JP7355099B2 - Transfer film for three-dimensional molding and method for manufacturing resin molded products - Google Patents

Description

The present invention relates to a transfer film for three-dimensional molding and a method for producing a resin molded product.

In resin molded products used for automobile interiors and exteriors, building interior materials, home appliances, etc., and resin molded products used for organic glass, etc. used as a substitute for inorganic glass, it is used for surface protection and design purposes. As such, a technique is used in which a protective layer is laminated using a three-dimensionally formed film. Three-dimensionally formed films used in such techniques can be broadly classified into laminate-type three-dimensionally formed films and transfer-type three-dimensionally formed films. A laminate type three-dimensional molded film is laminated on a supporting base material with the protective layer located on the outermost surface, and by laminating the molding resin on the supporting base material side, the supporting base material is formed in the resin molded product. is used so that it is captured. On the other hand, in a transfer-type three-dimensional molded film, a protective layer is laminated directly on the supporting base material or via a release layer provided if necessary, and after laminating the molding resin on the side opposite to the supporting base material. By peeling off the supporting base material, the resin molded product is used in such a manner that no supporting base material remains on the resin molded product. These two types of three-dimensional molded films are used depending on the shape of the resin molded product and the desired functions.

The protective layer provided on such three-dimensionally formed films is chemically cross-linked by irradiation with ionizing radiation, such as ultraviolet rays or electron beams, from the perspective of imparting excellent surface properties to resin molded products. It is said that it is preferable to use a resin composition containing an ionizing radiation-curable resin that is cured by irradiation. Such three-dimensionally formed films can be roughly divided into those whose protective layer has already been cured by ionizing radiation in the form of a three-dimensionally formed film, and those whose protective layer has been cured after forming into a resin molded product through molding. The former is considered preferable from the viewpoint of simplifying the post-processing process and increasing productivity. However, if the protective layer is hardened at the stage of forming a three-dimensionally formed film, the flexibility of the three-dimensionally formed film decreases, and there is a risk that cracks may occur in the protective layer during the forming process. It becomes necessary to select a resin composition that is suitable for use. In particular, in the case of the above-mentioned transfer-type three-dimensionally formed film, it is usually necessary to laminate other layers such as a design layer and an adhesive layer on top of the protective layer. Compared to the laminate type, the design of the resin composition is better because the supporting base material must be peeled off, and the exposed surface must exhibit excellent physical properties when the supporting base material is peeled off. The problem is 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, it is possible to achieve both three-dimensional moldability and scratch resistance even in a transfer-type three-dimensional molded film in which the protective layer is formed from a cured product of an ionizing radiation-curable resin composition. becomes possible.

JP2012-56236A Japanese Patent Application Publication No. 2013-111929

In the process of transferring the above-mentioned three-dimensional molding transfer film onto a molding resin to make a resin molded product, the area and shape of the layer to be transferred (transfer layer) such as a protective layer and the surface to be transferred of the molding resin are determined. Since it is difficult to achieve complete matching, the area of the transfer layer of the transfer film for three-dimensional molding is generally designed to be larger than the area of the transfer surface of the molding resin. After repeated studies, the inventor found that in conventional transfer films for three-dimensional molding, such as those disclosed in Patent Documents 1 and 2, the area of the transfer layer is designed to be larger than the area of the transfer surface of the molding resin. By doing so, when the transfer base material is peeled off after the transfer layer is laminated on the molding resin, the portions of the transfer layer that do not need to be peeled off from the transfer base material are pulled onto the transfer layer laminated on the molding resin. It has been confirmed that there are cases where the transfer layer is not cut at the edge of the surface to be transferred, and the transfer layer protrudes from the edge and remains, resulting in so-called "foil burrs."

Further, as a result of repeated studies by the present inventors, it has been found that in conventional transfer-type three-dimensionally formed films such as those disclosed in Patent Documents 1 and 2, when the support is peeled off from the transfer layer, It has been found that there are cases where the release layer remains on the surface of the transfer layer, resulting in poor transfer. For example, even if a small amount of the release layer remains on the surface of the transfer layer when the support is peeled off from the transfer layer, if the remaining amount is difficult to remove from the surface, the appearance of the surface of the resulting resin molded product This will lead to defects. The present inventors have found that the problem of poor transfer occurs particularly when the shape of the mold is complex, when the molding temperature is high, or when the molding depth is deep. The present inventors further investigated this problem as follows.

A resin molded article using a transfer film for three-dimensional molding is manufactured, for example, by sequentially performing the following steps (1a) to (4a).

(1a) First, turn the transfer layer side (opposite side of the support) of the transfer film for three-dimensional molding toward the side where the resin in the mold is injected, and then (2a) a step of injecting resin into the mold; (2a) a step of injecting resin into the mold;
(3a) a step of taking out the resin molded article (resin molded article with a support) from the mold after cooling the injected resin; and (4a) a step of peeling the support from the transfer layer of the resin molded article.

In addition, when the mold is deep drawing, there is a method of preheating the transfer film for three-dimensional molding before injection of the resin and then bringing it into close contact with the inner surface of the mold. Specifically, a resin molded article using a transfer film for three-dimensional molding is manufactured, for example, by sequentially performing the following steps (1b) to (5b). Although this preheating step significantly lengthens the molding time, the transfer film for three-dimensional molding becomes softer and can better follow the mold.

(1b) First, the step of heating the transfer film for three-dimensional molding from the transfer layer side with a heating plate, with the transfer layer side (the side opposite to the support) of the transfer film for three-dimensional molding facing into the mold;
(2b) a step of preforming (vacuum forming) the transfer film for three-dimensional molding so as to follow the shape inside the mold, bringing it into close contact with the inner surface of the mold, and clamping the mold;
(3b) a step of injecting the resin into the mold;
(4b) a step of taking out the resin molded product (resin molded product with support) from the mold after cooling the injected resin; and (5b) a step of peeling the support from the transfer layer of the resin molded product.

In the manufacturing process of such resin molded products, the temperature of the resin (molten resin) injected into the mold is much higher than the temperature of the mold, and the mold also functions to cool the resin molded product. . In addition, when high-temperature molten resin is injected into a mold, the transfer film for three-dimensional molding does not adhere tightly to the mold in areas where the shape of the mold is complex, so the mold cannot cool the resin. It is difficult to progress, and the high temperature state of this part may last for a long time compared to the part that contacted the mold. In addition, even when the molding temperature is high or the molding depth is deep, the high temperature state of the part where the transfer film for three-dimensional molding is not in close contact with the mold will similarly be affected by the high temperature of the part that has come into contact with the mold. It may last for a long time compared to In such cases, when peeling the support from the transfer layer of the resin molded product, the adhesive strength between the support and the transfer layer increases too much in the areas where the transfer film for three-dimensional molding is exposed to high temperatures, and the support It became clear that when the body was peeled off from the transfer layer, a transfer defect occurred in which the release layer of the support remained on the surface of the transfer layer.

Based on such a novel problem, the main object of the present invention is to provide a transfer film for three-dimensional molding in which foil burrs and defective transfer of a mold release layer are effectively suppressed. Furthermore, another object of the present invention is to provide a method for manufacturing a resin molded article using the transfer film for three-dimensional molding.

The present inventors conducted extensive studies to solve the above problems. As a result, after setting the upper limit of the peel strength between the release layer of the support and the protective layer of the transfer layer in a high-temperature environment to a predetermined value, we also established a predetermined relationship between the peel strength and the thickness of the protective layer. It has been found that by setting , it is possible to suppress both foil burrs and transfer defects of the release layer. More specifically, in a transfer film for three-dimensional molding comprising a support having at least a transfer base material and a mold release layer, and a transfer layer having a protective layer provided in contact with the mold release layer. , the peel strength between the release layer and the protective layer in an 80°C environment was less than 0.90 N/inch, and the peel strength value (N/inch) was divided by the protective layer thickness value (μm). It has been found that by setting the value to 0.10 or more, both foil burrs on the transfer film for three-dimensional molding and poor transfer of the release layer can be effectively suppressed. The present invention was completed through further studies based on this knowledge.

That is, the present invention provides the inventions of the following aspects.
Item 1. A transfer film for three-dimensional molding, comprising a support having at least a transfer base material and a release layer, and a transfer layer having a protective layer provided in contact with the release layer,
The peel strength between the release layer and the protective layer in an 80° C. environment is less than 0.90 N/inch, and
A transfer film for three-dimensional molding, wherein a value obtained by dividing the peel strength (N/inch) by the thickness (μm) of the protective layer is 0.10 or more.
Item 2. Item 2. The transfer film for three-dimensional molding according to Item 1, wherein the release layer is composed of a cured product of an ionizing radiation-curable resin composition.
Item 3. Item 2. The transfer film for three-dimensional molding according to Item 1, wherein the ionizing radiation-curable resin composition of the release layer contains polycarbonate (meth)acrylate.
Item 4. Item 4. The transfer film for three-dimensional molding according to any one of Items 1 to 3, wherein the thickness of the release layer is 5.0 μm or less.
Item 5. Item 5. The transfer film for three-dimensional molding according to any one of Items 1 to 4, wherein the protective layer is composed of a cured product of an ionizing radiation-curable resin composition.
Item 6. Item 6. The transfer film for three-dimensional molding according to item 5, wherein the ionizing radiation-curable resin composition of the protective layer contains polycarbonate (meth)acrylate.
Section 7. Item 7. The transfer film for three-dimensional molding according to any one of Items 1 to 6, wherein the transfer layer has at least one selected from the group consisting of a primer layer, a decorative layer, an adhesive layer, and a transparent resin layer.
Section 8. Laminating a molding resin layer on the transfer layer side of the transfer film for three-dimensional molding according to any one of Items 1 to 7;
Peeling the support from the transfer layer;
A method for manufacturing a resin molded product, comprising:

According to the present invention, it is possible to provide a transfer film for three-dimensional molding in which foil burrs and defective transfer of a mold release layer are effectively suppressed. Further, according to the present invention, it is also possible to provide a method for manufacturing a resin molded product using the transfer film for three-dimensional molding.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding of this invention. FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a resin molded product with a support obtained using the transfer film for three-dimensional molding of the present invention. FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a resin molded product obtained using the transfer film for three-dimensional molding of the present invention. It is a schematic diagram for explaining the evaluation method of foil burr in an example.

1. Transfer film for three-dimensional molding The transfer film for three-dimensional molding of the present invention includes a support having at least a base material for transfer and a release layer, and a protective layer provided in contact with the release layer. A transfer film for three-dimensional molding comprising a layer, wherein the peel strength between the release layer and the protective layer in an 80°C environment is less than 0.90 N/inch, and the peel strength (N /inch) divided by the thickness (μm) of the protective layer is 0.10 or more. By having such a configuration, the transfer film for three-dimensional molding of the present invention can effectively suppress foil burrs and defective transfer of the mold release layer. Hereinafter, the transfer film for three-dimensional molding of the present invention will be explained in detail.

In this specification, the numerical range indicated by "~" means "more than" or "less than". For example, the expression 2 to 15 mm means 2 mm or more and 15 mm or less. Further, as described later, the transfer film for three-dimensional molding of the present invention does not need to have a decorative layer or the like, and may be transparent, for example. Moreover, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning.

Laminated structure of transfer film for three-dimensional molding The transfer film for three-dimensional molding of the present invention has a transfer layer 9 on the release layer 2 of a support 10 having a transfer base material 1 and a release layer 2. The transfer layer 9 has a protective layer provided so as to be in contact with the release layer 2 . That is, the protective layer 3 included in the transfer layer 9 constitutes the surface of the transfer layer 9 on the support 1 side. In the transfer film for three-dimensional molding of the present invention, the base material for transfer 1 and the mold release layer 2 constitute a support 10, and the support 10 is configured to transfer the transfer film for three-dimensional molding to the molding resin layer 8. After being laminated, it is peeled off and removed. The surface of the resin molded product obtained by peeling off the support 10 is constituted by the protective layer 3.

A primer layer 4 may be provided on the side of the protective layer 3 opposite to the support 10, if necessary, for the purpose of improving the adhesion between the protective layer 3 and an adjacent layer. Further, the transfer layer 9 may be provided with a decorative layer 5 as necessary for the purpose of imparting decoration to the transfer film for three-dimensional molding. Further, for the purpose of increasing the adhesion of the molded resin layer 8, an adhesive layer 6 may be provided as necessary. Further, for the purpose of improving the adhesion between the protective layer 3 or the primer layer 4 and the adhesive layer 6, a transparent resin layer 7 may be provided as necessary. In the transfer film for three-dimensional molding of the present invention, the protective layer 3, primer layer 4, decorative layer 5, adhesive layer 6, transparent resin layer 7, etc. constitute the transfer layer 9, and the transfer layer 9 is the molding resin layer. 8 and becomes the resin molded article of the present invention.

The laminated structure of the transfer film for three-dimensional molding of the present invention is a laminated structure in which a transfer base material/mold release layer/protective layer is laminated in this order; Laminated structure in which transfer base material/release layer/protective layer/primer layer/decoration layer are laminated in this order; transfer base material/release layer/protective layer/primer layer/decoration layer /A laminated structure in which adhesive layers are laminated in this order; A laminated structure in which transfer base material/release layer/protective layer/primer layer/transparent resin layer/adhesive layer is laminated in this order. FIG. 1 shows one embodiment of the laminated structure of the transfer film for three-dimensional molding of the present invention, in which a three-dimensional molding in which a transfer base material/release layer/protective layer/primer layer/decoration layer/adhesive layer is laminated in this order. 1 shows a schematic diagram of a cross-sectional structure of one form of a transfer film for use in a commercial use. Further, FIG. 2 shows one embodiment of the laminated structure of the transfer film for three-dimensional molding of the present invention, in which a transfer base material/release layer/protective layer/primer layer/transparent resin layer/adhesive layer are laminated in this order. A schematic diagram of a cross-sectional structure of one form of a transfer film for three-dimensional molding is shown.

Composition of each layer forming the transfer film for three-dimensional molding [Support 10]
The transfer film for three-dimensional molding of the present invention has a transfer base material 1 and a release layer 2 as a support body 10. The protective layer 3, primer layer 4, decorative layer 5, adhesive layer 6, transparent resin layer 7, etc. formed on the support 10 constitute the transfer layer 9. In the present invention, after the transfer film for three-dimensional molding and the molding resin are integrally molded, the interface between the release layer 2 and the transfer layer 9 of the support 10 is peeled off, and the support 10 is peeled off and the resin molded product is formed. is obtained.

(Transfer base material 1)
In the present invention, the transfer base material 1 plays a role as a support member for a 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 typically a resin sheet made of thermoplastic resin is used. Examples of the thermoplastic resin include polyester resin; acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; acrylonitrile-butadiene-styrene resin (ABS resin); vinyl chloride resin 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 polycarboxylic acid and a polyhydric alcohol, and includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate. (PEN) and the like, and polyethylene terephthalate (PET) is particularly preferred in terms of heat resistance and dimensional stability.

The transfer base material 1 has an uneven shape on at least one surface as necessary for the purpose of imparting an uneven shape to the surface of the protective layer 3 to be described later and improving blocking resistance. It's okay. By laminating the protective layer 3 on the uneven surface of the transfer base material 1 via the release layer 2, an uneven shape corresponding to the uneven shape of the transfer base material 1 is formed on the surface of the protective layer 3. However, a matte design can be imparted to the surface of the protective layer 3. In addition, when providing an uneven shape to the surface of the transfer base material 1 in order to improve blocking resistance without imparting an uneven shape to the surface of the protective layer 3, the protective layer 3 of the transfer base material 1 What is necessary is to form an uneven shape only on the opposite surface, reduce the uneven shape of the transfer base material 1, or adjust the thickness of the release layer 2.

Methods for forming an uneven shape on the surface of the transfer base material 1 include physical methods such as sandblasting, hairline processing, laser processing, embossing, and chemical methods such as corrosion treatment with chemicals and solvents. An example of this method is to include fine particles in the transfer base material 1 so that the shape of the fine particles is exposed on the surface of the transfer base material 1. Among these, a method of incorporating fine particles into the transfer base material 1 is preferably used.

Typical examples of fine particles include synthetic resin particles and inorganic particles, but from the viewpoint of improving three-dimensional moldability, it is particularly preferable to use synthetic resin particles. The synthetic resin particles are not particularly limited as long as they are particles made of synthetic resin, such as acrylic beads, urethane beads, silicone beads, nylon beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and 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 with excellent scratch resistance on the protective layer 3. Examples of the inorganic particles include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide, and kaolin. One type of these fine particles may be used alone, or two or more types may be used in combination. The particle size of the fine particles is preferably about 0.3 to 25 μm, more preferably about 0.5 to 5 μm. The particle size of the fine particles in the present invention is determined by using a Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1, by injecting the powder to be measured from a nozzle using compressed air, and dispersing it in the air. Refers to the method using the spray-type dry measurement method.

The content of fine particles contained in the transfer base material 1 may be appropriately set depending on the purpose, and is preferably 1 to 100 parts by mass, for example, based on 100 parts by mass of the resin contained in the transfer base material 1. The amount is more preferably about 5 to 80 parts by mass. Furthermore, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, optical brighteners, and the like can be added to the transfer base material 1 as necessary.

A polyester sheet suitably used as the transfer base material 1 in the present invention is manufactured, for example, as follows. First, the above polyester resin and other raw materials are supplied to a well-known melt extrusion device such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester resin to melt it. Next, while extruding the molten polymer, it is rapidly cooled and solidified on a rotating cooling drum to a temperature below the glass transition temperature to obtain an unoriented sheet in a substantially amorphous state. This sheet is obtained by biaxially stretching the sheet and heat-setting it. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Furthermore, if necessary, the film may be stretched again in the longitudinal and/or transverse directions before or after heat setting. In the present invention, in order to obtain sufficient dimensional stability, the stretching ratio is preferably 7 times or less as an area ratio, more preferably 5 times or less, and even more preferably 3 times or less. Within this range, when the obtained polyester sheet is used as a transfer film for three-dimensional molding, the transfer film for three-dimensional molding will not shrink again in the temperature range when molding resin is injected, and will not shrink again in the temperature range when molding resin is injected. The required sheet strength can be obtained. Note that the polyester sheet may be manufactured as described above, or a commercially available one may be used.

Further, the transfer base material 1 can be subjected to physical or chemical surface treatment such as an oxidation method or a roughening method on one or both surfaces, if desired, for the purpose of improving adhesion with the release layer 2. . Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone/ultraviolet treatment, etc., and examples of the roughening method include sandblasting, solvent treatment, and the like. These surface treatments are appropriately selected depending on the type of the transfer substrate 1, but in general, a corona discharge treatment method is preferably used in terms of effectiveness and operability. Further, the transfer base material 1 may be subjected to a treatment such as forming an easily adhesive layer for the purpose of strengthening interlayer adhesion with the release layer. In addition, when using a commercially available polyester sheet, the commercially available product may be previously subjected to the above-mentioned surface treatment or may be provided with an easy-to-adhesive layer.

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

(Release layer 2)
The release layer 2 is provided on the surface of the transfer base material 1 on the side on which the transfer layer 9 is laminated, for the purpose of increasing the releasability between the support 10 and the transfer layer 9.

The release layer 2 may be a solid release layer that covers the entire surface (all over the surface), or may be provided on a part of the surface. Usually, a solid release layer is preferred in consideration of releasability, transferability, moldability, scratch resistance, abrasion resistance, and the like.

In the present invention, the peel strength between the mold release layer 2 and the protective layer 3 described below in an 80° C. environment is less than 0.90 N/inch. The upper limit of the peel strength in a high temperature environment of 80 ° C. environment is less than 0.90 N/inch, and the value obtained by dividing the peel strength by the thickness (μm) of the protective layer 3 is 0.10 or more. , foil burrs and transfer defects of the release layer are effectively suppressed.

The present inventors compared the ease of occurrence of transfer defects with transfer films for three-dimensional molding having protective layers 3 of similar thickness, and found that the mold release layer 2 and the protective layer 3 in a high temperature environment (80°C) It has been found that the greater the peel strength between the mold release layer 2 and the protective layer 3, the more easily the release layer 2 remains on the surface of the protective layer 3, and the more likely transfer defects are likely to occur. Therefore, it was considered that a predetermined upper limit value exists for the peel strength. On the other hand, the present inventors evaluated the ease with which foil burrs occur in transfer films for three-dimensional molding in which the peeling strength of the mold release layer 2 and the protective layer 3 in a high-temperature environment (80 ° C.) is about the same. However, it was confirmed that the lower the peel strength in a high temperature environment (80° C.), the more likely it is to occur. Furthermore, it has been found that the thinner the protective layer 3 is, the less likely foil burrs are to occur. Therefore, it has become clear that with regard to foil burrs, it is important to balance not only the peel strength but also the thickness of the protective layer 3. As described above, the present inventors have found that the peel strength between the release layer 2 and the protective layer 3 and the thickness of the protective layer 3 are closely related to achieving both foil burrs and transferability. . After further study, the present inventors found that the upper limit of the peel strength in a high temperature environment of 80°C is less than 0.90 N/inch, and that the peel strength is protected. It has been found that when the value divided by the thickness (μm) of layer 3 satisfies the relationship of 0.10 or more, foil burrs and transfer defects of the release layer are effectively suppressed.

From the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer, the peel strength between the release layer 2 and the protective layer 3 described below in an 80°C environment is preferably about 0.85 N/inch. The following examples include more preferably about 0.20 to 0.85 N/inch, still more preferably about 0.30 to 0.85 N/inch, and still more preferably about 0.40 to 0.80 N/inch. In the present invention, the method for measuring the peel strength between the mold release layer and the protective layer 3 in an 80°C environment is as follows.

<Method for measuring peel strength>
First, a transfer film for three-dimensional molding whose peel strength is to be measured, a mold for molding the same, and a resin to be laminated on the transfer film for three-dimensional molding (resin forming a molded resin layer) are prepared. The shape of the mold is a flat plate, and when the transfer film for three-dimensional molding is molded in the mold, the area elongation rate of the surface of the transfer film for three-dimensional molding is substantially 0%. shall be taken as a thing. Further, the temperature of the mold is set to 60°C. The resin injected into the transfer film for three-dimensional molding (the resin that forms the molding resin layer) is a mixed resin of ABS resin and polycarbonate resin (for example, CYCOLOY ^TM Resin XCY620) that is heated to 265°C and melted. shall be. Under the above molding conditions, a molded resin layer is laminated on the transfer film for three-dimensional molding according to the steps (1a) to (3a) above to obtain a decorated resin molded product with a support. Next, a 1-inch wide polyester adhesive tape (NITTO TAPE, No. 31B 75 High) is applied with a finger to the surface of the transfer base material layer of the decorative resin molded product with a support to make it stick tightly. Next, a cut is made with a cutter on the surface of the decorative resin molded product with support along the attached polyester adhesive tape. At this time, the incisions are made to penetrate through the transfer base material (if it has a release layer, also the release layer). Next, at the end of the polyester adhesive tape, about 10 mm of the polyester adhesive tape is peeled off in the length direction with fingers to prepare a sample. At this time, the transfer base material is also peeled off together with the polyester adhesive tape. Next, the sample is placed in a Tensilon tester (for example, Tensilon RTC-1250A manufactured by Orientec Co., Ltd.), and the load cell part of the Tensilon tester and the part from which the polyester adhesive tape has been peeled are connected. Next, the sample is heated for 1 minute using the heater attached to the Tensilon tester. At this time, the set temperature of the heater is 80°C. Next, the polyester adhesive tape was peeled off at a peeling speed of 100 mm/min so that the peeling direction was always 90° with respect to the surface of the transfer film for three-dimensional molding, and the load indicated on the load cell was applied to the peel strength ( N/inch).

The material constituting the release layer 2 is not particularly limited as long as the peel strength can be set to the above value. From the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer by appropriately setting the peel strength, the release layer 2 is composed of a cured product of an ionizing radiation-curable resin composition. It is preferable that Preferred ionizing radiation-curable resins used for forming the release layer 2 will be described in detail below.

(Ionizing radiation curable resin)
The ionizing radiation-curable resin used to form the release layer 2 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically contains polymerizable unsaturated bonds or epoxy groups in the molecule. A suitable mixture of at least one of prepolymers, oligomers, monomers, etc., having the following may be mentioned. Here, ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta that can polymerize or crosslink molecules, and ultraviolet rays (UV) or electron beams (EB) are usually used; It also includes electromagnetic waves such as rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Among ionizing radiation curable resins, electron beam curable resins are suitable for forming the release layer 2 because they can be made solvent-free, do not require a photopolymerization initiator, and can provide stable curing characteristics. used for.

As the monomer used as the ionizing radiation-curable resin, (meth)acrylate monomers having a radically polymerizable unsaturated group in the molecule are suitable, and polyfunctional (meth)acrylate monomers are particularly preferred. The polyfunctional (meth)acrylate monomer may be any (meth)acrylate monomer having two or more (bifunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule. Specifically, the polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. 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 dicyclopentenyl di(meth)acrylate, 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 hexa(meth)acrylate, and the like. These monomers may be used alone or in combination of two or more.

Furthermore, as the above-mentioned oligomer used as the ionizing radiation-curable resin, (meth)acrylate oligomers having radically polymerizable unsaturated groups in the molecule are suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth)acrylate oligomer having (two or more functionalities) is preferred. Examples of polyfunctional (meth)acrylate oligomers include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. , polybutadiene (meth)acrylate, silicone (meth)acrylate, oligomers having a cationically polymerizable functional group in the molecule (e.g., 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 at the terminal or side chain. It can be obtained by esterification with acrylic acid. The polycarbonate (meth)acrylate may be, for example, a polycarbonate-based urethane (meth)acrylate that is a urethane (meth)acrylate having a polycarbonate skeleton. Urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth)acrylate. Acrylic silicone (meth)acrylate can be obtained by radical copolymerization of a silicone macromonomer and a (meth)acrylate monomer. Urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol, polyester polyol, or caprolactone polyol with a polyisocyanate compound with (meth)acrylic acid. Epoxy (meth)acrylate can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin to esterify it. Furthermore, a carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate can be produced by, for example, esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth)acrylic acid, or by esterifying the hydroxyl groups of polyester oligomer with (meth)acrylic acid. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide with (meth)acrylic acid. Polyether (meth)acrylate can be obtained by esterifying the hydroxyl group of polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a 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 its main chain. Among these, polycarbonate (meth)acrylate (polycarbonate-based urethane (meth)acrylate, etc.), urethane (meth)acrylate, etc. are particularly preferred as the polyfunctional (meth)acrylate oligomer. These oligomers may be used alone or in combination of two or more.

Among the above-mentioned ionizing radiation-curable resins, caprolactone-based polyols and polyisocyanate compounds are preferred from the viewpoint of setting the above-mentioned peel strength appropriately and suppressing foil burrs and transfer defects of the mold release layer more effectively. It is preferable to use caprolactone-based urethane (meth)acrylate or polycarbonate (meth)acrylate (polycarbonate-based urethane (meth)acrylate, etc.) obtained by esterifying a polyurethane oligomer obtained by the reaction with (meth)acrylic acid. It is particularly preferable to use polycarbonate (meth)acrylate (such as polycarbonate-based urethane (meth)acrylate) and polyfunctional (meth)acrylate together.

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

The above-mentioned polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups at the terminal or side chain. A typical method for producing this polycarbonate polyol is a method involving a polycondensation reaction of a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as 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 may contain an ether bond in the group. 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, and 1,4-butane. Diol, 1,5-pentanediol, 3-methyl-1,5pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4- Examples include bis(2-hydroxyethoxy)benzene, neopentyl glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These diols may be used alone or in combination of two or more.

Examples of the trivalent or higher polyhydric alcohol (B) include alcohols such as trimethylolpurpane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, and sorbitol. Furthermore, 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 also be used. The polyhydric alcohols may be used alone or in combination of two or more.

Compound (C) serving as a carbonyl component is any compound selected from carbonic diester, phosgene, or their equivalents. Specific examples include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate, phosgene, and halogenated formate esters such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Examples include. These may be used alone or in combination of two or more.

Polycarbonate polyol is synthesized by polycondensation reaction of the above-described diol compound (A), trihydric or higher polyhydric alcohol (B), and carbonyl component compound (C) under general conditions. . For example, the 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) of the carbonyl component ( The molar ratio of A) to the polyhydric alcohol (B) is preferably 0.2 to 2 equivalents based on the hydroxyl groups of the diol compound and the polyhydric alcohol.

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

The method for producing the polycarbonate polyol described above is described, for example, in JP-A-64-1726. Furthermore, this polycarbonate polyol can also be produced by a transesterification reaction between a polycarbonate diol and a polyhydric alcohol having a valence of 3 or more, as described in JP-A-3-181517.

The molecular weight of the polycarbonate (meth)acrylate used in the present invention is preferably a weight average molecular weight of 500 or more, more preferably 1,000 or more as measured by GPC analysis and converted to standard polystyrene. , more preferably 2,000 or more. The upper limit of the weight average molecular weight of polycarbonate (meth)acrylate is not particularly limited, but from the viewpoint of controlling the viscosity so as not to become too high, it is preferably 100,000 or less, and more preferably 50,000 or less. More preferably, it is 2,000 or more and 50,000 or less, particularly preferably 5,000 to 20,000.

In the ionizing radiation-curable resin composition, polycarbonate (meth)acrylate is preferably used together with polyfunctional (meth)acrylate. The mass ratio of polycarbonate (meth)acrylate to the polyfunctional (meth)acrylate is more preferably polycarbonate (meth)acrylate: polyfunctional (meth)acrylate = 98:2 to 50:50. When the mass ratio of polycarbonate (meth)acrylate and polyfunctional (meth)acrylate is less than 98:2 (that is, when the amount of polycarbonate (meth)acrylate is 98% by mass or less with respect to 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 polycarbonate (meth)acrylate and polyfunctional (meth)acrylate is greater than 50:50 (that is, when the amount of polycarbonate (meth)acrylate is 50% by mass or more with respect to 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 more functional (meth)acrylate. Here, the term "bifunctional" refers to having two ethylenically unsaturated bonds {(meth)acryloyl groups} 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 from the viewpoint of setting the above-mentioned peel strength appropriately to more effectively suppress foil burrs and transfer defects of the release layer. , polyfunctional (meth)acrylate oligomers are preferred.

Examples of the above-mentioned polyfunctional (meth)acrylate oligomers 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 reacting a polyether polyol or a polyester polyol with a polyisocyanate with (meth)acrylic acid. Epoxy (meth)acrylate oligomers can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolac-type epoxy resin to esterify it. Furthermore, 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. Polyester (meth)acrylate-based oligomers can be obtained by, for example, esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol, or by esterifying the hydroxyl groups 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. A polyether (meth)acrylate oligomer can be obtained by esterifying the hydroxyl group of a polyether polyol with (meth)acrylic acid.

In addition, other polyfunctional (meth)acrylate oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers with (meth)acrylate groups in their side chains, and silicone (meth)acrylate oligomers with polysiloxane bonds in their main chains. ) Acrylate oligomers, aminoplast resins (meth)acrylate oligomers that are modified aminoplast resins that have many reactive groups in their small molecules, and the like.

In addition, the above-mentioned polyfunctional (meth)acrylate monomers 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(meth)acrylate Cyclopentenyl 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 (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(acryloxy) Examples include ethyl) isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. It will be done. The polyfunctional (meth)acrylate oligomers and polyfunctional (meth)acrylate monomers described above may be used alone or in combination of two or more.

In the present invention, a monofunctional (meth)acrylate may be appropriately used in combination with the polyfunctional (meth)acrylate for the purpose of reducing the viscosity, etc., as long as the purpose of the present invention is not impaired. Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and 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 polycarbonate (meth)acrylate in the ionizing radiation curable resin composition forming the mold release layer 2 is not particularly limited, but the above-mentioned peel strength is suitably set to prevent foil burrs and the mold release layer. From the viewpoint of suppressing transfer defects more effectively, the amount is preferably about 98 to 50% by mass, more preferably about 90 to 65% by mass.

When forming the mold release layer 2 using an ionizing radiation-curable resin, the mold release layer 2 is formed, for example, by preparing an ionizing radiation-curable resin composition, applying it, and crosslinking and curing it. . The ionizing radiation-curable resin composition may have a viscosity as long as it can form an uncured resin layer using the coating method described below.

In the present invention, the prepared coating solution is applied to a desired thickness by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., preferably by gravure coating, and then 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 or ultraviolet rays to harden the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage thereof can be appropriately selected depending on the resin used and the thickness of the layer, but the accelerating voltage is usually about 70 to 300 kV.

In addition, in electron beam irradiation, the higher the accelerating voltage, the higher the penetration ability, so when using a resin that is easily deteriorated by electron beam irradiation under the mold release layer 2, the penetration depth of the electron beam and the mold release The accelerating voltages are chosen such that the thicknesses of the layers 2 are substantially equal. In addition, when the mold release layer 2 is cured with an electron beam together with the protective layer 3 described below, the accelerating voltage is set so that the penetration depth of the electron beam and the total thickness of the mold release layer 2 and the protective layer 3 are substantially equal. Select. Thereby, it is possible to suppress irradiation of excess electron beams to the layers located under the mold release layer 2, and it is possible to minimize deterioration of each layer due to excessive electron beams.

The irradiation dose is such that the crosslinking density of the release layer 2 is a sufficient value, and is preferably 60 to 300 kGy (6 to 30 Mrad), more preferably 70 to 200 kGy (7 to 20 Mrad). By setting the irradiation dose within such a range, deterioration of the transfer base material 1 due to ionizing radiation transmitted through the release layer 2 can be suppressed. Note that the above example is a case where the number of functional groups in the polyfunctional (meth)acrylate is 2, and an appropriate irradiation dose is required depending on the number of functional groups.

Further, there are no particular restrictions on the electron beam source, and various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. Can be used.

When using ultraviolet rays as the ionizing radiation, it is sufficient to emit light rays containing ultraviolet rays with a wavelength of 190 to 380 nm. Examples of the ultraviolet light source include, but are not particularly limited to, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, an ultraviolet light emitting diode (LED-UV), and the like.

In addition to the ionizing radiation-curable resin composition, the release layer may also contain silicone resins, fluorine resins, acrylic resins (including acrylic-melamine resins, for example), polyester resins, polyolefin resins, and polystyrene resins. Thermoplastic resins such as resins, polyurethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, nitrified cotton, copolymers of monomers forming the thermoplastic resins, or (meth) A resin composition modified with acrylic acid or urethane can be used alone or in combination. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products of these are preferred. More specifically, acrylic-melamine resins alone, compositions containing acrylic-melamine resins, resin compositions mixed with polyester resins and urethane-modified copolymers of ethylene and acrylic acid, copolymers of acrylic resins, styrene, and acrylics. Examples include resin compositions mixed with emulsions of Among these, it is particularly preferable that the release layer is made of an acrylic-melamine resin alone or a composition containing 50% by mass or more of an acrylic-melamine resin.

The thickness of the release layer 2 is not particularly limited, but is preferably 5.0 μm from the viewpoint of suitably setting the peel strength and suppressing foil burrs and transfer defects of the release layer more effectively. Hereinafter, it is more preferably 2.5 μm or less, still more preferably 2.0 μm or less, and the lower limit is preferably about 0.2 μm in consideration of manufacturability and flatness.

(Transfer layer 9)
In the transfer film for three-dimensional molding of the present invention, the protective layer 3, primer layer 4, decorative layer 5, adhesive layer 6, transparent resin layer 7, etc. formed on the support 10 constitute the transfer layer 9. ing. In the present invention, after integrally molding the transfer film for three-dimensional molding and the molding resin, the interface between the support 10 and the transfer layer 9 (that is, the interface between the release layer 2 and the protective layer 3) is peeled off, and the three-dimensional A resin molded article is obtained in which the transfer layer 9 of the original molding transfer film is transferred to the molded resin layer 8. Each of these layers will be explained in detail below.

[Protective layer 3]
The protective layer 3 is a layer provided on the transfer film for three-dimensional molding so as to be located on the outermost surface of the resin molded product for the purpose of increasing the durability, chemical resistance, etc. of the resin molded product. In the transfer film for three-dimensional molding of the present invention, the protective layer 3 is in contact with the release layer 2.

As mentioned above, in the transfer film for three-dimensional molding of the present invention, the upper limit of the peel strength in a high temperature environment of 80°C is less than 0.90 N/inch, and the peel strength is determined by the thickness of the protective layer 3 ( The value divided by μm) is 0.10 or more.

From the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer, the value obtained by dividing the peel strength by the thickness (μm) of the protective layer 3 is preferably about 0.14 or more, more preferably about 0.20 or more, more preferably about 0.24 or more. The preferred range of the value obtained by dividing the peel strength by the thickness (μm) of the protective layer 3 is about 0.10 to 0.80, about 0.14 to 0.80, about 0.20 to 0.80, and about 0.10 to 0.80. Examples include about 24 to 0.80, about 0.10 to 0.70, about 0.14 to 0.70, about 0.20 to 0.70, and about 0.24 to 0.70.

The thickness of the protective layer 3 after curing is not particularly limited as long as the value obtained by dividing the peel strength by the thickness (μm) of the protective layer 3 is 0.10 or more, but foil burrs and poor transfer of the release layer can be avoided. From the viewpoint of suppressing this more effectively, the thickness is preferably about 0.5 to 10 μm, more preferably about 1 to 8 μm, and still more preferably about 1 to 5 μm. When the thickness falls within this range, sufficient physical properties as a protective layer such as durability and chemical resistance can be obtained, and ionizing radiation can be uniformly irradiated, resulting in uniform curing. This makes it possible and economically advantageous. In addition, when the thickness of the protective layer 3 after curing satisfies the above range, the three-dimensional moldability of the transfer film for three-dimensional molding is further improved, so it is highly adaptable to complex three-dimensional shapes such as those used in automobile interiors. You can get sex.

As for the material constituting the protective layer 3, the peel strength between the mold release layer 2 and the protective layer 3 in an 80°C environment is set to the above value, and the peel strength is divided by the thickness (μm) of the protective layer 3. There is no particular restriction as long as the value can be set to 0.10 or more, and the protective layer 3 can be made of a resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation-curable resin. From the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer, the protective layer 3 is preferably composed of a cured product of an ionizing radiation-curable resin composition. In addition, in the transfer film for three-dimensional molding of the present invention, the ionizing radiation-curable resin composition forming the protective layer 3 is uncured when laminated with the molded resin layer, and is not subjected to processing with a support after lamination. The decorative resin molded product or the decorated resin molded product from which the support has been peeled may be cured by irradiating it with ionizing radiation.

Examples of the ionizing radiation-curable resin used to form the protective layer 3 include the same resins as those exemplified in (Release layer 2).

From the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer, the ionizing radiation-curable resin composition forming the protective layer 3 is a caprolactone-based urethane (meth) exemplified in (Release layer 2). It preferably contains acrylate and polycarbonate (meth)acrylate (such as polycarbonate-based urethane (meth)acrylate), and particularly preferably contains polycarbonate (meth)acrylate (such as polycarbonate-based urethane (meth)acrylate). The details of the polycarbonate (meth)acrylate are as described in (Release layer 2).

Further, similarly to the release layer 2, in the ionizing radiation-curable resin composition of the protective layer 3, polycarbonate (meth)acrylate is preferably used together with polyfunctional (meth)acrylate. The mass ratio of polycarbonate (meth)acrylate to the polyfunctional (meth)acrylate is more preferably polycarbonate (meth)acrylate: polyfunctional (meth)acrylate = 98:2 to 50:50. When the mass ratio of polycarbonate (meth)acrylate and polyfunctional (meth)acrylate is less than 98:2 (that is, when the amount of polycarbonate (meth)acrylate is 98% by mass or less with respect to 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 polycarbonate (meth)acrylate and polyfunctional (meth)acrylate is greater than 50:50 (that is, when the amount of polycarbonate (meth)acrylate is 50% by mass or more with respect to 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 details of the polyfunctional (meth)acrylate are as explained in (Release layer 2), and any (meth)acrylate with two or more functionalities is sufficient, and the number of functional groups is preferably about 2 to 6. It will be done. The polyfunctional (meth)acrylate may be either an oligomer or a monomer, but a polyfunctional (meth)acrylate oligomer is preferred from the viewpoint of improving three-dimensional moldability. The polyfunctional (meth)acrylate oligomer and the polyfunctional (meth)acrylate monomer are as described above.

The content of caprolactone-based urethane (meth)acrylate or polycarbonate (meth)acrylate in the ionizing radiation-curable resin composition forming the protective layer 3 is not particularly limited, but it may reduce foil burrs and transfer defects of the mold release layer. From the viewpoint of more effective suppression, it 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 and an acrylic resin as an ionizing radiation-curable resin. Also, when using an ionizing radiation-curable resin composition containing polycarbonate (meth)acrylate and an acrylic resin, it is preferably used together with the above-mentioned polyfunctional (meth)acrylate.

The acrylic resin is not particularly limited. The acrylic resin is preferably a homopolymer of (meth)acrylic ester, a copolymer of two or more different (meth)acrylic ester monomers, or a copolymer of (meth)acrylic ester and other monomers. Examples include polymers, specifically methyl poly(meth)acrylate, ethyl poly(meth)acrylate, propyl poly(meth)acrylate, butyl poly(meth)acrylate, and methyl(meth)acrylate. Butyl (meth)acrylate copolymer, ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer A (meth)acrylic resin consisting of a single or copolymer containing a (meth)acrylic acid ester such as the following is suitably used. Among these, methyl poly(meth)acrylate is particularly preferred from the viewpoint of improving chemical resistance.

The weight average molecular weight of the acrylic resin is not particularly limited, but from the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer, it is preferably about 10,000 to 150,000, more preferably about 10,000 to 40,000. Can be mentioned.

Note that 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, the glass transition temperature (Tg) of the acrylic resin is preferably about 40 to 160°C, more preferably 80 to 120°C, from the viewpoint of more effectively suppressing foil burrs and defective transfer of the mold release layer. The degree is mentioned.

Note that 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 from the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer, it is preferable. is 25 parts by mass or less, more preferably about 0.5 to 25 parts by mass, and even more preferably about 2 to 8 parts by mass, based on 100 parts by mass of solids other than the acrylic resin in the ionizing radiation-curable resin composition. It will be done.

<Curing agent>
Moreover, in the present invention, the ionizing radiation-curable resin composition forming the protective layer 3 may further contain a curing agent, if necessary. By including the curing agent, the peel strength between the release layer 2 and the protective layer 3 can be suitably adjusted, and foil burrs and poor transfer of the release layer can be suppressed more effectively.

The curing agent is not particularly limited, but preferably includes isocyanate compounds. The isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group, but preferably includes a polyfunctional isocyanate compound having two or more isocyanate groups. Examples of polyfunctional isocyanates include aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate ( Examples include polyisocyanates such as aliphatic (or alicyclic) isocyanates such as HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Also included are adducts or multimers of these various isocyanates, such as tolylene diisocyanate adducts, tolylene diisocyanate trimers, and blocked isocyanate compounds. The isocyanate compounds may be used alone or in combination of two or more.

The content of the curing agent in the ionizing radiation-curable resin composition forming the protective layer 3 is not particularly limited, but from the viewpoint of more effectively suppressing foil burrs and transfer defects of the release layer, it is preferably is about 0.1 to 20 parts by mass, more preferably about 1 to 10 parts by mass, and even more preferably about 1 to 7 parts by mass, per 100 parts by mass of solids other than the curing agent in the ionizing radiation-curable resin composition. can be mentioned.

The ionizing radiation-curable resin composition forming the protective layer 3 may contain various additives depending on the desired physical properties of the protective layer 3. These additives include, for example, weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants, matting agents, and the like. These additives can be appropriately selected from those commonly used, and examples of matting agents include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

The protective layer 3 is formed by preparing an ionizing radiation-curable resin composition, applying it, and crosslinking and curing it. The viscosity of the ionizing radiation-curable resin composition may be any viscosity as long as it can form an uncured resin layer on the surface of the release layer 2, for example, by the coating method described below.

In the present invention, the prepared coating liquid is coated onto the surface of the transfer base material 1 or the release layer 2 to the above-mentioned thickness by gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. The resin is applied by a known method, preferably gravure coating, to form an uncured resin layer.

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

In electron beam irradiation, the higher the accelerating voltage, the higher the penetration ability, so if a resin that is easily deteriorated by electron beam irradiation is used under the protective layer 3, the electron beam penetration depth and the protective layer 3 The accelerating voltage is selected so that the thicknesses of the two are substantially equal. Thereby, it is possible to suppress irradiation of excess electron beams to layers located under the protective layer 3, and it is possible to minimize deterioration of each layer due to excessive electron beams.

In addition, the irradiation dose is an amount that provides a sufficient crosslinking density of the protective layer 3, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). .

By adding various additives to the protective layer 3, it can have hard coat function, anti-fog coat function, anti-fouling coat function, anti-glare coat function, anti-reflection coat function, ultraviolet shielding coat function, infrared shielding coat function, etc. It is also possible to perform processing to provide the function.

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

The resin used in the resin composition for forming the primer layer is not particularly limited, but includes, for example, polyol and/or its cured product, urethane resin, acrylic resin, (meth)acrylic-urethane copolymer resin, polyester resin, butyral resin. etc. Among these resins, preferred are polyols and/or cured products thereof, urethane resins, acrylic resins, and (meth)acrylic-urethane copolymer resins. These resins may be used alone or in combination of two or more.

In the present invention, the primer layer 4 is preferably formed from a resin composition containing a polyol and a urethane resin. The polyol may be any 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, etc., and acrylic polyol is preferable. Can be mentioned.

When polyol and urethane resin are used to form the primer layer 4, their mass ratio (polyol:urethane resin) is preferably about 5:5 to 9.5:0.5, more preferably 7:3. ~9:1 can be cited.

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

Specifically, the isocyanate includes polyvalent isocyanates having two or more isocyanate groups in the molecule; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogen Aliphatic (or cycloaliphatic) isocyanates such as added diphenylmethane diisocyanate can be mentioned. When using isocyanate as a curing agent, the content of isocyanate in the resin composition for forming a primer layer is not particularly limited. It is preferably 3 to 45 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the above polyol.

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

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

The (meth)acrylic-urethane copolymer resin is not particularly limited, but includes, for example, acrylic-urethane (polyester urethane) block copolymer resin. Further, as the curing agent, the various isocyanates described above are used. The ratio of acrylic to urethane in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited, but for example, the acrylic/urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 Examples include /2 to 2/8.

The thickness of the primer layer 4 is not particularly limited, but for example, 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, the amount is 1 to 10 g/m ² ). When the primer layer 4 has such a thickness, the weather resistance of the transfer film for three-dimensional molding can be further improved, and cracking, breakage, whitening, etc. of the protective layer 3 can be effectively suppressed.

The composition forming the primer layer 4 may contain various additives depending on the desired physical properties. These additives include, for example, weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants, matting agents, and the like. These additives can be appropriately selected from those commonly used, and examples of matting agents include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

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

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

[Decorative layer 5]
The decorative layer 5 is a layer provided as necessary to impart decorativeness to the resin molded product. The decorative layer 5 is usually composed of a pattern layer and/or a concealing layer. Here, the pattern layer is a layer provided to express patterns, letters, etc., and pattern-like designs, and the concealing layer is usually a solid layer on the entire surface and is provided to hide the coloring of the molding resin, etc. It is a layer. The concealing layer may be provided inside the picture layer to enhance the picture of the picture layer, or the concealing layer alone may form the decorative layer 5.

The pattern of the pattern layer is not particularly limited, but includes, for example, patterns of wood grain, stone grain, fabric grain, sand grain, geometric patterns, letters, and the like.

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

The coloring agent for the printing ink used to form the decorative layer 5 is not particularly limited, but includes, for example, metals such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, and brass, alloys, Or metallic pigments consisting of scaly 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 Pearlescent pigments made of foil powder such as lead carbonate; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, and calcium sulfide; white inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide Pigments: Inorganic pigments such as zinc white, Bengara, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black, etc.; isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, industhrene blue Examples include organic pigments (including dyes) such as RS and aniline black. These colorants may be used alone or in combination of two or more.

Further, the binder resin of the printing ink used to form the decorative layer 5 is not particularly limited, but examples include acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride resin, etc. Examples include vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, and rubber resins. These binder resins may be used alone or in combination of two or more.

In addition, the solvent or dispersion medium of the printing ink used to form the decorative layer 5 is not particularly limited, but examples include petroleum-based 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, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, etc. Ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; Chlorine organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; Water etc. These solvents or dispersion media may be used alone or in combination of two or more.

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

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

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

The decorative layer 5 may be a metal thin film layer. Examples of the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. The method for forming the metal thin film layer is not particularly limited, and examples thereof include vapor deposition methods such as vacuum evaporation method, sputtering method, ion plating method, etc. using the above-mentioned metals. Further, in order to improve the adhesion with adjacent layers, a primer layer using a known resin may be provided on the front or back surface of the metal thin film layer.

[Adhesive layer 6]
The adhesive layer 6 is necessary on the back surface (molded resin layer 8 side) of the decorative layer 5, transparent resin layer 7, etc. for the purpose of improving the adhesion between the transfer film for three-dimensional molding and the molded resin layer 8. This is a layer that is provided accordingly. The resin forming the adhesive layer 6 is not particularly limited as long as it can improve the adhesion and adhesion between these layers, and for example, a thermoplastic resin or a thermosetting resin may be used. Examples of the thermoplastic resin include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber resin, etc. . One type of thermoplastic resin may be used alone, or two or more types may be used in combination. Furthermore, examples of the thermosetting resin include urethane resin and epoxy resin. One type of thermosetting resin may be used alone, or two or more types may be used in combination.

Although the adhesive layer 6 is not necessarily a necessary layer, the transfer film for three-dimensional molding of the present invention can be applied to a decorating method by pasting onto a resin molded body prepared in advance, such as the vacuum pressure bonding method described below. If this is assumed, it is preferable that it be provided. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 6 by using a resin commonly used as a resin that exhibits adhesive properties by pressurization or heating among the various resins described above.

The thickness of the adhesive layer 6 is not particularly limited, but may be, for example, about 0.1 to 30 μm, preferably about 0.5 to 20 μm, and more preferably about 1 to 8 μm.

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

The transparent resin layer 7 contains a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, and a soft component, as necessary. (for example, rubber) and the like may be included.

The transparent resin layer 7 can be formed by a known printing method such as gravure printing, flexo 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.

The transfer film for three-dimensional molding of the present invention can be manufactured, for example, by a manufacturing method including the following steps. As mentioned above, the transfer film for three-dimensional molding of the present invention has a peel strength between the mold release layer 2 and the protective layer 3, and a value obtained by dividing the peel strength (N/inch) by the thickness of the protective layer (μm). is at a predetermined value, and the composition and thickness of the release layer and protective layer are adjusted as described above so as to satisfy the predetermined value. Further, as described above, the transfer layer 9 may include at least one layer such as the decorative layer 5, the primer layer 4, the adhesive layer 6, the transparent resin layer 7, etc., as necessary.

Step of forming a coating film for forming a mold release layer on the transfer substrate 1: irradiating the coating film for forming a mold release layer with ionizing radiation to form a mold release layer in which the coating film for mold release layer formation is cured. Step: Forming a coating film for forming a protective layer on the release layer. A step of irradiating the coating film for forming a protective layer with ionizing radiation to form a protective layer in which the coating film for forming a protective layer is cured.

2. Resin molded product and its manufacturing method The resin molded product of the present invention is formed by integrating the transfer film for three-dimensional molding of the present invention and a molding resin. Specifically, by laminating the molding resin layer 8 on the side opposite to the support 10 of the transfer film for three-dimensional molding, the molding resin layer 8, the transfer layer 9, and the support 10 are laminated in this order. A resin molded article with a support is obtained (see, for example, FIG. 3). Next, by peeling the support 10 from the resin molded product with the support, a resin molded product of the present invention in which at least the molded resin layer 8 and the transfer layer 9 are laminated is obtained (see, for example, FIG. 4). As shown in FIG. 4, the resin molded product of the present invention is further provided with at least one layer such as the decorative layer 5, primer layer 4, adhesive layer 6, transparent resin layer 7, etc., if necessary. Good too.

The resin molded article of the present invention can be manufactured by a manufacturing method including the following steps.
A step of laminating a molding resin layer on the side opposite to the support of the transfer film for three-dimensional molding,
Step of peeling the support from the transfer layer.

When the transfer film for three-dimensional molding is applied to, for example, an injection molding simultaneous transfer decoration method, examples of the method for producing the resin molded article of the present invention include, for example, a method including the following steps (1) to (5).

(1) First, the step of heating the transfer film for three-dimensional molding from the transfer layer side using a heating plate, with the transfer layer side (opposite side to the support) of the transfer film for three-dimensional molding for transfer facing into the mold. ,
(2) a step of preforming (vacuum forming) the transfer film for three-dimensional molding so as to follow the shape inside the mold, bringing it into close contact with the inner surface of the mold, and clamping the mold;
(3) The process of injecting resin into the mold,
(4) a step of taking out the resin molded product (resin molded product with support) from the mold after cooling the injected resin; and (5) a step of peeling the support from the transfer layer of the resin molded product.

In both steps (1) and (2) above, the temperature at which the transfer film for three-dimensional molding is heated is in the range of at least the vicinity of the glass transition temperature of the transfer base material 1 and below the melting temperature (or melting point). It is preferable. Usually, it is more preferable to carry out the reaction at a temperature near the glass transition temperature. Note that the above-mentioned "near the glass transition temperature" refers to a range of about ±5°C of the glass transition temperature, which is generally about 70 to 130°C when a polyester film suitable as the transfer substrate 1 is used. In addition, when using a mold with a not very 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 step (3) described later, the injection The transfer film for three-dimensional molding may be molded into the shape of a mold using the heat and pressure of the resin.

In both steps (3) above, a molding resin to be 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 by heating appropriately and in a fluid state. Then, cool and solidify. As a result, the transfer film for three-dimensional molding is integrated with and adheres to the formed resin molded article, resulting in a resin molded article with a support. The heating temperature of the molding resin depends on the type of molding resin, but is generally about 180 to 320°C. On the other hand, the temperature of the mold immediately before the molding resin is injected is much lower than the heating temperature of the molding resin, and is generally about 40 to 60°C. When the mold comes into contact with the hot molding resin, the temperature of the mold increases and the molding resin is cooled.

The thus obtained resin molded article with a support is cooled in step (4) and then taken out from the mold, and then the support 10 is peeled off from the transfer layer 9 in step (5) to produce a resin molded product. get. Furthermore, the step of peeling the support 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, step (5) may be included in step (4).

Furthermore, the resin molded article can also be produced by a vacuum pressure bonding method. In the vacuum crimping method, first, the transfer film for three-dimensional molding and the resin molded article of the present invention are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side, and are three-dimensionally molded. In the vacuum pressure bonding machine, the transfer film for three-dimensional molding is placed on the side of the first vacuum chamber, the resin molded body is placed on the second vacuum chamber side, and the side of the transfer film for three-dimensional molding on which the molded resin layer 8 is laminated faces the side of the resin molded body. The two vacuum chambers are placed in a vacuum state. The resin molded body is installed on a lifting platform provided on the second vacuum chamber side and capable of moving up and down. Next, the first vacuum chamber is pressurized and the molded body is pressed against the transfer film for three-dimensional molding using an elevator, and the transfer film for three-dimensional molding is moved using the pressure difference between the two vacuum chambers. It is attached to the surface of the resin molded body while being stretched. Finally, the two vacuum chambers are opened to atmospheric pressure, the support 10 is peeled off, and the excess portion of the transfer film for three-dimensional molding is trimmed as necessary to obtain the resin molded product of the present invention. can.

In the vacuum pressure bonding method, before the step of pressing the above-mentioned molded object onto the transfer film for three-dimensional molding, the transfer film for three-dimensional molding is heated in order to soften the transfer film for three-dimensional molding and improve moldability. It is preferable to include a step. The vacuum pressure bonding method including this step is sometimes particularly called a vacuum heat pressure bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the transfer film for three-dimensional molding, the thickness of the transfer film for three-dimensional molding, etc.; 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 depending on the application. The molding resin forming the molded 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 alone or in combination of two or more.

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

In addition, in the resin molded product with a support, the support 10 plays a role as a protective sheet for the resin molded product, so after manufacturing the resin molded product with a support, it is stored as it is without being peeled off, and it can be used to support the resin molded product when used. The body 10 may be peeled off. By using the resin molded product in this manner, it is possible to prevent the resin molded product from being damaged due to friction during transportation.

The resin molded product of the present invention can be used, for example, as an interior or exterior material for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; television receivers, air conditioners, etc. It can be used as a housing for home appliances; a container, etc.

The present invention will be explained in detail by showing Examples and Comparative Examples below. However, the present invention is not limited to the examples.

(Examples 1 to 7 and Comparative Examples 1 to 5)
[Manufacture of transfer film for three-dimensional molding]
As a transfer base material, a polyethylene terephthalate film (thickness: 50 μm) with an easily adhesive layer formed on one side was used. On the surface of the easily adhesive layer of the polyethylene terephthalate film, release layer material A or B listed in Table 1 was printed by gravure printing to form a coating film for forming a release layer (respectively, the thickness of the release layer was set to be 1.0 μm). Details of the release layer material A or B are as described below. When release layer material A was used, it was thermally cured at a temperature of 150° C. to form a release layer. When release layer material B was used, a release layer forming coating film was formed and then an electron beam was irradiated at an acceleration voltage of 165 kV and an irradiation dose of 7 Mrad to form a release layer.

Next, on the release layer of the obtained support, protective layer materials C, D, and E listed in Table 1 were applied so that the thickness after curing would be the thickness B (μm) listed in Table 1. was coated with a bar coater to form a coating film for forming a protective layer. Next, an electron beam was irradiated onto the protective layer forming coating film at an acceleration voltage of 165 kV and an irradiation dose of 5 Mrad to cure the protective layer forming coating film to form a protective layer.

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

[Release layer material]
A: Acrylic-melamine resin B: Ionizing radiation curable composition in which silicone is added to polycarbonate urethane acrylate to a content of 0.9% by mass

[Protective layer material]
C: Polycarbonate urethane acrylate and curing agent (hexamethylene diisocyanate, content in Table 1)
D: Polycaprolactone-based urethane acrylate and curing agent (hexamethylene diisocyanate, content in Table 1)
E: Resin composition containing pentaerythritol triacrylate (PETA) and polymethyl methacrylate (PMMA) at a mass ratio of 4:6

<Manufacture of resin molded products>
Put each transfer film for three-dimensional molding obtained above into a mold, and place the transfer film for three-dimensional molding into the mold (elliptical opening P (width in short axis direction y is 5 mm) as shown in Figure 5. ) was adsorbed to the shape formed on the resin molded product. In this state, the mold was closed and molten resin was injected into the mold. The molten resin was cooled, and the resin molded article with a support was taken out from the mold. The support was peeled off from the resin molded product with the support to produce a resin molded product. The temperature of the mold was set at 60°C, and the temperature of the molten resin was 265°C. The molten resin is a mixed resin of ABS resin and polycarbonate resin (CYCOLOY ^™ Resin XCY620) heated to 265° C. to melt it.

<Method for measuring peel strength>
For each transfer film for three-dimensional molding obtained above, the peel strength A between the release layer 2 and the protective layer 3 in an 80° C. environment was measured by the following method. The results are shown in Table 1. First, a transfer film for three-dimensional molding whose peel strength was to be measured, a mold for molding the same, and a resin to be laminated on the transfer film for three-dimensional molding (resin forming a molded resin layer) were prepared. The shape of the mold is a flat plate (a size that forms a resin molded product of 15 mm in length, 30 mm in width, and 3 mm in thickness), and when the transfer film for three-dimensional molding is molded in the mold, The area elongation rate of the surface of the transfer film for three-dimensional molding was substantially 0%. Moreover, the temperature of the mold was set at 60°C. The resin injected into the transfer film for three-dimensional molding (the resin that forms the molding resin layer) was a mixed resin of ABS resin and polycarbonate resin (CYCOLOY ^TM Resin XCY620) heated to 265°C and melted. . Under the above molding conditions, a molded resin layer was laminated on the transfer film for three-dimensional molding according to the steps (1a) to (3a) above to obtain a decorated resin molded product with a support. Next, a 1-inch wide polyester adhesive tape (NITTO TAPE, No. 31B 75 High) was attached with a finger to the surface of the transfer base material layer of the decorated resin molded product with a support. Next, a cut was made with a cutter on the surface of the decorative resin molded product with support along the attached polyester adhesive tape. At this time, the incisions were made to penetrate through the transfer base material (if it had a release layer, also the release layer). Next, at the end of the polyester adhesive tape, about 10 mm of the polyester adhesive tape was peeled off with fingers in the length direction to prepare a sample. At this time, the transfer base material was also peeled off together with the polyester adhesive tape. Next, the sample was placed in a Tensilon tester (Tensilon RTC-1250A manufactured by Orientec Co., Ltd.), and the load cell part of the Tensilon tester and the part from which the polyester adhesive tape was peeled were connected. Next, the sample was heated for 1 minute using a heater attached to the Tensilon tester. At this time, the set temperature of the heater was 80°C. Next, the polyester adhesive tape was peeled off at a peeling speed of 100 mm/min so that the peeling direction was always 90° with respect to the surface of the transfer film for three-dimensional molding, and the load indicated on the load cell was applied to the peel strength ( N/inch).

<Evaluation of foil burrs>
The appearance of foil burrs at the opening of each resin molded product obtained in the above <Manufacture of resin molded products> was visually observed. Specifically, foil burrs at the opening P shown in FIG. 5 of the resin molded product were evaluated based on the following criteria. As shown in FIG. 5, in the short axis direction y of the opening P, y1 is the end, y2 and y3 are lines dividing the opening into three in the short axis direction y, and y4 is the line opposite to y1. This is the end of the Table 1 shows the evaluation results for foil burrs.

A ⁺ : Since the foil burr does not reach the position from the end y1 to y2 in the short axis direction y direction, it is very easy to remove the foil burr with cellophane tape or the like, and this is particularly suitable for practical use.
A: The foil burr reaches the position from end y1 to y2 in the short axis direction y direction, but does not reach the position y3, so it is easy to remove the foil burr with cellophane tape, etc., and it is not suitable for practical use. Suitable above.
B: The foil burr reaches the positions y1 to y3 of the short axis direction y direction, but does not reach the position y4, so it is possible to remove the foil burr with cellophane tape etc. There is no practical problem.
C: Because the foil burr has reached the position from end y1 to y4 in the short axis direction y direction, it takes time to remove the foil burr with cellophane tape, and there is a possibility of contamination around the device due to foil spillage. increases, which poses a practical problem.

<Evaluation of transferability>
For each resin molded product obtained in the above <Manufacture of resin molded product>, the transfer state of the transfer layer was visually confirmed, and the transferability of the transfer film for three-dimensional molding was evaluated using the following criteria. The results are shown in Table 1.

A: No release layer or transfer base material remained on the surface of the resin molded product, and the transfer state was good.
B: A release layer or a transfer base material may slightly remain on the surface of the resin molded product, or may remain slightly, but it can be easily removed and has transferability with no practical problems.
C: The mold release layer and transfer base material remain on the surface of the resin molded product and cannot be easily removed, resulting in transferability that is problematic in practice.

<Evaluation of wear resistance>
The surface of each resin molded product obtained in the above <Manufacture of resin molded products> was rubbed with a cloth coated with sun lotion (manufactured by Thierry, sun lotion for test standard PV3964), and the surface of the decorated resin molded product was rubbed. Abrasion resistance was evaluated using the following criteria. The results are shown in Table 1. The abrasion resistance was evaluated using an abrasion test of 10,000 strokes at 10N in accordance with the DIN EN 60068-2-70/IEC 68-2-70 standard.

A: There is no peeling of the protective layer of the resin molded product, and there is no exposure of the lower layer due to wear of the protective layer.
C: The decorative layer is exposed due to peeling or abrasion of the protective layer of the resin molded product.

<Evaluation of scratch resistance>
Abrasive paper 281Q WOD Schleifpaper (manufactured by 3M) with a flat size of 215.9 mm x 279 mm was pasted on the tip of the test jig of the Martindale abrasion tester, and each resin molded product obtained in the above <Manufacture of resin molded products> The surface of the product was rubbed 100 times under a load of 800 gf, and the rate of decrease in the 20° gloss value after the test was evaluated according to the following criteria. The results are shown in Table 1. Those with a small reduction rate in gloss value had fewer scratches, and the scratches disappeared after a while. This indicates that the protective layer has self-healing properties.

A: The rate of decrease in gloss value is less than 5% after 5 minutes of the test, and the rate of decrease in gloss value has recovered to less than 1% after 30 minutes of the test, and has excellent scratch resistance in practical terms. .
B: The rate of decrease in gloss value after 5 minutes of the test is 5% or more and less than 30%, and the rate of decrease in gloss value has recovered to less than 5% after 30 minutes of the test, and the scratch resistance has no problem in practical use. have.
C: The rate of decrease in gloss value is 30% or more after 5 minutes of the test, and the rate of decrease in gloss value remains 30% or more even after 30 minutes of the test, and there is a problem in scratch resistance in practical terms.

<Evaluation of deep drawing formability>
Each of the three-dimensional molding transfer films described above was cut into a rectangular shape with 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 testing machine with an initial distance between tension chucks of 100 mm and a tensile speed of 100 mm/min. For the measurement, a film sample was set in a constant temperature bath set at a temperature of 100°C in advance, and after preheating for 60 seconds, a tensile test was performed to measure the amount of elongation (elongation at break) until the film cracked. The measurement was performed on three samples for each level, and the average value of the three samples was taken as the fracture elongation. Based on the breaking elongation, the deep drawability of the transfer film for three-dimensional molding was evaluated according to the following criteria. The results are shown in Table 1.

A: Fracture elongation of 80% or more. This is a level that can be used with molds commonly called deep drawing.
B: Fracture elongation of 50% or more and less than 80%. A level that does not pose a problem when molding.
C: Fracture elongation less than 50%. A level that causes problems in molding many molds.

As shown in Table 1, the transfer films for three-dimensional molding of Examples 1 to 7 had a peel strength between the release layer and the protective layer in an 80°C environment of less than 0.90 N/inch, and The value obtained by dividing the peel strength value (N/inch) by the protective layer thickness value (μm) was 0.10 or more, and foil burrs and release layer transfer defects were effectively suppressed. Furthermore, the transfer films for three-dimensional molding of Examples 1 to 7 had practically usable characteristics in terms of deep drawability, abrasion resistance, and scratch resistance.

1 Transfer base material 2 Release layer 3 Protective layer 4 Primer layer 5 Decorative layer 6 Adhesive layer 7 Transparent resin layer 8 Molded resin layer 9 Transfer layer 10 Support P Opening

Claims (5)

A transfer film for three-dimensional molding, comprising a support having at least a transfer base material and a release layer, and a transfer layer having a protective layer provided in contact with the release layer,
The peel strength between the release layer and the protective layer in an 80° C. environment is less than 0.90 N/inch, and
A transfer film for three-dimensional molding, wherein a value obtained by dividing the peel strength (N/inch) by the thickness (μm) of the protective layer is 0.20 or more. The transfer film for three-dimensional molding according to claim 1 , wherein the thickness of the release layer is 5.0 μm or less. 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 1 or 2, wherein the ionizing radiation-curable resin composition of the protective layer contains polycarbonate (meth)acrylate. The transfer film for three-dimensional molding according to any one of claims 1 to 3 , wherein the transfer layer has at least one selected from the group consisting of a primer layer, 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 1 to 3 ;
Peeling the support from the transfer layer;
A method for manufacturing a resin molded product, comprising: