JP6870675B2 - Transfer film for 3D molding - Google Patents

Description

The present invention relates to a transfer film for three-dimensional molding having excellent three-dimensional moldability and high scratch resistance, and a resin molded product using the same.

For the purpose of surface protection and designability of resin molded products used for automobile interior / exterior, building material interior materials, home appliances, etc., and resin molded products used for organic glass used as a substitute material for inorganic glass, etc. As a result, a technique of laminating a surface protective layer using a three-dimensional molded film is used. The three-dimensional molding film used in such a technique can be roughly classified into a laminate type three-dimensional molding film and a transfer type three-dimensional molding film. The laminated three-dimensional molded film is laminated on the support base material so that the surface protective layer is located on the outermost surface, and by laminating the molding resin on the support base material side, the support group is contained in the resin molded product. It is used so that the material is taken in. On the other hand, in the transfer type three-dimensional molding film, a surface protective layer is laminated directly on the support base material or via a release layer provided as needed, and a molding resin is laminated on the side opposite to the support base material. After that, the support base material is peeled off so that the support base material does not remain in the resin molded product. These two types of three-dimensional molded films are used properly according to the shape of the resin molded product and the desired function.

The surface protective layer provided on such a three-dimensional molded film is chemically crosslinked by irradiating ionizing radiation typified by ultraviolet rays or electron beams from the viewpoint of imparting excellent surface physical properties to the resin molded product. It is said that it is preferable to use a resin composition containing an ionizing radiation curable resin that cures. Such a three-dimensional molded film is roughly classified into one in which the surface protective layer is already cured by ionizing radiation in the state of the three-dimensional molded film and one in which the surface protective layer is cured after being made into a resin molded product by molding processing. The former is considered to be preferable from the viewpoint of simplifying the process after the molding process and increasing the productivity. However, if the surface protective layer is cured at the stage of the three-dimensional molded film, the flexibility of the three-dimensional molded film is reduced, and the surface protective layer may be cracked during the molding process. It becomes necessary to select an excellent resin composition. In particular, in the case of the above-mentioned transfer type three-dimensional molded film, it is usually necessary to laminate another layer such as a design layer or an adhesive layer on the surface protective layer, and it is supported from the surface protective layer in the molding process. Compared to the laminated type, the design of the resin composition is based on the fact that the base material must be peeled off and that the surface exposed by peeling off the supporting base material must exhibit excellent physical properties. Has the problem of being more difficult.

Under such conventional techniques, for example, Patent Documents 1 and 2 propose techniques for improving the scratch resistance and moldability of a transfer-type three-dimensional molded film.

Japanese Unexamined Patent Publication No. 2011-88420 Japanese Unexamined Patent Publication No. 2012-91498

According to the technique disclosed in Patent Document 1 or 2, it is possible to improve the scratch resistance and moldability of the transfer type three-dimensional molded film, but in recent years, the transfer type three-dimensional molded film has been further improved. Scratch resistance under harsh conditions is required.
Under such circumstances, it is a main object of the present invention to provide a transfer film for three-dimensional molding which is excellent in three-dimensional moldability and has even higher scratch resistance. Another object of the present invention is to provide a resin molded product using the transfer film for three-dimensional molding.

The present inventors have conducted diligent studies to solve the above problems. As a result, in a transfer film for three-dimensional molding in which at least a surface protective layer is laminated on a transfer substrate, the surface protective layer is formed by a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate. It has been found that by forming the film, a transfer film for three-dimensional molding having excellent three-dimensional moldability and high scratch resistance can be obtained. The present invention has been completed by further studies based on such findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A transfer film for three-dimensional molding in which at least a surface protective layer is laminated on a transfer substrate.
A transfer film for three-dimensional molding in which the surface protective layer is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate.
Item 2. Item 2. The transfer film for three-dimensional molding according to Item 1, wherein the ionizing radiation curable resin composition further contains an isocyanate compound.
Item 3. Item 3. The transfer film for three-dimensional molding according to Item 1 or 2, which has a primer layer directly above the surface protective layer.
Item 4. Item 3. The transfer film for three-dimensional molding according to Item 3, wherein the primer layer contains a polyol resin and / or a cured product thereof.
Item 5. Item 4. The transfer film for three-dimensional molding according to Item 4, wherein the polyol resin contains an acrylic polyol.
Item 6. Items 2 to 5 in which the ionizing radiation curable resin composition contains 1 to 10 parts by mass of the isocyanate compound with respect to 100 parts by mass of a solid content other than the isocyanate compound in the ionizing radiation curable resin composition. The transfer film for three-dimensional molding described in Crab.
Item 7. It has a primer layer directly above the surface protection layer and has a primer layer.
Item 2. The item 1 to 6, wherein at least one selected from the group consisting of a decorative layer, an adhesive layer, and a transparent resin layer is laminated on the side of the primer layer opposite to the surface protective layer. Transfer film for three-dimensional molding.
Item 8. The surface of the transfer substrate on the surface protective layer side has an uneven shape.
Item 2. The transfer film for three-dimensional molding according to any one of Items 1 to 7, wherein the surface protective layer is laminated directly on the transfer substrate.
Item 9. Item 8. The transfer film for three-dimensional molding according to Item 8, wherein the transfer base material contains fine particles, and the surface of the transfer base material on the surface protective layer side has an uneven shape due to the fine particles.
Item 10. Item 2. The item 1 to 7, wherein the release layer is laminated between the transfer base material and the surface protective layer, and the surface protective layer is laminated directly above the release layer. Transfer film for three-dimensional molding.
Item 11. Item 2. The transfer film for three-dimensional molding according to Item 10, wherein the surface of the release layer on the surface protective layer side has an uneven shape.
Item 12. Item 2. The transfer film for three-dimensional molding according to Item 11, wherein the release layer contains fine particles, and the surface of the release layer on the surface protective layer side has an uneven shape due to the fine particles.
Item 13. A step of laminating a layer made of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate on a transfer substrate, and
A step of irradiating the ionizing radiation curable resin composition with ionizing radiation and curing the layer made of the ionizing radiation curable resin composition to form a surface protective layer on the transfer substrate.
A method for producing a transfer film for three-dimensional molding.
Item 14. Item 3. The method for producing a transfer film for three-dimensional molding, wherein the ionizing radiation curable resin composition further contains an isocyanate compound.
Item 15. Item 3. The method for producing a transfer film for three-dimensional molding according to Item 13 or 14, further comprising a step of laminating a layer of the composition for forming a primer layer directly above the layer of the ionizing radiation curable resin composition.
Item 16. Item 3. The method for producing a transfer film for three-dimensional molding according to Item 15, wherein the composition for forming a primer layer contains a polyol resin.
Item 17. A step of laminating a molding resin layer on the side opposite to the transfer base material of the three-dimensional molding transfer film according to any one of Items 1 to 12.
A step of peeling the transfer substrate from the surface protective layer,
A method for manufacturing a resin molded product.
Item 18. A resin molded product obtained by the production method according to Item 17.

According to the present invention, it is possible to provide a transfer film for three-dimensional molding having excellent three-dimensional moldability and high scratch resistance. Further, according to the present invention, it is also possible to provide a resin molded product using the transfer film for three-dimensional molding.

It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding of this invention. It is a schematic diagram of the cross-sectional structure of one form of the resin molded article with a support of this invention. It is a schematic diagram of the cross-sectional structure of one form of the resin molded article of this invention. It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding of this invention.

1. 1. Transfer film for three-dimensional molding The transfer film for three-dimensional molding of the present invention is a transfer film for three-dimensional molding in which at least a surface protective layer is laminated on a transfer base material, and the surface protective layer is a caprolactone-based urethane (caprolactone-based urethane). It is characterized in that it is formed of a cured product of an ionizing radiation curable resin composition containing a meta) acrylate. The transfer film for three-dimensional molding of the present invention has such a structure, so that it has excellent three-dimensional moldability and high scratch resistance. As will be described later, the transfer film for three-dimensional molding of the present invention does not have to have a decorative layer or the like, and may be transparent, for example. Hereinafter, the transfer film for three-dimensional molding of the present invention will be described in detail.

Laminated structure of transfer film for three-dimensional molding The transfer film for three-dimensional molding of the present invention has at least a surface protective layer 3 on a transfer base material 1. A release layer 2 is provided on the surface of the transfer base material 1 on the surface protective layer 3 side, if necessary, for the purpose of improving the peelability between the transfer base material 1 and the surface protective layer 3. May be good. In the transfer film for three-dimensional molding of the present invention, the transfer base material 1 and the release layer 2 provided as needed constitute the support 10, and the support 10 is the transfer for three-dimensional molding. After the film is laminated on the molding resin layer 8 to form a resin molded product, it is peeled off and removed.

The transfer film for three-dimensional molding of the present invention may be provided with a primer layer 4 as necessary for the purpose of enhancing the adhesion between the surface protective layer 3 and the layer located below the surface protective layer 3. Further, the decorative layer 5 may be provided as necessary for the purpose of imparting decorativeness to the transfer film for three-dimensional molding. Further, the adhesive layer 6 may be provided, if necessary, for the purpose of improving the adhesion of the molding resin layer 8. Further, a transparent resin layer 7 may be provided, if necessary, for the purpose of improving the adhesion between the surface protective layer 3 or the primer layer 4 and the adhesive layer 6. In the transfer film for three-dimensional molding of the present invention, the surface protective layer 3, the primer layer 4 provided as needed, the decorative layer 5, the adhesive layer 6, the transparent resin layer 7, and the like constitute the transfer layer 9. The transfer layer 9 is transferred to the molding resin layer 8 to obtain the resin molded product of the present invention.

As the laminated structure of the transfer film for three-dimensional molding of the present invention, the laminated structure in which the transfer base material / surface protective layer is laminated in this order; the laminated structure in which the transfer base material / surface protective layer / primer layer are laminated in this order. ; Laminated structure in which transfer base material / release layer / surface protection layer / primer layer are laminated in this order; transfer base material / release layer / surface protection layer / primer layer / decorative layer are laminated in this order Structure: Laminated structure in which transfer base material / release layer / surface protection layer / primer layer / decorative layer / adhesive layer are laminated in this order; transfer base material / release layer / surface protection layer / primer layer / transparent resin Examples thereof include a laminated structure in which layers / adhesive layers are laminated in this order. FIG. 1 shows a three-dimensional structure in which a transfer base material / release layer / surface protection layer / primer layer / decorative layer / adhesive layer are laminated in this order as one aspect of the laminated structure of the three-dimensional molding transfer film of the present invention. The schematic diagram of the cross-sectional structure of one form of the transfer film for molding is shown. Further, in FIG. 4, as one aspect of the laminated structure of the transfer film for three-dimensional molding of the present invention, the transfer base material / release layer / surface protection layer / primer layer / transparent resin layer / adhesive layer are laminated in this order. The schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding is shown.

Composition of each layer forming a transfer film for three-dimensional molding [Support 10]
The transfer film for three-dimensional molding of the present invention has a transfer base material 1 and, if necessary, a release layer 2 as a support 10. A surface protective layer 3 formed on the transfer substrate 1, a primer layer 4 further formed as needed, a decorative layer 5, an adhesive layer 6, a transparent resin layer 7, and the like constitute the transfer layer 9. There is. In the present invention, after the transfer film for three-dimensional molding and the molding resin are integrally molded, the interface between the support 10 and the transfer layer 9 is peeled off, and the support 10 is peeled off and removed to obtain a resin molded product.

(Transfer base material 1)
In the present invention, the transfer base material 1 is used as a support 10 that plays a role as a support member in a transfer film for three-dimensional molding. The transfer substrate 1 used in the present invention is selected in consideration of vacuum forming suitability, and a resin sheet made of a thermoplastic resin is typically used. Examples of the thermoplastic resin include polyester resin; acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; acrylonitrile-butadiene-styrene resin (ABS resin); vinyl chloride resin and the like.

In the present invention, it is preferable to use a polyester sheet as the transfer base material 1 in terms of heat resistance, dimensional stability, moldability, and versatility. The polyester resin constituting the polyester sheet represents a polymer containing an ester group obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol, and is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or polyethylene naphthalate. (PEN) and the like can be preferably mentioned, and polyethylene terephthalate (PET) is particularly preferable in terms of heat resistance and dimensional stability.

The transfer base material 1 may have an uneven shape on at least one surface, if necessary, for the purpose of imparting an uneven shape to the surface of the surface protective layer 3 described later. By directly laminating the surface protective layer 3 on the surface having the uneven shape of the transfer base material 1, it is possible to form an uneven shape corresponding to the uneven shape of the transfer base material 1 on the surface of the surface protective layer 3. it can. For example, by laminating the surface protective layer 3 directly on the transfer base material 1 having a fine uneven shape on the surface, the uneven shape is transferred to the surface of the surface protective layer 3 and matted on the surface of the surface protective layer 3. Design can be given. A surface having such a fine uneven shape is generally more easily scratched than a smooth surface that can receive a load because the uneven shape is destroyed by receiving a load at a point. Although there is a problem, as will be described later, in the transfer film of the present invention, the surface protective layer 3 is formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate. Therefore, the scratch resistance of the surface is enhanced. Therefore, in the present invention, excellent scratch resistance is exhibited even for the surface protective layer 3 having a matte design based on a fine uneven shape.

As a method of forming an uneven shape on the surface of the transfer substrate 1, a physical method such as sandblasting, hairline processing, laser processing, embossing, or a chemical method such as corrosion treatment with a chemical or solvent is used. An example is a method in which the shape of the fine particles is exposed on the surface of the transfer base material 1 by containing the fine particles in the transfer base material 1. Among these, in order to transfer a fine uneven shape to the surface protective layer 3 to express a matte design, a method of containing fine particles in the transfer base material 1 is preferably used.

Typical examples of the fine particles include synthetic resin particles and inorganic particles, but it is particularly preferable to use synthetic resin particles from the viewpoint of improving three-dimensional moldability. The synthetic resin particles are not particularly limited as long as they are particles formed of synthetic resin, and are, for example, acrylic beads, urethane beads, silicone beads, nylon beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene. Beads and the like can be mentioned. Among these synthetic resin particles, acrylic beads, urethane beads, and silicone beads are preferable from the viewpoint of forming an uneven shape having excellent scratch resistance on the surface protective layer 3. 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 in the present invention is dispersed in the air by injecting the powder to be measured from the nozzle using compressed air using the Shimadzu laser diffraction type particle size distribution measuring device SALD-2100-WJA1. Refers to the injection type dry measurement method that is used for measurement.

The content of the fine particles contained in the transfer base material 1 is not particularly limited as long as a desired uneven shape is formed on the surface protective layer 3, and for example, with respect to 100 parts by mass of the resin contained in the transfer base material 1. The amount is preferably about 1 to 100 parts by mass, and more preferably about 5 to 80 parts by mass. Further, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, fluorescent whitening agents and the like can be blended in the transfer substrate 1 as needed.

The polyester sheet preferably used as the transfer base material 1 in the present invention is produced, for example, as follows. First, the above polyester resin and other raw materials are supplied to a well-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. It is obtained by stretching this sheet in the biaxial direction to form a sheet and heat-fixing it. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Further, if necessary, it may be stretched again in the vertical and / or horizontal directions before or after heat fixing. 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, still more preferably 3 times or less. Within this range, when the obtained polyester sheet is used for the transfer film for three-dimensional molding, the transfer film for three-dimensional molding does not shrink again in the temperature range when the molding resin is injected, and in the temperature range. The required sheet strength can be obtained. The polyester sheet may be manufactured as described above, or a commercially available polyester sheet may be used.

Further, when the release layer 2 described later is provided, the transfer substrate 1 is physically formed on one side or both sides, if desired, by an oxidation method or an unevenness method for the purpose of improving the adhesion to the release layer 2. Physical or chemical surface treatments can be applied. Examples of the oxidation method include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone / ultraviolet treatment method, and the like, and examples of the unevenness method include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the transfer substrate 1, but in general, the corona discharge treatment method is preferably used from the viewpoints of effectiveness and operability. Further, the transfer base material 1 may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of strengthening the interlayer adhesion between the transfer base material 1 and the layer provided on the transfer base material 1. When a commercially available polyester sheet is used, the commercially available product may be one that has been subjected to the above-mentioned surface treatment in advance or one that is provided with an easy-adhesive layer.

The thickness of the transfer substrate 1 is usually 10 to 150 μm, preferably 10 to 125 μm, and more preferably 10 to 80 μm. Further, as the transfer base material 1, a single-layer sheet of these resins or a multi-layer sheet made of the same or different resins can be used.

(Release layer 2)
The release layer 2 is a surface on the side where the surface protective layer 3 of the transfer base material 1 is laminated, if necessary, for the purpose of enhancing the peelability between the transfer base material 1 and the surface protective layer 3. It is provided in. The release layer 2 may be a solid release layer that covers the entire surface (the entire surface is solid), or may be provided on a part of the release layer 2. Usually, a solid release layer is preferable in consideration of peelability.

The release layer 2 is a silicone-based resin, a fluorine-based resin, an acrylic-based resin (including, for example, acrylic-melamine-based resin), a polyester-based resin, a polyolefin-based resin, a polystyrene-based resin, a polyurethane-based resin, and a cellulose-based resin. , Vinyl chloride-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 It can be formed by using a resin composition modified with urethane alone or in combination of two or more. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. A resin composition alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and a copolymer of an acrylic resin and styrene and acrylic. Examples thereof include a resin composition in which the above emulsion is mixed. Of these, it is particularly preferable to form the release layer 2 with the acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

The release layer 2 may have an uneven shape on the surface on the surface protective layer 3 side for the purpose of imparting an uneven shape to the surface of the surface protective layer 3 described later. By directly laminating the surface protective layer 3 on the surface having the uneven shape of the release layer 2, it is possible to form an uneven shape corresponding to the uneven shape of the release layer 2 on the surface of the surface protective layer 3. For example, by laminating the surface protective layer 3 directly on the release layer 2 having a fine uneven shape on the surface, the uneven shape is transferred to the surface of the surface protective layer 3, and the surface of the surface protective layer 3 is matte. A design can be given. As described in the above-mentioned [Transfer base material 1] column, a surface having a fine uneven shape that expresses a matte design generally has a problem that it is easily scratched. However, in the present invention, there is a problem. The surface protective layer 3 having a matte design based on a fine uneven shape also exhibits excellent scratch resistance.

As a method for forming an uneven shape on the surface of the release layer 2, the same method as in the above-mentioned [Transfer base material 1] column can be exemplified. Among these methods, a method in which fine particles are contained in the release layer 2 is preferable from the viewpoint of transferring a fine uneven shape to the surface protective layer 3 to express a matte design, and from the viewpoint of improving three-dimensional moldability. The method of including synthetic resin particles is particularly preferable.

The content of the fine particles contained in the release layer 2 is not particularly limited as long as a desired uneven shape is formed on the surface protective layer 3, and for example, with respect to 100 parts by mass of the resin contained in the release layer 2. About 1 to 100 parts by mass, preferably about 5 to 80 parts by mass can be mentioned.

When the release layer 2 contains fine particles, the release layer 2 is preferably formed of a cured product of a resin composition containing the fine particles and an ionizing radiation curable resin. In the transfer film for three-dimensional molding of the present invention, the release layer 2 is formed of such a cured product, and the surface protective layer 3 is an ionizing radiation curable resin containing a caprolactone-based urethane (meth) acrylate. Since it is formed of a cured product of the composition, fine uneven shapes due to fine particles are suitably transferred to the surface of the surface protective layer 3, and a matte design having excellent scratch resistance is imparted to the surface of the surface protective layer 3. can do. Hereinafter, the ionizing radiation curable resin used for forming the release layer 2 will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the release layer 2 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having the above. Here, the ionizing radiation is as described in the column of [Surface protection layer 3] described later.

As the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or higher), preferably three or more (trifunctional or higher) polymerizable unsaturated bonds 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 (). Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Meta) Acrylate, Ethylene Oxide Modified Di (Meta) Acrylate, Allylated Cyclohexyl Di (Meta) Acrylate, Isocyanurate Di (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Ethylene Oxide Modified Trimethylol Propantri (Meta) Acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propantri (meth) acrylate, tris (acryloxyethyl) isocyanurate , Propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.

Further, as the above-mentioned oligomer used as an ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (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, silicone (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. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyisocyanate 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, a polyester polyol, or a caprolactone-based polyol with a polyisocyanate compound 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. 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 alone or in combination of two or more.

Among the above-mentioned ionizing radiation curable resins, from the viewpoint of suitably transferring fine uneven shapes due to fine particles to the surface of the surface protective layer 3 and imparting a matte design having excellent scratch resistance to the surface of the surface protective layer 3. It is preferable to use at least one of polycarbonate (meth) acrylate and urethane (meth) acrylate.

When the release layer 2 is formed using the ionizing radiation curable resin, the release layer 2 is formed by preparing, for example, an ionizing radiation curable resin composition containing fine particles and an ionizing radiation curable resin, and applying the composition. It is carried out by cross-linking and curing. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer by the coating method described later.

In the present invention, the prepared coating liquid is applied by a known method such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, preferably gravure coat so as to have the above-mentioned thickness, and is uncured. A resin layer is formed.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the release layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the release layer 2, the electron beam transmission depth and mold release The acceleration voltage is selected so that the thicknesses of the layers 2 are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the release layer 2 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the release layer 2 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as cockloft Walton type, bandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an ultraviolet light emitting diode (LED-UV).

The thickness of the release layer 2 is usually about 0.01 to 5 μm, preferably about 0.05 to 3 μm.

(Transfer layer 9)
In the transfer film for three-dimensional molding of the present invention, a surface protective layer 3 formed on the support 10, a primer layer 4 further formed as needed, a decorative layer 5, an adhesive layer 6, and a transparent resin layer are formed. 7 and the like constitute the transfer layer 9. In the present invention, after the transfer film for three-dimensional molding and the molding resin are integrally molded, the interface between the support 10 and the transfer layer 9 is peeled off, and the transfer layer 9 of the transfer film for three-dimensional molding becomes the molding resin layer 8. A transferred resin molded product is obtained. Hereinafter, each of these layers will be described in detail.

[Surface protection layer 3]
The surface protective layer 3 is provided on the transfer film for three-dimensional molding so as to be located on the outermost surface of the resin molded product for the purpose of improving the scratch resistance, weather resistance, chemical resistance, etc. of the resin molded product. Is.

The present invention is characterized in that the surface protective layer 3 is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate. The transfer film for three-dimensional molding of the present invention has excellent three-dimensional moldability and high scratch resistance because the surface protective layer 3 has such a structure. The details of the mechanism by which the transfer film for three-dimensional molding of the present invention has such excellent properties are not clear, but can be considered as follows, for example. That is, in the transfer film of the present invention, since the surface protective layer 3 is formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate, the flexibility of the surface protective layer 3 It is considered that the scratch resistance is enhanced because it is rich in elasticity, has excellent three-dimensional moldability as a transfer film, and fine scratches on the surface return to flatness with time. Further, the surface protective layer 3 of the present invention is also excellent in chemical resistance, and can impart excellent chemical resistance to the resin molded product.

<Ionizing radiation curable resin>
The ionizing radiation curable resin used for forming the surface protective layer 3 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having the above. Here, ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules, and 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 suitable for forming the surface protective layer 3 because it can be made solvent-free, does not require a photopolymerization initiator, and stable curing characteristics can be obtained. Used for.

The surface protective layer 3 is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate as the ionizing radiation curable resin. In the present invention, "(meth) acrylate" means "acrylate or methacrylate", and other similar substances have the same meaning.

<Caprolactone urethane (meth) acrylate>
The caprolactone-based urethane (meth) acrylate used in the present invention is a resin having ionizing radiation curability, and can usually be obtained by reacting a caprolactone-based polyol, an organic polyisocyanate, and a hydroxy (meth) acrylate.

The caprolactone-based polyol preferably has two hydroxyl groups and has a weight average molecular weight of preferably 500 to 3000, more preferably 750 to 2000. Further, polyols other than caprolactone-based polyols, for example, polyols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol can be used by mixing one or more in any ratio.

As the organic polyisocyanate, a diisocyanate having two isocyanate groups is preferable, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate and the like are preferably mentioned. .. Further, as the hydroxy (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone-modified -2-hydroxyethyl (meth) acrylate and the like are preferably mentioned.

Caprolactone-based urethane (meth) acrylate can be synthesized by reacting these polycaprolactone-based polyols with organic polyisocyanates and hydroxy (meth) acrylates. As a synthetic method, a polycaprolactone-based polyol is reacted with an organic polyisocyanate to form a polyurethane prepolymer containing a -NCO group (isocyanate group) at both ends, and then reacted with a hydroxy (meth) acrylate. The method is preferred. The reaction conditions and the like may be in accordance with a conventional method. As the caprolactone-based urethane (meth) acrylate, a commercially available product can also be used.

The caprolactone-based urethane (meth) acrylate used in the present invention preferably has a weight average molecular weight (polystyrene-equivalent weight average molecular weight measured by the GPC method) of 1000 to 12000, more preferably 1000 to 10000. That is, the caprolactone-based urethane (meth) acrylate is preferably an oligomer. When the weight average molecular weight is within the above range (oligomer), the processability is excellent and the coating agent composition can obtain appropriate thixotropy, so that the surface protective layer can be easily formed.

The content of the caprolactone-based urethane (meth) acrylate in the ionizing radiation-curable resin composition forming the surface protective layer 3 is not particularly limited, but from the viewpoint of further improving the three-dimensional moldability and scratch resistance, the content is not particularly limited. It is preferably about 98 to 50% by mass, and more preferably about 95 to 60% by mass.

Conventionally, in the process of transferring a transfer film for three-dimensional molding to a molding resin to obtain a resin molded product, the area and shape of the transferred layer (transfer layer) such as a surface protective layer and the surface to be transferred of the molding resin are completely completed. Since it is difficult to match with, the area of the transfer layer of the transfer film for three-dimensional molding is generally designed to be larger than the area of the surface to be transferred of the molding resin. In such a transfer film for three-dimensional molding, the area of the transfer layer is designed to be larger than the area of the surface to be transferred of the molding resin, so that the transfer base material is peeled off after the transfer layer is transferred to the molding resin. At that time, the transfer layer of the portion that does not need to be peeled from the base material is pulled by the transfer layer transferred to the molding resin, the transfer layer is not cut at the end of the surface to be transferred, and the transfer layer protrudes from the end. May remain, so-called "foil burrs". From the viewpoint of effectively suppressing such foil burrs, in the present invention, it is preferable that the ionizing radiation curable resin composition forming the surface protective layer 3 further contains an isocyanate compound.

The details of the mechanism by which the ionizing radiation curable resin composition forming the surface protective layer 3 further contains an isocyanate compound thereby effectively suppresses foil burrs are not clear, but the following can be considered, for example. it can. That is, since the ionizing radiation curable resin composition contains an isocyanate compound in addition to the caprolactone-based urethane (meth) acrylate, the hardness of the cured product of the ionizing radiation curable resin composition is increased by these cross-linking reactions. It is thought that it has been done. Therefore, when the support 10 formed on the surface protective layer 3 is peeled off, the surface protective layer 3 is easily cut, and as a result, foil burrs remaining on the end portion of the molded product are effectively suppressed. It is thought that there is.

<Isocyanate compound>
The isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group, but a polyfunctional isocyanate compound having two or more isocyanate groups is preferable. Examples of the polyfunctional isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate (1,6-hexamethylene diisocyanate). HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other polyisocyanates such as aliphatic (or alicyclic) isocyanates can be mentioned. In addition, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, blocked isocyanate compounds, and the like can also be mentioned. One type of isocyanate compound may be used alone, or two or more types may be used in combination.

The content of the isocyanate compound in the ionizing radiation curable resin composition forming the surface protective layer 3 is not particularly limited, but is preferably ionizing radiation curing from the viewpoint of further improving the three-dimensional moldability and scratch resistance. About 1 to 10 parts by mass, more preferably about 3 to 7 parts by mass with respect to 100 parts by mass of the solid content other than the isocyanate compound in the sex resin composition. In particular, by setting the content of the isocyanate compound to 7 parts by mass or less, when the transfer substrate is peeled from the resin molded product, linear peeling unevenness remains on the surface of the surface protective layer, so-called release line is generated. It can be suppressed and is suitable.

<Other additive ingredients>
The ionizing radiation curable resin composition forming the surface protective layer 3 includes an ionizing radiation curable resin other than caprolactone-based urethane (meth) acrylate or a thermoplastic resin, depending on the desired physical properties to be provided in the surface protective layer 3. , In addition to thermosetting resin, various additives can be blended. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improvers, and leveling agents. Examples thereof include tincture imparting agents, coupling agents, plasticizers, defoaming agents, fillers, solvents, colorants, matting agents and the like. These additives can be appropriately selected from those commonly used, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, 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 also be used.

<Thickness of surface protective layer 3>
The thickness of the surface protective layer 3 after curing is not particularly limited, and examples thereof include 1 to 1000 μm, preferably 1 to 50 μm, and more preferably 1 to 30 μm. When the thickness in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained, and since it is possible to uniformly irradiate ionizing radiation, it is possible to cure uniformly. It will be possible and economically advantageous. Further, when the thickness of the surface protective layer 3 after curing satisfies the above range, the three-dimensional moldability of the transfer film for three-dimensional molding is further improved, which is high for complicated three-dimensional shapes such as automobile interior applications. Followability can be obtained. As described above, the transfer film for three-dimensional molding of the present invention is particularly high in the surface protective layer 3 because sufficiently high three-dimensional moldability can be obtained even if the thickness of the surface protective layer 3 is made thicker than that of the conventional one. It is also useful as a transfer film for three-dimensional molding of members requiring a thickness, for example, vehicle exterior parts.

<Formation of surface protective layer 3>
The surface protective layer 3 is formed, for example, by preparing an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate, applying the composition, and cross-linking and curing the composition. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer on the surface of the transfer base material 1 or the release layer 2 by the coating method described later.

In the present invention, the prepared coating liquid is applied onto the surface of the transfer substrate 1 or the release layer 2 so as to have the above-mentioned thickness, such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat, and the like. Is applied by a known method, preferably a gravure coat, to form an uncured resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 3. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protection layer 3, the electron beam transmission depth and surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 3 are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the surface protective layer 3 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the surface protective layer 3 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as cockloft Walton type, bandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an ultraviolet light emitting diode (LED-UV).

By adding various additives to the surface protective layer 3 thus formed, a hard coating function, an antifogging coating function, an antifouling coating function, an antiglare coating function, an antireflection coating function, and an ultraviolet shielding coating function, A process for imparting a function such as an infrared shielding coating function may be performed.

[Primer layer 4]
The primer layer 4 is a layer provided as needed for the purpose of enhancing the adhesion between the surface protective layer 3 and the layer located below it (opposite to the support 10). The primer layer 4 can be formed by a resin composition for forming a primer layer.

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

As the urethane resin, polyurethane 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 printing suitability when laminating the decorative layer 5 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 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.

In the present invention, the primer layer 4 contains a polyol resin and / or a cured product thereof, and the ionizing radiation curable resin composition forming the surface protective layer 3 contains a caprolactone-based urethane (meth) acrylate and an isocyanate compound. Is particularly preferred. As the resin of the primer layer 4, specifically, it is preferable to use the urethane resin having a polyol as a main agent and an isocyanate as a cross-linking agent (curing agent). By adopting such a configuration, foil burrs are suppressed more effectively. The details of this mechanism are not clear, but can be thought of as follows, for example. That is, in the transfer film for three-dimensional molding of the present invention, when the surface protective layer 3 is cured, the ionizing radiation curable resin composition containing the caprolactone-based urethane (meth) acrylate and the isocyanate compound constituting the surface protective layer 3 It is considered that the cured product of the product contains an isocyanate compound in which at least a part of the isocyanate groups remains unreacted. Further, when the primer layer 4 adjacent to the surface protective layer 3 contains a polyol resin and / or a cured product thereof, the primer layer 4 contains a polyol resin in which at least a part of hydroxyl groups remains unreacted and / or its curing. It is thought that things are included. Then, at the interface between the surface protective layer 3 and the primer layer 4, the isocyanate group existing in the surface protective layer 3 and the hydroxyl group existing in the primer layer 4 are bonded to each other, and the surface protective layer 3 and the primer layer 4 are brought into close contact with each other. It is thought that the sex is enhanced. By enhancing the adhesion between the surface protective layer 3 and the primer layer 4, when the support 10 formed on the surface protective layer 3 is peeled off, the surface protective layer 3 is cut off at the end of the molded product. As a result, it is considered that the foil burrs remaining on the end portion of the molded product are effectively suppressed.

The content of the polyol resin and / or the cured product thereof in the primer layer 4 is not particularly limited, but is preferably 40% by mass or more, more preferably 70% by mass or more. By setting the content of the polyol resin and / or the cured product thereof in the primer layer 4 within the above range, the occurrence of foil burrs can be controlled more effectively. There is no particular upper limit to the content of the polyol resin and / or its cured product in the primer layer 4, and it is a foil burr that substantially all of the resin components contained in the primer layer 4 are the polyol resin and / or its cured product. It is particularly preferable from the viewpoint of suppressing the occurrence of.

The thickness of the primer layer 4 is not particularly limited, and examples thereof include about 0.1 to 10 μm, preferably about 1 to 10 μm. When the primer layer 4 satisfies such a thickness, the weather resistance of the transfer film for three-dimensional molding can be further enhanced, and cracking, breaking, whitening, etc. of the surface protective layer 3 can be effectively suppressed.

Various additives can be added to the composition forming the primer layer 4 according to the desired physical properties to be provided. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, a defoaming agent, a filler, a solvent, a coloring agent, and a matting agent. These additives can be appropriately selected from those commonly used, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, 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 also be used.

The primer layer 4 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 with a 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 film for three-dimensional molding is coated. ..

The primer layer 4 may be formed on the surface protection layer 3 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 3 to form a primer layer 4. The surface protective layer 3 may be formed by irradiating the surface with ionizing radiation and curing the layer made of the ionizing radiation curable resin.

[Decorative layer 5]
The decorative layer 5 is a layer provided as needed to impart decorativeness to the resin molded product. The decorative layer 5 is usually composed of a pattern layer and / or a concealing layer. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters and a pattern pattern, and the concealing layer is usually a solid layer on the entire surface and is provided for concealing coloring or the like of a molding resin or the like. It is a layer. The concealing layer may be provided inside the pattern layer in order to enhance the pattern of the pattern layer, or the decorative layer 5 may be formed by the concealing layer alone.

The pattern of the pattern layer is not particularly limited, and examples thereof include a pattern composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, and the like.

The decorative layer 5 is formed by using a printing ink containing a colorant, a binder resin, and a solvent or a dispersion medium.

The colorant of the printing ink used for forming the decorative layer 5 is not particularly limited, and for example, metals such as aluminum, chromium, nickel, tin, titanium, iron phosphate, copper, gold, silver, and brass, and alloys. Or metallic pigment consisting of scaly foil powder of metal compound; 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, basic Pearl luster (pearl) pigments made of foil powder such as lead carbonate; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide; white inorganic substances such as titanium dioxide, zinc flower, antimony trioxide, etc. Pigments: Zinc flower, petal pattern, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments; isoindolinone yellow, Hansa yellow A, quinacridon red, permanent red 4R, phthalocyanine blue, induslen blue Examples thereof include organic pigments (including dyes) such as RS and aniline black. These colorants may be used alone or in combination of two or more.

The binder resin for the printing ink used for forming the decorative layer 5 is not particularly limited, but for example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-. Examples thereof include vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fibrous derivative, rubber resin and the like. These binder resins may be used alone or in combination of two or more.

The solvent or dispersion medium of the printing ink used for forming the decorative layer 5 is not particularly limited, and is, for example, a petroleum-based organic solvent such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; Ester-based organic solvents such as ethyl acetate, butyl acetate, -2-methoxyethyl acetate and -2-ethoxyethyl acetate; alcohols such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol. Organic solvent; Ketone organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Ether organic solvent such as diethyl ether, dioxane, tetrahydrofuran; Chlorine organic solvent such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene; Examples include water. These solvents or dispersion media may be used alone or in combination of two or more.

Further, the printing ink used for forming the decorative layer 5 includes, if necessary, an antioxidant, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, a defoaming agent, a lubricant and the like. It may be included.

The decorative layer 5 can be formed on an adjacent layer such as the surface protective layer 3 or the primer layer 4 by a known printing method such as gravure printing, flexographic printing, silk screen printing, or offset printing. When the decorative layer 5 is a combination of the pattern layer and the concealing layer, one layer may be laminated and dried, and then the other layer may be laminated and dried.

The thickness of the decorative layer 5 is not particularly limited, and examples thereof include 1 to 40 μm, preferably 3 to 30 μm.

The decorative layer 5 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 them. The method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above-mentioned 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.

[Adhesive layer 6]
The adhesive layer 6 is required on the back surface (molding resin layer 8 side) of the decorative layer 5, the transparent resin layer 7, etc. for the purpose of improving the adhesion between the three-dimensional molding transfer film and the molding resin layer 8. It is a layer provided accordingly. The resin forming the adhesive layer 6 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, 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.

Although the adhesive layer 6 is not necessarily a necessary layer, the transfer film for three-dimensional molding of the present invention is applied to a decoration method by sticking on a resin molded body prepared in advance, for example, a vacuum pressure bonding method described later. It is preferable that the above is provided. When used in the vacuum crimping method, it is preferable to form the adhesive layer 6 by using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.

The thickness of the adhesive layer 6 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 7]
In the transfer film for three-dimensional molding of the present invention, a transparent resin layer 7 may be provided, if necessary, for the purpose of improving the adhesion between the primer layer 4 and the adhesive layer 6. Since the transparent resin layer 7 can improve the adhesion between the primer layer 4 and the adhesive layer 6 in the embodiment in which the transfer film for three-dimensional molding of the present invention does not have the decorative layer 5, the three-dimensional shape of the present invention can be improved. It is particularly useful to provide a transfer film for molding when it is used for producing a resin molded product that requires transparency. The transparent resin layer 7 is not particularly limited as long as it is transparent, and includes any of colorless transparent, colored transparent, translucent and the like. Examples of the resin component forming the transparent resin layer 7 include the binder resin exemplified in the decorative layer 5.

The transparent resin layer 7 contains 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, if necessary. Various additives such as (for example, rubber) may be contained.

The transparent resin layer 7 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 7 is not particularly limited, but is generally about 0.1 to 10 μm, preferably about 1 to 10 μm.

The transfer film for three-dimensional molding of the present invention can be produced, for example, by a production method including the following steps.
A step of laminating a layer made of an ionizing radiation-curable resin composition containing a caprolactone-based urethane (meth) acrylate on a transfer substrate 1. The ionizing radiation-curable resin composition is irradiated with ionizing radiation to form an ionizing radiation-curable resin. A step of curing the layer composed of the composition to form the surface protective layer 3 on the transfer substrate 1.

When the primer layer 4 is formed, the layer made of the above-mentioned primer layer forming composition is laminated directly above the layer made of the ionizing radiation curable resin composition (on the surface opposite to the transfer base material 1). Further steps may be provided.

As described above, after the step of laminating the layer made of the ionizing radiation curable resin composition, after laminating the layer made of the primer layer forming composition on the layer made of the ionizing radiation curable resin composition, The step of irradiating the ionizing radiation curable resin composition with ionizing radiation and curing the layer made of the ionizing radiation curable resin composition to form the surface protective layer 3 on the transfer substrate may be performed. ..

2. Resin molded product and its manufacturing method The resin molded product of the present invention is formed by integrating the three-dimensional molding transfer film of the present invention and a molding resin. Specifically, by laminating the molding resin layer 8 on the side opposite to the support 10 of the transfer film for three-dimensional molding, at least the molding resin layer 8, the surface protection layer 3, and the support 10 are formed. A resin molded product with a support, which is laminated in order, is obtained (see, for example, FIG. 2). Next, by peeling the support 10 from the resin molded product with a support, the resin molded product of the present invention in which at least the molded resin layer 8 and the surface protective layer 3 are laminated in this order can be obtained (for example, FIG. 3). reference). As shown in FIG. 3, in the resin molded product of the present invention, at least one layer such as the above-mentioned primer layer 4, decorative layer 5, adhesive layer 6, and transparent resin layer 7 is further provided, if necessary. May be good.

The resin molded product of the present invention can be produced by a production method including the following steps.
A process of laminating a molding resin layer on the side opposite to the transfer base material of the transfer film for three-dimensional molding,
Step of peeling the transfer substrate from the surface protective layer

When the transfer film for three-dimensional molding is applied to, for example, the injection molding simultaneous transfer decoration method, examples of the method for producing the resin molded product of the present invention include methods including the following steps (1) to (5).
(1) First, the surface protective layer side (opposite side to the support) of the transfer film for three-dimensional molding for transfer is directed into the mold, and the transfer film for three-dimensional molding is heated from the surface protective layer side by a hot plate. Process,
(2) A step of pre-molding (vacuum forming) the transfer film for three-dimensional molding so as to follow the shape inside the mold so that the transfer film is brought into close contact with the inner surface of the mold and molded.
(3) The process of injecting resin into the mold,
(4) A step of taking out the resin molded product (resin molded product with a support) from the mold after cooling the injection resin, and (5) a step of peeling the support from the surface protective layer of the resin molded product.

In both of the above steps (1) and (2), the temperature at which the transfer film for three-dimensional molding is heated is in a range of not less than the glass transition temperature of the transfer substrate 1 and less than the melting temperature (or melting point). Is preferable. Usually, it is more preferable to carry out at a temperature near the glass transition temperature. The above-mentioned vicinity of the glass transition temperature refers to a range of the glass transition temperature of about ± 5 ° C., and is generally about 70 to 130 ° C. when a suitable polyester film is used as the transfer base material 1. When a mold having a less complicated shape is used, the step of heating the transfer film for three-dimensional molding and the step of pre-molding the transfer film for three-dimensional molding are omitted, and injection is performed in the step (3) described later. The transfer film for three-dimensional molding may be molded into the shape of a mold by the heat and pressure of the resin.

In both of the above steps (3), the molding resin described later is melted and injected into the cavity to integrate the three-dimensional molding transfer film and the molding resin. When the molding resin is a thermoplastic resin, it is made to flow 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 in a flowing state. Then, cool and solidify. As a result, the three-dimensional molding transfer film for three-dimensional molding is integrally attached to the formed resin molded body, and becomes a resin molded product with a support. The heating temperature of the molding resin depends on the type of the molding resin, but is generally about 180 to 320 ° C.

The resin molded product with a support thus obtained is resin-molded by being cooled in the step (4), taken out from the mold, and then peeling the support 10 from the surface protective layer 3 in the step (5). Get the goods. Further, the step of peeling the support 10 from the surface protective layer 3 may be performed at the same time as the step of taking out the decorative resin molded product from the mold. That is, the step (5) may be included in the step (4).

Further, the resin molded product can be manufactured by a vacuum crimping method. In the vacuum crimping method, first, the transfer film for three-dimensional molding and the resin molded body of the present invention are three-dimensionally molded in a vacuum crimping machine including a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. Inside the vacuum crimping machine so that the transfer film for use is on the first vacuum chamber side, the resin molded body is on the second vacuum chamber side, and the side on which the molding resin layer 8 of the transfer film for three-dimensional molding is laminated faces the resin molded body side. The two vacuum chambers are evacuated. The resin molded body is installed on an elevating table that can be raised and lowered up and down, which is provided on the second vacuum chamber side. Next, while pressurizing the first vacuum chamber, the compact is pressed against the transfer film for three-dimensional molding using an elevating table, and the pressure difference between the two vacuum chambers is used to form the transfer film for three-dimensional molding. It is attached to the surface of the resin molded product while being stretched. Finally, the resin molded product of the present invention can be obtained by opening the two vacuum chambers to atmospheric pressure, peeling off the support 10, and trimming the excess portion of the transfer film for three-dimensional molding as necessary. it can.

In the vacuum pressure bonding method, the transfer film for three-dimensional molding is heated in order to soften the transfer film for three-dimensional molding and improve the moldability before the step of pressing the molded body against the transfer film for three-dimensional molding. It is preferable to have a process. The vacuum crimping method including this step is sometimes called a vacuum heating crimping method in particular. The heating temperature in the step may be appropriately selected depending on the type of resin constituting the transfer film for three-dimensional molding, the thickness of the transfer film for three-dimensional molding, and the like. For example, the polyester resin film or acrylic as the transfer base material 1 may be selected. When a resin film is used, the temperature can usually be about 60 to 200 ° C.

In the resin molded product of the present invention, the molding resin layer 8 may be formed by selecting a resin according to the intended use. The molding resin that forms the molding resin layer 8 may be a thermoplastic resin or a thermosetting resin.

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

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

In the resin molded product with a support, the support 10 serves as a protective sheet for the resin molded product. Therefore, after the resin molded product with the support is manufactured, it is stored as it is without being peeled off and supported at the time of use. The body 10 may be peeled off. By using it in such an embodiment, it is possible to prevent the resin molded product from being scratched due to rubbing during transportation or the like.

Since the resin molded product of the present invention has excellent scratch resistance and moldability, for example, interior or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; buildings such as walls, floors and ceilings. Interior materials; housings for home appliances such as TV receivers and air conditioners; can be used as 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.

(Examples 1 to 6 and Comparative Example 1)
[Manufacturing of transfer film for 3D molding]
As the transfer base material, a polyethylene terephthalate film (thickness 50 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 easy-adhesive layer of the polyethylene terephthalate film by gravure printing. Next, on the release layer, an ionizing radiation curable resin composition containing the isocyanate compounds shown in Table 1 in the following ionizing radiation curable resin is coated with a barcoder so that the thickness after curing is 3 μm. Then, a coating film for forming a surface protective layer was formed. 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. On this surface protective layer, a resin composition for forming a primer layer containing the resin shown in Table 1 was applied 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) of a hairline pattern was formed by gravure printing using a black-based ink composition for use. Further, a transfer group is formed by forming an adhesive layer (thickness 4 μm) on the decorative layer by gravure printing using a resin composition for forming an adhesive layer containing an acrylic resin (softening temperature: 125 ° C.). A transfer film for three-dimensional molding was produced in which a material / release layer / surface protection layer / primer layer / decorative layer / adhesive layer were laminated in this order.

(Examples 7 to 15 and Comparative Example 2)
[Manufacturing of transfer film for 3D molding]
As the coating liquid for forming the release layer, a resin composition containing the synthetic resin particles shown in Table 2 and the following ionizing radiation curable resin was used, and the coating was applied to the surface of the easy-adhesive layer of the transfer substrate. The working liquid was applied with a bar coder, and an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) was irradiated from above the coating film to cure the coating film to form a release layer (1 μm). A transfer film for three-dimensional molding was produced in the same manner as in Examples 1 to 6 and Comparative Example 1 except for the above.
<Ionizing radiation curable resin>
A: Caprolactone-based urethane (meth) acrylate B: Pentaerythritol triacrylate 40 parts by mass, acrylic polymer (acrylic resin, copolymer of methyl methacrylate and methacrylic acid) 60 parts by mass C: Bifunctional polycarbonate acrylate (weight average molecular weight) 8000) A mixture of 94 parts by mass and 6 parts by mass of tetrafunctional urethane acrylate (weight average molecular weight 6000).

[Manufacturing of resin molded products]
Each of the transfer films for three-dimensional molding obtained above was placed in a mold, heated at 350 ° C. for 7 seconds with an infrared heater, preformed by vacuum forming to follow the shape inside the mold, and molded (molded). Maximum draw ratio 50%). After that, the injection resin is injected into the cavity of the mold, the three-dimensional molding transfer film and the injection resin are integrally molded, and at the same time as being taken out from the mold, the support (transfer base material and mold release layer) is removed. A resin molded product was obtained by peeling and removing.

Evaluation of Foil Burrs The resin molded product obtained above was visually observed to confirm the presence or absence of foil burrs, and the effect of suppressing foil burrs was evaluated according to the following criteria. The results are shown in Tables 1 and 2.
⊚: No foil burrs ○: Almost no foil burrs (the decoration on the parting line looks slightly jagged)
Δ: Foil burrs were generated, but the level was not a problem in practical use. ×: Foil burrs were prominently present.

Extensibility The resin molded product obtained above was visually observed to confirm the presence or absence of cracks on the surface of the resin molded product, and the extensibility of the transfer film for three-dimensional molding was evaluated according to the following criteria. The results are shown in Tables 1 and 2.
◯: No crack existed ×: Crack existed

Measurement of tensile elongation In an oven set at 80 ° C., a transfer film for three-dimensional molding (1 inch wide strip-shaped test piece) was heated for 60 seconds and pulled at 1000 mm / min using a Tencilon universal tester. The tensile elongation at the time of cracking was measured. The results are shown in Tables 1 and 2.

Gloss of surface protection layer (60 ° gloss value)
The surface gloss (60 ° gloss value) of the resin molded products obtained in Examples 7 to 15 and Comparative Example 2 was evaluated. The 60 ° gloss value was measured using a micro-TRI-gloss (Catalog No. 4520) manufactured by Byk Gardner. The results are shown in Table 2.

Scratch resistance (steel wool)
The surfaces of the resin molded products obtained in Examples 1 to 6 and Comparative Example 1 were rubbed 10 times with a load of 1.5 kgf using steel wool (# 0000), and the surface was visually observed to resist scratches on the steel wool. Gender was evaluated according to the following criteria. The results are shown in Table 1.
◯: No significant change in appearance ×: Significant change in appearance

Scratch resistance (sandpaper)
The surfaces of the resin molded products obtained in Examples 1 to 6 and Comparative Example 1 were rubbed 10 times with a load of 800 gf using sandpaper (abrasive paper having an average particle size of 9 μm alumina abrasive grains). Next, using Byk Gardner's micro-TRI-gloss (Catalog No. 4520), the gloss (20 °) of the surface of the transfer molded product before and after the test was measured, and the gloss after the test / gloss before the test was calculated. .. The scratch resistance to sandpaper was evaluated according to the following criteria. The results are shown in Table 1.
◯: (Gloss after test / Gloss before test) × 100 = 80% or more ×: (Gloss after test / Gloss before test) × 100 = Less than 80%

Scratch resistance (Gakushin type wear test)
The surfaces of the resin molded products obtained in Examples 7 to 15 and Comparative Example 2 were subjected to a Gakushin type wear test in accordance with JIS L0849 (wear tester type II (Gakushin type)). The device used for the test was a "Gakushin type wear tester" manufactured by Tester Sangyo Co., Ltd., and Kanakin No. 3 was used as a white cotton cloth for friction, and the test piece was evaluated after 2000 round trips with a load of 200 g. The evaluation criteria are as follows. The results are shown in Table 2.
◯: No scratches on the surface ×: Scratches or gloss changes on the surface occurred in more than 1/2

Release line By visually observing the resin molded product obtained above, a release line (linear peeling remaining on the surface of the surface protective layer when the transfer base material is peeled from the resin molded product) is applied to the surface of the resin molded product. It was confirmed whether or not unevenness) remained, and the suppression effect of the release line was evaluated according to the following criteria. The results are shown in Tables 1 and 2.
◯: No release line remained △: A small amount of release line remained, but there was no problem in practical use. ×: The release line remained remarkably.

Chemical resistance (sunscreen cosmetics)
0.5 g of a commercially available sunscreen cosmetic was uniformly applied to a portion having a length of 50 mm and a width of 50 mm on the surface of the resin molded product obtained above. This was left in an oven at 80 ° C. for 1 hour. After taking out the resin molded product and rinsing the surface with a cleaning solution, the condition of the part (test surface) to which the sunscreen cosmetic was applied was visually observed, and the chemical resistance of the sunscreen cosmetic was evaluated according to the following criteria. .. The results are shown in Tables 1 and 2. The sunscreen cosmetics are those of SPF 50 on the market, and the ingredients are 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) -1,3-propanedione 3%, salicylic acid 3,3. It contains 10% 5-trimethylcyclohexyl, 5% 2-ethylhexyl salicylate, and 10% 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
◯: No significant change in appearance ×: Significant change in appearance

* In Table 1, HMDI means 1,6-hexamethylene diisocyanate and XDI means xylene diisocyanate.
* In Table 1, the amount (parts by mass) of the isocyanate compound in the surface protective layer indicates the amount added to 100 parts by mass of the solid content other than the isocyanate compound contained in the ionizing radiation curable resin composition forming the surface protective layer.
* In Table 1, the amount of the isocyanate compound in the primer layer indicates the amount added to 100 parts by mass of the primer resin shown in the table.

From the results shown in Table 1, in the transfer film for three-dimensional molding of Examples 1 to 6, the surface protective layer is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate. It was excellent in moldability and showed excellent scratch resistance even in a very strict scratch resistance test using sandpaper. Further, in the transfer films for three-dimensional molding of Examples 1 to 6, it was possible to impart excellent chemical resistance to the resin molded product. Further, in the transfer films for three-dimensional molding of Examples 1, 3, 5, and 6, foil burrs were also effectively suppressed.
On the other hand, Comparative Example 1 in which pentaerythritol triacrylate and an acrylic polymer were used as the surface protective layer was inferior to any of Examples 1 to 6 in the scratch resistance test using steel wool and sandpaper.

* In Table 2, HMDI means 1,6-hexamethylene diisocyanate and XDI means xylene diisocyanate.
* In Table 2, the amount (parts by mass) of the isocyanate compound in the surface protective layer indicates the amount added to 100 parts by mass of the solid content other than the isocyanate compound contained in the ionizing radiation curable resin composition forming the surface protective layer.
* In Table 2, the amount of the isocyanate compound in the primer layer indicates the amount added to 100 parts by mass of the primer resin shown in the table.

From the results shown in Table 2, the surface protective layer was formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate, and the release layer contained synthetic resin particles. The transfer films for three-dimensional molding of Examples 7 to 15 were excellent in moldability and showed excellent scratch resistance even in the Gakushin friction test, which is a strict scratch resistance test. Further, by blending the synthetic resin particles in the release layer, a fine uneven shape was formed on the surface, the gloss of the surface was suppressed, and an excellent matte feeling was provided. Further, in the transfer films for three-dimensional molding of Examples 7 to 15, it was possible to impart excellent chemical resistance to the resin molded product. Further, in the transfer films for three-dimensional molding of Examples 7 to 15, foil burrs were also effectively suppressed.
On the other hand, in Comparative Example 2 in which pentaerythritol triacrylate and an acrylic polymer were used as the surface protective layer, the scratch resistance was inferior to any of Examples 7 to 15 in the Gakushin friction test. When a ruler was applied to the surface of the resin molded product of Comparative Example 1 and Comparative Example 2 and the surface of the resin molded product was rubbed 5 times while applying the thumb nail to the ruler, the surface of the resin molded product was not scratched. , In Comparative Example 2, it was scratched. From this, it can be understood that the scratch resistance tends to be lowered by blending the synthetic resin particles in the release layer and imposing fine irregularities on the surface protective layer.

1 Substrate for transfer 2 Release layer 3 Surface protection layer 4 Primer layer 5 Decorative layer 6 Adhesive layer 7 Transparent resin layer 8 Molding resin layer 9 Transfer layer 10 Support

Claims (16)

A transfer film for three-dimensional molding in which at least a surface protective layer is laminated on a transfer substrate.
The surface protective layer is formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate (excluding those containing a silicone compound having a reactive functional group).
The content of caprolactone-based urethane (meth) acrylate in the ionizing radiation-curable resin composition state, and are more than 50 wt%,
The surface of the transfer substrate on the surface protective layer side has an uneven shape.
The surface protective layer that is laminated, transfer film for three-dimensional molded directly on the transfer base material. The transfer film for three-dimensional molding according to claim 1, wherein the ionizing radiation curable resin composition further contains an isocyanate compound. The transfer film for three-dimensional molding according to claim 1 or 2, which has a primer layer directly above the surface protective layer. The transfer film for three-dimensional molding according to claim 3, wherein the primer layer contains a polyol resin and / or a cured product thereof. The transfer film for three-dimensional molding according to claim 4, wherein the polyol resin contains an acrylic polyol. The ionizing radiation curable resin composition further contains an isocyanate compound.
Claims 1 to 5, wherein the ionizing radiation curable resin composition contains 1 to 10 parts by mass of the isocyanate compound with respect to 100 parts by mass of a solid content other than the isocyanate compound in the ionizing radiation curable resin composition. The transfer film for three-dimensional molding according to any one. It has a primer layer directly above the surface protection layer and has a primer layer.
The invention according to any one of claims 1 to 6, wherein at least one selected from the group consisting of a decorative layer, an adhesive layer, and a transparent resin layer is laminated on the side of the primer layer opposite to the surface protective layer. Transfer film for 3D molding. The three-dimensional molding according to any one of claims 1 to 7, wherein the transfer base material contains fine particles, and the surface of the transfer base material on the surface protective layer side has an uneven shape due to the fine particles. Transfer film. The transfer film for three-dimensional molding according to any one of claims 1 to 8 , wherein the content of the caprolactone-based urethane (meth) acrylate in the ionizing radiation curable resin composition is 98 to 50% by mass. On the transfer substrate, a layer composed of an ionizing radiation curable resin composition containing 50% by mass or more of caprolactone-based urethane (meth) acrylate (excluding those containing a silicone compound having a reactive functional group). The process of laminating and
A step of irradiating the ionizing radiation curable resin composition with ionizing radiation and curing the layer made of the ionizing radiation curable resin composition to form a surface protective layer on the transfer substrate.
Equipped with a,
The surface of the transfer substrate on the surface protective layer side has an uneven shape.
Wherein the surface protective layer directly above the transfer base material is that is laminated, three-dimensional method of manufacturing a molding transfer film. The method for producing a transfer film for three-dimensional molding according to claim 10 , wherein the ionizing radiation curable resin composition further contains an isocyanate compound. The method for producing a transfer film for three-dimensional molding according to claim 10 or 11 , further comprising a step of laminating a layer of the composition for forming a primer layer directly above the layer of the ionizing radiation curable resin composition. The method for producing a transfer film for three-dimensional molding according to claim 12 , wherein the composition for forming a primer layer contains a polyol resin. The method for producing a transfer film for three-dimensional molding according to any one of claims 10 to 13 , wherein the content of the caprolactone-based urethane (meth) acrylate in the ionizing radiation curable resin composition is 98 to 50% by mass. .. A step of laminating a molding resin layer on the side opposite to the transfer base material of the three-dimensional molding transfer film according to any one of claims 1 to 9.
A step of peeling the transfer substrate from the surface protective layer, and
A method for manufacturing a resin molded product. A resin molded product obtained by the production method according to claim 15.

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