JP6451452B2 - Transfer sheet and decorative resin molded product using the same - Google Patents

Description

  The present invention provides a surface protection that allows formation of irregular shapes on the surface of a decorative resin molded product by a raised layer laminated on a transfer substrate, and can be transferred in an uncured or semi-cured state. The present invention relates to a transfer sheet provided with a layer, a decorative resin molded product using the transfer sheet, and a method for producing them.

  For the purpose of imparting scratch resistance and design, etc. to resin molded products used in vehicle interior parts, building material interior materials, home appliance housings, etc., and the formation of irregularities on the surface protective layer and molded product surface A technique for simultaneously performing the above is known. For example, Patent Document 1 prepares a transfer sheet in which a transfer layer made of a surface protective layer or the like is formed on the other side of a transfer substrate having a raised layer (convex pattern layer) on one side, and the transfer layer of the transfer sheet And the molded product are brought into close contact with each other by heating and pressing, and then the transfer substrate is peeled off to transfer only the transfer layer to the molded product surface, and at the same time, the unevenness of the raised layer is reflected on the transfer layer and the molded product surface. (See FIG. 1 of Patent Document 1). Patent Document 1 describes that the resin forming the raised layer is preferably an ultraviolet curable resin because of its high hardness.

  As the resin for forming the surface protective layer of such a transfer sheet, an ultraviolet curable resin is preferable from the viewpoint of scratch resistance and contamination resistance. Furthermore, when UV curable resin is used to form the surface protective layer, the UV curable resin is cured in the transfer sheet state, and in the transfer sheet state, it is left uncured or semi-cured, and curing is completed after transfer. There is technology to make. The method of curing the ultraviolet curable resin in the state of the transfer sheet is a preferable method from the viewpoint of manufacturing without the necessity of irradiating the resin molded product with ultraviolet rays after the transfer and curing it. The flexibility of the protective layer is reduced. For this reason, in applications that require particularly high three-dimensional formability, such as injection molding simultaneous transfer, it may be effective to use a method in which the surface protective layer before transfer is in an uncured or semi-cured state and cured after transfer. .

  For example, Patent Document 2 discloses a type of transfer sheet in which the surface protective layer is uncured before transfer and is cured after transfer. In Patent Document 2, an ultraviolet curable resin composition is applied to one side of a transfer base material in a concavo-convex shape to form a raised layer (mat type) that is cured by irradiation with ultraviolet light, and then the opposite side of the transfer base material. A transfer sheet is manufactured by applying an ultraviolet curable resin to form an uncured surface protective layer. However, in such a method, it may be difficult to uniformly apply a transfer layer such as a surface protective layer on the transfer substrate due to the influence of the uneven shape of the raised layer that has been cured in advance. For this reason, after forming an uncured or semi-cured surface protective layer on the surface of the transfer substrate, it may be desired to form a raised layer on the opposite surface of the transfer substrate.

JP-A-8-252899 JP 2006-198911 A

The inventors of the present invention examined forming a raised layer on the surface opposite to the transfer substrate after forming an uncured or semi-cured surface protective layer on the surface of the transfer substrate. Specifically, after an uncured or semi-cured surface protective layer is formed on the surface of the transfer substrate, the ultraviolet curable resin composition is applied to the opposite surface of the transfer substrate in a concavo-convex manner, and the ultraviolet curing is performed. An attempt was made to form a cured raised layer by irradiating the photosensitive resin composition with ultraviolet rays. However, in this method, there is a problem that the ultraviolet rays irradiated when forming the build-up layer pass through the transfer substrate and cure the uncured or semi-cured surface protective layer.
Under such circumstances, the present invention produced an uncured or semi-cured surface protective layer on the surface of the transfer substrate, and then formed a raised layer on the opposite surface of the transfer substrate to produce a transfer sheet. Even in this case, it is possible to form an uneven shape on the surface of the decorative resin molded article by the raised layer formed on the transfer base material, and the surface protection can be transferred in an uncured or semi-cured state. The main object is to provide a transfer sheet provided with a layer.

  The present inventors have intensively studied to solve the above problems. As a result, a transfer substrate composed of a single layer or a plurality of layers 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 group In the transfer sheet having the raised layer laminated on the second surface side of the material, the raised layer is formed of a cured product of the ultraviolet curable resin composition, and the surface protective layer is ultraviolet curable. The transfer substrate is formed of a resin composition, and the transfer substrate contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant, thereby forming an uncured or semi-cured surface protective layer as a transfer group. Even when a transfer sheet is manufactured by forming a raised layer on the surface opposite to the transfer substrate after being formed on the surface of the material, the decorative resin molded product is formed by the raised layer formed on the transfer substrate. It is possible to form a concavo-convex shape on the surface of Transfer sheet having a transferable protective surface layer in a state of curing it is obtained. 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 base material having a first surface and a second surface, consisting of a single layer or multiple layers, a surface protective layer laminated on the first surface side of the transfer base material, and the transfer base material A transfer sheet having a raised layer laminated on the second surface side,
The raised layer is formed of a cured product of an ultraviolet curable resin composition,
The surface protective layer is formed of an uncured or semi-cured ultraviolet curable resin composition,
The transfer substrate contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant.
Item 2. The transfer substrate has a substrate film layer;
Item 2. The transfer sheet according to Item 1, wherein the base film layer contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant.
Item 3. The transfer base material, in order from the first surface side, has a base film layer and a resin coat layer,
Item 3. The transfer sheet according to Item 1 or 2, wherein the resin coat layer contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant.
Item 4. The transfer substrate has a release layer and a substrate film layer in order from the first surface side,
Item 4. The transfer sheet according to any one of Items 1 to 3, wherein the release layer contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant.
Item 5. Item 5. The transfer sheet according to any one of Items 1 to 4, wherein the total content of the ultraviolet absorber, the ultraviolet reflector, and the colorant per unit area of the transfer substrate is 180 mg / m ² or more.
Item 6. A step of laminating an ultraviolet curable resin composition for forming a surface protective layer on the first surface of a transfer substrate containing at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant;
A step of laminating an ultraviolet curable resin composition for forming a raised layer on the second surface of the transfer substrate in an uneven shape;
Irradiating ultraviolet rays from the second surface side of the transfer substrate to cure the raised layer;
A method for producing a transfer sheet.
Item 7. The step of laminating the transfer sheet according to any one of Items 1 to 5 on a resin molded product, and peeling the transfer substrate and the overlay layer;
Irradiating the uncured or semi-cured surface protective layer with ultraviolet rays to cure the surface protective layer;
A method for producing a decorated resin molded product.

  According to the present invention, even when an uncured or semi-cured surface protective layer is formed on the surface of the transfer substrate and then formed by forming a raised layer on the opposite surface of the transfer substrate, the transfer substrate A transfer sheet provided with a surface protective layer capable of forming a concavo-convex shape on the surface of a decorative resin molded product and being transferred in an uncured or semi-cured state by a raised layer formed on Can be provided. By laminating the transfer sheet of the present invention on the surface of a resin molded product and curing the surface protective layer, a decorated resin molded product having high scratch resistance and an excellent design can be obtained. Moreover, according to this invention, these suitable manufacturing methods 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. Transfer sheet The transfer sheet of the present invention has a first surface and a second surface, a transfer substrate composed of a single layer or multiple layers, and surface protection laminated on the first surface side of the transfer substrate. A transfer sheet having a layer and a buildup layer laminated on the second surface side of the transfer substrate, wherein the buildup layer is formed of a cured product of an ultraviolet curable resin composition, and the surface protection The layer is formed of an uncured or semi-cured ultraviolet curable resin composition, and the transfer substrate contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant. To do. Since the transfer sheet of the present invention has such a configuration, an uncured or semi-cured surface protective layer is formed on the surface of the transfer substrate, and then a raised layer is formed on the opposite surface of the transfer substrate. Even when the transfer sheet is manufactured, it is possible to form an uneven shape on the surface of the decorative resin molded product by the raised layer formed on the transfer base material, and it is in an uncured or semi-cured state It can be set as the transfer sheet provided with the surface protection layer which can be transferred by.

  The transfer sheet of the present invention is a transfer sheet that is used after the transfer substrate and the raised layer are peeled from the final product. Specifically, the transfer sheet of the present invention is laminated on various transferred materials, for example, resin molded products, and the transfer substrate and the overlay layer are peeled off from the surface protective layer, and then the uncured or semi-cured surface protective layer. By curing, a decorated resin molded product is obtained. Such a decorative resin molded product has excellent scratch resistance and design properties 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 at least a transfer substrate 10 having a first surface 10a and a second surface 10b, and a surface protection layer laminated on the first surface 10a side of the transfer substrate 10. It has a laminated structure including the layer 5 and the raised layer 1 laminated on the second surface side of the transfer substrate.

  On the opposite side of the surface protective layer 5 from the transfer substrate 10, a primer layer 6 is laminated as necessary for the purpose of improving the adhesion between the surface protective layer 5 and a layer adjacent thereto. It may be. Moreover, the pattern layer 7 may be laminated | stacked on the opposite side to the transfer base material 10 of the surface protective layer 5 as needed for the purpose of providing decorating. Furthermore, the adhesive layer 8 may be laminated | stacked on the surface on the opposite side to the transfer base material 10 of the surface protective layer 5 as needed. In the transfer sheet of the present invention, a layer closer to the surface protective layer 5 than the transfer substrate 10 (that is, the surface protective layer 5, a primer layer 6, a pattern layer 7, an adhesive layer 8, 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 5 and can be peeled from the surface protective layer 5. 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 3. The base film layer 3 is a layer that can function as a support in the transfer base 10. Further, when the transfer substrate 10 is formed of a plurality of layers, examples of the layer included in the transfer substrate 10 include the resin coat layer 2 and the release layer 4 in addition to the substrate film layer 3. It is done. The resin coat layer 2 is provided between the base film layer 3 and the raised layer 1 as necessary for the purpose of improving the adhesion between these layers. Moreover, the mold release layer 4 is provided between the base film layer 3 and the surface protective layer 5 as needed for the purpose of improving the peelability between these layers.

  On the second surface 10 b side of the transfer substrate 10, the raised layer 1 is laminated.

  As a laminated structure of the transfer sheet of the present invention, a laminated structure in which a raised layer / a substrate film layer / a surface protective layer are laminated in this order; a raised layer / a resin coat layer / a substrate film layer / a surface protective layer are laminated in this order. Laminated structure; laminated layer / base film layer / release layer / surface protective layer laminated in this order; raised layer / resin coat layer / base film layer / release layer / surface protective layer in this order Laminated structure; laminated layer / base film layer / surface protective layer / pattern layer laminated in this order; laminated layer / base film layer / surface protective layer / primer layer / pattern layer laminated in this order Laminated structure; raised layer / base film layer / surface protective layer / adhesive layer laminated in this order; raised layer / base film layer / surface protective layer / primer layer / adhesive layer were laminated in this order Laminated structure; top layer / base material Laminated layer / surface protective layer / pattern layer / adhesive layer laminated in this order; laminated layer / base film layer / surface protective layer / primer layer / design layer / adhesive layer laminated structure in this order; Laminated layer / resin coat layer / base film layer / surface protective layer / primer layer / pattern layer / adhesive layer in this order; laminated layer / base film layer / release layer / surface protective layer / primer Layer / pattern layer / adhesive layer laminated in this order; overlay layer / resin coat layer / base film layer / release layer / surface protective layer / primer layer / design layer / adhesive layer laminated in this order Examples include a laminated structure. FIG. 1 shows a schematic diagram of a cross-sectional structure of an embodiment of a transfer sheet in which a raised layer / a base film layer / a surface protective layer are laminated in this order as an aspect of the laminated structure of the transfer sheet of the present invention. Further, in FIG. 2, as an aspect of the laminated structure of the transfer sheet of the present invention, the overlay layer / resin coat layer / base film layer / release layer / surface protective layer / primer layer / design layer / adhesive layer are in this order. The schematic diagram of the cross-section of one form of the laminated | stacked transfer sheet is shown.

Composition of each layer forming transfer sheet [transfer substrate 10]
The transfer substrate 10 is provided adjacent to the surface protective layer 5 and can be peeled from the uncured or semi-cured surface protective layer 5. The transfer substrate 10 is characterized by containing at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant (hereinafter sometimes simply referred to as “ultraviolet absorber or the like”). In the transfer sheet of the present invention, when the ultraviolet absorber is contained in the transfer substrate 10, when the build-up layer 1 is cured and formed by irradiation with ultraviolet rays from the build-up layer 1 side, the transfer substrate It is possible to effectively suppress the ultraviolet rays from being absorbed or reflected by the ultraviolet absorber contained in 10 and reaching the surface protective layer 5. For this reason, when transferring a transfer sheet to a resin molded product, a transfer sheet capable of forming a concavo-convex shape on the surface of a decorative resin molded product by a raised layer (after curing) formed on a transfer substrate. And it can be set as the transfer sheet provided with the surface protection layer which can be transferred in the uncured or semi-cured state.

  In the transfer substrate 10, the ultraviolet absorber or the like may be included in at least a part 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 3. When the transfer substrate 10 is formed of a plurality of layers, as the layer included in the transfer substrate 10, in addition to the substrate film layer 3, a resin coat layer 2, a release layer 4, and the like are formed. . When the transfer substrate 10 has these layers, it is preferable that at least one layer contains an ultraviolet absorber or the like.

  For example, when the transfer substrate 10 has the substrate film layer 3, the substrate film layer 3 may contain an ultraviolet absorber or the like. Moreover, when the transfer base material 10 has the base film layer 3 and the resin coat layer 2 in order from the first surface 10a side, the resin coat layer 2 may contain an ultraviolet absorber or the like. Good. Furthermore, when the transfer base material 10 has the release layer 4 and the base film layer 3 in order from the first surface 10a side, the release layer 4 may contain an ultraviolet absorber or the like. Good.

<Ultraviolet absorber>
As the ultraviolet absorber, for example, the following (1) to (5) can be preferably used.
(1) Benzophenone series: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, etc. ,
(2) Benzotriazole series: 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) phenylbenzo Triazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- ( 2H-benzotriazol-2-yl) phenol], etc.
(3) Acrylate series: ethyl-2-cyano-3,3′-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, etc.
(4) Salicylate type: phenyl salicylate, 4-t-butylphenyl salicylate, etc.
(5) Oxanilide type: 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxyn-5-t-butyl-2′-ethyloxalic acid bisanilide, etc.
(6) Triazine series: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione, 1,3,5-tri [[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] and the like.

  Among these, (6) triazine-based ultraviolet absorbers are preferable. An ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more types.

<Ultraviolet reflector>
As the ultraviolet reflector, for example, a metal or alloy such as aluminum, zinc, copper, brass, stainless steel, or a fluorescent brightener can be used, and the ultraviolet reflector is used alone. Alternatively, two or more types may be used in combination.

<Colorant>
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. A colorant may be used individually by 1 type and may be used in combination of 2 or more types.

<Contents of UV absorber, UV reflector, and colorant>
The total content of the ultraviolet absorber and the like in the transfer substrate 10 may be appropriately set from the viewpoint of effectively suppressing the ultraviolet rays irradiated when forming the build-up layer 1 from being transmitted through the transfer substrate 10. The amount per unit area of the transfer substrate 10 is preferably 180 mg / m ² or more, more preferably 250 mg / m ² or more. In addition, when a plurality of layers of the transfer base material 10 includes an ultraviolet absorber or the like, the total content of the ultraviolet absorber, the ultraviolet reflector, and the colorant included in each layer is such an amount. If it is.

  Among the ultraviolet absorbers, ultraviolet reflectors, and colorants, the transfer substrate 10 preferably contains an ultraviolet absorber from the viewpoint of particularly effectively suppressing the ultraviolet transmission of the transfer substrate 10.

[Base film layer 3]
The substrate film layer 3 is a layer that can function as a support in the transfer substrate 10 (and also the transfer sheet). The base film layer 3 used in the present invention is selected in consideration of suitability for vacuum forming, 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.

  In the present invention, it is preferable to use a polyester sheet as the base film layer 3 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.

  The transfer film layer 3 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 3 is physically or chemically such as an oxidation method or an unevenness method on one side or both sides as desired for the purpose of improving the adhesion with the resin coat layer 2 and the release layer 4 described later. Surface treatment can be applied. 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 3 is usually 10 to 150 μm, preferably 10 to 125 μm, and more preferably 10 to 80 μm. Moreover, as the base film layer 3, a single layer sheet of these resins or a multilayer sheet made of the same kind or different kinds of resins can be used.

[Resin coat layer 2]
The resin coat layer 2 is a layer provided on the side on which the build-up layer 1 of the base film layer 3 is laminated as necessary for the purpose of improving the adhesion between the base film layer 3 and the build-up layer 1. . The resin coat layer 2 can be formed of a resin.

  The resin for forming the resin coat layer 2 is not particularly limited, and a thermosetting resin, a thermoplastic resin, an ionizing radiation curable resin, or the like can be used. Examples thereof include a reaction product of an isocyanate and a polyol resin. These resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The resin coat layer 2 can be formed by applying a resin on the base film 3. The coating method is not particularly limited. For example, the resin constituting the resin coat layer 3 is made to have a thickness described later, such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, silk screen, etc. It can apply | coat by a well-known system, Preferably a gravure coat.

  The thickness of the resin coat layer 2 is usually 0.5 to 30 μm, preferably about 0.5 to 5 μm.

[Release layer 4]
The release layer 4 is provided on the side of the base film layer 3 on which the surface protective layer 5 is laminated, if necessary, for the purpose of enhancing the peelability between the base film layer 3 and the surface protective layer 5. Is a layer. The release layer 4 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 4 includes a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, and 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 4 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 4 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 substrate 10, and is transferred to a transfer target (molded resin layer 9 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.

  In the transfer layer 11, the surface protective layer 5 is provided on the outermost surface on the transfer substrate 10 side, and the surface protective layer 5 is in contact with the transfer substrate 10. As described above, the transfer layer 11 can be provided with the picture layer 7, the primer layer 6, the adhesive layer 8, and the like as necessary.

[Surface protective layer 5]
The surface protective layer 5 is a layer provided on the transfer sheet so as to be positioned on the outermost surface of the decorative resin molded product for the purpose of enhancing the scratch resistance, weather resistance, etc. of the decorative resin molded product.

  In the transfer sheet of the present invention, the surface protective layer 5 is formed of an uncured or semi-cured ultraviolet curable resin composition. Thereby, the transfer sheet of the present invention has high three-dimensional formability. In addition, after the transfer sheet is transferred to the transfer target, the transfer substrate 10 is peeled off, and the uncured or semi-cured surface protective layer 5 is cured by irradiating with ultraviolet rays. High scratch resistance and weather resistance can be imparted.

<UV curable resin>
An ultraviolet curable resin is a resin that crosslinks and cures when irradiated with ultraviolet rays. Specifically, a prepolymer, an oligomer, a monomer, or the like having a polymerizable unsaturated bond or an epoxy group in the molecule. The thing which mixed at least 1 sort (s) suitably among these is mentioned. Moreover, it is desirable to add about 0.1-5 mass parts of photoinitiators with respect to 100 mass parts of resin to an ultraviolet curable composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.

  As the monomer used as the ultraviolet curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is 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.

  Moreover, as said oligomer used as an ultraviolet curable resin, the (meth) acrylate oligomer which has a radically polymerizable unsaturated group in a molecule | numerator is suitable, and especially two or more polymerizable unsaturated bonds in a molecule | numerator ( A polyfunctional (meth) acrylate oligomer having two or more functions 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, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate. The acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. The urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction of a polyether polyol, a polyester polyol or a caprolactone polyol and a polyisocyanate compound with (meth) acrylic acid. 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.

<Other additive components>
Various additives can be blended in the ultraviolet curable resin composition forming the surface protective layer 5 according to desired physical properties to be provided in the surface protective layer 5. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant, and a matting agent. These additives can be appropriately selected from commonly used ones. Examples of the matting agent include silica particles and aluminum hydroxide particles. 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.

<Formation of surface protective layer 5>
The surface protective layer 5 can be formed, for example, by preparing an ultraviolet curable resin composition and applying it to the transfer substrate 10. In addition, the viscosity of a resin composition should just be a viscosity which can form an unhardened resin layer with the below-mentioned application | coating system.

  The coating method is not particularly limited. For example, the coating solution of the ultraviolet curable resin composition is a known coating such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, or a comma coat so as to have a thickness described later. It can be applied by a method, preferably a gravure coat.

  By adding various additives to the surface protective layer 5, 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, an infrared shielding coating function You may perform the process which provides functions, such as.

<Thickness of surface protective layer 5>
Although there is no restriction | limiting in particular about the thickness after drying of the surface protective layer 5, For example, about 1-100 micrometers, Preferably it is about 1-50 micrometers, More preferably, about 1-30 micrometers is mentioned. 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 ultraviolet curable resin can be uniformly cured, which is economically advantageous. . Furthermore, when the thickness of the surface protective layer 5 after drying satisfies the above range, the formability of the transfer sheet is further improved, so that high followability can be obtained for complicated shapes such as automotive interior applications.

[Primer layer 6]
The primer layer 6 is a layer provided as necessary for the purpose of improving the adhesion between the surface protective layer 5 and the layer located below (on the opposite side to the transfer substrate 10). The primer layer 6 can be formed of a resin.

  Although it does not restrict | limit especially as resin which forms the primer layer 6, 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 6, 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 increased, and cracking, breakage, whitening, and the like of the surface protective layer 5 can be effectively suppressed.

  Primer layer 6 is a resin that forms primer layer 6, 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 of forming a coating film of a primer layer 6 or an adhesive layer 8 described later on a thin sheet (film substrate) and then coating the surface of the target layer in the transfer sheet. .

[Picture layer 7]
The pattern layer 7 is a layer provided as necessary in order to give decorativeness to the resin molded product. The pattern layer 7 is formed by printing various patterns using ink and a printing machine. The pattern formed by the pattern layer 7 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-like 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 7, 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 7 is not restrict | limited, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

[Adhesive layer 8]
The adhesive layer 8 is provided under the surface protective layer 5 and the pattern layer 7 (on the side of the molded resin layer 9) for the purpose of improving the adhesion between the transfer sheet and the transfer target (molded resin layer 9 and the like). It is a layer provided as needed. The resin forming the adhesive layer 8 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 8 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 8 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 8 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.

[Heisei layer 1]
The build-up layer 1 is provided on the second surface 10b side of the transfer substrate 10 so as to form a concavo-convex shape, and the surface protective layer 5 is formed with a concavo-convex shape corresponding to the concavo-convex shape of the build-up layer 1 during transfer. It is a layer provided in.

  The raised layer 1 of the present invention is formed of a cured product of an ultraviolet curable resin composition. As an ultraviolet curable resin composition, the thing similar to what is used for the surface protective layer 5 can be used.

  The build-up layer 1 is formed by preparing an ultraviolet curable resin composition, applying it to the surface on the second surface 10b side of the transfer substrate 10, and irradiating ultraviolet rays to cure the ultraviolet curable resin. Is called. As described above, since the transfer base material 10 of the present invention contains an ultraviolet absorber or the like, the ultraviolet light can pass through the transfer base material 10 even when the ultraviolet light is irradiated when forming the build-up layer 1. Effectively suppressed. For this reason, the progress of curing of the surface protective layer 5 is suppressed, and the flexibility of the transfer sheet can be kept high.

  In the irradiation with ultraviolet rays, light 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.

  The raised layer 1 may be formed on the entire surface (entirely solid) on the surface of the transfer substrate 10 on the second surface 10b side, or may be partially formed. Here, the fact that the build-up layer 1 is formed on the entire surface of the transfer substrate 10 means that the entire surface of the transfer substrate 10 is covered with the build-up layer 1. This also means that the transfer substrate 10 is not exposed even in the recess.

  The height of the raised portion of the raised layer 1 is preferably about 5 to 50 μm, more preferably about 10 to 30 μm, from the viewpoint of forming an uneven shape on the surface of the molded resin layer 9. Here, the height of the convex portion of the raised layer 1 means the difference in film thickness between the convex portion and the concave portion when the raised layer 1 is formed on the entire surface, and the raised layer 1 is partially formed. When it is, it means the film thickness of the convex part.

2. Production method of transfer sheet The transfer sheet of the present invention can be produced by a method comprising the following steps.
Laminating an ultraviolet curable resin composition for forming the surface protective layer 5 on the first surface 10a of the transfer substrate 10 containing at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant;
A step of laminating an ultraviolet curable resin composition for forming the raised layer 1 on the second surface 10b of the transfer substrate 10 in an uneven shape;
A step of irradiating ultraviolet rays from the second surface 10b side of the transfer substrate 10 to cure the raised layer 1.

  When the primer layer 6, the pattern layer 7, the adhesive layer 8, etc. are provided on the transfer layer 11, after forming the uncured or semi-cured surface protective layer 5, these layers are formed on the surface protective layer 5. What is necessary is just to laminate | stack a layer. 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”.

3. Decorative resin molded product and method for producing the same The above-described transfer sheet of the present invention is formed on the surface on the second surface 10b side of the transfer base material 10 when transferred to various objects to be transferred (for example, resin molded products). The formed raised layer 1 can form a concavo-convex shape on the surface of the decorative resin molded product, and after peeling the transfer substrate 10 and the raised layer 1 from the resin molded product, an uncured or semi-cured surface protective layer By irradiating 5 with ultraviolet rays and curing the ultraviolet curable resin composition, it can be used for the purpose of producing a decorated resin molded article having excellent scratch resistance and design. Moreover, since the surface protective layer 5 is in an uncured or semi-cured state, the transfer sheet of the present invention can be used for applications requiring particularly high three-dimensional formability, such as an injection molding simultaneous transfer method.

The decorative resin molded product of the present invention is manufactured by laminating the molded resin layer 9 on the transfer sheet of the present invention. The decorative resin molded product of the present invention can be manufactured by, for example, a method including the following steps.
Laminating the above-mentioned transfer sheet of the present invention on a resin molded product (molded resin layer 9) and peeling the transfer substrate 10 and the overlay layer 1;
A step of curing the surface protective layer 5 by irradiating the uncured or semi-cured surface protective layer 5 with ultraviolet rays.

  More specifically, for example, by using the transfer sheet of the present invention as a sheet for simultaneous injection molding, and laminating the transfer sheet and a resin molded product (molded resin layer 9), the raised layer 1 and the uncured layer Or the transfer base material 10 including the semi-cured surface protection layer 5, the transfer layer 11, and the molded resin layer 9 are laminated in this order to obtain a decorative resin molded product with a transfer base material and a raised layer (FIG. 5). See).

  Next, the transfer layer 11 including at least the uncured or semi-cured surface protective layer 5 by peeling the transfer substrate 10 and the build-up layer 1 from the transfer resin and the decorative resin molded product with the build-up layer, A decorative resin molded product in which the molded resin layer 9 is laminated is obtained (see, for example, FIG. 6).

  Next, the decorative resin molded article of the present invention is obtained by irradiating the surface protective layer 5 with ultraviolet rays and curing the ultraviolet curable resin composition (see, for example, FIG. 6).

  In addition, as described above, when the transfer layer 11 of the present invention includes the primer layer 6, the pattern layer 7, the adhesive layer 8, and the like in addition to the surface protective layer 5, 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 (6).
(1) A step of heating the transfer sheet from the surface protective layer 5 side by a hot plate with the surface protective layer 5 side (the side opposite to the raised layer 1) of the transfer sheet facing into the mold (2) (3) Molding resin (resin for forming the molding resin layer 9) is molded in the mold by pre-molding (vacuum molding) so as to conform to the in-mold shape, and closely clamping to the inner surface 20 of the mold. Step of injecting (4) Step of taking out a decorated resin molded product (decorated resin molded product with a transfer substrate and a raised layer) from the mold after the molding resin has cooled (5) Uncured of the decorated resin molded product Or the process of peeling the transfer base material 10 and the build-up layer 1 from the semi-cured surface protective layer 5 (6) The process of irradiating the surface protective layer 5 with ultraviolet rays to obtain a decorated resin molded product.

  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. Since the surface protective layer 5 is in an uncured or semi-cured state, the transfer sheet of the present invention has high three-dimensional formability and can follow a complicatedly shaped mold.

  In the above step (2), the build-up layer 1 is pressed against the inner surface 20 of the mold. As a result, the transfer sheet is deformed, and the surface of the transfer substrate 10 and at least the surface protective layer 5 of the transfer layer 11 is uneven. (See FIGS. 3 to 4).

  In both the steps (3), a resin (resin forming the molded resin layer 9) 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 9 on which the concavo-convex shape is formed are laminated, so that the concavo-convex shape corresponding to the concavo-convex shape of the transfer layer 11 is also usually formed on the molded resin layer 9. 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 9 and adhered, and becomes a decorative resin molded product with a transfer substrate and a raised layer (see FIGS. 4 and 5). The heating temperature of the molding resin depends on the type of resin that forms the molding resin layer 9, but is generally about 180 to 320 ° C.

  The thus obtained transfer base material and decorative resin molded product with a raised layer are cooled in the step (4) and then taken out of the mold, and then the transfer base material 10 and the raised layer 1 are removed in the step (5). By peeling from the surface protective layer 5, a decorative resin molded article having an uncured or semi-cured surface protective layer 5 is obtained. Moreover, the process of peeling the transcription | transfer base material 10 and the buildup layer 1 from the surface protective layer 5 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).

  The decorative resin molded product is obtained by irradiating the surface protective layer 5 of the decorative resin molded product having the uncured or semi-cured surface protective layer 5 obtained in the step (5) with ultraviolet rays. The surface protective layer 5 can be cured by irradiation with ultraviolet rays in the same manner as the top layer 1 is cured.

  In the decorative resin molded product of the present invention, the molded resin layer 9 may be formed by selecting a resin according to the application. The molding resin for forming the molding resin layer 9 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) containing 300 mg / m ^{2 of} a triazine-based UV absorber (UVA), photopolymerization started on 100 parts by mass of an acrylic acrylate having a weight average molecular weight of 30000. The agent (one added with 2 parts by mass of 1-hydroxycyclohexylpheniketone) was applied using a bar coater to form a surface protective layer (10 μm). Further, on the surface protective layer, a primer layer (material composition: acrylic polyol, thickness 2 μm), a pattern layer (material composition: PMMA, thickness 5 μm), and an adhesive layer (material composition: PMMA, thickness 2 μm) are obtained by gravure printing. Formed in order. Next, an ultraviolet curable resin composition (material composition: acrylic acrylate (molecular weight 110,000, double bond equivalent 250 g / mol) 100 parts by mass on the opposite surface of the PET film was added to a photopolymerization initiator (1-hydroxycyclohexyl phenoxy). A hemispherical convex portion (a hemispherical convex portion is formed in a matrix) using an addition of 1.5 parts by mass of ketone) The area of one convex portion viewed from the stacking direction is 0.79 mm ² . The distance between adjacent convex portions (the width of the concave portion is 1 mm.) Is formed, and ultraviolet rays are irradiated from the surface on the build-up layer side (ultraviolet irradiation condition: 1000 mJ / cm ² ) to cure the build-up layer. A transfer sheet in which PET film / surface protective layer / primer layer / picture layer / adhesive layer were laminated in order was obtained.

Next, the transfer sheet was placed in a mold, heated with an infrared heater at 350 ° C. for 7 seconds, preformed so as to conform to the shape in the mold by vacuum forming, and clamped (maximum draw ratio 100%). Thereafter, the molding resin was injected into the cavity of the mold, and the decorative sheet and the molding resin were integrally molded to obtain a decorative resin molded product with a transfer substrate and a raised layer. Subsequently, the transfer base material and the overlay layer were peeled and removed from the transfer base material and the decorative resin molded product with the overlay layer. Next, the surface protective layer is cured from above the surface protective layer by irradiating with ultraviolet rays (ultraviolet irradiation condition: 1000 mJ / cm ² ), and is a tray having a size of 80 mm square, an aperture of 3 mm, and a corner portion of 11R. A decorative resin molded product having a shape was obtained.

Example 2
In Example 1, a transfer sheet and a decorative resin molded product were obtained in the same manner as in Example 1 except that a PET film (75 μm) containing 200 mg / m ^{2 of} triazine-based UVA was used.

Example 3
UV curable resin composition on one side of triazine-based UVA-free PET film (thickness 75 μm) (material composition: 100 parts by mass of acrylic acrylate having a weight average molecular weight of 30,000 and photopolymerization initiator (1-hydroxycyclohexylpheniketone) 2 parts by mass added) was applied using a bar coater to form a surface protective layer (10 μm). Further, on the surface protective layer, a primer layer (material composition: acrylic polyol, thickness 2 μm), a pattern layer (material composition: PMMA, thickness 5 μm), and an adhesive layer (material composition: PMMA, thickness 2 μm) are obtained by gravure printing. Formed in order. Next, a resin composition composed of triazine-based UVA, XDI curing agent, and acrylic polyol is laminated on the opposite surface of the PET film using a bar coater, and a resin coat layer is formed so that UVA is contained at 300 mg / m ^2. Formed. On top of that, an ultraviolet curable resin composition (material composition: acrylic acrylate (molecular weight 110,000, double bond equivalent 250 g / mol) 100 parts by mass, photopolymerization initiator (1-hydroxycyclohexylpheniketone) 1.5 parts by mass) The hemispherical protrusions (the hemispherical protrusions are formed in a matrix. The area of one protrusion as viewed from the stacking direction is 0.79 mm ^2. The distance between adjacent protrusions ( The width of the concave portion is 1 mm), and ultraviolet rays are irradiated from the surface on the raised layer side (ultraviolet irradiation condition 1000 mJ / cm ² ) to cure the raised layer, and the raised layer / PET film / surface protective layer / primer layer A transfer sheet in which / pattern layer / adhesive layer was laminated in order was obtained. Moreover, using the obtained decorative sheet, a decorative resin molded product was obtained in the same manner as in Example 1.

Comparative Example 1
In Example 1, a transfer sheet and a decorative resin molded product were produced in the same manner as in Example 1 except that a PET film not containing UVA was used.

<Evaluation of formability>
The decorative resin molded product obtained in each Example and Comparative Example was evaluated by the appearance after molding. The evaluation criteria are as follows.
○: No cracking or whitening of the coating film was observed on the surface protective layer, and the shape followed the shape well.
Δ: Slight coating cracking or slight whitening was confirmed in the surface protective layer, but there is no practical problem.
X: Coating surface cracking and whitening were observed in the surface protective layer without following the shape.

<Uneven appearance>
It was visually evaluated whether the concavo-convex pattern provided on the substrate was shaped after molding. The results are shown in Table 1.
○: Molded.
X: Not shaped.

DESCRIPTION OF SYMBOLS 1 Top layer 2 Resin coat layer 3 Base film layer 4 Release layer 5 Surface protective layer 6 Primer layer 7 Picture layer 8 Adhesive layer 9 Molding resin layer 10 Transfer base material 11 Transfer layer 20 Inner surface of mold

Claims (5)

A transfer base material having a first surface and a second surface, consisting of a single layer or multiple layers, a surface protective layer laminated on the first surface side of the transfer base material, and the transfer base material A transfer sheet having a raised layer laminated on the second surface side,
The raised layer is formed of a cured product of an ultraviolet curable resin composition,
The surface protective layer is formed of an uncured or semi-cured ultraviolet curable resin composition,
The transfer substrate has a release layer and a substrate film layer in order from the first surface side,
The transfer sheet, wherein the release layer contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant. The transfer substrate has a substrate film layer;
The transfer sheet according to claim 1 , wherein the base film layer contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant. The transfer base material, in order from the first surface side, has a base film layer and a resin coat layer,
The transfer sheet according to claim 1 or 2 , wherein the resin coat layer contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant. A step of laminating an ultraviolet curable resin composition for forming a surface protective layer on the first surface of a transfer substrate containing at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant;
A step of laminating an ultraviolet curable resin composition for forming a raised layer on the second surface of the transfer substrate in an uneven shape;
Irradiating ultraviolet rays from the second surface side of the transfer substrate to cure the raised layer;
With
The transfer substrate has a release layer and a substrate film layer in order from the first surface side,
The transfer sheet manufacturing method, wherein the release layer contains at least one of an ultraviolet absorber, an ultraviolet reflector, and a colorant. Laminating the transfer sheet according to any one of claims 1 to 3 on a resin molded product, and peeling the transfer substrate and the overlay layer;
Irradiating the uncured or semi-cured surface protective layer with ultraviolet rays to cure the surface protective layer;
A method for producing a decorated resin molded product.