further, in FIG. 2, as an embodiment of the laminated structure of the transfer sheet of the present invention, an unevenness-forming resin layer / base film layer / release layer / surface protective layer / primer layer / design layer / adhesive layer are laminated in this order. The schematic diagram of the cross-sectional structure of one form of the transferred sheet is shown.

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

[Base film layer 2]
The substrate film layer 2 is a layer that can function as a support in the transfer substrate 10 (and also the transfer sheet). The base film layer 2 used in the present invention is selected in consideration of suitability for vacuum forming, and typically a resin sheet made of a thermoplastic resin is 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.

  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. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like can be mentioned preferably, and polyethylene terephthalate (PET) is particularly preferable in terms of heat resistance and dimensional stability.

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

  The base film layer 2 may contain fine particles for the purpose of improving workability. Fine particles include inorganic particles such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide and kaolin, organic particles made of acrylic resin, and internal precipitation particles. And so on. The average particle diameter of the fine particles is preferably from 0.01 to 5.0 μm, more preferably from 0.05 to 3.0 μm. Moreover, 0.01-5.0 mass% is preferable and, as for content of the microparticles | fine-particles in a polyester resin, 0.1-1.0 mass% is more preferable. Moreover, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, fluorescent whitening agents, and the like can be blended as necessary.

  The polyester sheet used for this invention is manufactured as follows, for example. First, the above polyester-based resin and other raw materials are supplied to a known melt extrusion apparatus such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester-based resin to be melted. Next, while extruding the molten polymer, it is rapidly cooled and solidified on the rotary 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 in a biaxial direction to form a sheet and heat-setting. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Moreover, you may extend | stretch longitudinally and / or a horizontal direction again before or after performing heat setting as needed. In the present invention, in order to obtain sufficient dimensional stability, the draw ratio is preferably 7 times or less, more preferably 5 times or less, and further preferably 3 times or less, as an area ratio. If it is within this range, when the obtained polyester sheet is used for the transfer sheet of the present invention and used for the injection molding simultaneous transfer method, the transfer sheet does not shrink again in the temperature range when the injection resin is injected, The required sheet strength can be obtained in the temperature range. In addition, a polyester sheet may be manufactured as described above, or a commercially available one may be used.

  Moreover, the base film layer 2 is physically or chemically such as an oxidation method or a concavo-convex method on one side or both sides as desired for the purpose of improving the adhesion with the concavo-convex forming resin layer 1 or the release layer 3 described later. Surface treatment can be performed. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone treatment method. Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the base film, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability. The base film may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of enhancing interlayer adhesion between the base film and a layer provided thereon. In addition, when using a commercially available polyester sheet, the commercially available product that has been subjected to surface treatment as described above or that has an easy-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. Moreover, as the base film layer 2, a single layer sheet of these resins or a multilayer sheet made 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 necessary for the purpose of improving the peelability between the substrate film layer 2 and the surface protective layer 4. . That is, when the transfer base material 10 includes the release layer 3, the transfer base material 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 covering the entire surface (entirely solid), or may be provided in part. In general, a solid release layer is preferable in consideration of peelability.

  The release layer 3 is 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, or a cellulose resin. , Vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrified cotton, copolymers of monomers forming the thermoplastic resins, or those resins modified with (meth) acrylic acid or urethane It can be formed by using a single or a plurality of mixed resin compositions. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers that form these resins, and those obtained by urethane modification thereof are more preferable. More specifically, acrylic-melamine Resin, acrylic-melamine resin-containing composition, polyester resin and ethylene / acrylic acid copolymer modified with urethane, acrylic resin / styrene / acrylic copolymer And a resin composition mixed with the above emulsion. Among 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 an acrylic-melamine resin.

  The thickness of the release layer 3 is usually about 0.01 to 5 μm, and 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 substrate 10, and is transferred to a transfer target (molded resin layer 8 or the like). After being transferred to the transfer target, the transfer substrate 10 is peeled off, resulting in a decorative resin molded product in which the transfer layer 11 and the transfer target 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 substrate 10. As described above, the transfer layer 11 can be provided with a primer layer 5, a pattern layer 6, an adhesive layer 7, and the like as necessary.

[Surface protective layer 4]
In the transfer sheet of the present invention, the surface protective layer 4 is the most suitable for the decorative resin molded product in order to enhance the chemical resistance, scratch resistance, etc. It is a layer provided on the transfer sheet so as to be located on the surface.

  In this invention, it does not restrict | limit especially as resin which forms the surface protective layer 4, A thermosetting resin, a thermoplastic resin, an ionizing radiation curable resin etc. are mentioned, It selects suitably according to the use of a transfer sheet. Can do. Among these, ionizing radiation curable resins are preferred from the viewpoint of imparting excellent texture and three-dimensional effect to the surface of the decorative resin molded product while enhancing the scratch resistance of the transfer sheet. 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 state of the transfer sheet. It may be set as semi-cured, and may be cured after the surface protective layer 4 is transferred onto the resin molded product.

  The thermosetting resin is not particularly limited, and for example, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, carboxyl functional acrylic. Examples include resins, amide functional copolymers, and urethane resins.

  Moreover, it does not restrict | limit especially as a thermoplastic resin, Acrylic resin, such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Polyolefin resin, such as a polypropylene and polyethylene; Polycarbonate resin; Vinyl chloride resin; 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;

(Ionizing radiation curable resin)
The ionizing radiation curable resin used to form the surface protective layer 4 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. And a mixture of at least one of prepolymers, oligomers, monomers, and the like, as appropriate. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require an initiator for photopolymerization, and provides stable curing characteristics, and thus is suitable for forming the surface protective layer 4. Used for.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate 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 Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationic 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 in the terminal or side chain. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, a polycarbonate 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. Urethane (meth) acrylate can be obtained, for example, by esterifying, with (meth) acrylic acid, a polyurethane oligomer obtained by the reaction of polyether polyol, polyester polyol, caprolactone-based polyol or polycarbonate polyol and a polyisocyanate compound. it can. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group 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, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an 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 the 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, as the polyfunctional (meth) acrylate oligomer, polycarbonate (meth) acrylate, urethane (meth) acrylate, and the like are particularly preferable. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the transfer sheet of the present invention is used for three-dimensional molding, among the above-mentioned ionizing radiation curable resins, it is preferable to use polycarbonate (meth) acrylate from the viewpoint of obtaining excellent three-dimensional moldability. Moreover, it is more preferable to use combining a polycarbonate (meth) acrylate and urethane (meth) acrylate from a viewpoint which makes three-dimensional moldability and scratch resistance compatible. In addition, when using a polyfunctional (meth) acrylate monomer as the ionizing radiation curable resin, it is preferably used 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 preferred. When urethane (meth) acrylate is used as the ionizing radiation curable resin, from the viewpoint of achieving both three-dimensional moldability and scratch resistance, a polyurethane oligomer obtained by the reaction of a caprolactone-based polyol and a polyisocyanate compound ( It is preferable to use caprolactone-based urethane (meth) acrylate obtained by esterification with acrylic acid or the above-described 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 be cracked during three-dimensional molding. Therefore, it is preferable to use an ionizing radiation curable resin having excellent three-dimensional moldability.

(Additive ingredients)
In the surface protective layer 4, inorganic particles, organic particles, and various additives can be blended as other additive components according to desired physical properties to be provided in the surface protective layer 4.

  The inorganic particles are not particularly limited, but preferred examples include metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, and zinc oxide particles. Silica particles and alumina particles are preferable, and silica particles are particularly preferable. An inorganic particle may be used individually by 1 type, and may be used in combination of 2 or more types.

  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, and polyethylene beads. Of these, urethane beads, nylon beads, and acrylic beads are preferable. One kind of organic particles may be used alone, or two or more kinds thereof may be used in combination.

  Other additives include, for example, weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, and leveling agents. , Thixotropic agent, coupling agent, plasticizer, antifoaming agent, filler, solvent, colorant and the like. These additives can be appropriately selected from those commonly used. In addition, as the ultraviolet absorber or 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)
Although it does not restrict | limit in particular about the thickness (thickness after drying or hardening) of the surface protective layer 4, From a viewpoint of providing a texture and a three-dimensional effect to the surface of a decorative resin molded product, for example, 1-1000 micrometers, Preferably it is 1. -50 μm, more preferably 1-30 μm. Furthermore, 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 the surface protective layer 4 is formed using an ionizing radiation curable resin. Can be uniformly irradiated with ionizing radiation, so that it can be cured uniformly, 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 high followability can be obtained for complicated three-dimensional shapes such as automobile interior use.

(Formation of surface protective 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 it, and crosslinking and curing it. The cross-linking and curing of the surface protective layer 4 may be performed at the time of producing the transfer sheet as described above, or may be performed after the transfer onto the resin molded product. In addition, the viscosity of the ionizing radiation curable resin composition is a viscosity capable of forming an uncured resin layer 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 formed on the layer positioned below the surface protective layer 4 so as to have the thickness, such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, etc. The uncured resin layer is formed by applying a known method, preferably gravure coating.

  The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming the surface protective layer 4. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually includes an acceleration voltage of about 70 to 300 kV.

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

  The irradiation dose is preferably such that the crosslinking 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).

  Furthermore, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.

  When ultraviolet rays are used as the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. Although it does not restrict | limit especially as an ultraviolet source, For example, 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) etc. are mentioned.

  By adding various additives to the surface protective layer 4 thus formed, a hard coat function, an antifogging coat function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, You may perform the process which provides 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 improving the adhesion between the surface protective layer 4 and the layer located below (on the side opposite to the transfer substrate 10). The primer layer 5 can be formed of a resin.

  Although it does not restrict | limit especially as resin which forms the primer layer 5, For example, a urethane resin, an acrylic resin, (meth) acryl-urethane copolymer resin, a polyester resin, a butyral resin etc. are mentioned. Among these resins, a urethane resin, an acrylic resin, and a (meth) acryl-urethane copolymer resin are preferable. These resins may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  Among the urethane resins, from the viewpoint of improving the adhesion after crosslinking, preferably a combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a crosslinking agent; Includes a combination of acrylic polyol and hexamethylene diisocyanate.

  Although it does not restrict | limit especially as said acrylic resin, For example, the homopolymer of (meth) acrylic acid ester, the copolymer of 2 or more types of different (meth) acrylic acid ester monomers, or (meth) acrylic acid ester and others And a copolymer with the above monomer. More specifically, as a (meth) acrylic resin, poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylic acid Methyl- (meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl (meth) acrylate copolymer Examples include (meth) acrylic acid esters such as polymers. These acrylic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although it does not restrict | limit especially as (meth) acryl-urethane copolymer resin, For example, acrylic-urethane (polyester urethane) block copolymer resin is mentioned. Further, as the curing agent, the above-described various isocyanates are used. The ratio of the acrylic to urethane ratio in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acrylic / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 / 2 to 2/8.

  Although it does not restrict | limit especially about the thickness of the primer layer 5, For example, about 0.1-10 micrometers, Preferably about 1-10 micrometers is mentioned. When the primer layer satisfies such a thickness, the weather resistance of the transfer sheet can be further improved, and cracking, breakage, whitening and the like of the surface protective layer 4 can be effectively suppressed.

  Primer layer 5 is a resin that forms primer layer 5, using 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 normal coating method such as wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or the like, or transfer coating. Here, the transfer coating method is a method in which a coating film of the primer layer 5 or an adhesive layer 7 described later is formed on a thin sheet (film base material) and then coated on the target layer surface in the transfer sheet. .

[Picture layer 6]
The pattern layer 6 is a layer provided as necessary in order to give decorativeness to the resin molded product. 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. For example, a grain pattern simulating the surface of a rock such as a grain pattern, a marble pattern (for example, a travertine marble pattern), a cloth simulating a texture or a cloth pattern Patterns, tiled patterns, brickwork patterns, etc., and patterns such as marquetry and patchwork that combine these are also included. These patterns can be formed by multicolor printing with normal yellow, red, blue and black process colors, or by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. It is formed.

  As the pattern ink used for the pattern layer 6, a binder appropriately mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, 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. For example, carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, petal, cadmium red, ultramarine, cobalt blue, and other inorganic pigments, quinacridone red Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metallic pigments composed of scaly foils such as aluminum and brass, pearl luster composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate (pearl) ) Pigments.

  Although the thickness in particular of the pattern layer 6 is not restrict | limited, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

[Adhesive layer 7]
The adhesive layer 7 is provided under the surface protective layer 4 and the pattern layer 6 (on the molded resin layer 8 side) for the purpose of improving the adhesion between the transfer sheet and the transfer target (molded resin layer 8 and the like). It is a layer provided as needed. 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, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber-based resin. . A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the thermosetting resin include a urethane resin and an epoxy resin. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  Although the adhesive layer 7 is not necessarily a necessary layer, it is assumed that the transfer sheet of the present invention is applied to a decorating method by sticking on a resin molded body prepared in advance, such as a vacuum press-bonding method described later. Is preferably provided. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 7 using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.

  Although the thickness in particular of the contact bonding layer 7 is not restrict | limited, For example, about 0.1-30 micrometers, Preferably it is about 0.5-20 micrometers, More preferably, about 1-8 micrometers is mentioned.

[Unevenness-forming resin layer 1]
The unevenness-forming resin layer 1 is laminated on the second surface 10b side of the transfer base material 10, and has an embossed uneven shape provided by embossing on the surface opposite to the transfer base material. The unevenness forming resin layer 1 is a layer provided to form an uneven shape corresponding to the embossed uneven shape of the unevenness forming resin layer 1 on the surface protective layer 4 during transfer of the transfer sheet.

  The material for forming the unevenness-forming resin layer 1 is not particularly limited as long as it can provide the surface protective layer 4 with an uneven shape during transfer, and examples thereof include a cured product of an ionizing radiation curable resin or a thermoplastic resin. It is done. Examples of the ionizing radiation curable resin and the thermoplastic resin are the same as those exemplified in the above item [Surface protective layer 4].

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

  As a thermoplastic resin which forms the unevenness | corrugation formation resin layer 1, an acrylic resin is more preferable and an acrylic polyol is especially preferable.

  As the ionizing radiation curable resin for forming the unevenness forming resin layer 1, the same resin as that used for the surface protective layer can be used.

  The unevenness forming resin layer 1 may contain a filler. By including the filler in the concavo-convex resin layer 1, it is possible to prevent the concavo-convex resin layer 1 from adhering to the mold side and peeling from the surface protective layer 4 when taking out the decorative resin molded product 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 Organic particles such as beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene beads can be used. A filler may be used individually by 1 type and may be used in combination of 2 or more types. When the unevenness forming resin layer 1 contains a filler, the content thereof is not particularly limited, and examples thereof include 1 to 10% by mass.

  Although the thickness of the unevenness forming resin layer 1 is not particularly limited, for example, it is preferably about 5 to 100 μm, more preferably about 5 to 60 μm, and still more preferably about 10 to 40 μm. In addition, the thickness of the uneven | corrugated resin layer 1 means the distance of the lamination direction from the back surface (surface by the side of the surface protective layer 4) of the uneven | corrugated resin layer 1 to a convex part.

  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 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 unevenness-forming resin layer 1 having an embossed uneven shape on the surface of the resin layer. Specific examples of the embossing conditions are as follows.

  As an embossing method, an embossing method by heating and pressurization is usually used. The embossing method by heating and pressurizing is a method in which the surface of the resin layer of the above laminated sheet is softened by heating, pressurized with an embossing plate to form an uneven pattern on the embossing plate, and then cooled and fixed. The shape of the embossing plate used for embossing corresponds to the embossed uneven shape imparted to the unevenness-forming resin layer. For embossing, for example, a known single-wafer or rotary embossing machine can be used.

  The height difference of the embossed uneven shape provided by embossing is preferably about 5 to 100 μm, more preferably about 5 to 60 μm, and more preferably about 5 to 60 μm, from the viewpoint of imparting excellent texture and stereoscopic effect to the surface of the decorative resin molded product. Preferably about 10-40 micrometers is mentioned. In the transfer sheet of the present invention, the height difference of the embossed uneven shape refers to the distance in the stacking direction from the back surface (surface on the surface protective layer 4 side) of the unevenness-forming resin layer 1 to the convex portion, and the stacking direction to the concave portion. It means the difference with the distance.

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

  Although it does not restrict | limit especially as heating temperature in embossing, Preferably about 180 to 220 degreeC is mentioned.

  In the transfer sheet of the present invention, since the unevenness-forming resin layer 1 having the above embossed shape and the transfer base material 10 are provided, the transfer sheet has high dimensional stability, and the desired uneven shape is decorated with a resin. It can be given to a molded product.

2. Production method of transfer sheet The transfer sheet of the present invention can be produced by a method comprising the following steps.
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 10b of the transfer substrate 10 Preparing a laminated sheet comprising a resin layer laminated on the side;
A step of embossing from the resin layer side of the laminated sheet to form an unevenness forming resin layer 1 having an embossed uneven shape on the surface of the resin layer.

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

  Furthermore, in the present invention, by adopting the production method as described above, the transfer sheet of the present invention can have a configuration in which only one base film layer is laminated. By using the transfer sheet, it is possible to produce a decorative resin molded product having an excellent texture and three-dimensional effect on the surface.

3. Decorative resin molded product and method for producing the same The above-described transfer sheet of the present invention was formed on the second surface 10b side of the transfer substrate 10 when transferred to various transfer 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 the texture excellent on the surface can be obtained by peeling the transfer substrate 10 and the unevenness-forming resin layer 1 from the resin molded product. And a decorative resin molded product to which a three-dimensional effect is imparted.

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

  Next, the transfer substrate 11 and the unevenness forming resin layer 1 are peeled from the transfer base material and the decorative resin molded product with the unevenness forming resin layer, so that at least the transfer layer 11 including the surface protective layer 4 and the molding resin are removed. A decorative resin molded product in which the layer 8 is laminated is obtained (see, for example, FIG. 6).

  When the surface protective layer 4 is formed of an uncured or semi-cured curable resin, the surface decorative layer 4 can be obtained by further irradiating or heating the obtained decorative resin molded product with ionizing radiation. 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 product includes these Layers included.

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) Step of heating the transfer sheet from the surface protective layer 4 side with a hot plate with the surface protective layer 4 side (opposite side of the unevenness forming resin layer 1) of the transfer sheet facing the mold (2) (3) A molding resin (resin for forming the molding resin layer 8) is molded by pre-molding (vacuum molding) along the inner shape of the mold and closely contacting the inner surface 20 of the mold. (4) Step of taking out a decorative resin molded product (decorative resin molded product with a transfer substrate and a concavo-convex forming resin layer) from the mold after the molding resin has cooled (5) Decorative resin molding The process of peeling the transfer base material 10 and the uneven | corrugated resin layer 1 from the surface protective layer 4 of goods.

  In both steps (1) and (2), the temperature for heating the transfer sheet is preferably in the range of near the glass transition temperature of the transfer substrate 10 and less 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, said glass transition temperature vicinity refers to the range of about glass transition temperature +/- 5 degreeC, and when using a suitable polyester film as the transfer base material 10, it is about 70-130 degreeC generally. When using a mold having a less complicated shape, the step of heating the transfer sheet and the step of preforming the transfer sheet are omitted, and in the step (3) described later, the transfer sheet is heated by the heat and pressure of the molding resin. You may shape | mold in the shape of a metal mold | die.

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

  In the step (3), a resin (resin that forms the molded 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), the transfer layer 11 and the molded resin layer 8 on which the concavo-convex shape is formed are laminated. 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 injected at room temperature or appropriately heated and injected in a fluid state. Then, it is cooled and solidified. As a result, the transfer sheet is integrally attached to the molded resin layer 8 and adhered, and becomes a decorative resin molded product with a transfer substrate 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 thus obtained transfer base material and the decorative resin molded product with the unevenness-forming resin layer are cooled in the step (4) and then taken out of the mold, and then in the step (5), the transfer base material 10 and the unevenness formation. By peeling off 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. Moreover, the process of peeling the transcription | transfer base material 10 and the unevenness | corrugation formation resin layer 1 from the surface protective layer 4 may be performed simultaneously with the process of taking out a decorative resin molded product from a metal mold | die. That is, step (5) may be included in step (4). Thus, the decorative resin molded product of the present invention is obtained.

  In the decorative resin molded product of the present invention, the molded resin layer 8 may be formed by selecting a resin according to the application. The molding resin for 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, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a thermosetting resin, a urethane resin, an epoxy resin, etc. are mentioned, for example. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Since the decorative resin molded product of the present invention has excellent scratch resistance and excellent design properties, for example, interior materials or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames Interior materials for buildings such as walls, floors and ceilings; housings for home appliances such as television receivers and air conditioners; containers and the like.

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

Example 1
On one side of a PET film (thickness 75 μm, heat shrinkage rate of 1.8% at 180 ° C. for 5 minutes), a resin layer (thickness of about 20 μm, silica particles as an additive, film reinforcing material) And polyethylene wax). After curing the ionizing radiation curable resin composition (acrylic polymer / 3-functional acrylate monomer (mass ratio 7/3), UVA, HALS, leveling agent, coupling agent as additives) on the other side of the PET film The film was coated with a bar coder so as to have a thickness of 3 μm to form a coating film for forming a surface protective layer. An electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated from above the coating film to cure the surface protective layer-forming coating film, thereby forming a surface protective layer. Furthermore, 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) was laminated in this order by gravure printing to obtain a laminated sheet in which resin layer / PET film / surface protective layer / primer layer / design layer / adhesive layer were laminated in this order.

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

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
Transfer in the same manner as in Example 1 except that an ionizing radiation curable resin composition (acrylic polymer / 3-functional acrylate monomer (mass ratio 7/3)) was used to form the resin layer, and the thickness of the resin layer was 30 μm. A sheet was obtained.

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 resin layer was not provided and the transfer substrate was directly embossed.

  Next, the transfer sheet was put in a mold, preliminarily formed by vacuum forming along the shape in the mold, and clamped (maximum draw ratio 100%). Thereafter, 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 substrate and an unevenness-forming resin layer. Next, a decorative resin molded product was obtained by peeling off and removing the transfer base material and the concave-convex forming resin layer from the transfer base material and the decorative resin molded product with the concave-convex forming resin layer.

<Evaluation of uneven shape of decorative resin molded product>
The unevenness of the surface of the decorative resin molded product produced from each decorative sheet was evaluated visually and by hand. The evaluation criteria are as follows. The results are shown in Table 1.
◯: A feeling of unevenness is strongly felt.
Δ: A feeling of unevenness can be felt.
X: Unevenness is not felt.

DESCRIPTION OF SYMBOLS 1 Concave formation resin layer 2 Base film layer 3 Release layer 4 Surface protective 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 (12)

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;
An unevenness-forming resin layer that is laminated on the second surface side of the transfer substrate, and an embossed uneven shape is formed on the surface opposite to the transfer substrate;
A transfer sheet comprising:   The transfer sheet according to claim 1, wherein the unevenness forming resin layer is formed of a cured product of an ionizing radiation curable resin or a thermoplastic resin.   The transfer sheet according to claim 1, wherein the unevenness-forming resin layer has a thickness in the range of 10 to 100 μm.   The transfer sheet according to claim 1, wherein the height difference of the embossed uneven shape is in a range of 10 to 100 μm.   The transfer sheet according to any one of claims 1 to 4, wherein the embossed uneven recess does not reach the transfer substrate.   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 in any one of Claims 1-6 by which the pattern layer is laminated | stacked on the opposite side to the said transfer base material of the said surface protective layer.   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 base.   The transfer sheet according to any one of claims 1 to 8, wherein the transfer base material has a release layer and a base film layer in order from the first surface side.   The transfer sheet according to claim 1, wherein only one base film layer is laminated on the transfer sheet.   A method for producing a decorative resin molded product, comprising a step of laminating the transfer sheet according to any one of claims 1 to 10 on a resin molded product and peeling off the transfer substrate and the unevenness-forming resin layer. A method for producing a transfer sheet according to any one of claims 1 to 10,
A transfer substrate having a first surface and a second surface, a surface protective layer stacked on the first surface side of the transfer substrate, and a second surface side of the transfer substrate. Preparing a laminated sheet comprising a resin layer,
Embossing from the resin layer side of the laminated sheet, and forming a concavo-convex forming resin layer having an embossed concavo-convex shape on the surface of the resin layer;
A method for producing a transfer sheet.