WO2018159684A1

WO2018159684A1 - Three-dimensional molding transfer film and method for manufacturing same, and method for manufacturing resin molded article

Info

Publication number: WO2018159684A1
Application number: PCT/JP2018/007522
Authority: WO
Inventors: 直樹大田; 明寿野田; 横山　大輔; 雄二中津川
Original assignee: 大日本印刷株式会社
Priority date: 2017-02-28
Filing date: 2018-02-28
Publication date: 2018-09-07

Abstract

Provided is a three-dimensional molding transfer film that has excellent moldability, excellent scratch resistance, and can suitably apply a highly glossy design to a resin molded article. The three-dimensional molding transfer film comprises at least a protection layer on a transfer substrate, wherein the protection layer is formed of cured material of an ionizing radiation curable resin composition containing polycarbonate (meta)acrylate, and the protection layer has a Martens hardness of 6 N/mm2 or more and 40 N/mm2 or less. Alternatively, the three-dimensional molding transfer film comprises a transfer layer on a mold releasing layer of a support body having a transfer substrate and the mold releasing layer, wherein the mold releasing layer has a Martens hardness of 7 N/mm2 or more and 45 N/mm2 or less.

Description

Three-dimensional molding transfer film, method for producing the same, and method for producing resin molded products

The present invention relates to a transfer film for three-dimensional molding, a manufacturing method thereof, and a manufacturing method of a resin molded product.

For resin molded products used for automotive interior / exterior materials, interior materials for building materials, home appliances, etc., and resin molded products used for organic glass used as an inorganic glass substitute material, etc. As a technique, a protective layer is laminated using a three-dimensional molded film. The three-dimensional molded film used in such a technique can be roughly classified into a laminate type three-dimensional molded film and a transfer type three-dimensional molded film. Laminate type three-dimensional molded film is laminated so that the protective layer is located on the outermost surface on the support substrate, and the support substrate is placed in the resin molded product by laminating the molding resin on the support substrate side. Is used to be captured. On the other hand, the transfer type three-dimensional molded film has a protective layer laminated directly on the support substrate or via a release layer provided as necessary, and after molding resin is laminated on the opposite side of the support substrate The support substrate is peeled off so that the support substrate does not remain in the resin molded product. These two types of three-dimensional molded films are selectively used according to the shape of the resin molded product and the desired function.

As a protective layer provided on such a three-dimensional molded film, from the viewpoint of imparting excellent surface properties to the resin molded product, it is chemically crosslinked by irradiating with ionizing radiation typified by ultraviolet rays and electron beams. It is considered preferable to use a resin composition containing an ionizing radiation curable resin that cures. Such a three-dimensional molded film is roughly divided into a protective layer that has already been cured by ionizing radiation in the state of the three-dimensional molded film and a film that has been cured after being formed into a resin molded product by molding, From the viewpoint of improving the productivity by simplifying the process after the molding process, the former is considered preferable. However, when the protective layer is cured at the stage of the three-dimensional molded film, the flexibility of the three-dimensional molded film is lowered, and there is a risk that the protective layer may crack in the process of molding, so it has excellent moldability. It is necessary to select a resin composition. In particular, in the case of the above-described transfer-type three-dimensional molded film, it is usually necessary to laminate other layers such as a design layer and an adhesive layer on the protective layer, and from the protective layer to the supporting substrate in the molding process. The design of the resin composition is better than that of the laminate type because the surface must be peeled off and the surface exposed by peeling off the support substrate must express excellent physical properties. There is a problem that it is difficult.

Under such conventional techniques,

Patent Documents

1 and 2 disclose techniques for forming a protective layer using an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate. By using such a resin composition, a three-dimensional moldability and scratch resistance can be achieved even in a transfer type three-dimensional molded film in which the protective layer is formed of a cured product of an ionizing radiation curable resin composition. Is possible.

JP 2012-56236 A JP 2013-111929 A

If the three-dimensional molded film used for the production of the resin molded product is black with high gloss (for example, gloss value of 80 or more) such as piano black, the surface of the protective layer is scratched. There is a problem that it is very conspicuous. As a technique for solving such a problem of scratch resistance, a method of imparting self-repairability by using a soft material for the protective layer is known. However, as the research progressed, it became clear that when the protective layer was softened, the density of the protective layer was reduced, the reflectance was lowered, and it was difficult to make it high gloss.

Under such circumstances, the first embodiment of the present invention has excellent moldability, further excellent scratch resistance, and can suitably impart a high gloss design to a resin molded product. The main purpose is to provide a transfer film for three-dimensional molding. Furthermore, it is another object of the first embodiment of the present invention to provide a method for producing the three-dimensional molded film and a method for producing a resin molded product using the three-dimensional molded film.

In addition, as a result of repeated studies by the present inventors, in the transfer-type three-dimensional molded film, the physical properties of the release layer of the support substrate that is peeled off after the three-dimensional molding, the moldability of the three-dimensional molded film, The present inventors also found that the durability and chemical resistance of the resin molded product from which the supporting base material was peeled off after molding were affected.

Under such circumstances, the second embodiment of the present invention has excellent moldability, and can impart excellent durability and chemical resistance to the resin molded product after molding. The main object is to provide a transfer film for three-dimensional molding. Furthermore, the second embodiment of the present invention also aims to provide a method for producing a resin molded product using the three-dimensional molding transfer film.

The present inventors have intensively studied to solve the problem of the first embodiment. As a result, a transfer film for three-dimensional molding having at least a protective layer on the transfer substrate, wherein the protective layer is formed by a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate. In addition, the three-dimensional transfer film for which the Martens hardness of the protective layer is 6 N / mm ² or more and 40 N / mm ² or less has excellent moldability, excellent scratch resistance, and high gloss. It was found that the design can be suitably imparted to a resin molded product. The first embodiment of the present invention has been completed by further studies based on such knowledge.

That is, the first embodiment of the present invention provides the following aspects of the invention.
Item 1A. A transfer film for three-dimensional molding having at least a protective layer on a transfer substrate,
The protective layer is formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate,
A transfer film for three-dimensional molding, wherein the protective layer has a Martens hardness of 6 N / mm ² or more and 40 N / mm ² or less.
Item 2A. Item 3. The transfer film for three-dimensional molding according to Item 1A, which has at least the protective layer and the primer layer in this order on the transfer substrate.
Item 3A. Item 3. The transfer film for three-dimensional molding according to Item 2A, wherein the primer layer contains a polyol and / or a cured product thereof.
Item 4A. Item 3. The three-dimensional molding transfer film according to Item 3A, wherein the polyol contains an acrylic polyol.
Item 5A. Item 3. The three-dimensional item according to any one of Items 1A to 4A, which has at least one selected from the group consisting of a decorative layer, an adhesive layer, and a transparent resin layer on the opposite side of the protective layer from the transfer substrate. Transfer film for molding.
Item 6A. Laminating a layer made of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate on a transfer substrate;
The ionizing radiation curable resin composition is irradiated with ionizing radiation, the layer made of the ionizing radiation curable resin composition is cured, and the Martens hardness is 6 N / mm ² or more on the transfer substrate. Forming a protective layer of 40 N / mm ² or less;
A method for producing a transfer film for three-dimensional molding, comprising:
Item 7A. A step of laminating a molding resin layer on the protective layer side of the transfer film for three-dimensional molding according to any one of Items 1A to 5A;
Peeling the substrate for transfer from the protective layer;
A method for producing a resin molded product.

In addition, the present inventors have intensively studied to solve the problem of the second embodiment. As a result, it is a three-dimensional molding transfer film having a transfer layer on the release layer of the support having at least a transfer substrate and a release layer, and the Martens hardness of the release layer is 7 N / mm. ^The transfer film for three-dimensional molding that is ² or more and 45 N / mm ² or less has excellent moldability, and can impart excellent durability and chemical resistance to the molded resin product after molding. I found. The second embodiment of the present invention has been completed by further studies based on this knowledge.

That is, the second embodiment of the present invention provides the following aspects of the invention.
Item 1B. A transfer film for three-dimensional molding having a transfer layer on the release layer of the support having at least a transfer substrate and a release layer,
A transfer film for three-dimensional molding, wherein the release layer has a Martens hardness of 7 N / mm ² or more and 45 N / mm ² or less.
Item 2B. Item 3. The transfer film for three-dimensional molding according to Item 1B, wherein the release layer is composed of a cured product of an ionizing radiation curable resin composition.
Item 3B. Item 3. The transfer film for three-dimensional molding according to Item 1B or 2B, wherein the ionizing radiation curable resin composition of the release layer contains polycarbonate (meth) acrylate and polyfunctional (meth) acrylate.
Item 4B. Item 3. The transfer film for three-dimensional molding according to any one of Items 1B to 3B, wherein the release layer has a thickness of 2.0 μm or less.
Item 5B. The transfer layer has a protective layer;
Item 3. The transfer film for three-dimensional molding according to any one of Items 1B to 4B, wherein the protective layer is in contact with the release layer.
Item 6B. Item 5. The transfer film for three-dimensional molding according to Item 5B, wherein the protective layer is formed of a cured product of an ionizing radiation curable resin composition.
Item 7B. Item 6. The transfer film for three-dimensional molding according to Item 5B or 6B, wherein the ionizing radiation curable resin composition of the protective layer contains polycarbonate (meth) acrylate.
Item 8B. Item 8. The transfer film for three-dimensional molding according to any one of Items 1B to 7B, wherein the transfer layer has at least one selected from the group consisting of a decorative layer, an adhesive layer, and a transparent resin layer.
Item 9B. A step of laminating a molding resin layer on the transfer layer side of the transfer film for three-dimensional molding according to any one of Items 1B to 8B;
Peeling the support from the transfer layer;
A method for producing a resin molded product.

According to the first embodiment of the present invention, there is provided a transfer film for three-dimensional molding that has excellent moldability, is excellent in scratch resistance, and can suitably impart a high gloss design to a resin molded product. Can be provided. Moreover, according to the 1st embodiment of this invention, the manufacturing method of the said three-dimensional shaping | molding transfer film and the manufacturing method of the resin molded product using the said three-dimensional shaping | molding transfer film can also be provided.

In addition, according to the second embodiment of the present invention, the three-dimensional molding has excellent moldability and can impart excellent durability and chemical resistance to the molded resin product after molding. A transfer film can be provided. Moreover, according to the 2nd embodiment of this invention, the manufacturing method of the resin molded product using the said three-dimensional shaping | molding transfer film can also be provided.

It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional shaping | molding of this invention. It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional shaping | molding of this invention. It is a schematic diagram of the cross-sectional structure of one form of the resin molded product with a support of the present invention. It is a schematic diagram of the cross-sectional structure of one form of the resin molded product of this invention. It is explanatory drawing which shows typically the measuring method of Martens hardness.

1. Three-dimensional molding transfer film The three-dimensional molding transfer film according to the first aspect of the present invention is a three-dimensional molding transfer film having at least a protective layer on a transfer substrate, wherein the protective layer is polycarbonate ( It is formed of a cured product of an ionizing radiation curable resin composition containing (meth) acrylate, and the protective layer has a Martens hardness of 6 N / mm ² or more and 40 N / mm ² or less. In the transfer film for three-dimensional molding of the first embodiment, by having such a configuration, it has excellent moldability, is excellent in scratch resistance, and has a high gloss design suitable for resin molded products. Can be granted. Hereinafter, the three-dimensional forming transfer film of the first aspect will be described in detail.

The transfer film for 3D molding according to the second embodiment of the present invention is a transfer film for 3D molding having a transfer layer on a release layer of a support having at least a transfer substrate and a release layer. The release layer has a Martens hardness of 7 N / mm ² or more and 45 N / mm ² or less. In the transfer film for three-dimensional molding of the second embodiment, by having such a configuration, the transfer film has excellent moldability, and further has excellent durability and resistance to a molded resin product after molding. Chemical properties can be imparted. Hereinafter, the three-dimensional forming transfer film of the second embodiment will be described in detail.

In this specification, the numerical range indicated by “to” means “above” or “below”. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. As will be described later, the transfer film for three-dimensional molding of the present invention (the first embodiment and the second embodiment) may not have a decorative layer or the like, and may be, for example, transparent. Further, “(meth) acrylate” means “acrylate or methacrylate”, and other similar things have the same meaning. Further, in the present specification, the first embodiment and the second embodiment are described when the present invention is described without particularly indicating that the description is about the first embodiment or the second embodiment. It means that it is a common explanation.

Laminated structure of three-dimensional molding transfer film The three-dimensional molding transfer film of the first embodiment has at least a protective layer 3 on a transfer substrate 1. A primer layer 4 may be provided on the opposite side of the protective layer 3 from the transfer substrate 1 as necessary for the purpose of improving the adhesion between the protective layer 3 and the adjacent layer. In addition, a release layer 2 is provided on the surface of the transfer substrate 1 on the protective layer 3 side, if necessary, for the purpose of improving the peelability between the transfer substrate 1 and the protective layer 3. Also good. In the three-dimensional molding transfer film of the first embodiment, the transfer substrate 1 and the release layer 2 provided as necessary constitute a support 10, and the support 10 is three-dimensional. After the molding transfer film is laminated on the molding resin layer 8, it is peeled off.

The transfer film for three-dimensional molding of the first embodiment may be provided with a decoration layer 5 as necessary for the purpose of imparting decorativeness to the three-dimensional transfer film. Moreover, you may have the contact bonding layer 6 as needed for the purpose of improving the adhesiveness of the molding resin layer 8, etc. Moreover, you may provide the transparent resin layer 7 as needed for the purpose of improving the adhesiveness of the protective layer 3, the primer layer 4, and the contact bonding layer 6, etc. In the transfer film for three-dimensional molding according to the first embodiment, the protective layer 3, the primer layer 4, the decorative layer 5, the adhesive layer 6, the transparent resin layer 7 and the like further provided as necessary constitute the transfer layer 9. The transfer layer 9 is transferred to the molded resin layer 8 to form the resin molded product of the first embodiment.

As a laminated structure of the transfer film for three-dimensional molding of the first embodiment, a laminated structure in which a transfer substrate / protective layer is laminated in this order; a laminate in which a transfer substrate / protective layer / primer layer is laminated in this order Structure: Laminated structure in which transfer substrate / release layer / protective layer / primer layer are laminated in this order; Laminated structure in which transfer substrate / release layer / protective layer / primer layer / decorative layer are laminated in this order Laminated structure in which transfer substrate / release layer / protective layer / primer layer / decoration layer / adhesive layer are laminated in this order; transfer substrate / release layer / protective layer / primer layer / transparent resin layer / adhesive Examples include a laminated structure in which layers are laminated in this order.

The transfer film for three-dimensional molding of the second embodiment has a transfer layer 9 on the release layer 2 of the support 10 having the transfer substrate 1 and the release layer 2. In the transfer film for three-dimensional molding of the second embodiment, the transfer substrate 1 and the release layer 2 constitute a support body 10, and the support body 10 forms a transfer film for three-dimensional molding. After being laminated on the resin layer 8, it is peeled off.

In the second embodiment, the transfer layer 9 preferably has the protective layer 3. The protective layer 3 is preferably in contact with the release layer 2. Further, when the transfer layer 9 has the protective layer 3, on the opposite side of the protective layer 3 from the support 10, for the purpose of improving the adhesion between the protective layer 3 and the adjacent layer, as necessary, The primer layer 4 may be provided. In addition, the transfer layer 9 may be provided with a decoration layer 5 as needed for the purpose of imparting decoration to the transfer film for three-dimensional molding. Moreover, you may have the contact bonding layer 6 as needed for the purpose of improving the adhesiveness of the molding resin layer 8, etc. Moreover, you may provide the transparent resin layer 7 as needed for the purpose of improving the adhesiveness of the protective layer 3, the primer layer 4, and the contact bonding layer 6, etc. In the transfer film for three-dimensional molding of the second embodiment, the protective layer 3, the primer layer 4, the decorative layer 5, the adhesive layer 6, the transparent resin layer 7 and the like constitute the transfer layer 9, and the transfer layer 9 The molded resin layer 8 is transferred to the resin molded product of the second embodiment.

As the laminated structure of the transfer film for three-dimensional molding of the second embodiment, a laminated structure in which a transfer substrate / release layer / protective layer are laminated in this order; transfer substrate / release layer / protective layer / primer Laminated structure in which layers are laminated in this order; Laminated structure in which transfer substrate / release layer / protective layer / primer layer / decorative layer are laminated in this order; transfer substrate / release layer / protective layer / primer layer / Laminated structure in which decorative layer / adhesive layer is laminated in this order; laminated structure in which transfer substrate / release layer / protective layer / primer layer / transparent resin layer / adhesive layer are laminated in this order.

FIG. 1 shows a three-dimensional molding in which a transfer substrate / release layer / protective layer / primer layer / decoration layer / adhesive layer are laminated in this order as an embodiment 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 water is shown. Further, in FIG. 2, as one aspect of the laminated structure of the transfer film for three-dimensional molding of the present invention, a transfer substrate / release layer / protective layer / primer layer / transparent resin layer / adhesive layer were laminated in this order. The schematic diagram of the cross-section of one form of the transfer film for three-dimensional shaping | molding is shown.

Composition of each layer forming three-dimensional molding transfer film [support 10]
The three-dimensional molding transfer film of the first embodiment has a transfer substrate 1 and, if necessary, a release layer 2 as a support 10. The protective layer 3 formed on the transfer substrate 1, the primer layer 4, the decoration layer 5, the adhesive layer 6, the transparent resin layer 7 and the like further formed as necessary constitute the transfer layer 9. . In the first embodiment, after integrally molding the three-dimensional molding transfer film and the molding resin, the interface between the support 10 and the transfer layer 9 is peeled off, and the support 10 is peeled off to obtain a resin molded product. It is done.

The transfer film for three-dimensional molding of the second embodiment has a transfer substrate 1 and a release layer 2 as the support 10. A protective layer 3, a primer layer 4, a decoration layer 5, an adhesive layer 6, a transparent resin layer 7 and the like formed on the support 10 constitute a transfer layer 9. In the second embodiment, after the three-dimensional molding transfer film and the molding resin are integrally molded, the interface between the release layer 2 and the transfer layer 9 of the support 10 is peeled off, and the support 10 is peeled and removed. A resin molded product is obtained.

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

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

In the present invention, the transfer substrate 1 is provided with a concavo-convex shape on at least one surface as necessary for the purpose of imparting a concavo-convex shape to the surface of the protective layer 3 to be described later or improving blocking resistance. You may have. Further, by laminating the protective layer 3 on the surface of the transfer substrate 1 having the concavo-convex shape via the release layer 2, the concavo-convex shape corresponding to the concavo-convex shape of the transfer substrate 1 is formed on the surface of the protective layer 3. In the range which does not contradict the purpose of the present invention, a matte design can be imparted to the surface of the protective layer 3. Furthermore, as another method for imparting a matte design to the surface of the protective layer 3, there is a method of adding an organic or inorganic filler into the release layer 2. In addition, in the case where the blocking resistance is improved without imparting the irregular shape to the surface of the protective layer 3, the irregular shape is formed only on the surface opposite to the protective layer 3 of the transfer substrate 1 or the transfer layer 1 is transferred. What is necessary is just to reduce the uneven | corrugated shape of the base material 1 for an adjustment, or to adjust the thickness of the mold release layer 2.

In addition to physical methods such as sand blasting, hairline processing, laser processing, embossing, or chemical methods such as corrosion treatment with chemicals or solvents, the method for forming the uneven shape on the surface of the transfer substrate 1 is as follows. Examples of the method of causing the transfer substrate 1 to contain fine particles so that the shape of the fine particles is exposed on the surface of the transfer substrate 1 are exemplified. Among these, a method in which the transfer substrate 1 contains fine particles is preferably used.

As the fine particles, synthetic resin particles and inorganic particles are representatively exemplified, but it is particularly preferable to use synthetic resin particles from the viewpoint of improving the three-dimensional moldability. The synthetic resin particle is not particularly limited as long as it is a particle formed of a synthetic resin. For example, acrylic beads, urethane beads, silicone beads, nylon beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, polyethylene Examples include beads. Among these synthetic resin particles, acrylic beads, urethane beads, and silicone beads are preferably used from the viewpoint of forming an uneven shape excellent in scratch resistance on the protective layer 3. Examples of inorganic particles include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide, and kaolin. These fine particles may be used alone or in combination of two or more. The particle diameter 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 using the Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1, using the compressed air to inject the powder to be measured from the nozzle. It is based on a spray-type dry measurement system that measures the above.

The content of the fine particles contained in the transfer substrate 1 may be appropriately set according to the purpose. For example, the content is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin contained in the transfer substrate 1. About 5 to 80 parts by mass. In addition, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, fluorescent whitening agents, and the like can be blended in the transfer substrate 1 as necessary.

The polyester sheet suitably used as the transfer substrate 1 in the present invention is produced, for example, as follows. First, the above polyester-based resin and other raw materials are supplied to a known melt extrusion apparatus such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester-based resin to be melted. Next, while extruding the molten polymer, it is rapidly cooled and solidified on the rotary cooling drum to a temperature not higher than the glass transition temperature to obtain a substantially amorphous unoriented sheet. This sheet is obtained by stretching in a biaxial direction to form a sheet and heat-setting. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Moreover, you may extend | stretch longitudinally and / or a horizontal direction again before or after performing heat setting as needed. In the present invention, in order to obtain sufficient dimensional stability, the draw ratio is preferably 7 times or less, more preferably 5 times or less, and further preferably 3 times or less, as an area ratio. Within this range, when the obtained polyester sheet is used for a three-dimensional molding transfer film, the three-dimensional molding transfer film does not shrink again in the temperature range when the molding resin is injected, Necessary sheet strength can be obtained. In addition, a polyester sheet may be manufactured as described above, or a commercially available one may be used.

In addition, the transfer substrate 1 can be subjected to physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides as desired for the purpose of improving the adhesion to the release layer 2. . Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the transfer substrate 1, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Further, the transfer substrate 1 may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of enhancing interlayer adhesion between the transfer substrate 1 and a layer provided thereon. In addition, when using a commercially available polyester sheet, the commercially available product that has been subjected to surface treatment as described above or that has an easy-adhesive layer can be used.

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

(Release layer 2)
In the first embodiment, the release layer 2 is laminated with the transfer layer 9 of the transfer substrate 1 as necessary for the purpose of improving the peelability between the support 10 and the transfer layer 9. On the side surface. Furthermore, in the first embodiment, the release layer 2 also exhibits the function of improving the moldability of the three-dimensional molding transfer film and improving the durability and chemical resistance of the molded resin product after molding. obtain.

On the other hand, in the second embodiment, the release layer 2 is a surface on the side on which the transfer layer 9 of the transfer substrate 1 is laminated for the purpose of improving the peelability between the support 10 and the transfer layer 9. Provided. Furthermore, in the second embodiment, the release layer 2 exhibits the functions of improving the moldability of the three-dimensional molding transfer film and improving the durability and chemical resistance of the molded resin product after molding. .

In the present invention, the release layer 2 may be a solid release layer covering the entire surface (entirely solid), or may be provided in a part. In general, a solid release layer is preferable in consideration of peelability, moldability, durability of the molded resin product after molding, chemical resistance, and the like.

In the first embodiment, the Martens hardness of the release layer 2 is preferably in the range of 7 to 45 N / mm ² . When the Martens hardness of the release layer 2 is in such a specific range, the moldability of the transfer film for three-dimensional molding is improved, and the durability and chemical resistance are excellent with respect to the resin molded product after molding. Can be given. This mechanism can be considered as follows. That is, when the three-dimensional molding transfer film is laminated with the molding resin layer, high heat pressure is applied to both the support and the transfer layer of the three-dimensional molding transfer film. Is extended. At this time, when the hardness of the release layer is within the above specific range, it is effectively suppressed that the release layer is inappropriately deformed during molding, and accordingly, the transfer layer is inappropriately formed. It is considered that deformation is also suppressed. As a result, the transfer film for three-dimensional molding is not only excellent in moldability, but also the surface properties (durability and chemical resistance) of the resin molded product after the release layer is prevented from being deteriorated and the release layer is peeled off. ) Is considered to have improved.

In the first embodiment, from the viewpoint of effectively improving the moldability of the three-dimensional molding transfer film and imparting further excellent durability and chemical resistance to the molded resin product after molding, the Martens hardness of the release layer 2, preferably 7 ~ 30 N / mm ^2, more preferably about 7 ~ 27N / mm ^2, and more preferably about 10 ~ 25 N / mm ² approximately, particularly preferably 12 ~ 20 N / mm ² or so.

In the second embodiment, the Martens hardness of the release layer 2 is in the range of 7 to 45 N / mm ² . When the Martens hardness of the release layer 2 is in such a specific range, the moldability of the transfer film for three-dimensional molding is improved, and the durability and chemical resistance are excellent with respect to the resin molded product after molding. Can be given. This mechanism can be considered as follows. That is, when the three-dimensional molding transfer film is laminated with the molding resin layer, high heat pressure is applied to both the support and the transfer layer of the three-dimensional molding transfer film. Is extended. At this time, when the hardness of the release layer is within the above specific range, it is effectively suppressed that the release layer is inappropriately deformed during molding, and accordingly, the transfer layer is inappropriately formed. It is considered that deformation is also suppressed. As a result, the transfer film for three-dimensional molding is not only excellent in moldability, but also the surface properties (durability and chemical resistance) of the resin molded product after the release layer is prevented from being deteriorated and the release layer is peeled off. ) Is considered to have improved.

In the second embodiment, from the viewpoint of effectively improving the moldability of the transfer film for three-dimensional molding, and imparting further excellent durability and chemical resistance to the molded resin product after molding, the Martens hardness of the release layer 2, preferably 7 ~ 30 N / mm ^2, more preferably about 10 ~ 25 N / mm ^2, and more preferably about include about 12 ~ 20N / mm ^2.

In the present invention, the method for measuring the Martens hardness of the release layer is as follows.

<Measurement of Martens hardness of release layer>
The Martens hardness is a value measured using a surface film physical property tester (PICODERTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows. In this measurement method, a diamond indenter (Vickers indenter) having a facing angle of 136 ° as shown in FIG. 5A is used in an environment of a temperature of 25 ° C. and a relative humidity of 50%. A diamond indenter is pushed into the release layer, and the hardness is obtained from the indentation load F and the indentation depth h (indentation depth) by the following equation (1). The indentation conditions were as follows. First, a load of 0 to 0.1 mN was applied for 20 seconds to the release layer at room temperature (laboratory environmental temperature) as shown in FIG. 5B, and then 0.1 mN. Is held for 5 seconds, and finally unloading from 0.1 to 0 mN is performed in 20 seconds. For the transfer film for three-dimensional molding, the transfer layer is peeled off at the interface with the release layer using a cellophane tape, and a support having the transfer substrate and the release layer is obtained. Measurement is performed on the surface on the mold layer side.

In the first embodiment, the material constituting the release layer 2 is not particularly limited, but effectively improves the moldability of the three-dimensional molding transfer film, and the molded resin product after molding. From the viewpoint of imparting further excellent durability and chemical resistance, the release layer 2 is preferably composed of a cured product of an ionizing radiation curable resin composition.

In the second embodiment, the material constituting the release layer 2 is not particularly limited as long as the Martens hardness is in the above range, but it effectively improves the moldability of the transfer film for three-dimensional molding. And from the viewpoint of imparting even better durability and chemical resistance to the molded resin product after molding, the release layer 2 is composed of a cured product of an ionizing radiation curable resin composition. Is preferred.

Hereinafter, the ionizing radiation curable resin used for forming the release layer 2 of the present invention 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 crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. And a mixture of at least one of prepolymers, oligomers, monomers, and the like, as appropriate. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require an initiator for photopolymerization, and provides stable curing characteristics. Used for.

As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationic polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) . Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate. The acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. The urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction of a polyether polyol, a polyester polyol or a caprolactone polyol and a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. Among these, as the polyfunctional (meth) acrylate oligomer, polycarbonate (meth) acrylate, urethane (meth) acrylate, and the like are particularly preferable. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

In the first embodiment, the ionizing radiation curable resin composition forming the release layer 2 preferably contains polycarbonate (meth) acrylate.

Further, in the second embodiment, among the above-mentioned ionizing radiation curable resins, the moldability of the three-dimensional molding transfer film is effectively improved, and the resin molded product after molding is more excellent. From the viewpoint of imparting durability and chemical resistance, it is preferable to use polycarbonate (meth) acrylate, and it is particularly preferable to use polycarbonate (meth) acrylate and polyfunctional (meth) acrylate in combination.

Details of the polycarbonate (meth) acrylate are as described in [Protective layer 3] described later.

In the present invention, the polycarbonate (meth) acrylate is preferably used together with the polyfunctional (meth) acrylate in the ionizing radiation curable resin composition of the release layer 2 as well as the protective layer 3 described later. The mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is more preferably polycarbonate (meth) acrylate: polyfunctional (meth) acrylate = 98: 2 to 50:50. When the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is smaller than 98: 2 (that is, the amount of the polycarbonate (meth) acrylate is 98% by mass or less based on the total amount of the two components). The aforementioned durability and chemical resistance are further improved. On the other hand, when the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is larger than 50:50 (that is, the amount of the polycarbonate (meth) acrylate is 50% by mass or more based on the total amount of the two components). ), Three-dimensional formability is further improved. Preferably, the mass ratio of polycarbonate (meth) acrylate to polyfunctional (meth) acrylate is 95: 5 to 60:40.

In the present invention, the details of the polyfunctional (meth) acrylate are as described in [Protective layer 3], and any bifunctional or higher (meth) acrylate may be used, and the number of functional groups is preferably 2 to 6. Degree. The polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability. The polyfunctional (meth) acrylate oligomer and the polyfunctional (meth) acrylate monomer are as described above.

In the second embodiment, the content of the polycarbonate (meth) acrylate in the ionizing radiation curable resin composition forming the release layer 2 is not particularly limited, but the above-described moldability, durability, and chemical resistance are not limited. From the viewpoint of further improving the properties, it is preferably about 98 to 50% by mass, more preferably about 90 to 65% by mass.

In the present invention, when the release layer 2 is formed using an ionizing radiation curable resin, the release layer 2 is formed by, for example, preparing an ionizing radiation curable resin composition, applying it, and crosslinking and curing it. Is done. In addition, the viscosity of an ionizing radiation curable resin composition should just be a viscosity which can form a non-hardened resin layer with the below-mentioned coating system.

In the present invention, the prepared coating solution is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., preferably gravure coating, so as to have a desired thickness. A cured resin layer is formed.

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

In the electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a resin that is easily deteriorated by the electron beam irradiation is used under the release layer 2, the electron beam transmission depth and the mold release are used. The acceleration voltage is selected so that the thicknesses of the layers 2 are substantially equal. When the release layer 2 is cured with an electron beam together with the protective layer 3 described later, the accelerating voltage is set so that the transmission depth of the electron beam and the total thickness of the release layer 2 and the protective layer 3 are substantially equal. Is selected. Thereby, irradiation of the extra electron beam to the layer located under the release layer 2 can be suppressed, and deterioration of each layer due to the excess electron beam can be minimized.

Further, the irradiation dose is an amount that makes the crosslinking density of the release layer 2 a sufficient value, and an amount that makes the Martens hardness within the above range, preferably 60 to 300 kGy (6 to 30 Mrad). 70 to 200 kGy (7 to 20 Mrad) is preferable. By setting the irradiation dose in such a range, the Martens hardness of the release layer 2 can be set to the above range, and the transfer substrate 1 is deteriorated by ionizing radiation transmitted through the release layer 2. Can be suppressed. In addition, the said example is a case where the number of functional groups of polyfunctional (meth) acrylate is set to 2, and an appropriate irradiation dose is required according to the number of functional groups.

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

In the case where ultraviolet rays are used as ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet light 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).

In the present invention, as the thickness of the release layer 2, the moldability of the transfer film for three-dimensional molding is effectively improved, and the durability and chemical resistance are further improved with respect to the molded resin product after molding. Is preferably 5.0 μm or less, more preferably 2.5 μm or less, and even more preferably 2.0 μm or less. The lower limit is preferably 0. 0 in consideration of manufacturability and flatness. About 2 μm may be mentioned.

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

[Protective layer 3]
In the first embodiment, the protective layer 3 is provided on the three-dimensional molding transfer film so as to be positioned on the outermost surface of the resin molded product for the purpose of enhancing the scratch resistance and gloss of the resin molded product. Is a layer. The protective layer 3 is preferably in contact with the release layer 2.

On the other hand, in the second embodiment, the protective layer 3 is positioned on the outermost surface of the resin molded product for the purpose of enhancing the durability, chemical resistance, etc. of the resin molded product, It is a layer provided on a three-dimensional molding transfer film. The protective layer 3 is preferably in contact with the release layer 2.

The first embodiment is characterized in that the Martens hardness of the protective layer 3 is in the range of 6 to 40 N / mm ² . When the Martens hardness of the protective layer 3 is in such a specific range, the moldability of the transfer film for three-dimensional molding is improved, and excellent scratch resistance and high gloss are imparted to the molded resin product after molding. It becomes possible to do. In general, it is known that the refractive index increases as the resin density increases. For example, the formula R _ref = [(n ₁ −n ₂ ) / (n ₁ + n ₂ )] ² (the light beam has a refractive index n _From the surface reflectivity R _ref ) in the case of normal incidence from the material _{1 to} the material having the refractive index n ₂ , it can be seen that the reflectivity increases as the refractive index of the resin increases.

In the first embodiment, the moldability of the transfer film for three-dimensional molding is effectively improved, and further excellent scratch resistance and high gloss are imparted to the molded resin product after molding. and from the viewpoint of enhancing the adhesion between the primer layer, as the Martens hardness of the protective layer 3, preferably 7 ~ 35N / mm ^2, more preferably about 8 ~ 27N / mm ^2, and more preferably about 10 to An example is about 25 N / mm ² . In the present invention, the method for measuring the Martens hardness of the protective layer is as follows.

<Measurement of Martens hardness of protective layer>
First, a three-dimensional molding transfer film to be measured for peel strength, a mold for molding the same, and a resin (resin for forming a molding resin layer) to be laminated on the three-dimensional molding transfer film are prepared. The shape of the mold has a flat portion where the area elongation percentage of the surface of the three-dimensional molding transfer film is substantially 0% when the three-dimensional molding transfer film is molded in the mold. . The mold temperature is set to 60 ° C. As a resin (resin for forming a molding resin layer) to be injected onto a three-dimensional molding transfer film, a resin mixture of ABS resin and polycarbonate resin (for example, CYCOLOY ^™ Resin XCY620) is heated to 265 ° C. and melted. And In addition, a three-dimensional molding transfer film is placed in a mold, preformed so as to conform to the shape in the mold by vacuum molding, and then subjected to injection molding. After the injection molding, the Martens hardness is measured on the outermost protective layer of the resin molded product obtained by removing from the mold and peeling off the support. The Martens hardness is a value measured using a surface film physical property tester (PICODERTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows. In this measurement method, a diamond indenter (Vickers indenter) having a facing angle of 136 ° as shown in FIG. 5A is used in an environment of a temperature of 25 ° C. and a relative humidity of 50%. A diamond indenter is pushed into the protective layer, and the hardness is obtained from the indentation load F and the indentation depth h (indentation depth) by the following equation (1). As shown in FIG. 5 (b), the indentation condition was that a load of 0 to 0.1 mN was first applied to the protective layer at room temperature (laboratory environmental temperature) for 20 seconds, and then 0.1 mN. Hold the load for 5 seconds, and finally unload from 0.1 to 0 mN in 20 seconds.

In the first embodiment, the protective layer 3 is formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate. As will be described later, the protective layer 3 is preferably formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and an acrylic resin.

On the other hand, in the second embodiment, the material constituting the protective layer 3 is not particularly limited, and the protective layer 3 is made of a resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin. Preferably it is. From the viewpoint of effectively improving the moldability of the transfer film for three-dimensional molding and imparting further excellent durability and chemical resistance to the molded resin product after molding, the protective layer 3 is made of ionizing radiation. It is preferable that it is comprised with the hardened | cured material of curable resin composition.

Hereinafter, the battery radiation curable resin used for forming the protective layer of the present invention will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the protective layer 3 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group is present in the molecule. The prepolymer, the oligomer, the monomer, and the like that are appropriately mixed are included. Here, the ionizing radiation is as described in the release layer 2 described above.

The polycarbonate (meth) acrylate used in the present invention is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with (meth) acrylic acid. This (meth) acrylate preferably has two or more functional groups from the viewpoint of crosslinking and curing. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate.

The above polycarbonate (meth) acrylate is obtained, for example, by converting part or all of the hydroxyl groups of polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base, 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Alternatively, 3) a method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst can be used.

The above polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing this polycarbonate polyol is a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component. The diol compound (A) used as a raw material is represented by the general formula HO—R ¹ —OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

Specific examples of the diol compound (A) include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butane. Diol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4- Examples thereof include bis (2-hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in admixture of two or more.

Also, examples of the trihydric or higher polyhydric alcohol (B) include alcohols such as trimethylolpurpan, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, sorbitol. Further, alcohols having a hydroxyl group obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide to the hydroxyl group of these polyhydric alcohols may be used. These polyhydric alcohols may be used alone or in combination of two or more.

The compound (C) serving as the carbonyl component is any compound selected from carbonic acid diester, phosgene, and equivalents thereof. Specific examples thereof include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate, phosgene, and halogenated formates such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Etc. These may be used alone or in admixture of two or more.

The polycarbonate polyol is synthesized by subjecting the above-described diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. . For example, the charged molar ratio of the diol compound (A) to the polyhydric alcohol (B) is preferably in the range of 50:50 to 99: 1, and the diol compound (C) as the carbonyl component ( The charged molar ratio of A) to the polyhydric alcohol (B) is preferably 0.2 to 2 equivalents relative to the hydroxyl groups of the diol compound and polyhydric alcohol.

The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above charge ratio is 3 or more on average in one molecule, preferably 3 to 50, more preferably 3 to 20. Within this range, a necessary amount of (meth) acrylate groups are formed by the esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

The method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.

The molecular weight of the polycarbonate (meth) acrylate used in the present invention is preferably 500 or more, more preferably 1,000 or more, as measured by GPC analysis and converted to standard polystyrene. And more preferably 2,000 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but is preferably 100,000 or less and more preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the standpoint of achieving both scratch resistance and three-dimensional formability, it is more preferably 2,000 or more and 50,000 or less, and particularly preferably 5,000 to 20,000.

In the ionizing radiation curable resin composition, the polycarbonate (meth) acrylate is preferably used together with the polyfunctional (meth) acrylate. The mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is more preferably polycarbonate (meth) acrylate: polyfunctional (meth) acrylate = 98: 2 to 50:50. When the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is smaller than 98: 2 (that is, the amount of the polycarbonate (meth) acrylate is 98% by mass or less based on the total amount of the two components). Further, the aforementioned scratch resistance and gloss are further improved. On the other hand, when the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is larger than 50:50 (that is, the amount of the polycarbonate (meth) acrylate is 50% by mass or more based on the total amount of the two components). ), Three-dimensional formability is further improved. Preferably, the mass ratio of polycarbonate (meth) acrylate to polyfunctional (meth) acrylate is 95: 5 to 60:40.

The polyfunctional (meth) acrylate used in the present invention is not particularly limited as long as it is a bifunctional or higher (meth) acrylate. Here, bifunctional means having two ethylenically unsaturated bonds {(meth) acryloyl group} in the molecule. The number of functional groups is preferably about 2 to 6.

In addition, the polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability.

Examples of the polyfunctional (meth) acrylate oligomer include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers. Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Furthermore, other polyfunctional (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity having (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones (meta-methacrylate) having polysiloxane bonds in the main chain. ) Acrylate oligomers, aminoplast resin (meth) acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in small molecules.

Specific examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified di Cyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane Li (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified tri Methylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone Examples thereof include modified dipentaerythritol hexa (meth) acrylate. The polyfunctional (meth) acrylate oligomer and polyfunctional (meth) acrylate monomer described above may be used alone or in combination of two or more.

In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate, as long as the object of the present invention is not impaired, for the purpose of reducing the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

The content of the polycarbonate (meth) acrylate in the ionizing radiation curable resin composition forming the protective layer 3 is not particularly limited, but from the viewpoint of further improving the moldability, durability, and chemical resistance described above. Is preferably about 98 to 50% by mass, more preferably about 90 to 65% by mass.

<Acrylic resin>
The protective layer 3 is more preferably formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate as an ionizing radiation curable resin and an acrylic resin. Moreover, when using the ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate and an acrylic resin, it is preferable to use with the said polyfunctional (meth) acrylate.

The acrylic resin is not particularly limited. The acrylic resin is preferably a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a copolymer of (meth) acrylic acid ester and other monomers. Polymer, specifically, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate- (Meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer A (meth) acrylic resin made of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as the above is preferably used. Among these, from the viewpoint of improving scratch resistance, methyl poly (meth) acrylate is particularly preferable.

The weight average molecular weight of the acrylic resin is not particularly limited, but from the viewpoint of imparting excellent scratch resistance and high gloss to the resin molded product while effectively enhancing the moldability of the transfer film for three-dimensional molding, Preferably about 10,000 to 150,000, more preferably about 10,000 to 40,000.

In addition, the weight average molecular weight of the acrylic resin in this specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

In addition, as the glass transition temperature (Tg) of the acrylic resin, from the viewpoint of imparting excellent scratch resistance and high gloss to the resin molded product while effectively enhancing the moldability of the transfer film for three-dimensional molding, The temperature is preferably about 40 to 160 ° C, more preferably about 80 to 120 ° C.

In addition, the glass transition temperature (Tg) of the acrylic resin in this specification is a value measured with a differential scanning calorimeter (DSC).

The content of the acrylic resin in the ionizing radiation curable resin composition forming the protective layer 3 is not particularly limited, but it is effective for the resin molded product while effectively improving the moldability of the three-dimensional molding transfer film. From the viewpoint of imparting excellent scratch resistance and high gloss, it is preferably 25 parts by mass or less, more preferably 0.5 to 25 parts per 100 parts by mass of the solid content other than the acrylic resin in the ionizing radiation curable resin composition. About 2 parts by mass, more preferably about 2 to 8 parts by mass is mentioned.

<Curing agent>
In the present invention, the ionizing radiation curable resin composition forming the protective layer 3 may further contain a curing agent as necessary. By including the curing agent, the scratch resistance and gloss of the protective layer 3 can be further enhanced.

Although it does not restrict | limit especially as a hardening | curing agent, Preferably an isocyanate compound is mentioned. Although it will not restrict | limit especially if it is a compound which has an isocyanate group as an isocyanate compound, Preferably the polyfunctional isocyanate compound which has 2 or more of isocyanate groups is mentioned. Examples of the polyfunctional isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, 4,4-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate ( And polyisocyanates such as aliphatic (or alicyclic) isocyanates such as HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Further, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers, etc., blocked isocyanate compounds, and the like are also included. An isocyanate compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the curing agent in the ionizing radiation curable resin composition forming the protective layer 3 is not particularly limited, but is preferably ionizing radiation curable from the viewpoint of further improving the three-dimensional formability and scratch resistance. The amount is about 0.1 to 20 parts by mass, more preferably about 1 to 10 parts by mass, and still more preferably about 1 to 7 parts by mass with respect to 100 parts by mass of the solid content other than the curing agent in the resin composition.

Various additives can be blended in the ionizing radiation curable resin composition forming the protective layer 3 according to desired physical properties to be provided in the protective layer 3. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

The thickness of the protective layer 3 after curing is not particularly limited, and examples thereof include 1 to 1000 μm, preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 1 to 30 μm. When the thickness within such a range is satisfied, sufficient physical properties as a protective layer such as durability and chemical resistance can be obtained, and since it is possible to uniformly irradiate ionizing radiation, it can be uniformly cured. It becomes possible and it becomes economically advantageous. Furthermore, since the three-dimensional formability of the transfer film for three-dimensional molding is further improved when the thickness of the protective layer 3 after curing satisfies the above range, it is highly capable of following complicated three-dimensional shapes such as automotive interior applications. Sex can be obtained. As described above, the three-dimensional molding transfer film of the present invention can obtain a sufficiently high three-dimensional moldability even when the thickness of the protective layer 3 is larger than that of the conventional one. It is also useful as a transfer film for three-dimensional molding of a member that requires a high temperature, such as a vehicle exterior part.

The protective layer 3 is formed by preparing an ionizing radiation curable resin composition, applying it, and crosslinking and curing. In addition, the viscosity of ionizing radiation-curable resin composition should just be a viscosity which can form a non-hardened resin layer on the surface of the mold release layer 2, for example with the below-mentioned coating system.

In the present invention, the prepared coating solution is formed on the surface of the transfer substrate 1 or the release layer 2 so as to have the above thickness, such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. Is applied by a known method, preferably gravure coating, to form an uncured resin layer.

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

In the electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the protective layer 3, the electron beam transmission depth and the protective layer 3 are increased. The acceleration voltage is selected so that the thicknesses of the two are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the protective layer 3 can be suppressed, and deterioration of each layer due to the excess electron beam can be minimized.

Further, the irradiation dose is an amount such that the crosslink density of the protective layer 3 becomes a sufficient value, and is preferably 50 to 300 kGy (5 to 30 Mrad), more preferably 50 to 200 kGy (5 to 20 Mrad). In the first embodiment, in particular, by setting the irradiation dose in such a range, the Martens hardness of the protective layer 3 can be set to the above range, and the ionizing radiation transmitted through the protective layer 3 is used. Deterioration of the transfer substrate 1 and the release layer 2 can be suppressed.

By adding various additives to the protective layer 3, a hard coat function, an antifogging coat function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, etc. You may perform the process which provides this function.

[Primer layer 4]
In the present invention, the primer layer 4 is a layer provided as necessary for the purpose of improving the adhesion between the protective layer 3 and the layer located below (the side opposite to the support 10). The primer layer 4 can be formed of a primer layer forming resin composition.

The resin used for the primer layer-forming resin composition is not particularly limited. For example, polyol and / or cured product thereof, urethane resin, acrylic resin, (meth) acryl-urethane copolymer resin, polyester resin, butyral resin Etc. Among these resins, a polyol and / or a cured product thereof, a urethane resin, an acrylic resin, and a (meth) acryl-urethane copolymer resin are preferable. These resins may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, the primer layer 4 is preferably formed of a resin composition containing a polyol and a urethane resin. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like, preferably acrylic polyol is used. Can be mentioned.

When a polyol and a urethane resin are used for forming the primer layer 4, the mass ratio (polyol: urethane resin) is preferably about 5: 5 to 9.5: 0.5, more preferably 7: 3. About 9: 1. When the crosslinking density of the protective layer 3 is high, it is necessary to adjust the adhesion by increasing the ratio of the urethane resin.

Examples of cured polyols include urethane resins. As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent) can be used.

Specific examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule; aromatic isocyanate such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogen Aliphatic (or alicyclic) isocyanates such as added diphenylmethane diisocyanate can be mentioned. When using isocyanate as a curing agent, the content of isocyanate in the primer layer-forming resin composition is not particularly limited, but from the viewpoint of adhesion, and from the viewpoint of printing suitability when laminating a decorative layer 5 described later, The amount is preferably 3 to 45 parts by weight and more preferably 3 to 25 parts by weight with respect to 100 parts by weight of the polyol.

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

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

The (meth) acryl-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-described various isocyanates are used. The ratio of the acrylic to urethane ratio in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acrylic / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 / 2 to 2/8.

The thickness of the primer layer 4 is not particularly limited, but is about 0.1 to 10 μm, preferably about 1 to 10 μm (that is, the coating amount is about 0.1 to 10 g / m ² , preferably 1 to 10 g / m ^2). m ² ). When the primer layer 4 satisfies such a thickness, the weather resistance of the three-dimensional molding transfer film can be further improved, and cracking, breakage, whitening, and the like of the protective layer 3 can be effectively suppressed.

In the composition forming the primer layer 4, various additives can be blended according to desired physical properties to be provided. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant, and a matting agent. These additives can be appropriately selected from commonly used ones. Examples of the matting agent include silica particles and aluminum hydroxide particles. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

Primer layer 4 is a primer layer forming resin composition, gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, It is formed by a normal coating method such as wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or the like, or transfer coating. Here, the transfer coating method is a method of forming a coating film of a primer layer or an adhesive layer on a thin sheet (film substrate) and then coating the surface of the target layer in the transfer film for three-dimensional molding. .

The primer layer 4 may be formed on the protective layer 3 after curing. Moreover, after forming the primer layer 4 by laminating a layer made of the primer layer forming composition on the ionizing radiation curable resin composition layer forming the protective layer 3, the layer made of the ionizing radiation curable resin is formed. The protective layer 3 may be formed by irradiating with ionizing radiation and curing the layer made of ionizing radiation curable resin.

[Decoration layer 5]
In the present invention, the decorative layer 5 is a layer provided as necessary in order to impart decorative properties to the resin molded product. The decoration layer 5 is usually composed of a picture layer and / or a concealment layer. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters, and the concealing layer is usually a solid layer and is provided for concealing the coloring of the molded resin or the like. Is a layer. The concealing layer may be provided inside the picture layer to enhance the picture of the picture layer, or the decoration 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, letters, and the like.

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

The colorant of the printing ink used for forming the decorative layer 5 is not particularly limited, but for example, metals such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass, alloys, Or metallic pigments made of scale-like foil powder of metal compounds; 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 pigment made of foil powder such as lead carbonate; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide; white inorganics such as titanium dioxide, zinc white, antimony trioxide Pigment: Inorganic such as zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black Fee; isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, and organic pigments such as aniline black (including dyes) and the like. These colorants may be used alone or in combination of two or more.

Further, the binder resin of the printing ink used for forming the decorative layer 5 is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride- Examples thereof include vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fibrin derivatives, rubber resins, and the like. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

Moreover, the solvent or dispersion medium of the printing ink used for forming the decorative layer 5 is not particularly limited. For example, petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; Ester 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 solvents; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; dichloromethane Tan, carbon tetrachloride, trichlorethylene, chlorinated organic solvents such as tetrachlorethylene; water and the like. These solvents or dispersion media may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition, the printing ink used for forming the decorative layer 5 includes an anti-settling agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant, and the like as necessary. It may be included.

The decorative layer 5 can be formed on an adjacent layer such as the 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 a pattern layer and a concealing layer, one layer may be stacked and dried, and then the other layer may be stacked and dried.

The thickness of the decorative layer 5 is not particularly limited, but may be 1 to 40 μm, preferably 3 to 30 μm, for example.

The decoration 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 these. 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-described metal. Moreover, in order to improve adhesiveness with an adjacent layer, you may provide the primer layer using well-known resin in the surface and back surface of a metal thin film layer.

[Adhesive layer 6]
In the present invention, the adhesive layer 6 is used for the purpose of improving the adhesion between the transfer film for three-dimensional molding and the molded resin layer 8, and the like (on the molded resin layer 8 side) such as the decorative layer 5 and the transparent resin layer 7. ) If necessary. 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 resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, and the like. . A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the thermosetting resin include a urethane resin and an epoxy resin. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

Although the adhesive layer 6 is not necessarily a necessary layer, the transfer film for three-dimensional molding of the present invention is applied to a decorating method by sticking onto a resin molded body prepared in advance, such as a vacuum pressing method described later. Is preferably provided. When used in the vacuum pressure bonding 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, but may be 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 three-dimensional molding transfer film of the present invention, a transparent resin layer 7 may be provided as 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 three-dimensional molding transfer film of the present invention does not have the decorative layer 5, the three-dimensional structure of the present invention. It is particularly useful to provide the molding transfer film when it is used for the production of a resin molded product requiring transparency. The transparent resin layer 7 is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. Examples of the resin component that forms the transparent resin layer 7 include the binder resin exemplified in the decorative layer 5.

As necessary, the transparent resin layer 7 may include 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. Various additives such as rubber (for example, rubber) may be included.

The transparent resin layer 7 can be formed by a known printing method such as gravure printing, flexographic printing, silk screen printing, or 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.

[Manufacture of three-dimensional molding transfer film]
The transfer film for three-dimensional molding of the first embodiment can be manufactured by a manufacturing method including the following steps, for example.
A step of laminating a layer made of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate on a substrate for transfer. The ionizing radiation curable resin composition is irradiated with ionizing radiation to form the ionizing radiation curable resin composition. A step of curing a layer made of a material to form a protective layer having a Martens hardness of 6 to 40 N / mm ² on the transfer substrate.

Moreover, when the three-dimensional shaping | molding transfer film of a 1st embodiment has the mold release layer 2, it can manufacture by the manufacturing method provided with the following processes, for example.
Step of forming release layer forming coating on transfer substrate 1 Step of forming protective layer forming coating on release layer forming coating Release layer forming coating and protection A step of irradiating the layer forming coating film with ionizing radiation to form a release layer in which the release layer forming coating film is cured and a protective layer in which the protective layer forming coating film is cured. At this time, Martens hardness of the protective layer 6 ~ 40N / mm ^2, preferably adjusted to 7 ~ 35N / mm ^2, further Martens hardness of the release layer is 7 ~ 45N / mm ² It is preferable to adjust so that.

Moreover, the transfer film for three-dimensional shaping | molding of a 2nd embodiment can be manufactured with a manufacturing method provided with the following processes, for example.
Step of forming release layer forming coating film on transfer substrate 1 Irradiating the release layer forming coating film with ionizing radiation forms a release layer in which the release layer forming coating film is cured. Step (At this time, the mold release layer is adjusted so that the hardness is in the range of 7 to 45 N / mm ² )
A step of laminating a transfer layer on the release layer.

Moreover, when the three-dimensional shaping | molding transfer film of a 2nd embodiment has the protective layer 3, it can manufacture by the manufacturing method provided with the following processes, for example.
Step of forming release layer forming coating on transfer substrate 1 Step of forming protective layer forming coating on release layer forming coating Release layer forming coating and protection A step of irradiating the layer forming coating film with ionizing radiation to form a release layer in which the release layer forming coating film is cured and a protective layer in which the protective layer forming coating film is cured (in this case, the release layer) Is adjusted to be in the range of 7 to 45 N / mm ² ).

2. Resin molded product and method for producing the same The resin molded product of the present invention is formed by integrating the three-dimensional molding transfer film of the present invention and a molded resin. Specifically, in the first embodiment, by laminating the molding resin layer 8 on the side opposite to the support 10 of the three-dimensional molding transfer film, at least the molding resin layer 8, the protective layer 3, A resin molded product with a support in which the support 10 is laminated in this order is obtained (see, for example, FIG. 3). Next, by peeling the support 10 from the resin molded product with the support, the resin molded product of the present invention in which at least the molded resin layer 8 and the protective layer 3 are laminated in this order is obtained (see, for example, FIG. 4). ). In the second embodiment, the molding resin layer 8, the transfer layer 9, the support 10, and the molding resin layer 8 are laminated on the side opposite to the support 10 of the three-dimensional molding transfer film. Are laminated in this order to obtain a resin molded product with a support (see, for example, FIG. 3). Next, the support 10 is peeled from the resin molded product with the support to obtain the resin molded product of the present invention in which at least the molded resin layer 8 and the transfer layer 9 are laminated (see, for example, FIG. 4). As shown in FIG. 4, the resin molded product of the first embodiment is further provided with at least one layer such as the decorative layer 5, the primer layer 4, the adhesive layer 6, and the transparent resin layer 7 as necessary. In the resin molded product of the second embodiment, if necessary, at least one layer such as the protective layer 3, the decorative layer 5, the primer layer 4, the adhesive layer 6, and the transparent resin layer 7 is included. Further, it may be provided.

The resin molded product of the first embodiment can be manufactured by a manufacturing method including the following steps.
A step of laminating a molding resin layer on the opposite side of the transfer substrate of the three-dimensional molding transfer film;
Step of peeling the transfer substrate from the protective layer

Moreover, the resin molded product of the second embodiment can be manufactured by a manufacturing method including the following steps.
A step of laminating a molding resin layer on the opposite side of the three-dimensional molding transfer film support
Step of peeling the support from the transfer layer

In the first embodiment, when the three-dimensional molding transfer film is applied to, for example, the injection molding simultaneous transfer decorating method, as a method for producing a resin molded product of the first embodiment, for example, the following steps (1) to The method containing (5) is mentioned.
(1) First, the protective layer side (opposite to the support) of the transfer three-dimensional transfer film is directed into the mold, and the three-dimensional transfer film is transferred from the protective layer side by a hot platen. A step of heating (it is a step to be performed if necessary, and may not have the step),
(2) A step of pre-molding (vacuum molding) the three-dimensional molding transfer film along the inner shape of the mold and closely contacting the inner surface of the mold to clamp the mold;
(3) A step of injecting resin into the mold,
(4) A step of taking out a 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 protective layer of the resin molded product.

On the other hand, in the second embodiment, when the transfer film for three-dimensional molding is applied to, for example, the injection molding simultaneous transfer decoration method, as a method for producing a resin molded product of the second embodiment, for example, the following steps (1 ) To (5).
(1) First, optionally, the transfer layer side of the transfer three-dimensional molding transfer film (the side opposite to the support) is directed into the mold, and the three-dimensional molding transfer film is transferred from the transfer layer side by a hot platen. A step of heating (it is a step to be performed if necessary, and may not have the step),
(2) A step of pre-molding (vacuum molding) the three-dimensional molding transfer film along the inner shape of the mold and closely contacting the inner surface of the mold to clamp the mold;
(3) A step of injecting resin into the mold,
(4) A step of taking out a 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 transfer layer of the resin molded product.

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

In both 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 into a fluid state by heating and melting, and when the molding resin is a thermosetting resin, the uncured liquid composition is injected at room temperature or appropriately heated and injected in a fluid state. Then, it is cooled and solidified. As a result, the three-dimensional molding transfer film is integrally bonded to the formed resin molded body to form 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.

After the resin molded product with the support thus obtained is cooled in the step (4) and taken out of the mold, the support 10 is peeled off from the protective layer 3 in the step (5) in the first embodiment. Thus, a resin molded product is obtained. In the second embodiment, the resin molded product is obtained by peeling the support 10 from the transfer layer 9 in the step (5). Further, in the first embodiment, the step of peeling the support 10 from the protective layer 3 may be performed simultaneously with the step of taking out the decorative resin molded product from the mold, and in the second embodiment, the support The step of peeling the body 10 from the transfer layer 9 may be performed simultaneously with the step of taking out the resin molded product from the mold. That is, in the first embodiment and the second embodiment, step (5) may be included in step (4).

Furthermore, the resin molded product can be manufactured by a vacuum pressure bonding method. In the vacuum pressure bonding method, first, the three-dimensional molding transfer film and the resin molded body of the present invention are three-dimensionally molded in a vacuum pressure bonding machine including a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. Inside the vacuum press so that the transfer film for the first vacuum chamber is on the side of the first vacuum chamber, the resin molding is on the side of the second vacuum chamber, and the side on which the molding resin layer 8 of the three-dimensional molding transfer film is laminated faces the resin molding And set the two vacuum chambers in a vacuum state. The resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the three-dimensional molding transfer film using an elevator, and the pressure difference between the two vacuum chambers is used to form the three-dimensional molding transfer film. It sticks to the surface of the resin molding while stretching. Finally, the two vacuum chambers are opened to atmospheric pressure, the support 10 is peeled off, and an excess portion of the three-dimensional molding transfer film is trimmed as necessary to obtain the resin molded product of the present invention. it can.

In the vacuum pressure bonding method, before the step of pressing the molded body against the three-dimensional molding transfer film, the three-dimensional molding transfer film is heated in order to soften the three-dimensional molding transfer film and improve the moldability. It is preferable to provide a process. The vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the three-dimensional molding transfer film, the thickness of the three-dimensional molding transfer film, and the like. If 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 molded resin layer 8 may be formed by selecting a resin according to the application. The molding resin for forming the molding resin layer 8 may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

Further, examples of the thermosetting resin include urethane resin and epoxy resin. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

In the resin molded product with a support, since the support 10 serves as a protective sheet for the resin molded product, it is stored as it is without being peeled after the production of the resin molded product with a support and is supported at the time of use. The body 10 may be peeled off. By using in this manner, it is possible to prevent the resin molded product from being damaged due to rubbing during transportation.

Since the resin molded product of the present invention has excellent scratch resistance and chemical resistance, for example, interior materials or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; architectures such as walls, floors, and ceilings It can be used as an interior material of a product; a housing of a household electric appliance such as a television receiver or an air conditioner;

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 1A to 6A and Comparative Examples 1A to 2A)
[Manufacture of three-dimensional molding transfer film]
As a transfer substrate, a polyethylene terephthalate film (thickness 50 μm) having an easy-adhesive layer formed on one surface was used. Electron radiation curable resin composition comprising 85% by mass of bifunctional polycarbonate acrylate (weight average molecular weight: 8,000) and 15% by mass of pentaerythritol triacrylate (PETA) on the surface of the easy adhesive layer of the polyethylene terephthalate film ( (Including UVA 2.2%, HALS 0.6%) was printed by gravure printing to form a release layer-forming coating film (thickness 1.5 μm). Next, an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 7 Mrad was applied from above the coating film to cure the release layer forming coating film to form a release layer.

Next, in Examples 1A to 6A and Comparative Example 1A, an ionizing radiation curable resin composition described later was applied onto the release layer with a bar coder so that the thickness after curing would be the thickness shown in Table 1A. Then, a protective layer-forming coating film was formed. The content of pentaerythritol triacrylate (PETA) contained in the electron radiation curable resin composition used for forming the protective layer (the balance is polycarbonate acrylate and acrylic polymer) is as shown in Table 1A. On the other hand, in Comparative Example 2A, a resin composition (UVA2) containing polymethyl methacrylate (PMMA, weight average molecular weight 20,000, Tg 105 ° C.) and PETA in a mass ratio of PETA / PMMA = 4/6 on the release layer. .2% and HALS 0.6%) were coated with a bar coder so that the thickness after curing was the thickness shown in Table 1A to form a protective layer. Next, an electron beam having an acceleration voltage of 165 kV and an irradiation dose (unit: Mrad) described in Table 1A was irradiated on the coating film to cure the coating film for forming the protective layer, thereby forming a protective layer.

On this protective layer, a primer layer-forming resin composition having the composition shown in Table 1A was applied by gravure printing to form a primer layer (thickness: 1.5 μm). In addition, a decorative layer is formed on the primer layer containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin (acrylic resin 50 mass%, vinyl chloride-vinyl acetate copolymer resin 50 mass%). A black solid decorative layer (thickness 2 μm) was formed by gravure printing using the black ink composition for printing. Furthermore, by using a resin composition for forming an adhesive layer containing an acrylic resin (softening temperature: 125 ° C.) on the decorative layer, an adhesive layer (1.5 μm) is formed by gravure printing, thereby transferring a transfer substrate. Each three-dimensional molding transfer film in which the material / release layer / protective layer / primer layer / decoration layer / adhesive layer were laminated in this order was produced.

[Ingredients used to form protective layer]
Tetrafunctional polycarbonate acrylate (weight average molecular weight: 10,000)
Pentaerythritol triacrylate (PETA)
Acrylic polymer (acrylic resin, copolymer of methyl methacrylate and methacrylic acid, Tg 105 ° C., weight average molecular weight: about 20,000) 2.5% by weight

<Measurement of Martens hardness of protective layer>
First, a three-dimensional molding transfer film to be measured for peel strength, a mold for molding the same, and a resin (resin for forming a molding resin layer) to be laminated on the three-dimensional molding transfer film were prepared. The shape of the mold is such that when the three-dimensional molding transfer film is molded in the mold, the mold has a flat portion in which the area elongation percentage of the surface of the three-dimensional molding transfer film is substantially 0%. . The mold temperature was set to 60 ° C. As a resin (resin for forming a molding resin layer) to be injected onto the three-dimensional molding transfer film, a mixed resin of ABS resin and polycarbonate resin (CYCOLOY ^™ Resin XCY620) was heated to 265 ° C. and melted. . Further, the transfer film for three-dimensional molding was put in a mold, and pre-molded so as to conform to the shape in the mold by vacuum molding, and then injection-molded. After the injection molding, the Martens hardness was measured on the outermost protective layer of the resin molded product obtained by removing from the mold and peeling the support. The Martens hardness is a value measured using a surface film physical property tester (PICODERTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows. In this measurement method, a diamond indenter (Vickers indenter) having a facing angle of 136 ° as shown in FIG. 5A is used in an environment of a temperature of 25 ° C. and a relative humidity of 50%. A diamond indenter was pushed into the protective layer, and the hardness was determined from the indentation load F and the indentation depth h (indentation depth) by the following formula (1). The indentation condition was that a load of 0 to 0.1 mN was first applied for 20 seconds at room temperature (laboratory environment temperature) to the protective layer or the release layer as shown in FIG. The load was maintained at a load of 0.1 mN for 5 seconds, and finally unloading from 0.1 to 0 mN was performed in 20 seconds. The Martens hardness of the release layer was measured in the same manner as in Examples 1B to 7B and Comparative Examples 1B to 2B described later. The results are shown in Table 1A.

<Manufacture of resin molded products>
Each of the three-dimensional molding transfer films obtained above was placed in a mold, preformed so as to conform to the shape in the mold by vacuum molding, and clamped (maximum draw ratio 100%). Thereafter, 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 taken out from the mold, and at the same time, the support (transfer base material and release layer) is removed. A resin molded product was obtained by peeling and removing.

<Evaluation of formability>
In the production of the above resin molded product, the followability of the three-dimensional molding transfer film to the mold was visually evaluated according to the following criteria. The results are shown in Table 1A.
A: Appearance defects such as cracking and whitening were not observed in the appearance of the molded product. (Maximum elongation 100%)
B: Although fine cracks, whitening and the like are observed in the maximum extension portion, appearance defects such as cracks and whitening were not observed in the shallow drawn shape (elongation 50%).
C: Appearance defects such as cracking and whitening were observed in the shallow drawn shape (elongation 50%).

<Evaluation of scratch resistance>
With the support peeled off from each of the three-dimensional molding transfer films obtained above and the protective layer exposed, the surface of the protective layer was measured using a Martindale abrasion tester and the planar size was 215.9 mm x 279 mm. Abrasive paper 281Q WOD Schleifpapier (manufactured by 3M) was affixed to the tip of the test jig and rubbed 100 times with a load of 800 gf, and the rate of decrease in 20 ° gloss value after the test was evaluated according to the following criteria. The results are shown in Table 1A. Those with a small decrease in the gloss value had few scratches, and the scratches disappeared after a while. This indicates that the protective layer 3 has self-healing properties.
A: Less than 5% after 5 minutes of test. And recovered to less than 1% after 30 minutes of testing.
B: 5% or more and less than 30% after 5 minutes of the test. And recovered to less than 5% after 30 minutes of testing.
C: 30% or more after 5 minutes of the test and 30% or more after 30 minutes of the test.

<Evaluation of gloss>
The gloss was evaluated visually according to the following criteria in the state where the support was peeled off from each of the three-dimensional molding transfer films obtained above and the protective layer was exposed. The results are shown in Table 1A.
A: Glittering and dazzling when reflected from a fluorescent lamp.
B: Bright when reflected by a fluorescent lamp, but not so bright.
C: When a fluorescent lamp is reflected, it feels dim.

As shown in Table 1A, the three-dimensional molding transfer films of Examples 1A to 6A, in which the Martens hardness of the protective layer is in the range of 6 to 40 N / mm ² , are excellent in moldability and are scratch resistant. Excellent blackness and high-gloss black design (piano black).

(Examples 1B-7B and Comparative Examples 1B-2B)
[Manufacture of three-dimensional molding transfer film]
As a transfer substrate, a polyethylene terephthalate film (thickness 50 μm) having an easy-adhesive layer formed on one surface was used. For release layer formation, an electron radiation curable resin composition containing an electron radiation curable resin and pentaerythritol triacrylate (PETA), which will be described later, is printed on the surface of the polyethylene terephthalate film adhesive layer by gravure printing. A coating film was formed. The number of functional groups of the EB resin (the number of functional groups of the polycarbonate acrylate), the amount of PETA added (the balance is polycarbonate acrylate), and the thickness of the release layer are as shown in Table 1B. Next, an electron beam having an acceleration voltage of 165 kV and an irradiation dose (unit: Mrad) described in Table 1B was irradiated on the coating film to cure the release layer forming coating film to form a release layer. In Comparative Example 2B, a coating liquid containing an acrylic melamine resin as a main component was printed by gravure printing and thermally cured at 150 ° C. to form a release layer.

Next, an ionizing radiation curable resin composition described later was applied on the release layer with a bar coder so that the thickness after curing was 4 μm, thereby forming a protective layer-forming coating film. Next, an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 5 MRad was irradiated on the protective layer-forming coating film to cure the protective layer-forming coating film, thereby forming a protective layer.

On the protective layer, a primer layer-forming resin composition containing acrylic polyol was applied by gravure printing to form a primer layer (thickness 1.5 μm). In addition, a decorative layer is formed on the primer layer containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin (acrylic resin 50 mass%, vinyl chloride-vinyl acetate copolymer resin 50 mass%). A hairline decorative layer (thickness 5 μm) was formed by gravure printing using the black ink composition for printing. Further, the adhesive layer (thickness: 1.5 μm) is formed on the decorative layer by gravure printing using a resin composition for forming an adhesive layer containing an acrylic resin (softening temperature: 125 ° C.). Each three-dimensional forming transfer film in which a base material for the substrate / release layer / protective layer / primer layer / decoration layer / adhesive layer was laminated in order was produced.

[Components used to form release layer]
Bifunctional polycarbonate acrylate (weight average molecular weight: 8,000)
Tetrafunctional polycarbonate acrylate (weight average molecular weight: 8,000)
Pentaerythritol triacrylate (PETA)

[Ingredients used to form protective layer]
95% by mass of tetrafunctional polycarbonate acrylate (weight average molecular weight: 10,000)
Acrylic polymer (acrylic resin, copolymer of methyl methacrylate and methacrylic acid, Tg 105 ° C., weight average molecular weight: about 20,000) 2.5% by mass, other additives 2.5% by mass

<Measurement of Martens hardness of release layer>
The Martens hardness is a value measured using a surface film physical property tester (PICODERTOR HM-500, manufactured by Fisher Instruments Co., Ltd.), and a specific measurement method is as follows. In this measurement method, a diamond indenter (Vickers indenter) having a facing angle of 136 ° as shown in FIG. 5A is used in an environment of a temperature of 25 ° C. and a relative humidity of 50%. A diamond indenter was pushed into the release layer, and the hardness was determined from the indentation load F and the indentation depth h (indentation depth) by the following formula (1). The indentation conditions were as follows. First, a load of 0 to 0.1 mN was applied for 20 seconds to the release layer at room temperature (laboratory environmental temperature) as shown in FIG. 5B, and then 0.1 mN. Was held for 5 seconds, and finally unloading from 0.1 to 0 mN was performed for 20 seconds. For a three-dimensional molded film, the transfer layer is peeled off at the interface with the release layer using a cellophane tape, and a support having a transfer substrate and a release layer is obtained. The release layer of this support Measurements were made on the side surface. The Martens hardness of the release layer was measured in the same manner as in Examples 1B to 7B and Comparative Examples 1B to 2B described later. The results are shown in Table 1B.

<Evaluation of formability>
The support with a release layer was peeled off from each of the above three-dimensional molding transfer films, and the support was cut into a strip having a length of 150 mm and a width of 1 inch to prepare a sample for evaluation with only a colored layer. The sample was subjected to a tensile test using a tensile tester with an initial tensile chuck distance of 100 mm and a tensile speed of 100 mm / min. Measurement is performed by setting a film sample in a thermostat set at a temperature of 100 ° C in advance, performing a tensile test after preheating for 60 seconds, and measuring the amount of elongation (breaking elongation) until the release layer cracks. did. Three samples were measured for each level, and the average value of the three samples was taken as the breaking elongation. The results are shown in Table 1B.
A: Elongation at break 80% or more. A level that can be used with a die generally called deep drawing.
B: The breaking elongation is 50% or more and less than 80%. A level that does not cause a problem in molding.
C: Fracture elongation is less than 50%. A level that is problematic in many molds.

<Manufacture of resin molded products>
Each of the three-dimensional molding transfer films obtained above was placed in a mold, pre-formed by vacuum molding so as to conform to the shape in the mold, and clamped (maximum draw ratio 50%). Thereafter, 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 taken out from the mold, and at the same time, the support (transfer base material and release layer) is removed. A resin molded product was obtained by peeling and removing.

<Durability evaluation>
Each resin molded product obtained above was stored for 72 hours in a humid heat environment at a temperature of 90 ° C. and a relative humidity of 95%, and the durability (wet heat resistance) was evaluated visually according to the following criteria. The results are shown in Table 1B.
A: There is no gloss change of a molded product. The 60 ° gloss is 95% or more compared to before the test.
B ⁺ : Whitening is not observed in the molded product. 60 ° gloss is 90% or more and less than 95% compared to before testing.
B: Slight whitening is observed in the molded product, but there is no practical problem. 60 ° gloss is 90% or more and less than 95% compared to before testing.
C: Whitening was observed in the molded product, and the 60 ° gloss was less than 90% compared to before the test.

<Evaluation of chemical resistance>
On the surface of the protective layer of each resin molded product obtained above, one drop of 95% ethanol aqueous solution was dropped with a dropper at room temperature (25 ° C.) and left as it was for 10 minutes. Next, the molded product was dried in an oven at 60 degrees for 30 minutes, and changes in the surface of the protective layer were observed visually and with a gloss meter, and chemical resistance was evaluated according to the following criteria. The results are shown in Table 1B.
A: There is no gloss change of a molded product. The 60 ° gloss is 95% or more compared to before the test.
B ⁺ : Whitening is not observed in the molded product. 60 ° gloss is 90% or more and less than 95% compared to before testing.
B: Slight whitening is observed in the molded product, but there is no practical problem. 60 ° gloss is 90% or more and less than 95% compared to before testing.
C: Whitening was observed in the molded product, and the 60 ° gloss was less than 90% compared to before the test.

In Table 1B, EB resin means ionizing radiation curable resin.

As shown in Table 1B, the three-dimensional molding transfer films of Examples 1B to 7B in which the Martens hardness of the release layer is in the range of 7 to 45 N / mm ² are excellent in moldability. The resin molded product after molding was also excellent in durability and chemical resistance.

DESCRIPTION OF SYMBOLS 1 Transfer base material 2 Release layer 3 Protective layer 4 Primer layer 5 Decoration layer 6 Adhesive layer 7 Transparent resin layer 8 Molded resin layer 9 Transfer layer 10 Support body

Claims

A transfer film for three-dimensional molding having at least a protective layer on a transfer substrate,
The protective layer is formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate,
A transfer film for three-dimensional molding, wherein the protective layer has a Martens hardness of 6 N / mm 2 or more and 40 N / mm 2 or less.
The transfer film for three-dimensional molding according to claim 1, comprising at least the protective layer and the primer layer in this order on the transfer substrate.
The transfer film for three-dimensional molding according to claim 2, wherein the primer layer contains a polyol and / or a cured product thereof.
The transfer film for three-dimensional molding according to claim 3, wherein the polyol contains an acrylic polyol.
The tertiary according to any one of claims 1 to 4, comprising at least one selected from the group consisting of a decorative layer, an adhesive layer, and a transparent resin layer on the opposite side of the protective layer from the transfer substrate. Original transfer film.
Laminating a layer made of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate on a transfer substrate;
The ionizing radiation curable resin composition is irradiated with ionizing radiation, the layer made of the ionizing radiation curable resin composition is cured, and the Martens hardness is 6 N / mm 2 or more on the transfer substrate. Forming a protective layer of 40 N / mm 2 or less;
A method for producing a transfer film for three-dimensional molding, comprising:
Laminating a molding resin layer on the protective layer side of the transfer film for three-dimensional molding according to any one of claims 1 to 5,
Peeling the substrate for transfer from the protective layer;
A method for producing a resin molded product.
A transfer film for three-dimensional molding having a transfer layer on the release layer of the support having at least a transfer substrate and a release layer,
A transfer film for three-dimensional molding, wherein the release layer has a Martens hardness of 7 N / mm 2 or more and 45 N / mm 2 or less.
The transfer film for three-dimensional molding according to claim 8, wherein the release layer is composed of a cured product of an ionizing radiation curable resin composition.
The transfer film for three-dimensional molding according to claim 8 or 9, wherein the ionizing radiation curable resin composition of the release layer contains polycarbonate (meth) acrylate and polyfunctional (meth) acrylate.
The transfer film for three-dimensional molding according to any one of claims 8 to 10, wherein the release layer has a thickness of 2.0 µm or less.
The transfer layer has a protective layer;
The transfer film for three-dimensional molding according to any one of claims 8 to 11, wherein the protective layer is in contact with the release layer.
The transfer film for three-dimensional molding according to claim 12, wherein the protective layer is composed of a cured product of an ionizing radiation curable resin composition.
The transfer film for three-dimensional molding according to claim 12 or 13, wherein the ionizing radiation curable resin composition of the protective layer contains polycarbonate (meth) acrylate.
15. The transfer film for three-dimensional molding according to claim 8, wherein the transfer layer has at least one selected from the group consisting of a decorative layer, an adhesive layer, and a transparent resin layer.
Laminating a molding resin layer on the transfer layer side of the transfer film for three-dimensional molding according to any one of claims 8 to 15,
Peeling the support from the transfer layer;
A method for producing a resin molded product.