JP6287526B2 - Hard coat transfer foil and molded product using the hard coat transfer foil - Google Patents

Description

  The present invention relates to a hard coat transfer foil having a scratch-preventing surface protective layer and a molded article using the hard coat transfer foil.

  Conventionally, as a transfer foil obtained after transferring a surface excellent in scratch resistance, chemical resistance, etc., a surface protective layer made of an ultraviolet curable resin has been provided on the release surface of the release film. A transfer foil having a pattern layer, an adhesive layer and the like provided thereon has been proposed (Patent Document 1). The decorative transfer foil having such a scratch-resistant surface protective layer is often used for the purpose of protecting the surface of a soft plastic typified by a polycarbonate resin.

However, when a transfer foil having a surface protective layer is transferred onto a soft plastic such as a polycarbonate resin, the base is soft, so dent marks and cracks are likely to occur. In many cases, the surface hardness of the transferred material did not increase.
In order to solve this problem, for example, a hard coat transfer foil shown in Patent Document 2 has been proposed.

  In the hard coat transfer foil shown in Patent Document 2, a film layer is provided between the surface protective layer and the adhesive layer constituting the hard coat transfer foil so that the surface hardness is increased even when the base is a soft material such as polycarbonate resin. Is forming. Thereby, since the film layer serves as a reinforcing material, even when the base is a soft material such as a polycarbonate resin, the transfer object can be prevented from being recessed by transferring the transfer foil to the transfer object. .

Japanese Patent No. 2538479 JP 2013-59889 A

However, the technique described in Patent Document 2 has the following problems.
That is, in the hard coat transfer foil shown in Patent Document 2, a half cut groove is formed in the transfer foil by carrying out a predetermined cut (half cut) with a half punching mold or the like in advance before transferring the transfer foil to the transfer object. Is forming. The half cut groove is formed in the transfer foil for the following reason.

  First, when using a transfer foil having a film layer in in-mold molding (a method in which a transfer foil is inserted into a mold and transferred simultaneously with molding) or heat transfer, burrs may be a problem. . When the film layer is thin, there is often no problem, but the burr becomes larger as the film layer becomes thicker. This is because the generation of burrs can be eliminated by forming half-cut grooves in the transfer foil in advance.

  Moreover, the transfer foil which does not include a film layer can easily cut off the excess transfer foil transferred to the end of the molded product. On the other hand, the transfer foil including the film layer has improved mechanical strength as compared with the transfer foil not including the film layer due to the film layer. For this reason, the excess transfer foil transferred to the end of the molded product cannot be easily separated. Therefore, by forming a half cut groove in the transfer foil in advance according to the outer shape of the molded product, the film layer This is because the excess transfer foil transferred to the end portion of the molded product can be easily separated even with the transfer foil containing the.

However, the process of forming the half-cut groove in the transfer foil in advance not only has a very low yield, but also has a high cost for performing the process.
Therefore, the present invention has been made to solve this problem, and the object of the present invention is to provide a sufficient surface hardness even if the material to be transferred is a soft material such as a polycarbonate resin, and has a low level. An object of the present invention is to provide a hard coat transfer foil having high design properties at a low cost and a molded product using the hard coat transfer foil.

  In order to solve the above problems, a hard coat transfer foil according to an aspect of the present invention includes a support film, a release layer formed on one surface of the support film, and the support film of the release layer. A surface protective layer having an acryloyl group or a methacryloyl group formed on the surface opposite to the surface in contact with the surface protective layer, and formed on the side of the surface protective layer opposite to the surface in contact with the release layer. A hard coat transfer foil including at least an adhesive layer, wherein an intermediate layer made of a thermoplastic acrylic resin is formed between the surface protective layer and the adhesive layer, and the thickness of the intermediate layer is 8 μm or more and 25 μm or less. In addition, the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer is 65 ° C. or higher.

  According to this hard coat transfer foil, an intermediate layer made of a thermoplastic acrylic resin is formed between the surface protective layer and the adhesive layer. For this reason, even if the material to be transferred is a soft material such as polycarbonate resin, the intermediate layer serves as a reinforcing material and can provide sufficient surface hardness, and the transfer material can be transferred by transferring the transfer foil to the material to be transferred. Dents can be suppressed. As a result, the surface hardness of the transfer object can be improved. No burr is generated when a transfer foil having an intermediate layer made of thermoplastic acrylic resin is used for in-mold molding or heat transfer, and it is not necessary to previously form a half-cut groove in the transfer foil. . For this reason, it is possible to provide a hard coat transfer foil having high design properties at low cost.

  And since the thickness of the intermediate layer is 8 μm or more and 25 μm or less, the surface hardness of the transferred object can be effectively improved, and the transferred object is more recessed by transferring the transfer foil to the transferred object. Can be suppressed. When the thickness of the intermediate layer is less than 8 μm, the surface hardness of the transfer object cannot be effectively improved. On the other hand, if the thickness of the intermediate layer is larger than 25 μm, the burrs at the time of transfer become large, and technical problems such as large smears at the time of coating increase.

Furthermore, since the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer is 65 ° C. or higher, the surface hardness of the transferred material can be effectively improved, and the intermediate layer is melted at high temperature and high pressure during injection molding. The occurrence of washout that flows can be suppressed.
In the hard coat transfer foil, it is preferable that the thermoplastic acrylic resin of the intermediate layer has a weight average molecular weight of 650,000 to 1,000,000.

  According to this hard coat transfer foil, it is possible to effectively suppress the occurrence of washout in which the intermediate layer melts and flows at high temperature and high pressure during injection molding. When the weight average molecular weight of the thermoplastic acrylic resin is smaller than 65,000, the occurrence of washout cannot be suppressed. Moreover, when the weight average molecular weight of this thermoplastic acrylic resin is larger than 1 million, it is difficult to apply. If the weight average molecular weight of the thermoplastic acrylic resin is greater than 1,000,000, the viscosity at the time of dissolution is high, and a considerable amount of solvent dilution (lower solid content) is required for neat coating. For this reason, since the coating cost becomes high (at low speed and multiple times of coating), the weight average molecular weight of the thermoplastic acrylic resin is made larger than 1 million, and the thickness of the intermediate layer 5 is realized to be 8 μm or more and 25 μm or less. Not reasonable.

In the hard coat transfer foil, the intermediate layer may be divided into a first intermediate layer and a second intermediate layer.
Furthermore, a molded product according to another aspect of the present invention is characterized in that the hard coat transfer foil is transferred by injection molding or heat transfer.

  According to the hard coat transfer foil and the molded article using the hard coat transfer foil according to the present invention, even if the material to be transferred is a soft material such as polycarbonate resin, sufficient surface hardness can be imparted and the cost can be reduced. Thus, it is possible to provide a hard coat transfer foil having high design properties and a molded product using the hard coat transfer foil.

It is a cross-sectional schematic diagram of embodiment of the hard coat transfer foil which concerns on this invention. It is a cross-sectional schematic diagram of the modification of the hard coat transfer foil shown in FIG.

Hereinafter, embodiments of a hard coat transfer foil according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an embodiment of a hard coat transfer foil according to the present invention. FIG. 2 is a schematic cross-sectional view of a modified example of the hard coat transfer foil shown in FIG.
In FIG. 1, a hard coat transfer foil (hereinafter simply referred to as transfer foil) 10 includes a support film 1, a release layer 2, a surface protective layer 3, a primer layer 4, an intermediate layer 5, a decorative layer 6, and an adhesive layer 7. It is the laminated body which has.

  Here, the release layer 2 is formed on one surface of the support film 1 (upper surface in FIG. 1). The surface protective layer 3 is formed on the surface of the release layer 2 opposite to the surface on which the support film 1 is formed (upper surface in FIG. 1). Further, the primer layer 4 is formed on the surface of the surface protective layer 3 opposite to the surface on which the release layer 2 is formed (upper surface in FIG. 1). The intermediate layer 5 is formed on the surface of the primer layer 4 opposite to the surface on which the surface protective layer 3 is formed (upper surface in FIG. 1). The decorative layer 6 is formed on the surface of the intermediate layer 5 opposite to the surface on which the primer layer 4 is formed (upper surface in FIG. 1). The adhesive layer 7 is formed on the surface of the decorative layer 6 opposite to the surface on which the intermediate layer 5 is formed (the upper surface in FIG. 1).

In addition, although the decoration layer 6 is formed in the surface on the opposite side to the surface in which the primer layer 4 was formed of the intermediate | middle layer 5, even if formed between the primer layer 4 and the intermediate | middle layer 5 Good. Moreover, when there is no need, the decoration layer 6 can also be abbreviate | omitted.
As the support film 1, for example, a substrate such as a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a triacetyl cellulose film, a polycarbonate film, a nylon film, a cellophane film, or an acrylic film can be used. The usable support film 1 has a thickness of 25 μm to 150 μm, and preferably 38 μm to 50 μm.

  The release layer 2 is most important for peelability from the surface protective layer 3, and heat resistance, solvent resistance, and stretchability are also required. For this reason, it is preferable that the mold release layer 2 is a hardening system, for example, hardened | cured materials, such as a melamine resin, polyolefin resin, a urethane resin, and a cellulose acetate, can be used. As the curing crosslinking system, epoxy resin / amines, alkyd resin / acid catalyst, acrylic polyol resin / isocyanate compound, and acrylic oligomer / photoinitiator can be used. Although there is no restriction | limiting in particular in the thickness of the mold release layer 2, 0.1 micrometer-3 micrometers are suitable.

  The surface protective layer 3 is preferably made of a resin that is in a tack-free state before transfer and can be crosslinked by irradiating ultraviolet rays or electron beams after being transferred to the transfer object. The reason for crosslinking after transfer is that the transfer foil 10 is often used by injection molding or heat transfer, but if crosslinked in advance, cracks are likely to occur during transfer stretching, resulting in poor appearance. There are mainly the following three methods for realizing tack-free properties before transfer.

As the first method, a polymer acrylate or methacrylate is used. As a second method, a tack-free method is achieved by slightly curing with a crosslinking system such as polyol resin / isocyanate compound or epoxy resin / acyne. The third method is a method of slightly irradiating ultraviolet rays or an electron beam to bring it into a semi-cured state.
In the present embodiment, the ultraviolet curable resin refers to a resin that is cured by ultraviolet rays (UV). Typical resins for radical polymerization reaction are resins having an acryloyl group in the molecule, and epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate oligomers, polymer monofunctional, bifunctional, or polyfunctional. Functional polymerizable (meth) acrylic monomers such as tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol Mixtures of monomers such as triacrylate and pentaerythritol tetraacrylate, oligomers and polymers are used. Among them, urethane acrylate or acrylic acrylate having a weight average molecular weight of about 5,000 to 300,000 is preferable in order to realize tack-free only by solvent drying. When cured with an electron beam, the resin is crosslinked and cured only with the above resin, but an ultraviolet polymerization initiator must be added in an amount of 0.5 to 10% by weight for crosslinking and curing with ultraviolet rays. In addition, in this embodiment, a weight average molecular weight refers to the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

In order to improve various physical properties, a leveling agent, wax, silica fine particles and the like may be added. The thickness of the surface protective layer 3 is preferably 3 μm to 10 μm.
The primer layer 4 is a layer for maintaining close contact between the surface protective layer 3 and the intermediate layer 5, and is a polyol resin such as polyester polyol or acrylic polyol and / or a hydroxyl group-containing resin such as a hydroxyl group-containing vinyl chloride resin and an isocyanate. A resin made of a compound is preferable. Moreover, the thickness of the primer layer 4 is not particularly limited, but is preferably 0.5 μm to 3 μm.

  The intermediate layer 5 is a layer that serves as a hardness reinforcing layer for supplementing the hardness of the surface protective layer 3. The ultraviolet curable resin used for the surface protective layer 3 generally has a high surface hardness but poor flexibility. Therefore, in the case of a flexible casing base material such as a polycarbonate / ABS alloy resin that is often used for a casing base material of a notebook computer or home appliance, a material having high hardness is used for the surface protective layer 3. In many cases, however, the surface protective layer 3 is destroyed without being able to withstand the dents and impacts of the casing base material when scratches occur.

Therefore, as a result of earnest research on materials having a hardness reinforcing effect and having performances during injection molding and thermal transfer (for example, stretchability, heat resistance, burrs, interlayer adhesion), thermoplastic acrylic resins have been optimal.
The thickness (3 μm to 10 μm) of the general surface protective layer 3 is not sufficient to suppress the dent of the transferred material when scratches occur, and when the surface protective layer 3 itself made of an ultraviolet curable resin is thickened, Problems such as warpage due to curing shrinkage and poor adhesion occur. On the other hand, the ultraviolet curable resin used for the surface protective layer 3 is often more expensive than other materials, and it is not realistic to make the surface protective layer 3 thick.

On the other hand, there is generally a two-component curable acrylic resin (acrylic polyol / isocyanate compound) as a material with high hardness, but the two-component curable acrylic resin is tough and has high heat resistance. The foil breakage is poor and burrs are likely to occur.
Thermoplastic acrylic resins include homopolymers and copolymers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, biacrylic acetate, styrene Acrylic or the like can be used. A representative example of the thermoplastic acrylic resin product that can be obtained is Dainar (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd. In addition, extender pigments, waxes, and leveling materials can be added to adjust peelability and improve coating surface properties.

  The thickness of the intermediate layer 5 is preferably larger than the thickness of the surface protective layer 3 in order to suppress the dent of the transfer object, and needs to be 8 μm or more and 25 μm or less. When the thickness of the intermediate layer 5 is less than 8 μm, a clear effect due to the addition of the intermediate layer 5 does not appear. On the other hand, if the thickness of the intermediate layer 5 exceeds 25 μm, technical problems remain such as large burrs during transfer and large smears during coating.

  Further, due to the difference in the weight average molecular weight of the thermoplastic acrylic resin of the intermediate layer 5 and the glass transition temperature, a washout occurs in which the intermediate layer 5 melts and flows at high temperature and high pressure during injection molding. In order to suppress the occurrence of this washout, the weight average molecular weight of the thermoplastic acrylic resin of the intermediate layer 5 is set to 650,000 or higher, and the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer is set to 65 ° C. or higher. This is very important. In order to effectively improve the surface hardness of the transfer object, the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer 5 needs to be 65 ° C. or higher. Here, if the weight average molecular weight of the thermoplastic acrylic resin is smaller than 65,000, the occurrence of washout cannot be suppressed. Further, even when the weight average molecular weight of the thermoplastic acrylic resin is larger than 1,000,000, the occurrence of washout cannot be suppressed if the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer 5 is less than 65 ° C.

  Moreover, when the weight average molecular weight of the thermoplastic acrylic resin of the intermediate | middle layer 5 is larger than 1 million, it is difficult to apply. If the weight average molecular weight of the thermoplastic acrylic resin is greater than 1,000,000, the viscosity at the time of dissolution is high, and a considerable amount of solvent dilution (lower solid content) is required for neat coating. For this reason, since the coating cost becomes high (at low speed and multiple times of coating), the weight average molecular weight of the thermoplastic acrylic resin is made larger than 1 million, and the thickness of the intermediate layer 5 is realized to be 8 μm or more and 25 μm or less. Not reasonable.

In FIG. 1, the intermediate layer 5 is formed between the primer layer 4 and the decorative layer 6, but may be formed between the decorative layer 6 and the adhesive layer 7.
The intermediate layer 5 is formed by dissolving a thermoplastic acrylic resin in an organic solvent, and applying a predetermined coating method (gravure coater, micro gravure coater, reverse gravure coater, comma coater, die coater, Meyer coater, screen printing), A thermoplastic acrylic resin can be formed by melt extrusion using a T die.

  The decoration technique that can be adopted in the present embodiment of the decoration layer 6 includes not only general printing with color inks, but also special printing such as pearl, fluorescence, mirror, retroreflection, magnetic printing, and uneven structure by heat and ultraviolet rays. It is possible to employ an embossing process for forming (various lens effects and holograms) and a thin film forming technique for forming aluminum, silver, chromium, titanium oxide, zinc sulfide, etc. by vacuum deposition or sputtering.

  As the adhesive layer 7, a known heat-sealable adhesive or pressure-sensitive adhesive can be used. For example, as the adhesive layer 7, vinyl acetate resin, ethylene vinyl acetate copolymer resin, vinyl acetate resin, acrylic resin, butyral resin, epoxy resin, polyester resin, polyurethane resin, acrylic adhesive, rubber adhesive, silicon Type adhesive, urethane type adhesive and the like. The thickness of the adhesive layer 7 is preferably in the range of 0.5 μm to 10 μm.

Next, a modification of the hard coat transfer foil shown in FIG. 1 will be described with reference to FIG. 2, members that are the same as those shown in FIG. 1 are given the same reference numerals, and descriptions thereof may be omitted.
The hard coat transfer foil (hereinafter simply referred to as transfer foil) 10 shown in FIG. 2 has the same basic configuration as the transfer foil 10 shown in FIG. 1, but is different in the way of providing an intermediate layer. That is, in the transfer foil 10 shown in FIG. 2, the intermediate layer is divided into the first intermediate layer 8 and the second intermediate layer 9. Then, the first intermediate layer 8 is formed on the surface of the primer layer 4 opposite to the surface on which the surface protective layer 3 is formed (the upper surface in FIG. 2). The decorative layer 6 is formed on the surface opposite to the surface on which the primer layer 4 is formed (the upper surface in FIG. 2). Moreover, the 2nd intermediate | middle layer 9 is formed in the surface (upper surface in FIG. 2) of the decorating layer 6 on the opposite side to the surface in which the 1st intermediate | middle layer 8 was formed. The adhesive layer 7 is formed on the surface of the second intermediate layer 9 opposite to the surface on which the decoration layer 6 is formed (the upper surface in FIG. 2).

Here, the material composition of the 1st intermediate | middle layer 8 and the 2nd intermediate | middle layer 9 is the same material composition as the intermediate | middle layer 5 shown in FIG. 1 mentioned above, and each thickness is the 1st intermediate | middle layer 8 and the 2nd intermediate | middle layer. The total film thickness obtained by adding the layer 9 is 8 μm or more and 25 μm or less.
Thus, by dividing the intermediate layer into the first intermediate layer 8 and the second intermediate layer 9, the warp of the transfer foil 10 can be reduced as compared with the transfer foil 10 shown in FIG.

  According to the hard coat transfer foil 10 according to the present embodiment, an intermediate layer made of a thermoplastic acrylic resin is formed between the surface protective layer and the adhesive layer. For this reason, even if the material to be transferred is a soft material such as polycarbonate resin, the intermediate layer serves as a reinforcing material and can provide sufficient surface hardness, and the transfer material can be transferred by transferring the transfer foil to the material to be transferred. Dents can be suppressed. As a result, the surface hardness of the transfer object can be improved. No burr is generated when a transfer foil having an intermediate layer made of thermoplastic acrylic resin is used for in-mold molding or heat transfer, and it is not necessary to previously form a half-cut groove in the transfer foil. . For this reason, it is possible to provide a hard coat transfer foil having high design properties at low cost.

  And since the thickness of the intermediate layer is 8 μm or more and 25 μm or less, the surface hardness of the transferred object can be effectively improved, and the transferred object is more recessed by transferring the transfer foil to the transferred object. Can be suppressed. When the thickness of the intermediate layer is less than 8 μm, the surface hardness of the transfer object cannot be effectively improved. On the other hand, if the thickness of the intermediate layer is larger than 25 μm, the burrs at the time of transfer become large, and technical problems such as large coating spots at the time of coating increase.

Furthermore, since the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer is 65 ° C. or higher, the surface hardness of the transferred material can be effectively improved, and the intermediate layer is melted at high temperature and high pressure during injection molding. The occurrence of washout that flows can be suppressed.
Next, a method for manufacturing the hard coat transfer foil 10 shown in FIG. 1 will be briefly described.
First, the release layer 2 is formed on one surface of the support film 1. Next, the surface protective layer 3 having an acryloyl group or a methacryloyl group is formed on the surface of the release layer 2 opposite to the surface on which the support film 1 is formed. Next, the intermediate layer 5 and the surface protective layer 3 different from the above layers are bonded with the primer layer 4 interposed therebetween. Next, the decoration layer 6 is formed on the surface of the intermediate layer 5 opposite to the surface on which the primer layer 4 is formed. Thereafter, the adhesive layer 7 is formed on the surface of the decorative layer 6 opposite to the surface on which the intermediate layer 5 is formed. Thereby, the hard coat transfer foil 10 can be manufactured.

Example 1
On the support film 1, a biaxially stretched polyester film (G440E50 manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 50 μm, an acrylic melamine resin (Tesfine manufactured by Hitachi Chemical Co., Ltd.) is formed by a gravure method with a Dry 0.2 μm thickness. A release layer 2 was obtained. Here, “Dry 0.2 μm thickness” means that the thickness becomes 0.2 μm when dried. Similarly, “Dry OO μm thickness” described below means that the thickness becomes OO μm when dried.

Subsequently, a surface-protecting layer 3 was formed on the release layer 2 by applying a tack-free UV curable resin (RC29-117 manufactured by DIC) with a dry thickness of 5 μm by a reverse gravure method.
Next, a polyester polyol / isocyanate compound-based ink (TM-595, manufactured by Toyo Ink Co., Ltd.) is applied as a primer layer (adhesion layer) 4 on the surface protective layer 3 by a gravure method at a Dry 1.0 μm thickness, and then intermediate Ink obtained by dissolving a thermoplastic acrylic resin (Dainal (registered trademark) BR-83 manufactured by Mitsubishi Rayon Co., Ltd.) as a layer 5 in toluene and methyl ethyl ketone was formed in a thickness of Dry 8 μm by a reverse gravure method to obtain an intermediate layer 5. Here, the glass transition temperature of the used thermoplastic acrylic resin is 105 ° C., and the weight average molecular weight is 40,000.

Subsequently, the intermediate layer 5 is subjected to predetermined color printing to form a decorative layer 6. As the adhesive layer 7, vinyl acetate resin (Solvine A (manufactured by Nissin Chemical Industry Co., Ltd.)) is added to toluene and An ink dissolved in methyl ethyl ketone was applied with a dry thickness of 1 μm by a gravure method to obtain a hard coat transfer foil 10.
Further, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin, thereby obtaining a molded product to which the hard coat transfer foil 10 was transferred.

(Example 2)
A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the coating film thickness of the thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to Dry 20 μm.
Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.

(Example 3)
A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the coating film thickness of the thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to Dry 25 μm thickness.
Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.

Example 4
The thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to Mitsubishi Rayon Co., Ltd. Dianal BR-90 (glass transition temperature 65 ° C., weight average molecular weight 230,000), and the thermoplastic acrylic resin A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the coating film thickness was changed to Dry 10 μm thickness.
Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.

(Example 5)
The thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to M-4003 (glass transition temperature 105 ° C., weight average molecular weight 1 million) manufactured by Negami Kogyo Co., Ltd., and the thermoplastic acrylic resin was applied. A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the film thickness was changed to Dry 10 μm.
Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.

(Example 6)
The thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to Dianal BR-50 (glass transition temperature: 105 ° C., weight average molecular weight: 650,000) manufactured by Mitsubishi Rayon Co., Ltd. A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the acrylic resin coating thickness was changed to Dry 10 μm.
Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.

(Example 7)
On the support film 1, a biaxially stretched polyester film (G440E50 manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 50 μm, an acrylic melamine resin (Tesfine manufactured by Hitachi Chemical Co., Ltd.) is formed by a gravure method with a Dry 0.2 μm thickness. A release layer 2 was obtained.
Subsequently, a surface-protecting layer 3 was formed on the release layer 2 by applying a tack-free UV curable resin (RC29-117 manufactured by DIC) with a dry thickness of 5 μm by a reverse gravure method.
Next, a polyester polyol / isocyanate compound-based ink (TM-595 manufactured by Toyo Ink Co., Ltd.) was applied as a primer layer (adhesion layer) 4 on the surface protective layer 3 by a gravure method in a Dry 1.0 μm thickness.

  Subsequently, the primer layer 4 is subjected to predetermined color printing to form a decorative layer 6, and then a thermoplastic acrylic resin (Dianar (registered trademark) BR-83 manufactured by Mitsubishi Rayon Co., Ltd.) as the intermediate layer 5 is added with toluene and Ink dissolved in methyl ethyl ketone was formed with a thickness of Dry 8 μm by reverse gravure method to obtain an intermediate layer 5. Here, the glass transition temperature of the used thermoplastic acrylic resin is 105 ° C., and the weight average molecular weight is 40,000.

Subsequently, an ink in which a vinyl chloride resin (Solvine A (manufactured by Nissin Chemical Industry Co., Ltd.) (solvein is a registered trademark)) is dissolved in toluene and methyl ethyl ketone as an adhesive layer 7 is applied on the intermediate layer 5 to a dry thickness of 1 μm by the gravure method. A hard coat transfer foil 10 was obtained.
Further, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin, thereby obtaining a molded product to which the hard coat transfer foil 10 was transferred.

(Example 8)
On the support film 1, a biaxially stretched polyester film (G440E50 manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 50 μm, an acrylic melamine resin (Tesfine manufactured by Hitachi Chemical Co., Ltd.) is formed by a gravure method with a Dry 0.2 μm thickness. A release layer 2 was obtained.
Subsequently, a surface-protecting layer 3 was formed on the release layer 2 by applying a tack-free UV curable resin (RC29-117 manufactured by DIC) with a dry thickness of 5 μm by a reverse gravure method.

  Next, a polyester polyol / isocyanate compound-based ink (TM-595 manufactured by Toyo Ink Co., Ltd.) is applied as a primer layer (adhesion layer) 4 on the surface protective layer 3 by a gravure method with a Dry 1.0 μm thickness, An ink obtained by dissolving a thermoplastic acrylic resin (Dianar (registered trademark) BR-83 manufactured by Mitsubishi Rayon Co., Ltd.) as toluene 1 and methyl ethyl ketone in a thickness of 4 μm by a reverse gravure method is formed. Got. Here, the glass transition temperature of the used thermoplastic acrylic resin is 105 ° C., and the weight average molecular weight is 40,000.

  Subsequently, after a predetermined color printing is performed on the first intermediate layer 8 to form the decorative layer 6, a thermoplastic acrylic resin (Dianal (registered trademark) BR- manufactured by Mitsubishi Rayon Co., Ltd.) as the second intermediate layer 9 is formed. 83) was dissolved in toluene and methyl ethyl ketone to form a Dry 4 μm thick ink by reverse gravure method, whereby a second intermediate layer 9 was obtained. Here, the glass transition temperature of the used thermoplastic acrylic resin is 105 ° C., and the weight average molecular weight is 40,000.

Further, as an adhesive layer 7, an ink in which a vinyl chloride resin (Solvine A (manufactured by Nissin Chemical Industry Co., Ltd.) manufactured by Nissin Chemical Industry Co., Ltd.) is dissolved in toluene and methylethylketone is applied by a gravure method to a dry thickness of 1 μm. Got.
Further, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin, thereby obtaining a molded product to which the hard coat transfer foil 10 was transferred.

Example 9
The thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to Dianal BR-87 (glass transition temperature: 105 ° C., weight average molecular weight: 25,000) manufactured by Mitsubishi Rayon Co., Ltd. A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the acrylic resin coating thickness was changed to Dry 10 μm.
Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.

(Comparative Example 1)
On the support film 1, a biaxially stretched polyester film (G440E50 manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 50 μm, an acrylic melamine resin (Tesfine manufactured by Hitachi Chemical Co., Ltd.) is formed by a gravure method with a Dry 0.2 μm thickness. A release layer 2 was obtained.
Subsequently, a surface-protecting layer 3 was formed on the release layer 2 by applying a tack-free UV curable resin (RC29-117 manufactured by DIC) with a dry thickness of 5 μm by a reverse gravure method.
Next, a polyester polyol / isocyanate compound-based ink (TM-595 manufactured by Toyo Ink Co., Ltd.) was applied as a primer layer (adhesion layer) 4 on the surface protective layer 3 by a gravure method in a Dry 1.0 μm thickness.

Subsequently, the primer layer 4 is subjected to predetermined color printing to form a decoration layer 6, and a vinyl acetate resin (Solvine A (manufactured by Nissin Chemical Industry Co., Ltd.)) is added as toluene and an adhesive layer 7. An ink dissolved in methyl ethyl ketone was applied with a dry thickness of 1 μm by a gravure method to obtain a hard coat transfer foil 10.
Further, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin, thereby obtaining a molded product to which the hard coat transfer foil 10 was transferred.

(Comparative Example 2)
A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the coating film thickness of the thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to Dry 5 μm thickness.
Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.

(Comparative Example 3)
The thermoplastic acrylic resin as the intermediate layer 5 used in Example 1 was changed to Mitsubishi Rayon Co., Ltd. Dianal BR-101 (glass transition temperature 50 ° C., weight average molecular weight 160,000), and the thermoplastic acrylic resin A hard coat transfer foil 10 was obtained in the same manner as in Example 1 except that the coating film thickness was changed to Dry 10 μm thickness.

Subsequently, the hard coat transfer foil 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to obtain a molded product to which the hard coat transfer foil 10 was transferred.
The molded articles obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were irradiated with ultraviolet rays having an exposure amount of 1000 mJ / cm ^{2 with} a 120 W / cm high-pressure mercury lamp and completely cured. Next, evaluation items and evaluation criteria for these molded products are shown below.

(Bari)
A: No burr at all B: There is a burr of less than 1 mm. Pass level.
Δ: There are burrs of 1 mm to less than 5 mm.
X: There is a burr of 5 mm or more.
(Washout)
○: No washout is visible.
Δ: There is a washout of less than 1 mm.
X: There is a washout of 1 mm or more.
(Pencil curing test)
Conforms to JIS K5600-5-4.
The evaluation results of each example and each comparative example are shown in Table 1.

  When the molded products obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated for hardness by a pencil curing test (JIS K5600-5-4), they had an intermediate layer, and the thickness of the intermediate layer was 8 μm or more and 25 μm or less. In addition, for Examples 1 to 9 in which the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer was 65 ° C. or higher, the pencil hardness was all 2H or higher, and hardening with improved hardness was observed. However, in the molded product of Example 9, the weight average molecular weight was as small as 25,000, washout occurred, and the appearance was poor.

  On the other hand, Comparative Example 1 without an intermediate layer, Comparative Example 2 with an intermediate layer having a thickness as small as 5 μm, and an intermediate layer with a thickness as large as 10 μm but a glass transition temperature as low as 50 ° C. In Comparative Example 3, the pencil hardness was H, and the hardness was not improved. In Comparative Example 3, since the glass transition temperature was as low as 50 ° C., washout occurred and the appearance was poor.

  According to the hard coat transfer foil and the molded article using the hard coat transfer foil according to the present invention, even if the material to be transferred is a soft material such as polycarbonate resin, sufficient surface hardness can be imparted and the cost can be reduced. Thus, it is possible to provide a hard coat transfer foil having high design properties and a molded product using the hard coat transfer foil. Therefore, the hard coat transfer foil according to the present invention and the molded product using the hard coat transfer foil are anti-scratch measures and decoration for panel members used in home appliances, housing equipment, office equipment, automobile parts, etc. Can be used.

DESCRIPTION OF SYMBOLS 1 Support film 2 Release layer 3 Surface protective layer 4 Primer layer 5 Intermediate layer 6 Decorating layer 7 Adhesive layer 8 1st intermediate layer 9 2nd intermediate layer 10 Hard coat transfer foil

Claims (4)

A support film;
A release layer formed on one side of the support film;
A surface protective layer having an acryloyl group or a methacryloyl group, formed on the surface of the release layer opposite to the surface in contact with the support film;
A hard coat transfer foil comprising at least an adhesive layer formed on the surface protective layer on the side opposite to the surface in contact with the release layer,
An intermediate layer made of a thermoplastic acrylic resin is formed between the surface protective layer and the adhesive layer,
A hard coat transfer foil, wherein the intermediate layer has a thickness of 8 μm or more and 25 μm or less, and the glass transition temperature of the thermoplastic acrylic resin of the intermediate layer is 65 ° C. or more.   The hard coat transfer foil according to claim 1, wherein the thermoplastic acrylic resin of the intermediate layer has a weight average molecular weight of 650,000 to 1,000,000.   The hard coat transfer foil according to claim 1, wherein the intermediate layer is divided into a first intermediate layer and a second intermediate layer.   A molded product, wherein the hard coat transfer foil according to any one of claims 1 to 3 is transferred by injection molding or heat transfer.

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