JP6972855B2 - Manufacturing method of transfer film for three-dimensional molding and resin molded products - Google Patents

Description

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

For resin molded products used for automobile interior / exterior, building material interior materials, home appliances, etc., and resin molded products used for organic glass used as a substitute material for inorganic glass, the purpose is to protect the surface and impart design. As a method, a technique of laminating a protective layer using a three-dimensional molded film is used. The three-dimensional molded film used in such a technique can be roughly classified into a laminated type three-dimensional molded film and a transfer type three-dimensional molded film. The laminated three-dimensional molded film is laminated on the support base material so that the protective layer is located on the outermost surface, and by laminating the molding resin on the support base material side, the support base material is contained in the resin molded product. Is used to be incorporated. On the other hand, in the transfer type three-dimensional molded film, a protective layer is laminated directly on the supporting base material or via a release layer provided as necessary, and after laminating the molding resin on the side opposite to the supporting base material. By peeling off the support base material, the support base material is used so as not to remain in the resin molded product. These two types of three-dimensional molded films are used properly according to the shape of the resin molded product and the desired function.

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

Under such prior art, Patent Documents 1 and 2 disclose a technique for forming a protective layer using an ionizing radiation curable resin composition containing a 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 a protective layer is formed of a cured product of an ionizing radiation curable resin composition. Is possible.

Japanese Unexamined Patent Publication No. 2012-56236 Japanese Unexamined Patent Publication No. 2013-111929

In the process of transferring a transfer film for three-dimensional molding to a molding resin as described above to obtain a resin molded product, the area and shape of the transferred layer (transfer layer) such as a protective layer and the surface to be transferred of the molding resin are determined. Since it is difficult to make a perfect match, the area of the transfer layer of the transfer film for three-dimensional molding is generally designed to be larger than the area of the surface to be transferred of the molding resin. As a result of repeated studies by the present inventor, for example, in the conventional transfer film for three-dimensional molding as disclosed in Patent Documents 1 and 2, the area of the transfer layer is designed to be larger than the area of the surface to be transferred of the molding resin. As a result, when the transfer base material is peeled off after the transfer layer is laminated on the molding resin, the transfer layer of the portion that does not need to be peeled off from the transfer base material is pulled by the transfer layer laminated on the molding resin. It was confirmed that the transfer layer may not be cut at the end of the surface to be transferred, and so-called "foil burrs" may occur in which the transfer layer protrudes from the end and remains.

Further, as a result of repeated studies by the present inventors, for example, in the conventional transfer type three-dimensional molded film as disclosed in Patent Documents 1 and 2, when the support is peeled off from the transfer layer, the support is used. It has been found that the release layer remains on the surface of the transfer layer, and transfer defects may occur. 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, the appearance of the surface of the obtained resin molded product is as long as the residual amount is difficult to remove from the surface. It leads to defects. The present inventors have found that the problem of transfer failure arises especially when the shape of the mold is complicated, when the molding temperature is high, or when the molding depth is deep. Then, the present inventors further examined this problem as follows.

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

(1a) First, the transfer layer side (opposite side to the support) of the three-dimensional molding transfer film is directed to the side in the mold where the resin is injected, and the opposite side (support side of the three-dimensional molding transfer film). ), A process in which a transfer film for three-dimensional molding is brought into close contact with the inner surface of the mold by vacuum suction and the mold is compacted.
(2a) Step of injecting resin into the mold,
(3a) A step of taking out the resin molded product (resin molded product with a support) from the mold after cooling the injection resin, and (4a) a step of peeling the support from the transfer layer of the resin molded product.

Further, when the mold is deep-drawn, there is a method of preheating the transfer film for three-dimensional molding before injecting the resin and then bringing it into close contact with the inner surface of the mold. Specifically, a resin molded product 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 extends the molding time, the transfer film for three-dimensional molding becomes soft and the followability to the mold can be improved.

(1b) First, a step of heating the transfer film for three-dimensional molding from the transfer layer side by a hot 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 inner shape of the mold so that the film is brought into close contact with the inner surface of the mold and compacted.
(3b) Step of injecting resin into the mold,
(4b) A step of taking out the resin molded product (resin molded product with a support) from the mold after cooling the injection resin, and (5b) a step of peeling the support from the transfer layer of the resin molded product.

In the manufacturing process of such a resin molded product, the temperature of the resin (molten resin) injected into the mold is much higher than the temperature of the mold, and the mold also exhibits a cooling function of the resin molded product. .. In addition, when the high-temperature molten resin is injected into the mold, the transfer film for three-dimensional molding does not adhere to the mold in the part where the shape of the mold is complicated, so that the mold cools. It is difficult to proceed, and the high temperature state of the portion may take a long time as compared with the portion in contact with the mold. Further, even when the molding temperature is high or the molding depth is deep, in the portion where the transfer film for three-dimensional molding is not in close contact with the mold, similarly, the portion where the high temperature state of the portion is in contact with the mold. It may take a long time compared to. In such a case, when the support is peeled off from the transfer layer of the resin molded product, the adhesive strength between the support and the transfer layer becomes too high in the portion where the transfer film for three-dimensional molding is exposed to high temperature, and the support is supported. It was clarified that when the body was peeled off from the transfer layer, the release layer of the support had a transfer defect remaining on the surface of the transfer layer.

Based on such a novel problem, it is a main object of the present invention to provide a transfer film for three-dimensional molding in which transfer defects of foil burrs and release layers are effectively suppressed. Another object of the present invention is to provide a method for manufacturing a resin molded product using the transfer film for three-dimensional molding.

The present inventors have made diligent 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 to a predetermined value in a high temperature environment, the peel strength and the thickness of the protective layer have a predetermined relationship. It was found that the suppression of foil burrs and the suppression of transfer defects in the release layer can be achieved at the same time by setting to. More specifically, in a transfer film for three-dimensional molding including at least a support having a transfer base material and a release layer, and a transfer layer having a protective layer provided so as to contact the release layer. The release strength between the release layer and the protective layer in an environment of 80 ° C. was set to less than 0.90 N / inch, and the value of the release strength (N / inch) was divided by the value of the thickness of the protective layer (μm). It has been found that by setting the value to 0.10 or more, both the foil burr of the transfer film for three-dimensional molding and the transfer defect of the release layer are effectively suppressed. The present invention has been completed by further studies based on such findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A three-dimensional molding transfer film comprising at least a transfer substrate and a support having a release layer, and a transfer layer having a protective layer provided so as to contact the release layer.
The peel strength between the release layer and the protective layer in an environment of 80 ° C. is less than 0.90 N / inch, and
A transfer film for three-dimensional molding, wherein the 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 2. The transfer film for three-dimensional molding according to any one of Items 1 to 3, wherein the release layer has a thickness of 5.0 μm or less.
Item 5. Item 2. The transfer film for three-dimensional molding according to any one of Items 1 to 4, wherein the protective layer is made of a cured product of an ionizing radiation curable resin composition.
Item 6. Item 5. 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.
Item 7. Item 2. 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.
Item 8. A step of laminating a molding resin layer on the transfer layer side of the transfer film for three-dimensional molding according to any one of Items 1 to 7.
The step of peeling the support from the transfer layer and
A method for manufacturing a resin molded product.

According to the present invention, it is possible to provide a transfer film for three-dimensional molding in which transfer defects of foil burrs and release layers 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.

It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding of this invention. It is a schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding of this invention. It is a schematic diagram of the cross-sectional structure of one form of the resin molded product with a support obtained by using the transfer film for three-dimensional molding of the present invention. It is a schematic diagram of the cross-sectional structure of one form of the resin molded product obtained by using the transfer film for three-dimensional molding of the present invention. It is a schematic diagram for demonstrating the evaluation method of the foil burr in an Example.

1. 1. Transfer film for three-dimensional molding The transfer film for three-dimensional molding of the present invention has at least a support having a transfer base material and a release layer, and a protective layer provided so as to be in contact with the release layer. A transfer film for three-dimensional molding including a layer, wherein the release strength between the release layer and the protective layer in an environment of 80 ° C. is less than 0.90 N / inch, and the release strength (N). The value obtained by dividing (/ inch) by the thickness (μm) of the protective layer is 0.10 or more. By having such a structure, the transfer film for three-dimensional molding of the present invention can effectively suppress transfer defects of foil burrs and release layers. Hereinafter, the transfer film for three-dimensional molding of the present invention will be described in detail.

In this specification, the numerical range indicated by "~" means "greater than or equal to" and "less than or equal to". For example, the notation of 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 may not have a decorative layer or the like, and may be transparent, for example. Further, "(meth) acrylate" means "acrylate or methacrylate", and other similar substances 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 a 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 transfer base material 1 and the release layer 2 constitute the support 10, and the support 10 forms the transfer film for three-dimensional molding into the molding resin layer 8. After being laminated on the surface, it is peeled off and removed. The surface of the resin molded product obtained by peeling and removing the support 10 is composed of 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 the adjacent layer. Further, the transfer layer 9 may be provided with the decorative layer 5 as necessary for the purpose of imparting decorativeness to the transfer film for three-dimensional molding. Further, the adhesive layer 6 may be provided, if necessary, for the purpose of enhancing the adhesion of the molded resin layer 8. Further, a transparent resin layer 7 may be provided, if necessary, for the purpose of improving the adhesion between the protective layer 3 or the primer layer 4 and the adhesive layer 6. In the transfer film for three-dimensional molding of the present invention, the protective layer 3, the primer layer 4, the decorative layer 5, the adhesive layer 6, the transparent resin layer 7, and the like constitute the transfer layer 9, and the transfer layer 9 is the molding resin layer. Transferred to No. 8 to obtain the resin molded product of the present invention.

As the laminated structure of the transfer film for three-dimensional molding of the present invention, the laminated structure in which the transfer base material / release layer / protective layer are laminated in this order; the transfer base material / release layer / protective layer / primer layer is this. Laminated structure in which the transfer substrate / release layer / protective layer / primer layer / decorative layer are laminated in this order; transfer substrate / release layer / protective layer / primer layer / decorative layer / A laminated structure in which adhesive layers are laminated in this order; a laminated structure in which a transfer substrate / a release layer / a protective layer / a primer layer / a transparent resin layer / an adhesive layer are laminated in this order can be mentioned. FIG. 1 shows, as one aspect of the laminated structure of the transfer film for three-dimensional molding of the present invention, three-dimensional molding in which a transfer substrate / release layer / protective layer / primer layer / decorative layer / adhesive layer are laminated in this order. The schematic diagram of the cross-sectional structure of one form of the transfer film for use is shown. Further, in FIG. 2, as one aspect of the laminated structure of the transfer film for three-dimensional molding of the present invention, the transfer substrate / release layer / protective layer / primer layer / transparent resin layer / adhesive layer are laminated in this order. The schematic diagram of the cross-sectional structure of one form of the transfer film for three-dimensional molding is shown.

Composition of each layer forming a transfer film for three-dimensional molding [Support 10]
The transfer film for three-dimensional molding of the present invention has a transfer base material 1 and a release layer 2 as a support 10. The protective layer 3, the primer layer 4, the decorative layer 5, the adhesive layer 6, the transparent resin layer 7, and the like formed on the support 10 constitute the transfer layer 9. 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 removed to form a resin molded product. Is obtained.

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

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

The transfer substrate 1 has an uneven shape on at least one surface, if necessary, for the purpose of imparting an uneven shape to the surface of the protective layer 3 described later and improving blocking resistance. You may. By laminating the protective layer 3 on the surface of the transfer base material 1 having an uneven shape 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. Further, in the case of imparting an uneven shape to the surface of the transfer base material 1 in order to improve the blocking resistance without imparting the uneven shape to the surface of the protective layer 3, the protective layer 3 of the transfer base material 1 is used. It is sufficient to form an uneven shape only on the surface on the opposite side, reduce the uneven shape of the transfer substrate 1, or adjust the thickness of the release layer 2.

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

Typical examples of the fine particles include synthetic resin particles and inorganic particles, but it is particularly preferable to use synthetic resin particles from the viewpoint of improving three-dimensional moldability. The synthetic resin particles are not particularly limited as long as they are particles formed of synthetic resin, and are, for example, acrylic beads, urethane beads, silicone beads, nylon beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene. Beads and the like can be mentioned. Among these synthetic resin particles, acrylic beads, urethane beads, and silicone beads are preferable from the viewpoint of forming an uneven shape having excellent scratch resistance on the protective layer 3. Examples of the inorganic particles include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide, kaolin and the like. These fine particles may be used alone or in combination of two or more. The particle size of the fine particles is preferably about 0.3 to 25 μm, more preferably about 0.5 to 5 μm. The particle size of the fine particles in the present invention is dispersed in the air by injecting the powder to be measured from the nozzle using compressed air using the Shimadzu laser diffraction type particle size distribution measuring device SALD-2100-WJA1. It refers to the one by the jet type dry measurement method to measure by letting.

The content of the fine particles contained in the transfer substrate 1 may be appropriately set according to the purpose, and is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin contained in the transfer substrate 1, for example. The degree, more preferably about 5 to 80 parts by mass. Further, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, fluorescent whitening agents and the like can be added to the transfer substrate 1 as needed.

The polyester sheet suitably used as the transfer base material 1 in the present invention is produced, for example, as follows. First, the above polyester resin and other raw materials are supplied to a well-known melt extruder such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester resin to melt. Then, while extruding the molten polymer, it is rapidly cooled and solidified on a rotary cooling drum so as to have a temperature equal to or lower than the glass transition temperature to obtain a substantially amorphous unoriented sheet. It is obtained by stretching this sheet in the biaxial direction to form a sheet and heat-fixing it. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Further, if necessary, it may be stretched again in the vertical and / or horizontal directions before or after heat fixing. In the present invention, in order to obtain sufficient dimensional stability, the stretch ratio is preferably 7 times or less, more preferably 5 times or less, still more preferably 3 times or less. Within this range, when the obtained polyester sheet is used for the transfer film for three-dimensional molding, the transfer film for three-dimensional molding does not shrink again in the temperature range when the molding resin is injected, and in the temperature range. The required sheet strength can be obtained. The polyester sheet may be manufactured as described above, or a commercially available polyester sheet may be used.

Further, the transfer substrate 1 can be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if desired, for the purpose of improving the 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 method, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments are appropriately selected depending on the type of the transfer substrate 1, but in general, the corona discharge treatment method is preferably used from the viewpoints of effectiveness and operability. Further, the transfer substrate 1 may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of enhancing the interlayer adhesion with the release layer. When a commercially available polyester sheet is used, the commercially available product may be one that has been subjected to the above-mentioned surface treatment in advance or one that is provided with an easy-adhesive layer.

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

(Release layer 2)
The release layer 2 is provided on the surface of the transfer substrate 1 on the side where the transfer layer 9 is laminated, for the purpose of enhancing the peelability between the support 10 and the transfer layer 9.

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

In the present invention, the peel strength between the release layer 2 and the protective layer 3 described later in an environment of 80 ° C. is less than 0.90 N / inch. The upper limit of the peel strength in a high temperature environment of 80 ° C. 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 susceptibility of transfer defects to the transfer films for three-dimensional molding having the protective layer 3 having the same thickness, and found that the release layer 2 and the protective layer 3 in a high temperature environment (80 ° C.). It has been found that the larger the peeling strength is, the more easily the release layer 2 remains on the surface of the protective layer 3 and the more likely it is that transfer defects occur. Therefore, it is considered that a predetermined upper limit value exists for the peel strength. On the other hand, the present inventors evaluated the susceptibility of foil burrs to a transfer film for three-dimensional molding in which the release strength between the 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 smaller 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, the less likely it is that foil burrs will occur. Therefore, it was clarified that it is important to balance not only the peel strength but also the thickness of the protective layer 3 with respect to the foil burr. 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 the compatibility between the foil burr and the transferability. .. As a result of further studies, the present inventors have found that the upper limit of the peel strength in the high temperature environment of 80 ° C. is less than 0.90 N / inch, and further protects the peel strength. It has been found that when the value divided by the thickness (μm) of the layer 3 satisfies the relationship of 0.10 or more, transfer defects of the foil burr and the release layer are effectively suppressed.

From the viewpoint of more effectively suppressing transfer defects of the foil burr and the release layer, the peel strength between the release layer 2 and the protective layer 3 described later in an environment of 80 ° C. is preferably about 0.85 N / inch. Hereinafter, it is more preferably about 0.20 to 0.85 N / inch, further preferably about 0.30 to 0.85 N / inch, and even more preferably about 0.40 to 0.80 N / inch. In the present invention, the method for measuring the peel strength between the release layer and the protective layer 3 in an environment of 80 ° C. is as follows.

<Measurement method of peel strength>
First, a transfer film for three-dimensional molding to be measured for peel strength, a mold for molding the transfer film, and a resin (resin for forming a molding resin layer) to be laminated on the transfer film for three-dimensional molding 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 becomes substantially 0%. It shall be. The temperature of the mold is set to 60 ° C. As the resin (resin that forms the molding resin layer) to be injected into the transfer film for three-dimensional molding, a mixed resin of ABS resin and polycarbonate resin (for example, CYCOLOY ^TM Resin XCY620) is heated to 265 ° C. and melted. And. Under the above molding conditions, the molding resin layer is laminated on the transfer film for three-dimensional molding by the above steps (1a) to (3a) to obtain a decorative resin molded product with a support. Next, a 1-inch wide polyester adhesive tape (NITTO TAPE, No. 31B 75 high) is attached to the surface of the transfer substrate layer of the decorative resin molded product with a support with a finger to bring it into close contact. Next, a notch is made on the surface of the decorative resin molded product with a support along the pasted polyester adhesive tape with a cutter. At this time, the notch is made to penetrate the transfer substrate (and the release layer if it has a release layer). Next, at the end of the polyester adhesive tape, the polyester adhesive tape is peeled off with a finger about 10 mm in the length direction to prepare a sample. At this time, the transfer substrate 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 portion of the Tensilon tester and the portion from which the polyester adhesive tape has been peeled off are connected. Next, the sample is heated for 1 minute with the heater attached to the Tensilon tester. At this time, the set temperature of the heater is 80 ° C. Next, the polyester adhesive tape is peeled off at a peeling speed of 100 mm / min so that the peeling direction of the polyester adhesive tape is always 90 ° with respect to the surface of the transfer film for three-dimensional molding, and the load indicated on the load cell is applied to the peeling strength (peeling 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. The release layer 2 is composed of a cured product of an ionizing radiation curable resin composition from the viewpoint of more effectively suppressing transfer defects of the foil burr and the release layer by appropriately setting the peel strength. Is preferable. Hereinafter, preferable ionizing radiation curable resins used for forming the release layer 2 will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the release layer 2 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having the above. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used, but in addition, X It also includes electromagnetic waves such as rays and γ rays, and charged particle beams such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the release layer 2 because it can be made solvent-free, does not require a photopolymerization initiator, and stable curing characteristics can be obtained. Used for.

As the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or higher), preferably three or more (trifunctional or higher) polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (). Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Meta) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylol propanetri (meth) acrylate, ethylene oxide-modified trimethylol propanetri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate, tris (acryloxyethyl) isocyanurate , Propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.

Further, as the above-mentioned oligomer used as an ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomers having a cationically polymerizable functional group in the molecule (for example, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. .. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, a polycarbonate-based urethane (meth) acrylate which is a urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol with a polyhydric isocyanate compound and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol, a polyester polyol, or a caprolactone-based polyol with a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can also be used. The polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylates can be obtained by adding (meth) acrylic acid to the ends or side chains of silicones that have a polysiloxane bond in the main chain. Among these, as the polyfunctional (meth) acrylate oligomer, polycarbonate (meth) acrylate (polycarbonate-based urethane (meth) acrylate and the like), urethane (meth) acrylate and the like are particularly preferable. These oligomers may be used alone or in combination of two or more.

Among the above-mentioned ionizing radiation curable resins, from the viewpoint of more effectively suppressing transfer defects of the foil burrs and the release layer by appropriately setting the peeling strength, the caprolactone-based polyol and the polyisocyanate compound are used. It is preferable to use caprolactone-based urethane (meth) acrylate obtained by esterifying the polyurethane oligomer obtained by the reaction with (meth) acrylic acid, or polycarbonate (meth) acrylate (polycarbonate-based urethane (meth) acrylate, etc.). , Polycarbonate (meth) acrylate (polycarbonate-based urethane (meth) acrylate, etc.) and polyfunctional (meth) acrylate are particularly preferable.

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

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

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

The compound (C) to be a carbonyl component is a compound selected from a carbonic acid diester, phosgene, or an equivalent thereof. Specific examples thereof include carbonate diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate, phosgene, and halogenated formic acid esters such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. And so on. These may be used alone or in combination of two or more.

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

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

The method for producing a polycarbonate polyol described above is described in, for example, Japanese Patent Application Laid-Open No. 64-1726. Further, as described in Japanese Patent Application Laid-Open No. 3-181517, 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.

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

In the ionizing radiation curable resin composition, the polycarbonate (meth) acrylate is preferably used together with the polyfunctional (meth) acrylate. The mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is more preferably polycarbonate (meth) acrylate: polyfunctional (meth) acrylate = 98: 2 to 50:50. When the mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is smaller than 98: 2 (that is, the amount of the polycarbonate (meth) acrylate is 98% by mass or less with respect to the total amount of the two components). , The above-mentioned durability and chemical resistance are further improved. On the other hand, when the mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is larger than 50:50 (that is, the amount of the 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 may be any bifunctional or higher functional (meth) acrylate, and is not particularly limited. Here, the bifunctional means having two ethylenically unsaturated bonds {(meth) acryloyl group} in the molecule. The number of functional groups is preferably about 2 to 6.

Further, the polyfunctional (meth) acrylate may be either an oligomer or a monomer, but from the viewpoint of appropriately setting the peel strength and suppressing transfer defects of the foil burr and the release layer more effectively. , Polyfunctional (meth) acrylate oligomers are preferred.

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

Further, as other polyfunctional (meth) acrylate oligomers, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and a silicone (meth) having a polysiloxane bond in the main chain. ) Acrylate-based oligomers, aminoplast resin (meth) acrylate-based oligomers obtained by modifying an aminoplast resin having many reactive groups in a small molecule, and the like.

Specific examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-. Hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified di Cyclopentenyldi (meth) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, isocyanurate di (meth) acrylate, trimethyl propanthry (meth) acrylate, ethylene oxide-modified trimethyl propanthry (Meta) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propantri (meth) acrylate, tris (acryloxy) 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. Be done. The polyfunctional (meth) acrylate oligomer and the polyfunctional (meth) acrylate monomer described above may be used alone or in combination of two or more.

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

The content of the polycarbonate (meth) acrylate in the ionizing radiation curable resin composition forming the release layer 2 is not particularly limited, but the above-mentioned peel strength is appropriately set to be suitable for the foil burrs and the release layer. From the viewpoint of more effectively suppressing transfer defects, it is preferably about 98 to 50% by mass, more preferably about 90 to 65% by mass.

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

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

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

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the release layer 2, the electron beam transmission depth and mold release The acceleration voltage is selected so that the thicknesses of the layers 2 are substantially equal. Further, when the release layer 2 is cured by an electron beam together with the protective layer 3 described later, the acceleration voltage is such that the transmission depth of the electron beam and the total thickness of the release layer 2 and the protective layer 3 are substantially equal to each other. To select. As a result, it is possible to suppress the irradiation of the layer located below the release layer 2 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is an amount at which the crosslink density of the release layer 2 becomes 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 in such a range, deterioration of the transfer substrate 1 due to ionizing radiation transmitted through the release layer 2 can be suppressed. In the above example, the number of functional groups of the polyfunctional (meth) acrylate is 2, and an appropriate irradiation dose is required according to the number of functional groups.

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

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

In addition to the ionizing radiation curable resin composition, the release layer includes a silicone-based resin, a fluororesin, an acrylic-based resin (for example, an acrylic-melamine-based resin is included), a polyester-based resin, a polyolefin-based resin, and a polystyrene-based resin. Resins, polyurethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as vitrified cotton, copolymers of monomers forming the thermoplastic resins, or these resins (meth). It can be formed by using a resin composition modified with acrylic acid or urethane, alone or in combination of two or more. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. A resin composition alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and a copolymer of an acrylic resin and styrene and acrylic. Examples thereof include a resin composition mixed with the above emulsion. Of these, it is particularly preferable to form the release layer with an acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

The thickness of the release layer 2 is not particularly limited, but is preferably 5.0 μm from the viewpoint of appropriately setting the peel strength and further effectively suppressing transfer defects of the foil burr and the release layer. Hereinafter, it is more preferably 2.5 μm or less, further preferably 2.0 μm or less, and the lower limit value 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, the primer layer 4, the decorative layer 5, the adhesive layer 6, the transparent resin layer 7, and the like formed on the support 10 constitute the transfer layer 9. ing. In the present invention, after the transfer film for three-dimensional molding and the molding resin are integrally molded, 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 to form a tertiary. A resin molded product is obtained in which the transfer layer 9 of the original molding transfer film is transferred to the molding resin layer 8. Hereinafter, each of these layers will be described in detail.

[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 enhancing 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 described 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 set to the thickness of the protective layer 3 (the thickness of the protective layer 3 ( The value divided by μm) is 0.10 or more.

From the viewpoint of more effectively suppressing transfer defects of the foil burr and 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 peeling 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 0. Examples thereof 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 transfer defects of the foil burrs and the release layer are not particularly limited. From the viewpoint of more effectively suppressing the above, preferably about 0.5 to 10 μm, more preferably about 1 to 8 μm, still more preferably about 1 to 5 μm. When the thickness in such a range is satisfied, sufficient physical properties as a protective layer such as durability and chemical resistance can be obtained, and ionizing radiation can be uniformly irradiated, so that the material is uniformly cured. It will be possible and economically advantageous. Further, when the thickness of the protective layer 3 after curing satisfies the above range, the three-dimensional formability of the transfer film for three-dimensional molding is further improved, so that it can follow a complicated three-dimensional shape such as an automobile interior application. You can get sex.

As the material constituting the protective layer 3, the peel strength between the release layer 2 and the protective layer 3 in an environment of 80 ° C. is set to the above value, and the peel strength is divided by the thickness (μm) of the protective layer 3. As long as the value can be set to 0.10 or more, the protective layer 3 can be made of a resin such as a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin without particular limitation. From the viewpoint of more effectively suppressing transfer defects of the foil burr and the release layer, the protective layer 3 is preferably composed of a cured product of an ionizing radiation curable resin composition. In the transfer film for three-dimensional molding of the present invention, the ionized radiation curable resin composition forming the protective layer 3 is uncured when laminated with the molded resin layer, and is added with a support after the lamination. The decorative resin molded product or the decorative resin molded product from which the support has been peeled off may be cured by irradiating it with ionizing radiation.

As the ionizing radiation curable resin used for forming the protective layer 3, the same one as exemplified in (Release layer 2) is exemplified.

From the viewpoint of more effectively suppressing transfer defects of the foil burr and the release layer, the ionized radiation curable resin composition forming the protective layer 3 is the caprolactone-based urethane (meth) exemplified in (release layer 2). It is preferable to contain acrylate and polycarbonate (meth) acrylate (polycarbonate-based urethane (meth) acrylate and the like), and it is particularly preferable to contain polycarbonate (meth) acrylate (polycarbonate-based urethane (meth) acrylate and the like). The details of the polycarbonate (meth) acrylate are as described in (Release layer 2).

Further, as in the release layer 2, the polycarbonate (meth) acrylate is preferably used together with the polyfunctional (meth) acrylate in the ionizing radiation curable resin composition of the protective layer 3. The mass ratio of the 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 the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is smaller than 98: 2 (that is, the amount of the polycarbonate (meth) acrylate is 98% by mass or less with respect to the total amount of the two components). , The above-mentioned durability and chemical resistance are further improved. On the other hand, when the mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is larger than 50:50 (that is, the amount of the 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 described in (Release layer 2), and any bifunctional or higher functional (meth) acrylate may be used, and the number of functional groups is preferably about 2 to 6. Be done. The polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability. The polyfunctional (meth) acrylate oligomer and the polyfunctional (meth) acrylate monomer are as described above.

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 the foil burrs and transfer defects of the release layer are more likely to occur. From the viewpoint of more effective suppression, the content is preferably about 98 to 50% by mass, more preferably about 90 to 65% by mass.

<Acrylic resin>
It is more preferable that the protective layer 3 is formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate as the ionizing radiation curable resin and an acrylic resin. Further, when an ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate and an acrylic resin is used, 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 acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a combination of (meth) acrylic acid ester and another monomer. Polymers include, specifically, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate-. (Meta) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl acrylate copolymer (meth) acrylate copolymer A (meth) acrylic resin comprising a single or a copolymer containing the (meth) acrylic acid ester such as the above is preferably used. Among these, methyl poly (meth) acrylate is particularly preferable from the viewpoint of enhancing chemical resistance.

The weight average molecular weight of the acrylic resin is not particularly limited, but is preferably about 1000 to 150,000, more preferably about 1000 to 40,000 from the viewpoint of more effectively suppressing transfer defects of the foil burr and the release layer. Can be mentioned.

The weight average molecular weight of the acrylic resin in the present specification is a value measured by a gel permeation chromatography method using polystyrene as a standard substance.

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 transfer defects of the foil burr and the release layer. The degree is mentioned.

The glass transition temperature (Tg) of the acrylic resin in the present specification is a value measured by 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 is preferable from the viewpoint of more effectively suppressing transfer defects of the foil burr and the release layer. Is 25 parts by mass or less, more preferably about 0.5 to 25 parts by mass, still more preferably about 2 to 8 parts by mass with respect to 100 parts by mass of the solid content other than the acrylic resin in the ionizing radiation curable resin composition. Be done.

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

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

The content of the curing agent in the ionizing radiation curable resin composition forming the protective layer 3 is not particularly limited, but is preferable from the viewpoint of more effectively suppressing transfer defects of foil burrs and the release layer. Is about 0.1 to 20 parts by mass, more preferably about 1 to 10 parts by mass, still more preferably about 1 to 7 parts by mass with respect to 100 parts by mass of the solid content other than the curing agent in the ionizing radiation curable resin composition. Can be mentioned.

Various additives can be added to the ionizing radiation curable resin composition forming the protective layer 3 according to the desired physical properties to be provided in the protective layer 3. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, a matting agent and the like. These additives can be appropriately selected from commonly used additives, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

The protective layer 3 is formed by preparing an ionizing radiation curable resin composition, applying the same, and cross-linking and curing. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer on the surface of the release layer 2, for example, by the coating method described later.

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

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

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

The irradiation dose is an amount at which the crosslink density of the protective layer 3 becomes a sufficient value, 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, a hard coat function, an anti-fog coat function, an anti-fouling coat function, an anti-glare coat function, an anti-reflection coat function, an ultraviolet ray shielding coat function, an infrared ray shielding coat function, etc. You may perform the process of imparting the function of.

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

The resin used in the resin composition for forming the primer layer is not particularly limited, and is, for example, a polyol and / or a cured product thereof, a urethane resin, an acrylic resin, a (meth) acrylic-urethane copolymer resin, a polyester resin, and a butyral resin. And so on. Among these resins, preferred examples include 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 of a resin composition containing a polyol and a urethane resin. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyols, polyethylene glycols, polypropylene glycols, acrylic polyols, and polyether polyols, and acrylic polyols are preferable. Can be mentioned.

When a polyol and a urethane resin are used to form the primer layer 4, the mass ratio (polyurethane: urethane resin) of these is preferably about 5: 5 to 9.5: 0.5, more preferably 7: 3. ~ 9: 1 is mentioned.

Examples of the cured product of the polyol include urethane resin. As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a cross-linking agent (curing agent) can be used.

Specific examples of the isocyanate include 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, and hydrogen. Examples thereof include aliphatic (or alicyclic group) isocyanates such as added diphenylmethane diisocyanate. When isocyanate is used as a curing agent, the content of isocyanate in the resin composition for forming a primer layer is not particularly limited, but from the viewpoint of adhesion and printability when laminating the decorative layer 5 or the like described later, it is considered. 3 to 45 parts by mass is preferable with respect to 100 parts by mass of the above-mentioned polyol, and 3 to 25 parts by mass is more preferable.

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

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

The (meth) acrylic-urethane copolymer resin is not particularly limited, and examples thereof include an acrylic-urethane (polyester urethane) block copolymer resin. Further, as the curing agent, the above-mentioned various isocyanates are used. The ratio of 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. / 2 to 2/8 can be mentioned.

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

Various additives can be added to the composition forming the primer layer 4 according to the desired physical characteristics to be provided. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, a matting agent and the like. These additives can be appropriately selected from commonly used additives, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

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

The primer layer 4 may be formed on the protective layer 3 after curing. Further, a layer made of a primer layer forming composition is laminated on a layer of an ionizing radiation curable resin composition forming a protective layer 3 to form a primer layer 4, and then a layer made of an ionizing radiation curable resin is formed. 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 needed to impart decorativeness to the resin molded product. The decorative layer 5 is usually composed of a pattern layer and / or a concealing layer. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters, and the concealing layer is usually a solid layer on the entire surface and is provided for concealing coloring or the like of a molding resin or the like. It is a layer. The concealing layer may be provided inside the pattern layer in order to enhance the pattern of the pattern layer, or the decorative layer 5 may be formed by the concealing layer alone.

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

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

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

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

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

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

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

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

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

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

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

The thickness of the adhesive layer 6 is not particularly limited, and examples thereof include about 0.1 to 30 μm, preferably about 0.5 to 20 μm, and more preferably about 1 to 8 μm.

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

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

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

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

The transfer film for three-dimensional molding of the present invention can be manufactured, for example, by a manufacturing method including the following steps. As described above, in the transfer film for three-dimensional molding of the present invention, the peel strength between the release layer 2 and the protective layer 3 and the peel strength (N / inch) are divided by the thickness (μm) of the protective layer. Is characterized by being at a predetermined value, and the composition and thickness of the release layer and the 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, and the transparent resin layer 7, if necessary.

Step of forming a release layer forming coating film on the transfer substrate 1 The release layer forming coating film is irradiated with ionizing radiation to form a release layer in which the release layer forming coating film is cured. Step A step of 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. 2. Resin molded product and its manufacturing method The resin molded product of the present invention is formed by integrating the three-dimensional molding transfer film of the present invention and the molding resin. Specifically, by laminating the molding resin layer 8 on the side opposite to the support 10 of the three-dimensional molding transfer film, the molding resin layer 8, the transfer layer 9, and the support 10 are laminated in this order. A resin molded product with a support is obtained (see, for example, FIG. 3). Next, by peeling the support 10 from the resin molded product with a support, the resin molded product of the present invention in which at least the molded resin layer 8 and the transfer layer 9 are laminated can be obtained (see, for example, FIG. 4). As shown in FIG. 4, in the resin molded product of the present invention, at least one layer such as the decorative layer 5, the primer layer 4, the adhesive layer 6, and the transparent resin layer 7 is further provided, if necessary. May be good.

The resin molded product of the present invention can be manufactured by a manufacturing method including the following steps.
A process of laminating a molding resin layer on the side opposite to the support of a transfer film for three-dimensional molding,
The process 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 product of the present invention include methods including the following steps (1) to (5).

(1) First, a step of heating the transfer film for three-dimensional molding from the transfer layer side by a hot plate with the transfer layer side (the side opposite to the support) of the transfer film for three-dimensional molding for transfer facing into the mold. ,
(2) A step of pre-molding (vacuum forming) the transfer film for three-dimensional molding so as to follow the shape inside the mold so that the film is brought into close contact with the inner surface of the mold and compacted.
(3) The process of injecting resin into the mold,
(4) A step of taking out the resin molded product (resin molded product with a support) from the mold after cooling the injection resin, and (5) a step of peeling the support from the transfer layer of the resin molded product.

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

In both of the above steps (3), the molding resin described later is melted and injected into the cavity to integrate the three-dimensional molding transfer film and the molding resin. If the molding resin is a thermoplastic resin, it is made to flow by heating and melting, and if the molding resin is a thermosetting resin, the uncured liquid composition is injected at room temperature or appropriately heated in a flowing state. Then, cool and solidify. As a result, the transfer film for three-dimensional molding is integrated with the formed resin molded body and adhered to the resin molded product with a support. The heating temperature of the molding resin depends on the type of the molding resin, but is generally about 180 to 320 ° C. 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 high-temperature molding resin, the temperature of the mold rises and the molding resin is cooled.

The resin molded product with a support thus obtained is a resin molded product obtained by cooling in the step (4), taking it out of the mold, and then peeling the support 10 from the transfer layer 9 in the step (5). To get. Further, the step of peeling the support 10 from the transfer layer 9 may be performed at the same time as the step of taking out the resin molded product from the mold. That is, the step (5) may be included in the step (4).

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

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

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

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

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

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

The resin molded product of the present invention is, for example, an interior or exterior material of a vehicle such as an automobile; a fitting such as a window frame or a door frame; an interior material of a building such as a wall, a floor or a ceiling; a television receiver, an air conditioner or the like. It can be used as a housing for home appliances; as a container, etc.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

(Examples 1 to 7 and Comparative Examples 1 to 5)
[Manufacturing of transfer film for 3D molding]
As the transfer substrate, a polyethylene terephthalate film (thickness 50 μm) having an easy-adhesive layer formed on one surface was used. The release layer material A or B shown in Table 1 was printed on the surface of the easy-adhesive layer of the polyethylene terephthalate film by gravure printing to form a coating film for forming a release layer (thickness of each release layer). Was set to 1.0 μm). Details of the release layer material A or B will be described later. When the release layer material A was used, it was thermally cured at a temperature of 150 ° C. to form a release layer. When the release layer material B was used, a release layer forming coating film was formed, and then an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 7 Mrad was irradiated to form a release layer.

Next, the protective layer materials C, D, and E shown in Table 1 are placed on the release layer of the obtained support, respectively, so that the thickness after curing is the thickness B (μm) shown in Table 1. Was coated with a bar coater to form a coating film for forming a protective layer. Next, an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 5 mad was irradiated from the protective layer-forming coating film to cure the protective layer-forming coating film to form a protective layer.

A resin composition for forming a primer layer containing an acrylic polyol and hexamethylene diisocyanate was applied onto this protective layer by gravure printing to form a primer layer (thickness 1.5 μm). Further, a decorative layer is formed on the primer layer containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin (acrylic resin 50% by mass, vinyl chloride-vinyl acetate copolymer resin 50% by mass). A decorative layer (thickness 5 μm) of a hairline pattern was formed by gravure printing using a black-based ink composition for use. Further, it is supported 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 transfer film for three-dimensional molding was produced in which a body (base material for transfer / release layer) and a transfer layer (protective layer / primer layer / decorative layer / adhesive layer) were laminated in this order.

[Release layer material]
A: Acrylic-melamine resin B: An ionizing radiation curable composition obtained by adding silicone to a polycarbonate urethane acrylate so as to have a silicone content of 0.9% by mass.

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

<Manufacturing of resin molded products>
Each of the transfer films for three-dimensional molding obtained above is placed in a mold, and the transfer film for three-dimensional molding is placed in a mold (an elliptical opening P as shown in FIG. 5 (width in the minor axis direction y is 5 mm). ) Was adsorbed on the shape) formed on the resin molded product. In this state, the mold was closed and the molten resin was injected into the mold. The molten resin was cooled, and the resin molded product with a support was taken out from the mold. A resin molded product was manufactured by peeling the support from the resin molded product with a support. The temperature of the mold was set to 60 ° C, and the temperature of the molten resin was set to 265 ° C. The molten resin is obtained ^{by heating a mixed resin (CYCOLOY TM} Resin XCY620) of ABS resin and polycarbonate resin to 265 ° C. and melting the resin.

<Measurement method of peel strength>
For each of the transfer films for three-dimensional molding obtained above, the peel strength A between the release layer 2 and the protective layer 3 in an environment of 80 ° C. was measured by the following method. The results are shown in Table 1. First, a transfer film for three-dimensional molding to be measured for peel strength, a mold for molding the transfer film, and a resin (resin for forming a molding resin layer) to be laminated on the transfer film for three-dimensional molding were prepared. The shape of the mold is a flat plate (size in which a resin molded product having a length of 15 mm, a width of 30 mm, and a thickness of 3 mm is formed), and when a transfer film for three-dimensional molding is molded in the mold, It was assumed that the area elongation rate of the surface of the transfer film for three-dimensional molding was substantially 0%. The temperature of the mold was set to 60 ° C. As the resin (resin forming the molding resin layer) to be injected into the transfer film for three-dimensional molding, a mixed resin (CYCOLOY ^TM Resin XCY620) of ABS resin and polycarbonate resin was heated to 265 ° C. and melted. .. Under the above molding conditions, a molding resin layer was laminated on the transfer film for three-dimensional molding in the above steps (1a) to (3a) to obtain a decorative resin molded product with a support. Next, a 1-inch wide polyester adhesive tape (NITTO TAPE, No. 31B 75 high) was attached to the surface of the transfer substrate layer of the decorative resin molded product with a support with a finger to bring it into close contact. Next, a notch was made with a cutter on the surface of the decorative resin molded product with a support along the attached polyester adhesive tape. At this time, the notch penetrated the transfer substrate (and the release layer if it had a release layer). Next, at the end of the polyester adhesive tape, the polyester adhesive tape was peeled off with a finger about 10 mm in the length direction to prepare a sample. At this time, the transfer substrate 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 portion of the Tensilon tester and the portion from which the polyester adhesive tape was peeled off were connected. Next, the sample was heated for 1 minute with the heater attached to the Tensilon tester. At this time, the set temperature of the heater was set to 80 ° C. Next, the polyester adhesive tape is peeled off at a peeling speed of 100 mm / min so that the peeling direction of the polyester adhesive tape is always 90 ° with respect to the surface of the transfer film for three-dimensional molding, and the load indicated on the load cell is applied to the peeling strength (peeling strength (). N / inch).

<Evaluation of foil burrs>
The state of the foil burr at the opening of each resin molded product obtained in the above <manufacturing of the resin molded product> was visually observed. Specifically, the foil burrs in the opening P shown in FIG. 5 of the resin molded product were evaluated according to the following criteria. As shown in FIG. 5, in the short axis direction y of the opening P, y1 is an end portion, y2 and y3 are lines that divide the opening into three in the short axis direction y, and y4 faces y1. It is the end to do. Table 1 shows the evaluation results of the foil burrs.

A ⁺ : Since the foil burrs do not reach the positions from the ends y1 to y2 in the minor axis direction y direction, it is very easy to remove the foil burrs with cellophane tape or the like, which is particularly suitable for practical use.
A: The foil burr reaches the position from the end y1 to y2 in the minor axis direction y direction, but does not reach the position of y3, and the foil burr can be easily removed by cellophane tape or the like, which is practical. Suitable for.
B: The foil burr reaches the position from the end y1 to y3 in the minor axis direction y direction, but does not reach the position of y4, so that the foil burr can be removed by cellophane tape or the like. There is no problem in practical use.
C: Since the foil burr reaches the position from the end y1 to y4 in the short axis direction y direction, it takes time to remove the foil burr with cellophane tape or the like, and there is a possibility of contamination around the device due to foil spillage. Is increasing, and there is a practical problem.

<Evaluation of transferability>
For each resin molded product obtained in the above <Manufacturing 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 according to the following criteria. The results are shown in Table 1.

A: The release layer and the transfer base material did not remain on the surface of the resin molded product, and the transfer state was good.
B: A release layer or a transfer base material may remain slightly or slightly remain on the surface of the resin molded product, but it can be easily removed and there is no problem in practical use.
C: The release layer and the transfer base material remain on the surface of the resin molded product and cannot be easily removed, so that the transferability is practically problematic.

<Evaluation of wear resistance>
The surface of each resin molded product obtained in the above <Manufacturing of resin molded product> is rubbed with a cloth coated with sun lotion (Sun lotion for test standard PV3964 manufactured by thirry), and the surface of the decorative resin molded product is rubbed. Abrasion resistance was evaluated according to the following criteria. The results are shown in Table 1. The evaluation of wear resistance was a wear test of 10000 strokes at 10 N, and was evaluated in accordance with the standard of DIN EN 60068-2-70 / IEC 68-2-70.

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 of the protective layer of the resin molded product or wear of the protective layer.

<Evaluation of scratch resistance>
Abrasive paper 281Q WOD Schleifpapier (manufactured by 3M) having a plane size of 215.9 mm × 279 mm is attached to the tip of the test jig of the Martindale wear tester, and each resin molding obtained in the above <Manufacturing of resin molded product> is performed. The surface of the product was rubbed 100 times with 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 decrease rate of gloss value had few scratches, and the scratches disappeared after a while. This indicates that the protective layer is self-healing.

A: The rate of decrease in gloss value is less than 5% after 5 minutes from the test, and the rate of decrease in gloss value has recovered to less than 1% after 30 minutes from the test, and it has excellent scratch resistance in practical use. ..
B: The rate of decrease in gloss value is 5% or more and less than 30% after 5 minutes from the test, and the rate of decrease in gloss value has recovered to less than 5% after 30 minutes from the test. Have.
C: The rate of decrease in the gloss value is 30% or more after 5 minutes from the test, and the rate of decrease in the gloss value remains at 30% or more even after 30 minutes from the test, and there is a problem in practical scratch resistance.

<Evaluation of deep drawing formability>
Each of the above three-dimensional molding transfer films was cut into strips having a length of 150 mm and a width of 1 inch to prepare a sample for evaluation of only the colored layer. The sample was subjected to a tensile test using a tensile tester with an initial tensile chuck distance of 100 mm and a tensile speed of 100 mm / min. For the measurement, the film sample was set in a constant temperature bath set to a temperature of 100 ° C. in advance, a tensile test was performed after preheating for 60 seconds, and the amount of elongation (breaking elongation) until the film cracked was measured. The measurement was performed with 3 samples for each level, and the average value of the 3 samples was taken as the fracture elongation. Based on the elongation at break, 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: Destruction elongation of 80% or more. A level that can be handled even with a mold generally called deep drawing.
B: Fracture elongation is 50% or more and less than 80%. A level that does not pose a problem in molding.
C: Destruction elongation is less than 50%. A level that poses a problem in molding in many molds.

As shown in Table 1, the transfer films for three-dimensional molding of Examples 1 to 7 have a release strength between the release layer and the protective layer in an environment of 80 ° C. of less than 0.90 N / inch, and The value obtained by dividing the value of the peeling strength (N / inch) by the value of the thickness of the protective layer (μm) was 0.10 or more, and transfer defects of the foil burr and the release layer were effectively suppressed. Further, the transfer films for three-dimensional molding of Examples 1 to 7 have characteristics that can be practically used in terms of deep drawing formability, abrasion resistance, and scratch resistance.

1 Transfer substrate 2 Release layer 3 Protective layer 4 Primer layer 5 Decorative layer 6 Adhesive layer 7 Transparent resin layer 8 Molding resin layer 9 Transfer layer 10 Support P opening

Claims (10)

A three-dimensional molding transfer film comprising at least a transfer substrate and a support having a release layer, and a transfer layer having a protective layer provided so as to contact the release layer.
The peel strength between the release layer and the protective layer in an environment of 80 ° C. is less than 0.90 N / inch, and
Divided by the thickness ([mu] m) of the protective layer of the peel strength (N / inch) is state, and are 0.10 or more,
The release layer, that is composed with a cured product of an ionizing radiation curable resin composition, a transfer film for three-dimensional molding. A three-dimensional molding transfer film comprising at least a transfer substrate and a support having a release layer, and a transfer layer having a protective layer provided so as to contact the release layer.
The peel strength between the release layer and the protective layer in an environment of 80 ° C. is less than 0.90 N / inch, and
The value obtained by dividing the peel strength (N / inch) by the thickness (μm) of the protective layer is 0.10 or more.
A transfer film for three-dimensional molding, wherein the ionizing radiation curable resin composition of the release layer contains a polycarbonate (meth) acrylate. A three-dimensional molding transfer film comprising at least a transfer substrate and a support having a release layer, and a transfer layer having a protective layer provided so as to contact the release layer.
The peel strength between the release layer and the protective layer in an environment of 80 ° C. is less than 0.90 N / inch, and
The value obtained by dividing the peel strength (N / inch) by the thickness (μm) of the protective layer is 0.10 or more.
A transfer film for three-dimensional molding, wherein the protective layer is made of a cured product of an ionizing radiation curable resin composition. The transfer film for three-dimensional molding according to claim 3 , wherein the release layer is composed of a cured product of an ionizing radiation curable resin composition. The transfer film for three-dimensional molding according to claim 3 , wherein the ionizing radiation curable resin composition of the release layer contains polycarbonate (meth) acrylate. The transfer film for three-dimensional molding according to claim 1 or 2, wherein the protective layer is made of a cured product of an ionizing radiation curable resin composition. The transfer film for three-dimensional molding according to claim 6, 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 7 , wherein the release layer has a thickness of 5.0 μm or less. The transfer film for three-dimensional molding according to any one of claims 1 to 8 , 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. A step of laminating a molding resin layer on the transfer layer side of the transfer film for three-dimensional molding according to any one of claims 1 to 9.
The step of peeling the support from the transfer layer and
A method for manufacturing a resin molded product.

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