JP6906981B2 - Manufacturing method of transfer sheet for three-dimensional molding and decorative resin molded product - Google Patents

Description

The present invention relates to a transfer sheet for three-dimensional molding, a method for producing a decorative resin molded product using the transfer sheet, and an intermediate for producing the decorative resin molded product.

A surface protective layer is usually provided on the surface of a resin molded product used for interior / exterior of automobiles, interior materials of building materials, home appliances, etc. for the purpose of imparting scratch resistance, designability, and the like. As a technique for providing a surface protective layer on the surface of a resin molded body, for example, a technique for transferring the surface protective layer to the surface of a resin molded body by in-mold molding using a transfer sheet for three-dimensional molding is known.

For example, Patent Documents 1 and 2 describe a transfer sheet including a transfer base material, a raised portion provided on one surface of the transfer base material, and a transfer layer provided on the other surface of the transfer base material. Is placed in an injection molding die, the resin is injected, the transfer sheet and the resin molded body are integrated, and then the transfer base material is peeled off. According to this method, the transfer layer can be transferred to the surface of the resin molded product, and the transfer layer can be given an uneven shape by the ridge.

Japanese Patent Application Laid-Open No. 2008-510638 Japanese Unexamined Patent Publication No. 2012-183808

If the hardness of the ridge is low, the ridge may be pressed against the injection mold during in-mold molding, and the ridge may stick to the injection mold, while the hardness of the ridge is high. If the value is high, the transfer sheet may be deformed along the molding surface of the injection molding die during in-mold molding, which may cause cracks in the raised portion. If the ridge is attached to the injection molding die, the injection molding die cannot be used for continuous production, and the production efficiency is lowered. If the ridge is cracked, the ridge cannot give the transfer layer a desired uneven shape. However, Patent Documents 1 and 2 do not consider these issues at all.

Therefore, the present invention utilizes a transfer sheet for three-dimensional molding, which can prevent sticking of the ridge to the injection molding die and cracking of the ridge, which may occur during in-mold molding. It is an object of the present invention to provide a method for producing a decorative resin molded product and an intermediate for producing the decorative resin molded product.

In order to solve the above problems, the present invention provides the following inventions.
[1] A transfer base material layer having a first main surface and a second main surface located on the opposite side of the first main surface, and a raised portion provided on the first main surface of the transfer base material layer. A transfer sheet for three-dimensional molding including a transfer layer provided on the second main surface of the transfer base material layer, wherein the Martens hardness of the raised portion is 50 N / mm ² or more and 150 N / mm ² or less. The transfer sheet for three-dimensional molding.
[2] The transfer sheet for three-dimensional molding according to [1], wherein the raised portion is formed of a cured product of an ionizing radiation curable resin composition.
[3] The transfer sheet for three-dimensional molding according to [2], wherein the ionizing radiation curable resin composition contains 30% by mass or more and 70% by mass or less of a polyfunctional monomer.
[4] The transfer sheet for three-dimensional molding according to any one of [1] to [3], wherein the transfer layer has a surface protective layer.
[5] The transfer sheet for three-dimensional molding according to [4], wherein the surface protective layer is formed of a cured product, a semi-cured product, or an uncured product of an ionizing radiation curable resin composition.
[6] The following steps:
(A) The three-dimensional molding transfer sheet according to any one of [1] to [5] is used as an injection molding die, and the main surface of the transfer sheet on the ridge side is the molding of the injection molding die. The process of arranging so as to face the surface,
(B) After the step (a), the resin in a fluid state is injected into the cavity formed by molding the injection molding mold, and the transfer sheet is integrated with the transfer layer of the transfer sheet. After the step of forming the intermediate body including the resin molded body and the step (c) step (b), the transfer base material layer is peeled off from the intermediate body, and the transfer layer and the transfer layer are integrated. A method for producing a decorative resin molded product, which comprises a step of obtaining a decorative resin molded product including the resin molded product.
[7] Manufacture a decorative resin molded product comprising the transfer sheet for three-dimensional molding according to any one of [1] to [5] and a resin-forming body integrated with the transfer layer of the transfer sheet. Intermediate to do.
[8] The above-mentioned [7], wherein the transfer base material layer and the transfer layer are concave-convex shaped, and the raised portion is located in a concave portion of the transfer base material layer formed by the uneven shaping. Intermediate.

According to the present invention, a transfer sheet for three-dimensional molding capable of preventing sticking of a raised portion to an injection molding die and cracking of the raised portion, which may occur during in-mold molding, is used. A method for producing a decorative resin molded product and an intermediate for producing the decorative resin molded product are provided.

FIG. 1 is a cross-sectional view schematically showing the structure of a transfer sheet for three-dimensional molding according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing the configuration of a decorative resin molded product according to an embodiment of the present invention. FIG. 3 is a cross-sectional view for explaining a method of manufacturing the decorative resin molded product shown in FIG. 2 using the transfer sheet shown in FIG. FIG. 4 is a cross-sectional view (continuation of FIG. 3) for explaining a method of manufacturing the decorative resin molded product shown in FIG. 2 using the transfer sheet shown in FIG. FIG. 5A is a diagram for explaining a diamond indenter (Vickers indenter) used for measuring the Martens hardness of the ridge. FIG. 5B is a diagram for explaining the measurement conditions of the Martens hardness of the raised portion.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

<Transfer sheet for 3D molding>
Hereinafter, a transfer sheet for three-dimensional molding according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing the structure of a transfer sheet for three-dimensional molding according to an embodiment of the present invention.

As shown in FIG. 1, the three-dimensional molding transfer sheet 1 according to the embodiment of the present invention is a transfer group having a second main surface S2 located on the opposite side of the first main surface S1 and the first main surface S1. It includes a material layer 2, a raised portion 3 provided on the first main surface S1 of the transfer base material layer 2, and a transfer layer 4 provided on the second main surface S2 of the transfer base material layer 2. In addition, "for three-dimensional molding" includes not only the use of manufacturing a three-dimensional molded body (molded body having a three-dimensional shape) but also the use of manufacturing a two-dimensional molded body (molded body having a sheet shape). Will be done.

Transfer Base Material Layer As shown in FIG. 1, the transfer base material layer 2 has a first main surface S1 and a second main surface S2 located on the opposite side of the first main surface S1. The ridge 3 is supported, and the transfer layer 4 is supported on the second main surface S2.

The transfer base layer 2 can be peeled off from the transfer layer 4 (in the present embodiment, the surface protective layer 41 located closest to the transfer base layer 2 among the layers constituting the transfer layer 4).

As shown in FIG. 1, the transfer base material layer 2 includes a base material sheet 21, a resin layer 22 provided on one main surface of the base material sheet 21 (main surface on the side of the raised portion 3), and a base material sheet. It has a release layer 23 provided on the other main surface (main surface on the transfer layer 4 side) of 21.

[Base sheet]
The base sheet 21 supports the resin layer 22 on one main surface (main surface on the raised portion 3 side) and the release layer 23 on the other main surface (main surface on the transfer layer 4 side).

The base sheet 21 can be appropriately selected in consideration of vacuum forming suitability and the like. As the base sheet 21, for example, a thermoplastic resin sheet can be used. The base sheet 21 may be a single-layer sheet or a multi-layer sheet. The two or more resin layers constituting the multi-layer sheet may be made of the same type of resin or different kinds of resins. Examples of the thermoplastic resin constituting the thermoplastic resin sheet include polyester resin, (meth) acrylic resin, polyolefin resin (for example, polyethylene (high density, medium density or low density), polypropylene (isotactic type or syndi)). (Octic type), polybutene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, etc.), polyvinyl chloride resin, polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin and the like.

As the base sheet 21, it is preferable to use a polyester resin sheet from the viewpoints of heat resistance, dimensional stability, moldability, versatility and the like. The polyester resin constituting the polyester resin sheet is a polymer containing an ester group obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol, and specific examples thereof include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). ), Polyethylene terephthalate (PEN), etc. Of these, polyethylene terephthalate (PET) is preferable from the viewpoint of heat resistance, dimensional stability, and the like.

The polyester resin sheet can be produced, for example, as follows. First, the polyester resin and other raw materials are supplied to a known melt extrusion device such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester resin to melt. Then, while extruding the molten polymer, it is rapidly cooled and solidified on a rotary cooling drum so as to have a temperature equal to or lower than the glass transition temperature to obtain an unaligned sheet in a substantially amorphous state. A polyester resin sheet can be obtained by stretching this sheet in the biaxial direction to form a sheet and heat-fixing the sheet. The stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. If necessary, it may be stretched again in the vertical and / or horizontal directions before or after heat fixing. From the viewpoint of obtaining sufficient dimensional stability, the draw ratio is preferably adjusted to 7 times or less, more preferably 5 times or less, and even more preferably 3 times or less as the area ratio. Within this range, when the decorative resin molded product is manufactured using the transfer sheet 1, the base sheet 21 does not shrink again in the temperature range of the injection resin, and the required sheet strength is obtained in the temperature range. be able to. As the polyester resin sheet, the one manufactured as described above may be used, or a commercially available one may be used.

The base sheet 21 may have an uneven shape on at least one main surface. When the base sheet 21 has an uneven shape on at least one main surface, when the decorative resin molded product is manufactured by in-mold molding using the transfer sheet 1, the uneven shape of the base sheet 21 is the surface protective layer 41. Therefore, it is possible to form an uneven shape corresponding to the uneven shape of the base sheet 21 on the surface protective layer 41. For example, by forming a fine uneven shape on the surface protective layer 41, it is possible to impart a matte (low gloss) design feeling to the surface protective layer 41. The uneven shape of the base sheet 21 may be transferred to at least the surface protective layer 41 among the layers constituting the transfer layer 4, and may be transferred to layers other than the surface protective layer 41 among the layers constituting the transfer layer 4. , May be transcribed or not transcribed.

Examples of the method for forming the uneven shape on the main surface of the base sheet 21 include physical methods such as sandblasting, hairline processing, laser processing and embossing, chemical methods such as corrosion treatment with chemicals such as solvents, and groups. Examples thereof include a method of incorporating fine particles into the material sheet 21. In the case of imparting a fine uneven shape to the surface protective layer 41 to express a matte (low gloss) design feeling, a method of containing fine particles in the base sheet 21 can be preferably used.

Examples of the fine particles include synthetic resin particles and inorganic particles, but from the viewpoint of improving three-dimensional moldability, it is preferable to use synthetic resin particles. Examples of the synthetic resin particles include acrylic beads, urethane beads, silicone beads, nylon beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, polyethylene beads and the like. Among these synthetic resin particles, acrylic beads, urethane beads, silicone beads and the like are preferable from the viewpoint of forming an uneven shape having excellent scratch resistance on the surface protective layer 41. Examples of the inorganic particles include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide, kaolin and the like. These fine particles may be used alone or in combination of two or more. The particle size of the fine particles is preferably about 0.3 to 25 μm, more preferably about 0.5 to 5 μm. The particle size of the fine particles is measured by using the Shimadzu laser diffraction type particle size distribution measuring device SALD-2100-WJA1 to inject the powder to be measured from the nozzle using compressed air and disperse it in the air. Refers to the particle size measured by the jet-type dry measurement method.

The amount of fine particles contained in the base sheet 21 is not particularly limited as long as a desired uneven shape can be formed on the surface protective layer 41, but the amount of the fine particles is not particularly limited as long as the surface protective layer 41 can form a desired uneven shape. It is preferably about 1 to 100 parts by mass, and more preferably about 5 to 80 parts by mass.

The base sheet 21 may contain one or more additives such as a stabilizer, a lubricant, an antioxidant, an antistatic agent, an antifoaming agent, and a fluorescent whitening agent, if necessary. can.

One or both main surfaces of the base sheet 21 may be subjected to a physical or chemical surface treatment such as an oxidation method or an unevenness method. Thereby, the adhesion between the base sheet 21 and the layers provided on one or both main surfaces of the base sheet 21 can be improved. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method and the like, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments can be appropriately selected depending on the type of the base sheet 21, but in general, the corona discharge treatment method is preferably used from the viewpoint of effectiveness, operability, and the like. An adhesive layer may be formed on one or both main surfaces of the base sheet 21 for the purpose of enhancing the interlayer adhesion and the like. As the base material sheet 21, a commercially available product subjected to the above-mentioned surface treatment or a commercially available product provided with an adhesive layer may be used.

The thickness of the base sheet 21 is usually about 10 to 150 μm, preferably about 10 to 125 μm, and more preferably about 10 to 80 μm.

[Resin layer]
The resin layer 22 is a layer provided on one main surface (main surface on the three sides of the raised portion) of the base sheet 21 as needed. The resin layer 22 may be omitted in some cases. The resin layer 22 can be provided, for example, for the purpose of improving the adhesion between the base sheet 21 and the raised portion 3. The resin layer 22 is located on the most raised portion 3 side of the layers constituting the transfer base material layer 2, and forms the first main surface S1 of the transfer base material layer 2. When the resin layer 22 is omitted, the first main surface S1 of the transfer base material layer 2 is formed by the main surface on the raised portion 3 side of the base material sheet 21.

The resin layer 22 can be formed by the resin composition. Examples of the resin contained in the resin composition include thermosetting resins, thermoplastic resins, ionizing radiation curable resins and the like. The resin contained in the resin composition may be one kind or two or more kinds. Examples of the thermoplastic resin include (meth) acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; polyethylene terephthalates (PET). Such as polyester resin; acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic acid ester resin and the like. Examples of the thermosetting resin include polyol resin, unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, and guanamine. Examples thereof include resins, melamine-urea cocondensate resins, silicon resins, polysiloxane resins and the like. Examples of the polyol resin include acrylic polyols; polyester polyols; urethane polyols such as polyester urethane polyols and acrylic urethane polyols; polyolefin polyols such as polyethylene polyols, polypropylene polyols, polybutadiene polyols, and polyisoprene polyols. If necessary, the thermosetting resin is blended with components involved in the curing reaction of the thermosetting resin, for example, a catalyst, a curing agent (including a cross-linking agent, a polymerization initiator, a polymerization accelerator, etc.) and the like. May be good. Specific examples of the ionizing radiation curable resin are the same as the specific examples listed in the description of the raised portion 3, and thus the description thereof will be omitted here.

The resin layer 22 can be formed by applying the resin composition to one main surface of the base sheet 21. Examples of the coating method include gravure coat, bar coat, roll coat, reverse roll coat, comma coat, silk screen and the like.

The resin layer 22 may have an uneven shape on the main surface on the side of the raised portion 3. When the resin layer 22 has an uneven shape on its main surface, the uneven shape of the resin layer 22 is transferred to the surface protective layer 41 when a decorative resin molded product is manufactured by in-mold molding using the transfer sheet 1. Therefore, the surface protective layer 41 can be formed with an uneven shape corresponding to the uneven shape of the resin layer 22. For example, by forming a fine uneven shape on the surface protective layer 41, it is possible to impart a matte (low gloss) design feeling to the surface protective layer 41. The uneven shape of the resin layer 22 may be transferred to at least the surface protective layer 41 among the layers constituting the transfer layer 4, and the layers other than the surface protective layer 41 among the layers constituting the transfer layer 4 may be transferred. It may or may not be transcribed.

Examples of the method for forming the uneven shape on the surface of the resin layer 22 include physical methods such as sandblasting, hairline processing, laser processing and embossing, chemical methods such as corrosion treatment with chemicals such as solvents, and resin layer 22. Examples thereof include a method of incorporating fine particles into the resin. In the case of imparting a fine uneven shape to the surface protective layer 41 to express a matte (low gloss) design feeling, a method of containing fine particles in the resin layer 22 can be preferably used. Specific examples of the fine particles contained in the resin layer 22 are the same as the specific examples listed in the description of the base sheet 21, and thus the description thereof will be omitted here.

The amount of fine particles contained in the resin layer 22 is not particularly limited as long as a desired uneven shape can be formed on the surface protective layer 41, but is preferably 1 to 100 parts by mass of the resin contained in the resin layer 22. It is about 100 parts by mass, more preferably about 5 to 80 parts by mass.

The thickness of the resin layer 22 is usually about 0.5 to 30 μm, preferably about 0.5 to 5 μm.

[Release layer]
The release layer 23 is releasable from the transfer base layer 2 and the transfer layer 4 (in the present embodiment, the surface protective layer 41 located closest to the transfer base layer 2 among the layers constituting the transfer layer 4). This is a layer provided on the main surface of the base sheet 21 on the transfer layer 4 side, if necessary, for the purpose of improving the above. The release layer 23 may be omitted in some cases. The release layer 23 is located closest to the transfer layer 4 among the layers constituting the transfer base layer 2, and forms the second main surface S2 of the transfer base layer 2. Since the release layer 23 forms the second main surface S2 of the transfer base material layer 2, the peelability between the transfer base material layer 2 and the transfer layer 4 (surface protection layer 41) can be improved. When the release layer 23 is omitted, the second main surface S2 of the transfer base material layer 2 is formed by the main surface of the base material sheet 21 on the transfer layer 4 side.

The release layer 23 may be a layer provided on a part of the main surface of the base sheet 21 on the transfer layer 4 side, but the transfer base layer 2 and the transfer layer 4 (surface protection layer 41) are separated from each other. From the viewpoint of improving the properties, it is preferable that the solid layer covers the entire main surface of the base sheet 21 on the transfer layer 4 side (that is, is provided in a solid shape on the entire surface).

The release layer 23 is, for example, silicon-based resin, fluorine-based resin, acrylic-based resin (including acrylic-melamine-based resin), polyester-based resin, polyolefin-based resin, polystyrene-based resin, polyurethane-based resin, cellulose-based resin, chloride. Vinyl-vinyl acetate copolymer resin, thermoplastic resin such as nitrified cotton, copolymer of monomer forming the thermoplastic resin, ionizing radiation curable resin, or these resins are (meth) acrylic acid or urethane. It can be formed by using a resin composition modified with or in combination of one or more. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, or urethane-modified products thereof are preferable. More specifically, an acrylic-melamine resin alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and an acrylic resin. Examples thereof include a resin composition obtained by mixing an emulsion of a copolymer of styrene and acrylic.

The thickness of the release layer 23 is usually about 0.01 to 5 μm, preferably about 0.05 to 3 μm.

As shown in FIG. 1, the ridge 3 is provided on a part of the first main surface S1 of the transfer base material layer 2. Of the first main surface S1 of the transfer base material layer 2, the portion where the raised portion 3 is not provided is exposed. The raised portion 3 is formed as a convex portion protruding from the first main surface S1 of the transfer base material layer 2, and is a portion of the first main surface S1 of the transfer base material layer 2 where the raised portion 3 is not provided. Is relatively recessed. As a result, unevenness is formed on the main surface of the transfer sheet 1 on the three sides of the raised portion. When a decorative resin molded product is manufactured by in-mold molding using the transfer sheet 1, the transfer base material layer 2 and the transfer layer 4 are uneven due to the uneven shape formed on the main surface of the transfer sheet 1 on the side of the raised portion 3. It is shaped.

The Martens hardness of the raised portion 3 is 50 N / mm ² or more and 150 N / mm ² or less. When the Martens hardness of the ridge 3 is 50 N / mm ² or more, the ridge 3 is pressed against the injection molding die when the decorative resin molded product is manufactured by in-mold molding using the transfer sheet 1. This makes it possible to prevent the ridge 3 from sticking to the injection molding die. Further, when the Martens hardness of the upper portion 3 is 150 N / mm ² or less, when the decorative resin molded product is manufactured by in-mold molding using the transfer sheet 1, the transfer sheet 1 is the molding surface of the injection molding die. It is possible to prevent the cracking of the raised portion 3 that may occur due to the deformation along the above. Martens hardness of raised portion 3, 50 N / mm ² or more 150 N / mm ² can be appropriately adjusted within the following range, preferably 60N / mm ² or more 140 N / mm ² or less, more preferably 80 N / mm ² More than 120 N / mm ² or less.

The Martens hardness of the raised portion 3 is measured using a surface film physical property tester (PICODENTOR HM-500, manufactured by Fisher Instruments Co., Ltd.) in an environment of a temperature of 23 ° C. and a relative humidity of 38%. Specifically, using a diamond indenter (Vickers indenter) having a facing angle of 136 ° shown in FIG. 5A, the diamond indenter is pushed into the ridge 3, and the pushing load F and the pushing depth h (indentation depth) are as follows. formula:
Martens hardness = F / (26.43 × h ² )
To obtain the Martens hardness. In pushing, as shown in FIG. 5B, a load of 0 to 2 mN is first applied to the ridge 3 in an environment of a temperature of 23 ° C. and a relative humidity of 38% in 2 seconds, and then a load of 2 mN is applied for 5 seconds. Hold and finally unload from 2 to 0 mN in 2 seconds. The Martens hardness at 10 points is measured for one ridge, and the average value is taken as the Martens hardness of the ridge.

The number of the raised portions 3 provided on the first main surface S1 of the transfer base material layer 2 is not particularly limited, and can be appropriately adjusted according to the shape to be imparted to the decorative resin molded product and the like. The number of the raised portions 3 is usually a plurality. Adjacent ridges 3 may be separated from each other or their ends may be connected to each other.

The raised portion 3 can be formed by a cured product of an ionizing radiation curable resin composition. In this case, the Martens hardness of the raised portion 3 can be adjusted to a desired range by adjusting the type, content ratio, etc. of the ionizing radiation curable resin contained in the ionizing radiation curable resin composition.

Hereinafter, the ionizing radiation curable resin contained in the ionizing radiation curable resin composition will be described. Unless otherwise specified, the following description of the ionizing radiation-curable resin and the ionizing radiation-curable resin composition describes the ionizing radiation-curable resin and the ionizing radiation-curable resin that can be used in parts or members other than the raised portion 3. It also applies to resin compositions.

[Ionizing radiation curable resin]
The ionizing radiation curable resin is a resin that undergoes a cross-linking polymerization reaction by irradiation with ionizing radiation and changes into a three-dimensional polymer structure. Ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but in addition, X It also includes electromagnetic waves such as rays and γ-rays, and charged particle beams such as α-rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin is preferable in that it can be made solvent-free and stable curing characteristics can be obtained.

As the ionizing radiation curable resin, for example, one or more of a monomer, an oligomer, a prepolymer, etc. having a polymerizable unsaturated bond, a cationically polymerizable functional group, etc. in the molecule, which can be crosslinked by irradiation with ionizing radiation, should be used. Can be done. The ionizing radiation curable resin contained in the ionizing radiation curable resin composition may be one kind or two or more kinds.

Examples of the monomer used as the ionizing radiation curable resin include (meth) acrylate monomers having a radically polymerizable unsaturated group in the molecule, and polyfunctional (meth) acrylate monomers are particularly preferable. In addition, "(meth) acrylate" means acrylate or methacrylate.

The polyfunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more (bifunctional or higher), preferably three or more (trifunctional or higher) polymerizable unsaturated bonds in the molecule. Not limited. 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, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethyl propantri (meth) acrylate, ethylene oxide-modified trimethyl propanthry (meth) acrylate, di Pentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropantri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propion Examples thereof include acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. One type of polyfunctional (meth) acrylate may be used alone, or two or more types may be used in combination. A monofunctional (meth) acrylate may be used in combination with the polyfunctional (meth) acrylate for the purpose of lowering the viscosity thereof.

Examples of the oligomer used as the ionizing radiation curable resin include (meth) acrylate oligomers having a radically polymerizable unsaturated group in the molecule, and in particular, two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having the above (bifunctional or higher) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicon (meth) acrylate, oligomers having a cationically polymerizable functional group in the molecule (for example, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. .. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton or the like. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyhydric isocyanate compound, and a hydroxy (meth) acrylate. 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 a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with the oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate in which this epoxy (meth) acrylate is partially modified with a dibasic carboxylic acid anhydride can also be used. Polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the 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. Silicon (meth) acrylate can be obtained by adding (meth) (meth) acrylic acid to the terminal or side chain of silicon having a polysiloxane bond in the main chain. Among these, urethane (meth) acrylate oligomers from the viewpoint of effectively suppressing cracking of the raised portion during molding and further enhancing the design and scratch resistance due to the uneven shape of the raised portion after molding. Is preferable. These oligomers may be used alone or in combination of two or more.

The lower limit of the weight average molecular weight of the ionizing radiation curable resin is preferably 500 or more, more preferably 1000 or more, and the upper limit is preferably 80,000 or less, further preferably 50,000 or less. When the weight average molecular weight of the ionizing radiation curable resin is in the above range, it is easy to adjust the viscosity of the resin composition to a viscosity suitable for coating. The "weight average molecular weight" is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

In addition to the ionizing radiation curable resin, the ionizing radiation curable resin composition may contain one or more additives, if necessary. Examples of the additive include an ultraviolet absorber, a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a cross-linking agent, an infrared absorber, an antistatic agent, an adhesive improver, a leveling agent, a thixo property-imparting agent, and a cup. Examples include ring agents, plasticizers, antifoaming agents, fillers, solvents, colorants and the like.

The ionizing radiation curable resin composition used for forming the raised portion 3 preferably contains a polyfunctional monomer. In this case, the Martens hardness of the raised portion 3 can be adjusted to a desired range by adjusting the functional number, content, etc. of the polyfunctional monomer contained in the ionizing radiation curable resin composition. The content of the polyfunctional monomer in the ionizing radiation curable resin composition is preferably 30 parts by mass or more and 70 parts by mass or less, and more preferably 40 parts by mass or more and 60 parts by mass per 100 parts by mass of the ionizing radiation curable resin composition. Hereinafter, it is even more preferably 50 parts by mass or more and 60 parts by mass or less. That is, the ionizing radiation curable resin composition is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less, and even more preferably 50% by mass or more and 60% by mass or less. Contains monomer. The polyfunctional monomer is not particularly limited as long as it has two or more polymerizable unsaturated groups or cationically polymerizable functional groups, but a trifunctional or higher functional monomer is preferable, and a tetrafunctional or higher functional monomer is more preferable. Examples of the polyfunctional monomer include the above-mentioned polyfunctional (meth) acrylate monomer and the like.

The raised portion 3 can be formed, for example, by preparing an ionizing radiation curable resin composition, applying it to the transfer base material layer 2, and cross-linking and curing it. Examples of the coating method include a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat and the like. The uncured resin layer thus formed can be irradiated with ionizing radiation such as an electron beam or ultraviolet rays to cure the uncured resin layer to form the ridge 3.

When ultraviolet rays are used as the ionizing radiation for curing the ionizing radiation curable resin composition, the ultraviolet sources include, for example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp. A light source such as a lamp can be used. The wavelength of ultraviolet rays is, for example, about 190 to 380 nm. When an electron beam is used as the ionizing radiation for curing the ionizing radiation curable resin composition, the electron beam source may be, for example, Cockcroftwald type, Bandegraft type, Resonant transformer type, Insulated core transformer type, etc. A linear type, a dynamitron type, a high frequency type or the like electron beam accelerator can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 2 to 15 Mrad.

The height of the raised portion 3 is not particularly limited, but is usually 5 μm or more and 50 μm or less, preferably 10 μm or more and 40 μm or less, and more preferably 20 μm or more and 30 μm or less. The height of the ridge 3 (thickness of the ridge 3) is measured as the height of the highest portion of the ridge 3 with reference to the first main surface S1 of the transfer base material layer 2.

Of the first main surface S1 of the transfer base material layer 2, the area of the region where one ridge 3 is provided (bottom area of the ridge 3) is not particularly limited and should be imparted to the decorative resin molded product. It can be appropriately set according to the shape and the like, but is, for example, 90 mm ² or less, preferably 20 mm ² , and more preferably 5 mm ² or less. The lower limit of the area is not particularly limited, but is preferably ^{0.01 mm 2 or more from the viewpoint of forming a visually recognizable uneven shape.} The areas of the two or more regions where the raised portion 3 is provided may be the same or different.

The ratio of the total area of the region where the raised portion 3 is provided to the area of the first main surface S1 of the transfer base material layer 2 is not particularly limited, but is usually 90% or less, preferably 60% or less, more preferably 55%. It is as follows.

The plan-view shape of the raised portion 3 is not particularly limited, and examples thereof include a circle, an ellipse, a triangle, a quadrangle, a polygon, a star, a line, an arc, a geometric pattern, and a character. The plan-view shapes of the different ridges 3 may be the same or different. The raised portion 3 may form a pattern as a whole.

Transfer Layer As shown in FIG. 1, the transfer layer 4 has a surface protective layer 41, a primer layer 42, a decorative layer 43, and an adhesive layer 44 in this order from the transfer base material layer 2 side. When the decorative resin molded product is manufactured by in-mold molding using the transfer sheet 1, the transfer base material layer 2 is finally peeled off and removed, and the transfer layer 4 remains in the decorative resin molded product.

As shown in FIG. 1, the transfer layer 4 has a first main surface T1 and a second main surface T2 located on the opposite side of the first main surface T1. The first main surface T1 of the transfer layer 4 is in contact with the second main surface S2 of the transfer base layer 2, and forms an interface between the transfer base layer 2 and the transfer layer 4.

[Surface protective layer]
The surface protective layer 41 is a layer provided as necessary for the purpose of improving scratch resistance, weather resistance, chemical resistance, etc. of the decorative resin molded product. The surface protective layer 41 may be omitted in some cases. The surface protective layer 41 is located closest to the transfer base material layer 2 among the layers constituting the transfer layer 4, and forms the first main surface T1 of the transfer layer 4. The surface protective layer 41 is provided so as to be in contact with the second main surface S2 of the transfer base layer 2, and forms an interface between the transfer base layer 2 and the transfer layer 4. In the decorative resin molded product produced by in-mold molding using the transfer sheet 1, the surface protective layer 41 is located on the outermost side of the decorative resin molded product and forms the surface of the decorative resin molded product.

The surface protective layer 41 can be formed of, for example, a resin composition. The resin contained in the resin composition is not particularly limited as long as it can improve the scratch resistance, weather resistance, chemical resistance, etc. of the decorative resin molded product, and is, for example, a thermoplastic resin or thermosetting. Examples thereof include sex resins and ionizing thermosetting resins, and among these, ionizing thermosetting resins are preferable. Examples of the thermoplastic resin include (meth) acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; polyethylene terephthalates (PET). Such as polyester resin; acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic acid ester resin and the like. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. Examples of the thermosetting resin include polyol resin, unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, and guanamine. Examples thereof include resins, melamine-urea cocondensate resins, silicon resins, polysiloxane resins and the like. Examples of the polyol resin include acrylic polyols; polyester polyols; urethane polyols such as polyester urethane polyols and acrylic urethane polyols; polyolefin polyols such as polyethylene polyols, polypropylene polyols, polybutadiene polyols, and polyisoprene polyols. One type of thermosetting resin may be used alone, or two or more types may be used in combination. If necessary, the thermosetting resin is blended with components involved in the curing reaction of the thermosetting resin, for example, a catalyst, a curing agent (including a cross-linking agent, a polymerization initiator, a polymerization accelerator, etc.) and the like. May be good. Specific examples of the ionizing radiation curable resin are the same as the specific examples listed in the description of the raised portion 3, and thus the description thereof will be omitted here.

The surface protective layer 41 may be formed of a cured product of the ionizing radiation curable resin composition, or may be formed of an uncured or semi-cured product of the ionizing radiation curable resin composition. When the surface protective layer 41 is formed of an uncured or semi-cured product of an ionizing radiation curable resin composition, the surface protective layer 41 is molded with a decorative resin by, for example, in-mold molding using the transfer sheet 1. It can be cured in the same manner as in the ridge 3 during or after the production of the product.

The surface protective layer 41 is placed on the transfer base material layer 2 or on the layer located below the surface protective layer 41, for example, a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat, or the like. It can be formed by applying by the method of. When the surface protective layer 41 is formed of a cured product of an ionizing radiation curable resin composition, the surface is protected by forming the uncured resin layer and then curing the uncured resin layer in the same manner as in the case of the ridge 3. Layer 41 can be formed.

The ionizing radiation curable resin composition forming the surface protective layer 41 may contain one or more additives, if desired. Examples of the additive include an ultraviolet absorber, a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a cross-linking agent, an infrared absorber, an antistatic agent, an adhesive improver, a leveling agent, a thixo property-imparting agent, and a cup. Examples include ring agents, plasticizers, antifoaming agents, fillers, solvents, colorants, matting agents and the like.

The thickness of the surface protective layer 41 is not particularly limited, but is usually about 1 to 1000 μm, preferably about 1 to 50 μm, and more preferably about 1 to 10 μm.

[Primer layer]
The primer layer 42 is, for example, a layer provided as necessary for the purpose of improving the adhesion between the surface protection layer 41 and the layer located on the lower side thereof (the side opposite to the transfer base material layer 2). be. The primer layer 42 may be omitted in some cases.

The primer layer 42 can be formed by the resin composition. Examples of the resin contained in the resin composition include urethane resin, acrylic resin, (meth) acrylic-urethane copolymer resin, polyester resin, butyral resin, and the like, among these, urethane resin, acrylic resin, and the like. (Meta) Acrylic-urethane copolymer resin and the like are preferable. The resin contained in the resin composition may be one kind or two or more kinds.

As the urethane resin, polyurethane containing a polyol (polyhydric alcohol) as a main component and an isocyanate as a cross-linking agent (curing agent) can be used. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyols, polyethylene glycols, polypropylene glycols, acrylic polyols, and polyether polyols. Specific examples of the isocyanate include polyisocyanates having two or more isocyanate groups in the molecule; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanates, isophorone diisocyanates, and hydrogenated tolylene diisocyanates. Examples thereof include aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate. When isocyanate is used as a curing agent, the content of isocyanate in the resin composition for forming a primer layer is not particularly limited, but from the viewpoint of adhesion and printability when laminating the decorative layer 43 and the like described later, it is considered. 3 to 45 parts by mass is preferable with respect to 100 parts by mass of the above-mentioned polyol, and 3 to 25 parts by mass is more preferable.

Among the above urethane resins, from the viewpoint of improving adhesion after cross-linking, a combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking material is preferable; more preferably. , A combination of acrylic polyol and hexamethylene diisocyanate can be mentioned.

The acrylic resin is not particularly limited, and is, for example, a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a (meth) acrylic acid ester and others. Examples thereof include a copolymer with the monomer of. More specifically, the (meth) acrylic resin includes methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and (meth) acrylate. Methyl- (meth) butyl acrylate copolymer, ethyl (meth) acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl acrylate Examples thereof include (meth) acrylic acid esters such as copolymers.

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

One kind or two or more kinds of additives can be blended in the composition forming the primer layer 42. Examples of the additive include an ultraviolet absorber, a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a cross-linking agent, an infrared absorber, an antistatic agent, an adhesive improver, a leveling agent, a thixo property-imparting agent, and a cup. Examples include ring agents, plasticizers, antifoaming agents, fillers, solvents, colorants, matting agents and the like.

The primer layer 42 uses a resin composition for forming a primer layer, and is a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, and a solid coat by silk screen. It is formed by a usual coating method such as wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or transfer coating method. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film base material), and then the surface of the target layer in the transfer sheet for three-dimensional molding is coated. ..

The primer layer 42 may be formed on the surface protection layer 41 after curing. Further, a layer made of an ionizing radiation curable resin is formed by laminating a layer made of a composition for forming a primer layer on a layer of an ionizing radiation curable resin composition forming the surface protective layer 41 to form a primer layer 42. The surface protective layer 41 may be formed by irradiating the surface with ionizing radiation and curing the layer made of the ionizing radiation curable resin.

The thickness of the primer layer 42 is not particularly limited, and examples thereof include about 0.1 to 10 μm, preferably about 1 to 10 μm.

[Decorative layer]
The decorative layer 43 is, for example, a layer provided as needed for the purpose of imparting decorativeness to the decorative resin molded product. The decorative layer 43 may be omitted in some cases.

Examples of the decorative layer 43 include a colored layer, a pattern layer, and a combination thereof.

The colored layer imparts a desired color to the decorative resin molded product produced by using the three-dimensional molding transfer sheet 1. The colored layer is, for example, a solid layer that covers the entire surface of the lower layer of the colored layer (that is, is provided in a solid shape on the entire surface) in order to conceal the coloring of the resin molded product or the like. The color of the colored layer is usually an opaque color, but it may be a transparent color. Examples of the method for forming the colored layer include coating methods such as roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, and dip coating method. Be done. The colored layer may be formed by a printing method described later.

The pattern layer imparts a desired pattern to the decorative resin molded product produced by using the three-dimensional molding transfer sheet 1. The picture layer is, for example, a print layer. The patterns that make up the pattern layer include, for example, the spring and autumn wood regions of the annual ring cross section, the wood grain pattern composed of conduits, leather (skin grain) patterns, and stones on the surface of stone materials such as marble, granite, and sand rock. Examples include eye patterns, grain patterns, tiled patterns, granite patterns, cloth patterns, geometric figures, characters, symbols, and abstract patterns. Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method.

The ink used for forming the decorative layer 43 is, for example, a mixture of components such as a colorant and a binder resin and a solvent or a dispersion medium.

Colorants contained in the ink include, for example, metallic pigments made of scaly foil powders of metals such as aluminum, chromium, nickel, tin, titanium, iron phosphate, copper, gold, silver and brass, alloys, or metal compounds. Pearl luster (pearl) consisting of mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, and basic lead carbonate foil powder. ) Pigments: Fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide; white inorganic pigments such as titanium dioxide, zinc flower, antimony trioxide; zinc flower, petals, vermilion, ultramarine, Inorganic pigments such as cobalt blue, titanium yellow, yellow lead, and carbon black; organic pigments such as isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, induslen blue RS, and aniline black (including dyes). ) Etc. can be mentioned. As the colorant, one type may be used alone, or two or more types may be used in combination.

Examples of the binder resin contained in the ink include acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, and alkyd resin. , Petroleum-based resin, ketone resin, epoxy-based resin, melamine-based resin, fluorine-based resin, silicon-based resin, fibrous derivative, rubber-based resin and the like. As the binder resin, one type may be used alone, or two or more types may be used in combination.

Examples of the solvent or dispersion medium contained in the ink include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, -2-methoxyethyl acetate, and acetate. Ester-based organic solvents such as -2-ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone-based organic solvent; ether-based organic solvent such as diethyl ether, dioxane, tetrahydrofuran; chlorine-based organic solvent such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene; water and the like. As the solvent or dispersion medium, one type may be used alone, or two or more types may be used in combination.

The ink used to form the decorative layer 43 contains, if necessary, an antioxidant, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant and the like. You may.

The decorative layer 43 can be formed, for example, on an adjacent layer (for example, a primer layer 42, etc.) by the method described above. When the decorative layer 43 is a combination of the pattern layer and the colored layer, one layer may be formed and dried, and then the other layer may be laminated and dried.

The decorative layer 43 may be a metal thin film layer. Examples of the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. Examples of the method for forming the metal thin film layer include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metal. Further, in order to improve the adhesion with the adjacent layer, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer.

The thickness of the decorative layer 43 is not particularly limited, but is, for example, 1 to 40 μm, preferably 3 to 30 μm.

[Adhesive layer]
The adhesive layer 44 is a layer provided as needed for the purpose of improving the adhesion between the transfer sheet 1 and the transferred body (for example, a resin molded body). The adhesive layer 44 may be omitted in some cases. The adhesive layer 44 forms the second main surface T2 of the transfer layer 4.

The resin forming the adhesive layer 44 is not particularly limited as long as it can improve the adhesiveness or the adhesiveness, and examples thereof include a thermoplastic resin and a thermosetting resin. 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, rubber resin and the like. .. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. Examples of the thermosetting resin include urethane resin and epoxy resin. One type of thermosetting resin may be used alone, or two or more types may be used in combination.

The thickness of the adhesive layer 44 is not particularly limited, and examples thereof include about 0.1 to 30 μm, preferably about 0.5 to 20 μm, and more preferably about 1 to 8 μm.

[Transparent resin layer]
When the transfer layer 4 does not have the decorative layer 43, for example, a transparent resin layer (not shown) may be provided as necessary for the purpose of improving the adhesion between the primer layer 42 and the adhesive layer 44. The transparent resin layer is particularly useful when the transfer sheet 1 for three-dimensional molding is used in the production of a decorative resin molded product that requires transparency. The transparent resin layer is not particularly limited as long as it has transparency, and the transparency includes any of colorless transparent, colored transparent, translucent and the like. As the resin forming the transparent resin layer, for example, the binder resin exemplified with respect to the decorative layer 43 can be used.

The transparent resin layer may contain a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, and a soft component (as needed). For example, one kind or two or more kinds of additives such as rubber) may be contained.

The transparent resin layer can be formed by a known printing method such as gravure printing, flexographic printing, silk screen printing, and offset printing.

The thickness of the transparent resin layer is not particularly limited, but is, for example, 0.1 to 10 μm, preferably 1 to 10 μm.

<Decorative resin molded product>
Hereinafter, a decorative resin molded product according to an embodiment of the present invention will be described with reference to the drawings. FIG. 2 is a cross-sectional view schematically showing the configuration of a decorative resin molded product according to an embodiment of the present invention.

As shown in FIG. 2, the decorative resin molded product 10 according to the embodiment of the present invention includes a transfer layer 4 and a resin molded body 5 integrated with the transfer layer 4. The decorative resin molded product 10 does not have the transfer base material layer 2. As shown in FIG. 2, the transfer layer 4 is unevenly shaped, and the second main surface T2 of the transfer layer 4 is convex at a position corresponding to the concave portion formed on the first main surface T1 of the transfer layer 4. A portion is formed, and a concave portion is formed at a position corresponding to the convex portion formed on the first main surface T1 of the transfer layer 4. The resin molded body 5 is integrated with the transfer layer 4 on the second main surface T2 side of the transfer layer 4, and the surface of the resin molded body 5 has an uneven shape of the second main surface T2 of the transfer layer 4. The corresponding uneven shape is formed.

The decorative resin molded product 10 includes, for example, interior or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; interior materials of buildings such as walls, floors and ceilings; TV receivers, air conditioners and the like. Household appliances; Can be used for various purposes such as containers.

The decorative resin molded product 10 can be manufactured, for example, by in-mold molding using the transfer sheet 1. In in-mold molding, injection molding and transfer are performed at the same time in the injection molding die. An intermediate body 11 for manufacturing a decorative resin molded product 10 including a transfer sheet 1 and a resin forming body 5 integrated with a transfer layer 4 of the transfer sheet 1 by in-mold molding using the transfer sheet 1. By peeling the transfer base material layer 2 from the intermediate body 11, the decorative resin molded product 10 can be manufactured.

One embodiment of the method of manufacturing a decorative resin molded product by in-mold molding using the transfer sheet 1 is described in the following steps:
(A) A step of arranging the transfer sheet 1 on an injection molding die so that the main surface of the transfer sheet 1 on the three sides of the raised portion 3 faces the molding surface of the injection molding die.
(B) After the step (a), the resin in a fluid state is injected into the cavity formed by molding the injection molding die, and the transfer sheet 1 and the transfer layer 4 of the transfer sheet 1 are integrated. After the step of forming the intermediate body 11 including the resin molded body 5 and the step (c) step (b), the transfer base material layer 2 is peeled off from the intermediate body 11 and integrated with the transfer layer 4 and the transfer layer 4. The step of obtaining a decorative resin molded product 10 including the modified resin molded product 5 is included.

In the step (a), the transfer sheet 1 is arranged on the injection molding die 6 so that the main surface of the transfer sheet 1 on the raised portion 3 side faces the molding surface 60 of the injection molding die 6 (FIG. 3). reference). The injection molding die is composed of, for example, a fixed die and a movable die. When an injection molding die composed of a fixed mold and a movable mold is used, the injection molding die 6 shown in FIG. 3 is a fixed mold, the transfer sheet 1 is arranged on the fixed mold side, and injection molding is performed. The molding material used for is supplied from the fixed mold side. As the fixed mold, for example, a female mold that is also used as a vacuum forming mold provided with suction holes for injection molding can be used.

The transfer sheet 1 may be heated and softened after the step (a) and before the step (b). In one embodiment, the transfer sheet 1 is placed on the injection molding die 6 so that the main surface of the transfer sheet 1 on the side of the raised portion 3 faces the molding surface 60 of the injection molding die 6, and then the hot plate is used. The transfer sheet 1 is heated from the transfer layer 4 side to soften it. The temperature at which the transfer sheet 1 is heated can be appropriately adjusted within the range below the melting temperature (or melting point), but is preferably a temperature near the glass transition temperature of the base sheet 21. The temperature near the glass transition temperature refers to the range of the glass transition temperature of about ± 5 ° C., and is usually about 70 to 130 ° C. when a suitable polyester film is used as the base sheet 21.

After the step (a) and before the step (b), the main surface of the transfer sheet 1 on the raised portion 3 side is brought into close contact with the molding surface 60 of the injection molding die 6, and the transfer sheet 1 is reserved. Molding (online premolding) may be used. In one embodiment, the transfer sheet 1 is placed on the injection molding die 6 so that the main surface of the transfer sheet 1 on the side of the raised portion 3 faces the molding surface 60 of the injection molding die 6, and then the hot plate is used. The transfer sheet 1 is heated from the transfer layer 4 side to be softened, and the softened transfer sheet 1 is vacuum-sucked from the molding surface 60 side of the injection molding die 6 to the molding surface 60 of the injection molding die 6. Pre-molding (online pre-molding) is performed by bringing them into close contact with each other. Preforming is preferably performed after the transfer sheet 1 is heated and softened, but if the shape of the molding surface 60 of the injection molding die 6 is not complicated, the premolding is performed without heating the transfer sheet 1. You may go.

In the step (b), as shown in FIG. 3, after the step (a), the resin 7 in a fluid state is injected into the cavity formed by molding the injection molding die 6. The resin filled in the cavity solidifies to form a resin molded body integrated with the transfer layer 4 of the transfer sheet 1. The arrow in FIG. 3 indicates the direction in which the resin 7 is injected.

In step (b), as shown in FIG. 4, the transfer base material layer 2 and the transfer layer 4 are formed into irregularities by the heat and pressure of the injected resin 7. Specifically, as shown in FIG. 4, a portion of the transfer base material layer 2 and the transfer layer 4 in which the ridge 3 is not interposed between the transfer base layer 2 and the molding surface 60 of the injection molding die 6 is injected. It is pressed toward the molding surface 60 of the molding die 6 and is shaped convexly toward the molding surface 60 of the injection molding die 6. As a result, of the transfer base material layer 2 and the transfer layer 4, the portion where the ridge 3 is interposed between the transfer base layer 2 and the molding surface 60 of the injection molding die 6 is formed in a relatively concave shape. In this way, as shown in FIG. 4, an intermediate 11 including the transfer sheet 1 and the resin molded body 5 integrated with the transfer layer 4 of the transfer sheet 1 is formed. The intermediate 11 is formed in the injection molding die 6. The intermediate 11 is an intermediate for manufacturing the decorative resin molded product 10. In the intermediate 11, the transfer base material layer 2 and the transfer layer 4 are unevenly shaped, and the ridge 3 is located in the concave portion of the transfer base material layer 2 formed by the uneven shape. In the intermediate body 11, a concavo-convex shape corresponding to the concavo-convex shape of the transfer layer 4 is formed on the surface of the resin molded body 5 on the transfer layer 4 side.

The resin 7 (resin constituting the resin molded body 5) can be appropriately selected depending on the use of the decorative resin molded product 10. Examples of the resin 7 include a thermoplastic resin and a thermosetting resin. The resin 7 may be one kind or two or more kinds. Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, vinyl chloride resins and the like. Examples of the thermosetting resin include urethane resin and epoxy resin.

When the resin 7 is a thermoplastic resin, a resin which has been made into a fluid state by heating and melting is used, and when the resin 7 is a thermosetting resin, the uncured liquid composition is heated at room temperature or appropriately. used. The heating temperature of the molding resin depends on the type of resin, but is generally about 180 to 320 ° C.

In the step (c), after the step (b), the transfer base material layer 2 is peeled off from the intermediate 11, and the decorative resin molding including the transfer layer 4 and the resin molded body 5 integrated with the transfer layer 4 is provided. Obtain item 10. When the transfer base layer 2 is peeled from the intermediate 11, the ridge 3 is also removed together with the transfer base layer 2, and the transfer layer 4 remains in the decorative resin molded product 10. When the release layer 23 forms the second main surface S2 of the transfer base material layer 2, the peelability between the transfer base material layer 2 and the transfer layer 4 (surface protection layer 41) can be improved. By peeling the transfer base material layer 2 from the intermediate 11, the surface protective layer 41 is exposed, and the surface protective layer 41 forms the surface of the decorative resin molded product 10. The step (c) can be performed, for example, when the decorative resin molded product 10 is taken out from the injection molding mold.

<Example 1>
[Manufacturing of transfer sheet for 3D molding]
As the base sheet, a polyethylene terephthalate film (thickness 75 μm) having an easy-adhesive layer formed on one surface was used. A release layer (thickness 1 μm) was formed by printing a coating liquid containing a melamine-based resin as a main component on the surface of the base sheet on the side of the easy-adhesive layer by gravure printing. Next, an ionizing radiation curable resin composition containing polycarbonate urethane acrylate as a main component is applied onto the release layer with a barcoder so that the thickness after curing is 3 μm, and is applied for forming a surface protective layer. A film was formed. Next, an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) was irradiated from the coating film to cure the coating film for forming the surface protective layer to form the surface protective layer. A resin composition for forming a primer layer was applied on the surface protective layer by gravure printing to form a primer layer (thickness 1.5 μm). Further, a decorative layer containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin (acrylic resin 50% by mass, vinyl chloride-vinyl acetate copolymer resin 50% by mass) is formed on the primer layer. A decorative layer (thickness 5 μm) was formed by gravure printing using a black-based ink composition for vinyl chloride. Further, an adhesive layer (thickness 4 μm) was formed on the decorative layer by gravure printing using a resin composition for forming an adhesive layer containing an acrylic resin (softening temperature: 125 ° C.). In this way, a laminate in which the base sheet / release layer / surface protection layer / primer layer / decorative layer / adhesive layer were laminated in this order was produced.

Next, using the following ionizing radiation curable resin composition, a pattern in which a large number of circular tops in a plan view are arranged is formed on the back surface side (opposite side of the release layer) of the base sheet (the side opposite to the mold release layer). The bottom area of one ridge was 1.8 mm ² , the ratio of the total area of the ridge to the surface area of the base sheet was about 31%), and the ridge was laminated by screen printing. Next, ultraviolet rays were irradiated from above the top of the plate under the condition of 160 W / cm to cure the printing plate while maintaining the plate shape. In this way, a large number of ridges having a height of 30 μm were formed on the base sheet. The height of the top (ink film thickness) was measured using a film thickness meter (Nikon Digimicro Counter MFC-101).

By the above procedure, a decorative sheet for three-dimensional molding in which a ridge, a base sheet, a release layer, a surface protective layer, a primer layer, a decorative layer, and an adhesive layer are laminated in this order was produced.

[Ionizing radiation curable resin composition]
The composition of the ionizing radiation curable resin used to form the ridge was adjusted as follows.
Photosensitive urethane acrylate oligomer: 35% by mass
Photosensitive polyfunctional monomer: 53% by mass
Photopolymerization initiator: 8% by mass
Silicon-based high-concentration defoamer: 3% by mass
Slip agent (organic modified polysiloxane): 0.5% by mass
Curing accelerator (photopolymerization initiator): 0.5% by mass

[Measurement of Martens hardness at the top]
With respect to the transfer sheet for three-dimensional molding produced above, the Martens hardness at the top was measured. The Martens hardness of the raised portion was measured using a surface film physical property tester (PICODENTOR HM-500, manufactured by Fisher Instruments Co., Ltd.) in an environment of a temperature of 23 ° C. and a relative humidity of 38%. Specifically, using a diamond indenter (Vickers indenter) having a facing angle of 136 ° shown in FIG. 5A, the diamond indenter is pushed into the ridge, and the following formula is obtained from the pushing load F and the pushing depth h (indentation depth). :
Martens hardness = F / (26.43 × h ² )
To determine the Martens hardness. For pushing, in an environment with a temperature of 23 ° C. and a relative humidity of 38%, a load of 0 to 2 mN is first applied in 2 seconds to the upper part of the ridge, and then a load of 2 mN is held for 5 seconds. Finally, unloading from 2 to 0 mN was performed in 2 seconds. The Martens hardness at 10 points was measured for one ridge, and the average value was taken as the Martens hardness of the ridge.

[Manufacturing of decorative resin molded products]
The transfer sheet for three-dimensional molding produced above was placed on a mold so that the main surface on the raised top side of the transfer sheet faced the molding surface of the mold, and the mold was clamped. After that, the injection resin was injected into the cavity of the mold, the transfer sheet for three-dimensional molding and the injection resin were integrally molded, and the transfer sheet for three-dimensional molding and the transfer layer of the transfer sheet were integrated. An intermediate body including a resin molded body was formed. When the resin molded product integrated with the transfer layer was taken out from the mold, the transfer base material layer (base material sheet and mold release layer) was peeled off from the intermediate body, and the transfer layer and the transfer layer were integrated. A decorative resin molded product provided with a resin molded body was obtained.

[Evaluation of sticking to the mold]
When the resin molded product integrated with the transfer layer is taken out from the mold, it is visually confirmed whether or not the peeled transfer base material layer is attached to the mold, and the peeled transfer base material layer is the gold. "A" when it is not attached to the mold, "B" when the peeled transfer base material layer is not attached to the mold but the dirt of the raised ink is transferred to the mold, the peeled transfer When the base material layer was attached to the mold and there was a problem in practical use, it was evaluated as "C".

[Evaluation of pattern elongation]
Due to the cracking of the raised portion caused by the three-dimensional molding transfer sheet being deformed along the molding surface of the mold during molding, the uneven shape of the transfer layer of the decorative resin molded product is defective (desired uneven shape). Visually check whether or not there is a defective part), and if there is no defective part, it is "A", if there is a defective part but there is no problem in practical use, it is "B", and there is a defective part. If there is a problem in practical use, it is evaluated as "C".

<Example 2>
Similar to Example 1, the transfer sheet for three-dimensional molding and the decorative resin molded product were manufactured, and various measurements and evaluations were performed except that the height of the raised portion was changed to 40 μm.

<Example 3>
Similar to Example 1, the tertiary was the same as in Example 1, except that the compounding ratio of the photosensitive polyfunctional monomer was changed from 53% by mass to 58% by mass and the compounding ratio of the photosensitive urethane acrylate oligomer was changed from 35% by mass to 30% by mass. The transfer sheet for original molding and the decorative resin molded product were manufactured, and various measurements and evaluations were performed.

<Example 4>
Similar to Example 1, the tertiary was the same as in Example 1, except that the compounding ratio of the photosensitive polyfunctional monomer was changed from 53% by mass to 63% by mass and the compounding ratio of the photosensitive urethane acrylate oligomer was changed from 35% by mass to 25% by mass. The transfer sheet for original molding and the decorative resin molded product were manufactured, and various measurements and evaluations were performed.

<Comparative example 1>
Similar to Example 1, the tertiary was the same as in Example 1, except that the compounding ratio of the photosensitive polyfunctional monomer was changed from 53% by mass to 48% by mass and the compounding ratio of the photosensitive urethane acrylate oligomer was changed from 35% by mass to 40% by mass. The transfer sheet for original molding and the decorative resin molded product were manufactured, and various measurements and evaluations were performed.

<Comparative example 2>
The compounding ratio of the photosensitive polyfunctional monomer was changed from 53% by mass to 48% by mass, the compounding ratio of the photosensitive urethane acrylate oligomer was changed from 35% by mass to 40% by mass, and the height of the ridge was changed to 40 μm. Except for the above, the transfer sheet for three-dimensional molding and the decorative resin molded product were manufactured, and various measurements and evaluations were carried out in the same manner as in Example 1.

The results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1. In addition, Table 1 shows the average value of the measured Martens hardness at 10 points, and the maximum value and the minimum value among the measured Martens hardness at 10 points.

As shown in Table 1, the maltensity hardness of the ridge can be adjusted by adjusting the polyfunctional monomer compounding ratio, and the martence hardness of the ridge can be adjusted to 50 N / mm ² or more and 150 N / mm ² or less. As a result, it was possible to prevent sticking of the ridge to the mold and cracking of the ridge, which may occur during in-mold molding.

1 ... Transfer sheet for three-dimensional molding 2 ... Transfer base material layer S1 ... First main surface of transfer base material layer S2 ... Second main surface of transfer base material layer 21 ... Base material Sheet 22 ... Resin layer 23 ... Release layer 3 ... Top 4 ... Transfer layer T1 ... First main surface of transfer layer T2 ... Second main surface of transfer layer 41.・ ・ Surface protection layer 42 ・ ・ ・ Primer layer 43 ・ ・ ・ Decorative layer 44 ・ ・ ・ Adhesive layer 5 ・ ・ ・ Resin molded body 6 ・ ・ ・ Injection molding mold 60 ・ ・ ・ Injection molding mold molding Surface 7 ... Resin 10 ... Decorative resin molded product 11 ... Intermediate

Claims (9)

A transfer base layer having a first main surface and a second main surface located on the opposite side of the first main surface, a raised portion provided on the first main surface of the transfer base layer, and the transfer group. A three-dimensional molding transfer sheet including a transfer layer provided on the second main surface of the material layer.
The transfer sheet for three-dimensional molding, wherein the Martens hardness of the upper portion is 50 N / mm ² or more and 150 N / mm ^{2 or less.} The transfer sheet for three-dimensional molding according to claim 1, wherein the raised portion is formed of a cured product of an ionizing radiation curable resin composition. The transfer sheet for three-dimensional molding according to claim 2, wherein the ionizing radiation curable resin composition contains 30% by mass or more and 70% by mass or less of a polyfunctional monomer. The transfer sheet for three-dimensional molding according to any one of claims 1 to 3, wherein the transfer layer has a surface protective layer. The transfer sheet for three-dimensional molding according to claim 4, wherein the surface protective layer is formed of a semi-cured product or an uncured product of an ionizing radiation curable resin composition. The transfer sheet for three-dimensional molding according to any one of claims 1 to 5, wherein the transfer base material layer has a release layer forming the second main surface of the transfer base material layer. The following steps:
(A) Molding of the three-dimensional molding transfer sheet according to any one of claims 1 to 6 into an injection molding die, and the main surface of the transfer sheet on the ridge side is the injection molding die. The process of arranging so as to face the surface,
(B) After the step (a), the resin in a fluid state is injected into the cavity formed by molding the injection molding mold, and the transfer sheet is integrated with the transfer layer of the transfer sheet. After the step of forming the intermediate body including the resin molded body and the step (c) step (b), the transfer base material layer is peeled off from the intermediate body, and the transfer layer and the transfer layer are integrated. A method for producing a decorative resin molded product, which comprises a step of obtaining a decorative resin molded product including the resin molded product. A decorative resin molded product comprising the transfer sheet for three-dimensional molding according to any one of claims 1 to 6 and a resin-forming body integrated with the transfer layer of the transfer sheet. Intermediate body. The intermediate according to claim 8, wherein the transfer base material layer and the transfer layer are unevenly shaped, and the ridge is located in a concave portion of the transfer base material layer formed by the uneven shape. ..

Images