WO2015056433A1

WO2015056433A1 - In-mold transfer foil, method for manufacturing same, decorative molded article, and method for manufacturing same

Info

Publication number: WO2015056433A1
Application number: PCT/JP2014/005180
Authority: WO
Inventors: 渡邉　学; 友美樋爪
Original assignee: 凸版印刷株式会社
Priority date: 2013-10-16
Filing date: 2014-10-10
Publication date: 2015-04-23
Also published as: TW201532811A; JP2015077713A; JP6206074B2

Abstract

　Provided are an in-mold transfer foil and a method for manufacturing the in-mold transfer foil capable of providing a molded article having a high surface strength while forming concave/convex features on the surface of the molded article, and a decorative molded article and a method for manufacturing the decorative molded article. This in-mold transfer foil has a mold separation layer (3), a hard coating layer (4) containing a UV-curable resin, and an adhesive layer (6) provided in the sequence listed on one surface of a base film (2); and a convex/concave feature formation layer (1) provided on the other surface of the base film (2); the convex/concave feature formation layer (1) containing a UV-curable resin, and a UV-shielding layer being provided between the hard coating layer (4) and the convex/concave feature formation layer (1).

Description

In-mold transfer foil and method for producing the same, decorative molded product and method for producing the same

The present invention relates to an in-mold transfer foil and a method for producing the same, and a decorative molded product and a method for producing the same. And a manufacturing method thereof.

Molded products using the in-mold transfer foil are used in equipment bodies such as daily necessities and daily necessities, containers for food and various articles, housings for electronic equipment and office supplies, and the like.
The in-mold transfer foil is a transfer foil for plastic decorative molding in which, for example, a release layer, a print layer, and an adhesive layer are formed on a base film serving as a base material. Further, in-mold injection molding is performed by supplying an in-mold transfer foil between a pair of injection molding dies, filling a cavity formed by the injection molding dies with heat-pressed molding resin, and then forming a base film. And a mold release method in which the release layer is peeled off and the printed layer is transferred to a molding resin for decoration. The print layer is generally called a decorative print layer.

As an in-mold transfer foil for obtaining molded products with high surface strength, a hard coat layer made of an ultraviolet curable resin is formed on the release layer, and a printed layer, an adhesive layer, etc. are further formed thereon There is. In the case of this in-mold transfer foil, formability may be impaired if the hard coat layer is cured by irradiating ultraviolet rays before decorative molding. For this reason, it is desirable to irradiate the surface of the molded product with ultraviolet rays after the decorative molding to cure the hard coat layer.
Since the printing layer in the conventional in-mold transfer foil has a structure in which characters, designs, etc. are simply printed on a base film in a flat manner, there is a problem that the three-dimensional effect on the surface of the molded product is poor. As a method of giving a three-dimensional feeling to the surface of the molded product, there is a method of providing a concavo-convex pattern in advance on the side where the base film comes into contact with the inside of a pair of injection molds that constitute a cavity during molding. is there.

However, with such a method for forming irregularities, only one irregularity pattern can be supported for one injection mold, and a large number of injection molds must be prepared to accommodate various irregularities. There is. For this reason, the said uneven | corrugated formation method raises the problem that cost becomes high. In addition, since the position of the concavo-convex pattern is determined by the supply position of the in-mold transfer foil, it is difficult to associate the pattern of the in-mold transfer foil with the concavo-convex pattern in the above-described concavo-convex formation method.
Therefore, as a method of forming irregularities on the surface of the molded product, a release layer, a printing layer, and an adhesive layer for adhering the printed layer to the surface of the molded product are provided on one surface of the base film. There has been proposed a method in which an unevenness formation layer by printing is provided on the other surface (see, for example, Patent Document 1). An in-mold transfer foil is also proposed in which this unevenness forming layer is formed of a thermosetting resin and has a hard coat layer containing an ultraviolet curable resin as a transfer layer (see, for example, Patent Document 2).

Japanese Laid-Open Patent Publication No. 1-120398 JP 2012-183808 A

By the way, since an industrial product is expected to be used for a long time or in a harsh environment, the in-mold transfer foil used for decorating the industrial product is required to have a high surface strength of the molded product after the transfer. Therefore, it is desirable to use an in-mold transfer foil in which a hard coat layer is formed on a release layer and a printed layer, an adhesive layer and the like are further formed thereon for decorating industrial products.
However, most of the hard coat layers used in the in-mold transfer foil are made of an ultraviolet curable resin. For this reason, when an unevenness forming layer is provided on the surface opposite to the release layer of the base film, if an ultraviolet curable resin is used as the resin for forming the unevenness forming layer, the unevenness forming layer is cured. Before the decorative molding, the in-mold transfer foil must be irradiated with ultraviolet rays. At that time, the hard coat layer made of an ultraviolet curable resin itself is also cured, so that the moldability of the in-mold transfer foil is impaired, and there is a problem that defective products such as cracks are likely to occur.

In addition, when a thermosetting resin is used for the concavo-convex formation layer as in Patent Document 2, the deformation of the concavo-convex shape due to heat during curing and the time required for curing from several hours to several days, There was a problem that the shape was deformed. Further, the thermosetting resin is less usable than a UV curable resin without a solvent, and is often used after being diluted with a solvent. For this reason, when a thermosetting resin is used, there is a problem that thickening is difficult and the three-dimensional effect is poor.
On the other hand, there is also a method of forming a release layer, a hard coat layer, a printing layer, an adhesive layer, etc. in this order on a base film having a concavo-convex forming layer in advance. As a result, wrinkles and printing defects occur, and it is difficult to manufacture an in-mold transfer foil.
This invention is made | formed in view of such a condition, The place made into the subject can provide the molded article which has high surface strength, forming an unevenness | corrugation in the molded article surface. It is to provide an in-mold transfer foil and a manufacturing method thereof, and a decorative molded product and a manufacturing method thereof.

In order to achieve the above-mentioned problems, the present invention takes the following measures.
One embodiment of the present invention includes a release layer, a hard coat layer containing an ultraviolet curable resin, and an adhesive layer in this order on one surface of a base film, and an uneven surface on the other surface of the base film. In the in-mold transfer foil provided with a forming layer, the unevenness forming layer includes an ultraviolet curable resin, and an ultraviolet blocking layer is provided between the hard coat layer and the unevenness forming layer. This is an in-mold transfer foil.
Another embodiment of the present invention is the in-mold transfer foil, wherein the base film is the ultraviolet blocking layer.
Another embodiment of the present invention is an in-mold transfer foil in which the ultraviolet blocking layer is provided between the base film and the unevenness forming layer.
One embodiment of the present invention is an in-mold transfer foil, wherein the ultraviolet blocking layer is provided between the base film and the release layer.

Another embodiment of the present invention is the in-mold transfer foil, wherein the ultraviolet blocking layer is a cured product of an acrylic polymer having a hydroxyl group and an ultraviolet absorbing functional group and an isocyanate compound.
One embodiment of the present invention is the in-mold transfer foil further including a printing layer having a predetermined pattern pattern between the hard coat layer and the adhesive layer.
Another embodiment of the present invention is a manufacturing method for manufacturing the in-mold transfer foil, wherein the unevenness forming layer of the base film is formed by irradiation with ultraviolet rays for crosslinking and curing the unevenness forming layer. It is the manufacturing method of the in-mold transfer foil characterized by performing from the surface side.
Another embodiment of the present invention is a decorative molded product manufactured by an in-mold injection molding method using the in-mold transfer foil.
Moreover, one aspect of the present invention is characterized in that, using the in-mold transfer foil, the surface of a decorative molded product produced by an in-mold injection molding method is irradiated with ultraviolet rays to completely cure the hard coat layer. It is a manufacturing method of the decorative molded product.

According to the in-mold transfer foil according to one aspect of the present invention, the ultraviolet ray irradiated when forming the concavo-convex forming layer made of an ultraviolet curable resin is blocked by the ultraviolet blocking layer, so that the hard coat layer is crosslinked and cured. There is no progress. Therefore, it is possible to maintain excellent moldability (for example, crack resistance, etc.), and at the time of transfer, the uneven shape according to the uneven pattern is formed on the surface of the molded product according to the thickness of the resin constituting the uneven formation layer. Can be formed.
In addition, according to the in-mold transfer foil according to one aspect of the present invention, since the uneven shape can be formed on the surface of the molded product without imparting the uneven shape to the surface of the injection mold, It is economical because it is not necessary to produce a mold having a pattern.
In addition, a hard coat layer containing an ultraviolet curable resin can be provided as a transfer layer on the opposite surface of the base film provided with an unevenness forming layer made of an ultraviolet curable resin without cross-linking and curing. Have. Furthermore, it is possible to produce a molded product having high surface strength and excellent three-dimensional effect by irradiating the surface of the molded product with ultraviolet rays after transfer.

It is a cross-sectional schematic diagram of the in-mold transfer foil which concerns on 1st embodiment of this invention. It is a cross-sectional schematic diagram of the in-mold transfer foil which concerns on 2nd embodiment of this invention. It is a cross-sectional schematic diagram of the in-mold transfer foil which concerns on 3rd embodiment of this invention. It is the cross-sectional schematic diagram which showed the mode at the time of inject | pouring molding resin into the cavity of the injection mold from the contact bonding layer side of the in-mold transfer foil which concerns on 1st embodiment of this invention. It is a cross-sectional schematic diagram of the decorative molded product which has shape | molded using the in-mold transfer foil which concerns on 1st embodiment of this invention, and has an unevenness | corrugation on the surface.

First, an in-mold injection molding method using an in-mold transfer foil will be briefly described, and then details of the in-mold transfer foil according to the first to third embodiments of the present invention will be sequentially described with reference to the drawings. To do.
(In-mold injection molding method)
The in-mold injection molding method includes (1) a step of preparing an in-mold transfer foil, (2) a step of inserting the in-mold transfer foil into an injection mold, and (3) to an injection mold. A step of transferring the transfer layer of the in-mold transfer foil onto the surface of the injected resin by injecting and intimately bonding the resin; and (4) opening the injection molding die after cooling the injected resin. This is an injection molding method having at least four steps of peeling a film and a release layer and taking out a molded product. In the present invention, ultraviolet rays and UV have the same meaning.

(First embodiment)
Hereinafter, the overall structure of the in-mold transfer foil according to the first embodiment of the present invention will be described with reference to the drawings.
The in-mold transfer foil according to the first embodiment shown in FIG. 1 includes a base film 2 having an ultraviolet blocking ability, a release layer 3 on one surface of the base film 2, and a hard coat layer containing an ultraviolet curable resin. 4 and the adhesive layer 6 are provided in this order, and the concave-convex forming layer 1 containing an ultraviolet curable resin is provided on the other surface of the base film 2. In addition, an anchor layer, a decoration layer by color ink, a metal vapor deposition layer, etc. may be formed between the hard-coat layer 4 and the contact bonding layer 6, and the printing layer 5 is formed in FIG. The case is illustrated. Hereinafter, the detail of each said layer is demonstrated.

(Base film 2)
As the base film 2 having the ultraviolet blocking ability, various materials can be used depending on the application as long as it has the ultraviolet blocking ability and has heat resistance, mechanical strength, solvent resistance, etc. required in the manufacturing and molding processes. Can be applied. For example, the base film 2 can be made of a material obtained by mixing or synthesizing a material having ultraviolet blocking ability and various polymers. Here, the ultraviolet blocking ability means the ability to block or reduce the transmission of ultraviolet rays by absorbing or reflecting light within the range of 200 nm to 380 nm as the wavelength of light.
As a standard of ultraviolet blocking ability, it is desirable that the transmittance of i-line (wavelength 365 nm) is less than 10%. This is because when forming irregularities with an ultraviolet curable resin, it is necessary to irradiate the irregularity-forming layer 1 with ultraviolet rays having a light amount in the range of 500 mJ / cm ² or more and 1000 mJ / cm ² or less. If the hard coat layer 4 is irradiated with ultraviolet rays of about 100 mJ / cm ² or more before the injection molding, the hard coat layer 4 cannot follow the stretching during the injection molding due to the progress of the crosslinking reaction. This is because cracks are generated.

Examples of materials having an ultraviolet blocking ability include metal fillers typified by aluminum, metal oxides such as titanium oxide, zinc oxide, and cesium oxide, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and cyanoacrylate ultraviolet rays. An organic ultraviolet absorber such as an absorbent, a salicylate ultraviolet absorber, an oxanilide ultraviolet absorber, or a colored pigment such as carbon black can be used. Here, when it is necessary to align the concavo-convex pattern of the concavo-convex forming layer 1 with the printing layer 5, a metal oxide or an organic ultraviolet absorber having transparency in the visible light region, or these ultraviolet absorbers are used. A covalently bonded resin is preferably used.
Examples of the material for forming the base film 2 include polyester resins, polyamide resins, polyolefin resins, vinyl resins, acrylic resins, and cellulose resins, from the viewpoint of heat resistance and mechanical strength. For example, it is preferable to use polyester resins such as polyethylene terephthalate and polyethylene naphthalate. Among these, polyethylene terephthalate is particularly preferably used from the viewpoint of cost.

(Release layer 3)
The material of the release layer 3 is not particularly limited as long as it is a resin having necessary release properties. In the in-mold transfer foil according to the first embodiment, for example, an olefin-modified acrylic melamine resin or acrylic urethane resin is preferably used. Moreover, as a formation method of the mold release layer 3, a well-known printing method and coating method can be used, for example.
(Hard coat layer 4)
The hard coat layer 4 is a layer that becomes the outermost surface layer of the molded product when the base film 2 is peeled off after transfer. As a material of the hard coat layer 4, an ultraviolet curable resin that is cured by ultraviolet rays can be used, and examples thereof include a resin containing at least an acryloyl group or a methacryloyl group. With such an ultraviolet curable hard coat layer 4, the surface of the molded product can be immediately cured by ultraviolet irradiation, and the production efficiency of the molded product can be improved. In addition, according to the in-mold transfer foil according to the first embodiment, since the hard coat layer 4 is molded in an uncured state and is completely cured after molding, it is possible to achieve both moldability improvement and surface physical property improvement. It is. Moreover, as a formation method of the hard-coat layer 4, a well-known printing method and the coating method can be used, for example.

(Print layer 5)
As a material of the printing layer 5, for example, a colored ink containing a pigment or dye of an appropriate color as a colorant can be used. Moreover, as a formation method of the printing layer 5, well-known printing methods, such as an offset printing method, a gravure printing method, a screen printing method, an inkjet method, can be used, for example. Among these, it is preferable to print by a gravure printing method from the viewpoints that multicolor printing and gradation expression are possible and that it is suitable for mass production. An anchor layer (not shown) may be provided between the print layer 5 and the hard coat layer 4 in order to improve the adhesion with the hard coat layer 4. As a method for forming the anchor layer, for example, a printing method such as a gravure printing method or a screen printing method can be used, but it is desirable to print by a gravure printing method from the viewpoint of film thickness or productivity.
(Adhesive layer 6)
The adhesive layer 6 adheres each of the above layers to the surface of the molded product. As a material for the adhesive layer 6, a heat-sensitive or pressure-sensitive resin suitable for the molding resin 7 can be appropriately used. As a method for forming the adhesive layer 6, for example, a printing method such as a gravure printing method or a screen printing method can be used, but it is desirable to print by a gravure printing method from the viewpoint of film thickness or productivity. In addition, when the printing layer 5 has sufficient adhesiveness with respect to a molded article and also has an effect as an adhesive layer, the adhesive layer 6 may not be provided.

(Unevenness forming layer 1)
The unevenness forming layer 1 provided on the surface opposite to the surface on which the release layer 3 of the base film 2 is formed contains an ultraviolet curable resin, and can be formed by various forming methods. The concavo-convex forming layer 1 is, for example, a screen printing method using a UV thick ink, a UV inkjet method, or a liquid ultraviolet curable resin sandwiched between a releasable concavo-convex film and a base film, and UV irradiation from the releasable concavo-convex film side. Thus, the liquid ultraviolet curable resin can be cured, and then the release-type uneven film can be peeled off to form the unevenness forming layer 1 on the base film 2.
Moreover, as a material of the uneven | corrugated formation layer 1, the ultraviolet curable resin similar to the hard-coat layer 4 can be used, For example, resin etc. which contain an acryloyl group or a methacryloyl group at least can be used.
According to the concavo-convex forming method using these ultraviolet curable resins, the reproducibility of the concavo-convex shape is improved as compared with the case where a thermosetting resin is used, and the manufacturing time can be shortened.

(Second embodiment)
Hereinafter, the overall structure of the in-mold transfer foil according to the second embodiment will be described with reference to the drawings.
The in-mold transfer foil according to the second embodiment shown in FIG. 2 includes a base film 9, a release layer 3 on one surface of the base film 9, a hard coat layer 4 containing an ultraviolet curable resin, and an adhesive layer. 6 in this order, and the other surface of the base film 9 has an ultraviolet blocking layer 10 and an unevenness forming layer 1 made of an ultraviolet curable resin. In addition, between the hard coat layer 4 and the adhesive layer 6, an anchor layer, a decorative layer with color ink, a metal vapor deposition layer, or the like may be formed. In the case where the printed layer 5 is formed in FIG. 2. Is illustrated. Hereinafter, the detail of each said layer is demonstrated.

(Base film 9)
As the base film 9, various materials can be applied depending on the use as long as the base film 9 has heat resistance, mechanical strength, solvent resistance, and the like necessary in the manufacturing and molding processes. Examples of the material for forming the base film 9 include polyester resins, polyamide resins, polyolefin resins, vinyl resins, acrylic resins, and cellulose resins, from the viewpoint of heat resistance and mechanical strength. For example, it is preferable to use polyester resins such as polyethylene terephthalate and polyethylene naphthalate. Among these, polyethylene terephthalate is particularly preferably used from the viewpoint of cost.

(Release layer 3)
The material of the release layer 3 is not particularly limited as long as it is a resin having necessary release properties. In the in-mold transfer foil according to the second embodiment, for example, an olefin-modified acrylic melamine resin or acrylic urethane resin is preferably used. Moreover, as a formation method of the mold release layer 3, a well-known printing method and coating method can be used, for example.
(Hard coat layer 4)
The hard coat layer 4 is a layer that becomes the outermost surface layer of the molded product when the base film 9 is peeled off after the transfer. As a material of the hard coat layer 4, an ultraviolet curable resin that is cured by ultraviolet rays can be used, and examples thereof include a resin containing at least an acryloyl group or a methacryloyl group. With such an ultraviolet curable hard coat layer 4, the surface of the molded product can be immediately cured by ultraviolet irradiation, and the production efficiency of the molded product can be improved. In addition, according to the in-mold transfer foil according to the second embodiment, the hard coat layer 4 is molded in an uncured state and undergoes a process of complete curing after the molding, so that both moldability improvement and surface physical property improvement are possible. It is. Moreover, as a formation method of the hard-coat layer 4, a well-known printing method and the coating method can be used, for example.

(Print layer 5)
As a material of the printing layer 5, for example, a colored ink containing a pigment or dye of an appropriate color as a colorant can be used. Moreover, as a formation method of the printing layer 5, well-known printing methods, such as an offset printing method, a gravure printing method, a screen printing method, an inkjet method, can be used, for example. Among these, it is preferable to print by a gravure printing method from the viewpoints that multicolor printing and gradation expression are possible and that it is suitable for mass production. An anchor layer (not shown) may be provided between the printing layer 5 and the hard coat layer 4 in order to improve the adhesion with the hard coat layer 4. As a method for forming the anchor layer, for example, a printing method such as a gravure printing method or a screen printing method can be used, but it is desirable to print by a gravure printing method from the viewpoint of film thickness or productivity.
(Adhesive layer 6)
The adhesive layer 6 adheres each of the above layers to the surface of the molded product. As a material for the adhesive layer 6, a heat-sensitive or pressure-sensitive resin suitable for the molding resin 7 can be appropriately used. As a method for forming the adhesive layer 6, for example, a printing method such as a gravure printing method or a screen printing method can be used, but it is desirable to print by a gravure printing method from the viewpoint of film thickness or productivity. In addition, when the printing layer 5 has sufficient adhesiveness with respect to a molded article and also has an effect as an adhesive layer, the adhesive layer 6 may not be provided.

(UV blocking layer 10)
The ultraviolet blocking layer 10 provided on the surface opposite to the surface on which the release layer 3 of the base film 9 is formed is a material having adhesiveness with the base film 9 and the concavo-convex forming layer 1, and the wavelength of light By absorbing or reflecting light in the range of 200 nm or more and 380 nm or less, a material having the performance of blocking or reducing the transmission of ultraviolet rays can be used.
Examples of such materials having ultraviolet blocking ability include metal fillers typified by aluminum, metal oxides such as titanium oxide, zinc oxide, and cesium oxide, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and cyano. Organic ultraviolet absorbers such as acrylate ultraviolet absorbers, salicylate ultraviolet absorbers, and oxanilide ultraviolet absorbers, and colored pigments such as carbon black can be used. Here, when it is necessary to align the concavo-convex pattern of the concavo-convex forming layer 1 with the printing layer 5, a metal oxide or an organic ultraviolet absorber having transparency in the visible light region, or these ultraviolet absorbers are used. A covalently bonded resin is preferably used.

However, UV absorbers are generally low molecular in many cases, and there is a concern about migration to the unevenness forming layer 1. When the ultraviolet absorber is transferred, UV curing at the time of forming the unevenness becomes insufficient, and for example, the unevenness of the unevenness forming layer 1 may be poorly blocked or the uneven shape may be deformed by heat at the time of injection molding.
Therefore, as the resin used for the ultraviolet blocking layer 10, it is preferable to use a polymer (ultraviolet absorbing polymer) having an ultraviolet absorbing functional group in the molecule. Specifically, a benzotriazole type acrylic ultraviolet absorbing polymer or the like can be used. Furthermore, from the viewpoint of adhesion between the base film 9 and the unevenness forming layer 1, the material of the ultraviolet blocking layer 10 is a cured product of an acrylic polymer having a hydroxyl group and an ultraviolet absorbing functional group and an isocyanate compound. Is preferred.

Thus, by using a two-component curable acrylic resin as the material of the ultraviolet blocking layer 10, not only can it withstand thermal deformation during injection molding, but also the adhesion is enhanced due to its high affinity with the concavo-convex forming layer 1. . Furthermore, since an isocyanate compound reacts also on the surface of the base film 9 to form a covalent bond, adhesion with the base film 9 can be ensured.
Here, the isocyanate compound refers to, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and prepolymers thereof.
As a standard of ultraviolet blocking ability, it is desirable that the transmittance of i-line (wavelength 365 nm) is less than 10%. This is because when forming irregularities with an ultraviolet curable resin, it is necessary to irradiate the irregularity-forming layer 1 with ultraviolet rays having a light amount in the range of 500 mJ / cm ² or more and 1000 mJ / cm ² or less. If the hard coat layer 4 is irradiated with ultraviolet rays of about 100 mJ / cm ² or more before the injection molding, the hard coat layer 4 cannot follow the stretching during the injection molding due to the progress of the crosslinking reaction. This is because cracks are generated.

(Unevenness forming layer 1)
The unevenness forming layer 1 includes an ultraviolet curable resin, and can be formed by various forming methods. The concavo-convex forming layer 1 is, for example, a screen printing method using UV thick ink, a UV inkjet method, or a liquid UV curable resin sandwiched between a releasable concavo-convex film and a base film 9, and UV from the releasable concavoconvex film side The liquid ultraviolet curable resin can be cured by irradiation, and then formed by a forming method such as a method of providing the concavo-convex forming layer 1 on the base film 9 by peeling the releasable concavo-convex film.
Moreover, as a material of the uneven | corrugated formation layer 1, the ultraviolet curable resin similar to the hard-coat layer 4 can be used, For example, resin etc. which contain an acryloyl group or a methacryloyl group at least can be used.
According to the concavo-convex forming method using these ultraviolet curable resins, the reproducibility of the concavo-convex shape is improved as compared with the case where a thermosetting resin is used, and the manufacturing time can be shortened.

(Third embodiment)
Hereinafter, the entire structure of the in-mold transfer foil according to the third embodiment will be described with reference to the drawings.
The in-mold transfer foil according to the third embodiment shown in FIG. 3 includes a base film 9, a hard coat containing an ultraviolet blocking layer 11, a release layer 3, and an ultraviolet curable resin on one surface of the base film 9. The layer 4 and the adhesive layer 6 are provided in this order, and the concave-convex forming layer 1 made of an ultraviolet curable resin is provided on the other surface of the base film 9. In addition, between the hard coat layer 4 and the adhesive layer 6, an anchor layer, a decoration layer with color ink, a metal vapor deposition layer, or the like may be formed. In the case where the print layer 5 is formed in FIG. 3. Is illustrated. Hereinafter, the detail of each said layer is demonstrated.

(Base film 9)
As the base film 9, various materials can be applied depending on the use as long as the base film 9 has heat resistance, mechanical strength, solvent resistance, and the like necessary in the manufacturing and molding processes. Examples of the material for forming the base film 9 include polyester resins, polyamide resins, polyolefin resins, vinyl resins, acrylic resins, and cellulose resins, from the viewpoint of heat resistance and mechanical strength. Polyester resins such as polyethylene terephthalate and polyethylene naphthalate are preferably used. Among these, polyethylene terephthalate is particularly preferably used from the viewpoint of cost.

(UV blocking layer 11)
The ultraviolet blocking layer 11 is a material having adhesiveness with the base film 9 and the release layer 3 and absorbs or reflects light having a light wavelength in the range of 200 nm to 380 nm, thereby transmitting ultraviolet light. Materials with the ability to block or reduce can be used.
Examples of such materials having ultraviolet blocking ability include metal fillers typified by aluminum, metal oxides such as titanium oxide, zinc oxide, and cesium oxide, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and cyano. Organic ultraviolet absorbers such as acrylate ultraviolet absorbers, salicylate ultraviolet absorbers, and oxanilide ultraviolet absorbers, and colored pigments such as carbon black can be used. Here, when it is necessary to align the concavo-convex pattern of the concavo-convex forming layer 1 with the printing layer 5, a metal oxide or an organic ultraviolet absorber having transparency in the visible light region, or these ultraviolet absorbers are used. A covalently bonded resin is preferably used.

However, ultraviolet absorbers are generally low molecular in many cases, and the ultraviolet absorbers may migrate to other layers during the production process of the in-mold transfer foil, causing problems. For example, when the hard coat layer 4 is transferred, curing failure may occur. Further, when the adhesive layer 6 is moved to and bleed out to the surface, adhesion failure with the molding resin may occur. In addition, since it becomes liquid in the resin temperature range (200 ° C. to 300 ° C.) at the time of injection molding, it may cause a print pattern flow (washout) near the gate.
Therefore, as the resin used for the ultraviolet blocking layer 11, it is preferable to use a polymer (ultraviolet absorbing polymer) having an ultraviolet absorbing functional group in the molecule. Specifically, a benzotriazole type acrylic ultraviolet absorbing polymer or the like can be used. Furthermore, from the viewpoint of adhesion between the base film 9 and the release layer 3, the material of the ultraviolet blocking layer 11 is a cured product of an acrylic polymer having a hydroxyl group and an ultraviolet absorbing functional group and an isocyanate compound. Is preferred.

Thus, by using a two-component curable acrylic resin as the material of the ultraviolet blocking layer 11, not only can it withstand thermal deformation during injection molding, but also has a high affinity with the release layer 3 (acrylic resin). Adhesion increases. Furthermore, since the isocyanate compound reacts with the hydroxyl group contained in the surface of the base film 9 and the release layer 3 to form a covalent bond, adhesion with each layer can be secured.
Here, the isocyanate compound refers to, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and prepolymers thereof.
As a standard of ultraviolet blocking ability, it is desirable that the transmittance of i-line (wavelength 365 nm) is less than 10%. This is because, when forming irregularities with an ultraviolet curable resin, it is necessary to irradiate the irregularity-forming layer 1 with ultraviolet rays having an integrated light amount in the range of 500 mJ / cm ² or more and 1000 mJ / cm ² or less. If the hard coat layer 4 formed is irradiated with ultraviolet rays of about 100 mJ / cm ² or more before injection molding, the hard coat layer 4 cannot follow stretching during injection molding due to the progress of the crosslinking reaction. This is because cracks are generated.

(Release layer 3)
The material of the release layer 3 is not particularly limited as long as it is a resin having necessary release properties. In the in-mold transfer foil according to the third embodiment, for example, an olefin-modified acrylic melamine resin or acrylic urethane resin is preferably used. Moreover, as a formation method of the mold release layer 3, a well-known printing method and coating method can be used, for example.
(Hard coat layer 4)
The hard coat layer 4 is a layer that becomes the outermost surface layer of the molded product when the base film 9 is peeled off after the transfer. As a material of the hard coat layer 4, an ultraviolet curable resin that is cured by ultraviolet rays can be used, and examples thereof include a resin containing at least an acryloyl group or a methacryloyl group. With such an ultraviolet curable hard coat layer 4, the surface of the molded product can be immediately cured by ultraviolet irradiation, and the production efficiency of the molded product can be improved. In addition, according to the in-mold transfer foil according to the third embodiment, the hard coat layer 4 is molded in an uncured state and is subjected to a process of complete curing after the molding, so that it is possible to improve both moldability and surface physical properties. It is. Moreover, as a formation method of the hard-coat layer 4, a well-known printing method and the coating method can be used, for example.

(Print layer 5)
As a material of the printing layer 5, for example, a colored ink containing an appropriate color pigment or dye as a colorant can be used. Moreover, as a formation method of the printing layer 5, well-known printing methods, such as an offset printing method, a gravure printing method, a screen printing method, an inkjet method, can be used, for example. Among these, it is preferable to print by a gravure printing method from the viewpoints that multicolor printing and gradation expression are possible and that it is suitable for mass production. An anchor layer (not shown) may be provided between the printing layer 5 and the hard coat layer 4 in order to improve the adhesion with the hard coat layer 4. As a method for forming the anchor layer, for example, a printing method such as a gravure printing method or a screen printing method can be used, but it is desirable to print by a gravure printing method from the viewpoint of film thickness or productivity.
(Adhesive layer 6)
The adhesive layer 6 adheres each of the above layers to the surface of the molded product. As a material for the adhesive layer 6, a heat-sensitive or pressure-sensitive resin suitable for the molding resin 7 can be appropriately used. As a method for forming the adhesive layer 6, for example, a printing method such as a gravure printing method or a screen printing method can be used, but it is desirable to print by a gravure printing method from the viewpoint of film thickness or productivity. In addition, when the printing layer 5 has sufficient adhesiveness with respect to a molded article and also has an effect as an adhesive layer, the adhesive layer 6 may not be provided.

(Unevenness forming layer 1)
The concavo-convex forming layer 1 provided on the surface opposite to the surface on which the release layer 3 is formed of the base film 9 contains an ultraviolet curable resin and can be formed by various forming methods. The concavo-convex forming layer 1 is, for example, a screen printing method using UV thick ink, a UV inkjet method, or a liquid UV curable resin sandwiched between a releasable concavo-convex film and a base film 9, and UV from the releasable concavoconvex film side The liquid ultraviolet curable resin can be cured by irradiation, and then formed by a forming method such as a method of providing the concavo-convex forming layer 1 on the base film 9 by peeling the releasable concavo-convex film.
Moreover, as a material of the uneven | corrugated formation layer 1, the ultraviolet curable resin similar to the hard-coat layer 4 can be used, For example, resin etc. which contain an acryloyl group or a methacryloyl group at least can be used.
According to the concavo-convex forming method using these ultraviolet curable resins, the reproducibility of the concavo-convex shape is improved as compared with the case where a thermosetting resin is used, and the manufacturing time can be shortened.

(In-mold transfer foil manufacturing method according to each embodiment)
In the in-mold transfer foil according to each of the first to third embodiments, ultraviolet irradiation for crosslinking and curing the unevenness forming layer 1 is performed from the surface side of the

base films

2 and 9 on which the unevenness forming layer 1 is formed. Manufactured by. Here, in the manufacturing method of the in-mold transfer foil according to each embodiment, the ultraviolet irradiation may be performed from the side of the

base films

2 and 9 on which the unevenness forming layer 1 is formed. Absent. That is, after laminating all the above-described layers, the in-mold according to each embodiment is performed by irradiating ultraviolet rays for crosslinking and curing the concavo-convex forming layer 1 from the side of the

base films

2 and 9 on which the concavo-convex forming layer 1 is formed. A transfer foil may be manufactured. Alternatively, after performing ultraviolet irradiation for crosslinking and curing the unevenness forming layer 1 from the side of the

base films

2 and 9 on which the unevenness forming layer 1 is formed, the release layer 3, the hard coat layer 4, the printing layer 5, and adhesion The in-mold transfer foil according to each embodiment may be manufactured by laminating the layer 6.

(Decorated molded product and its manufacturing method)
Each layer is laminated as described above to prepare in-mold transfer foils according to the first to third embodiments. By using these in-mold transfer foils and performing in-mold injection molding, a molded product having an uneven shape on the surface can be produced.
In each of the first to third embodiments, the case where the print layer 5 having a predetermined pattern pattern is present between the hard coat layer 4 and the adhesive layer 6 is shown. In addition, for example, there are metal deposited layers such as aluminum, tin, indium and chromium, transparent reflective layers such as titanium oxide and zinc sulfide, multilayer reflective films, or embossed layers such as holograms provided by hot-pressure embossing, etc. Good.

Hereinafter, the in-mold injection molding process using the in-mold transfer foil will be described in detail with reference to FIGS. 4 and 5. Here, the in-mold transfer foil according to the first embodiment will be described as an example.
In mold injection molding, first, an in-mold transfer foil is inserted into an injection mold 8 and a molding resin 7 is injection-molded into the cavity of the injection mold 8 from the printed layer 5 side of the in-mold transfer foil. As a result, the in-mold transfer foil is transferred to the surface of the molding resin 7. Next, after cooling the injected molding resin 7, the injection mold 8 is opened, the base film 2 and the release layer 3 of the in-mold transfer foil are peeled off, and the molded product is taken out in a known order. Do.

When the molding resin 7 is injected into the cavity of the injection mold 8, pressure is applied to the in-mold transfer foil inserted into the injection mold 8, and the unevenness provided on the in-mold transfer foil Deformation corresponding to the shape of the formation layer 1 occurs in the base film 2 and the transfer layer (for example, the release layer 3, the hard coat layer 4, the print layer 5, and the adhesive layer 6) (see FIG. 4). As a result, when the injection mold 8 is opened and the molded product is taken out, the concave / convex shape corresponding to the pattern of the concave / convex forming layer 1 is formed on the surface of the molded product on the decorative layer (for example, printing layer 5) side. (See FIG. 5). In this way, a molded article having a concavo-convex shape is produced.
Finally, the hard coat layer 4 is completely cured by irradiating the surface of the molded product with ultraviolet rays.
Through the above steps, a decorative molded product using the in-mold transfer foil according to each embodiment described above is manufactured.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited only to a following example.
<Example 1>
Using a polyethylene terephthalate resin film (HB manufactured by Teijin DuPont Films) that absorbs ultraviolet rays as a base film having ultraviolet blocking ability, a melamine resin release layer and an ultraviolet curable acrylic resin hard coat on the base film A layer was formed. Thereafter, each layer was formed by a gravure printing method using urethane-based ink as a printing layer and acrylic resin as an adhesive layer.
Next, unevenness was formed by screen printing on the side opposite to the release layer forming surface of the base film using an ultraviolet curable resin (UVFIX screen ink) made by Teikoku ink as an unevenness forming layer. Thereafter, ultraviolet rays were irradiated from the surface side on which the concavo-convex forming layer was formed (high pressure mercury lamp integrated light amount 800 mJ / cm ² ) to crosslink and cure the concavo-convex forming layer, whereby the in-mold transfer foil of Example 1 was obtained.
This in-mold transfer foil was inserted into an injection mold and clamped to injection-mold a PC (polycarbonate) / ABS (acrylonitrile butadiene styrene) resin. Then, after cooling, the injection mold was opened, and the base film of the in-mold transfer foil was peeled from the molded product together with the release layer. Thereafter, the surface of the molded product was irradiated with ultraviolet rays having an integrated light quantity of 1000 mJ / cm ² using a high-pressure mercury lamp, and the hard coat layer was crosslinked and cured. Thereby, the molded article of Example 1 having high surface strength was obtained while forming irregularities on the molded article surface.

<Example 2>
A polyethylene terephthalate resin film was used as the base film, and a release layer, a hard coat layer, a print layer, and an adhesive layer were formed on the base film in the same manner as in Example 1.
Next, on the side opposite to the release layer forming surface of the base film, a two-component curable UV absorbing polymer (Shin Nakamura Chemical Vana Resin UVA-55MHB) is used as the UV blocking layer, and Nippon Polyurethane Coronate L is used as the curing agent. Thus, an ultraviolet blocking layer was formed.
Next, an unevenness was formed on the ultraviolet blocking layer by screen printing using an ultraviolet curable resin (UVFIX screen ink) manufactured by Teikoku ink as an unevenness forming layer. Thereafter, ultraviolet rays were irradiated from the surface side on which the unevenness forming layer was formed (high pressure mercury lamp integrated light amount 800 mJ / cm ² ), and the unevenness forming layer was crosslinked and cured to obtain an in-mold transfer foil of Example 2.
This in-mold transfer foil was inserted into an injection mold and clamped to inject PC / ABS resin. Then, after cooling, the injection mold was opened, and the base film of the in-mold transfer foil was peeled from the molded product together with the release layer. Thereafter, the surface of the molded product was irradiated with ultraviolet rays having an integrated light quantity of 1000 mJ / cm ² using a high-pressure mercury lamp, and the hard coat layer was crosslinked and cured. Thereby, the molded product of Example 2 having high surface strength was obtained while forming irregularities on the molded product surface.

<Example 3>
A polyethylene terephthalate resin film was used as the base film, and an ultraviolet blocking layer, a melamine resin release layer, and an ultraviolet curable acrylic resin hard coat layer were formed on the base film. Here, a two-pack curable UV absorbing polymer (Vanaresin UVA-55MHB manufactured by Shin-Nakamura Chemical Co., Ltd.) was used as the UV blocking layer, and Coronate L manufactured by Nippon Polyurethane was used as the curing agent. The release layer and the hard coat layer were formed in the same manner as in Example 1. Thereafter, a printing layer and an adhesive layer were formed by the gravure printing method as in Example 1.
Next, unevenness was formed on the side opposite to the release layer forming surface of the base film by using the UV inkjet method as the unevenness forming layer. The UV light source of the UV inkjet device used was an LED, and the concavo-convex forming layer was crosslinked and cured by irradiating the ultraviolet ray from the surface side on which the concavo-convex forming layer was formed. In this way, an in-mold transfer foil of Example 3 was obtained.
This in-mold transfer foil was inserted into an injection mold and clamped to inject PC / ABS resin. Then, after cooling, the injection mold was opened, and the base film of the in-mold transfer foil was peeled from the molded product together with the release layer. Thereafter, the surface of the molded product was irradiated with ultraviolet rays having an integrated light quantity of 1000 mJ / cm ² using a high-pressure mercury lamp, and the hard coat layer was crosslinked and cured. Thereby, the molded product of Example 3 having high surface strength was obtained while forming irregularities on the molded product surface.

<Comparative Example 1>
A polyethylene terephthalate resin film (50T60 manufactured by Toray Industries, Inc.) was used as a base film, and a melamine resin release layer and an ultraviolet curable acrylic resin hard coat layer were formed on the base film. Thereafter, each layer was formed by a gravure printing method using urethane-based ink as a printing layer and acrylic resin as an adhesive layer.
Next, the uneven | corrugated formation layer was formed like Example 1 on the opposite side to the release layer formation surface of a base film, and the in-mold transfer foil of the comparative example 1 was obtained.
Using this in-mold transfer foil, injection molding and ultraviolet irradiation of the molded product were performed in the same manner as in Examples 1 to 3, and a molded product of Comparative Example 1 was obtained.

(Comparison result)
When the appearance of the molded product of Comparative Example 1 was inspected, cracks at the corners of the molded product that were not observed in the molded products of Examples 1 to 3 occurred greatly. Further, at the end of the molded product of Comparative Example 1, there was a portion that was not partially transferred, and as compared with the molded products of Examples 1 to 3, the unevenness transferability was poor.
Although the present invention has been described with reference to a limited number of embodiments, the scope of rights is not limited thereto, and modifications of each embodiment based on the above disclosure are obvious to those skilled in the art.

The in-mold transfer foil according to the present invention can be used for surface protection and decoration of panel members used for home appliances, housing equipment, office equipment, automobile parts and the like.

DESCRIPTION OF SYMBOLS 1 ... Concave-forming layer 2 ... Base film having ultraviolet blocking ability 3 ... Release layer 4 ... Hard coat layer 5 ... Printing layer 6 ... Adhesive layer 7 ... Molding resin 8 ... Mold for injection molding 9 ... Base film 10 ... Ultraviolet Blocking layer 11 ... UV blocking layer

Claims

An in-mold having a release layer, a hard coat layer containing an ultraviolet curable resin, and an adhesive layer in this order on one surface of the base film, and an unevenness forming layer on the other surface of the base film In transfer foil,
The unevenness forming layer contains an ultraviolet curable resin,
An in-mold transfer foil comprising an ultraviolet blocking layer between the hard coat layer and the unevenness forming layer.
The in-mold transfer foil according to claim 1, wherein the base film is the ultraviolet blocking layer.
The in-mold transfer foil according to claim 1, wherein the ultraviolet blocking layer is provided between the base film and the unevenness forming layer.
The in-mold transfer foil according to claim 1, wherein the ultraviolet blocking layer is provided between the base film and the release layer.
The in-mold transfer foil according to claim 3 or 4, wherein the ultraviolet blocking layer is a cured product of an acrylic polymer having a hydroxyl group and an ultraviolet absorbing functional group and an isocyanate compound.
The in-mold transfer foil according to any one of claims 1 to 5, further comprising a printed layer having a predetermined pattern pattern between the hard coat layer and the adhesive layer.
A manufacturing method for manufacturing the in-mold transfer foil according to any one of claims 1 to 6,
A method for producing an in-mold transfer foil, wherein ultraviolet irradiation for crosslinking and curing the unevenness forming layer is performed from a surface side of the base film on which the unevenness forming layer is formed.
A decorative molded product manufactured by an in-mold injection molding method using the in-mold transfer foil according to any one of claims 1 to 6.
Using the in-mold transfer foil according to any one of claims 1 to 6, the surface of a decorative molded product produced by an in-mold injection molding method is irradiated with ultraviolet rays to completely form the hard coat layer. A method for producing a decorative molded product, characterized by curing.