JPH075000B2 - Transfer foil - Google Patents

Description

TECHNICAL FIELD The present invention relates to a transfer foil, and more particularly to a transfer foil that is excellent in weather resistance and abrasion resistance and is suitable for hard coat applications such as the field of automobile exteriors.

[Prior Art] Conventionally, as a protective layer in a transfer foil, an acrylic resin,
Urethane type, melamine type, phenol type, urea type, diacrylic phthalate type, polyester type, epoxy type,
Alkyd-based, maleated rosin, polyvinyl butyral-based, cellulose-based, polyamide-based, vinyl chloride-vinyl acetate copolymer-based, various thermosetting resins such as UV curable resin, UV curable resin or a coating layer of thermoplastic polymer is used. It had been.

However, when it is used in the field of exterior applications that require durability, especially weather resistance and abrasion resistance, it can be used for choking coatings,
There were many problems due to physical and chemical factors such as crazing, scratches and deterioration of adhesion, and there were problems in practical use.

[Object of the Invention] In view of the above-mentioned conventional problems, the present invention is an exterior having excellent weather resistance and wear resistance for applications including the field of automobile exterior where durability performance, particularly weather resistance performance and wear resistance performance are severe. To provide a transfer foil for use.

[Configuration of Invention] That is, the present invention is a transfer foil in which at least a protective layer (3) and an adhesive layer (4) are sequentially formed on a substrate (1) directly or via a treatment layer (2). 2. The transfer foil, wherein the protective layer (3) is composed of a coating film of a silicon-based hard coating agent alone or an acrylic-modified silicon-based hard coating agent obtained by hydrolysis of an alkylalkoxysilane.

That is, in the transfer foil of the present invention, conventionally used as a protective layer in the transfer foil, acrylic, urethane, melamine, phenol, urea, diacrylphthalate, polyester, epoxy, alkyd , Maleic rosin, polyvinyl butyral-based, cellulose-based, polyamide-based, vinyl chloride-vinyl acetate copolymer-based, various thermosetting resins such as UV curable resin, instead of a coating layer of UV curable resin or thermoplastic polymer, In particular in the automotive exterior field where weather resistance and wear resistance are severe, which was solved by using a silicon-based hard coating agent obtained by hydrolysis of alkylalkoxysilane alone or a coating of an acrylic modified silicon-based hard coating agent. Even if it is used for hard coat applications, it has excellent weather resistance and耗性 is also to complete the transfer foil for exterior that shows.

That is, the present invention relates to a transfer foil obtained by sequentially forming at least a protective layer (3) and an adhesive layer (4) on a base material (1) directly or via a treatment layer (2). 3) adopts a specific protective layer (3) consisting of a coating film of a silicon-based hard coating agent obtained by hydrolysis of an alkylalkoxysilane or an acrylic-modified silicone-based hard coating agent. It is possible to provide a transfer foil exhibiting weather resistance and abrasion resistance that is sufficiently excellent even when used in hard coat applications such as the automotive exterior field where severe weather resistance and abrasion resistance are severe. Is.

As the substrate (1) in the transfer foil of the present invention, any one having sufficient self-holding property can be used, and examples thereof include polyester, polypropylene, polycarbonate, unplasticized polyvinyl chloride, polyethylene, polyamide, polyamideimide, Polyethylene, cellulose acetate, polycarbonate, resin such as fluororesin, or film or sheet such as cellophane paper or glassine paper, film or sheet of stainless steel or other metal or sheet release paper or release film Used. In particular, as the substrate (1), it is preferable to use a film-shaped material of the above-mentioned resins having a thickness of about 9 to 50 μm, because the transfer foil without wrinkles or cracks can be continuously mass-produced. .

When the base material (1) does not have good releasability from the protective layer (3), a thermoplastic resin such as paraffin wax, silicone resin, fluorine resin, cellulose resin, acrylic resin, or thermosetting resin is used. Type polyester resin, thermosetting polyurethane resin, epoxy resin, polyimide resin, polyesterimide resin, polyamideimide resin, melamine resin, phenol resin, urea resin, guanamine resin,
The treatment layer (2) may be formed by applying a thermosetting resin such as diallyl phthalate resin or a surfactant.

The transfer foil of the present invention is used in the field of exterior applications requiring durability, particularly weather resistance and abrasion resistance,
The protective layer (3) of the transfer foil of the present invention is required to have sufficient durability, particularly weatherability and abrasion resistance, and is used in the field of exterior applications, such as physical properties such as choking, crazing, scratches, and reduction in adhesion of the coating film. It is required to have sufficient durability against chemical factors.

However, there is no one satisfying such extremely strict requirements until now, and as a result of intensive studies by the present inventor, the only silicone-based hard coating agent or acrylic obtained by hydrolysis of alkylalkoxysilane was the only one. Only the coating film of the modified silicone type hard coating agent can be used as the protective layer (3) of the transfer foil of the present invention, and the object of the present invention can be achieved. Protective layer (3)
The thickness of the coating film of the hard coat agent is 0.5 to 10 μm
It is preferable to use a range of extent, from the viewpoint of continuous mass production of transfer foil without wrinkles or cracks,
If it is thinner than 0.5 μm, it is a stable and homogeneous protective layer (3).
Is not obtained, and it is difficult to obtain a transfer foil exhibiting sufficiently excellent weather resistance and abrasion resistance, and when it is more than 10 μm, transfer formation of a delicate pattern becomes difficult, which is not preferable. Further, the protective layer (3) forming the protective layer (3) may be appropriately colored with a coloring agent in advance.

As the adhesive layer (4) of the transfer foil of the present invention, an adhesive that does not impair the texture of the material to be transferred such as flexibility and rigidity depending on the material of the material to be transferred is required in addition to adhesiveness.

As such an adhesive, an acrylic resin type, a vinyl acetate resin type, a vinyl chloride resin type, a rosin-modified maleic acid resin type,
Adhesives such as polyester resin-based, ketone resin-based, synthetic rubber-based, and polyamide resin-based adhesives are appropriately used.

The thickness of the adhesive layer is usually selected from the range of 0.2 to 5 μm. If the thickness is less than 0.2 μm, a sufficient adhesive effect cannot be obtained. On the other hand, if the thickness exceeds 5 μm, the adhesive layer is too thick and transfer formation of a delicate pattern becomes difficult, which is not preferable. In addition, the drying speed becomes slow and it is inefficient. In addition, the original adhesive strength cannot be obtained, and adverse effects such as residual solvent occur.
Further, as the adhesive forming the adhesive layer, one which is appropriately colored with a coloring agent in advance can be used as long as it is transparent or translucent.

In the transfer foil of the present invention, a transparent anchor layer (5) may be provided between the protective layer (3) and the adhesive (4) for the purpose of improving adhesive coatability between the two. Depending on the material of the transferred material, it is required that the texture of the material of the transferred material such as flexibility and rigidity is not impaired.

Examples of the transparent anchor layer (5) having such properties include thermoplastic resins such as acrylic resin, vinyl chloride resin, and cellulose resin, or thermosetting resins such as cellulose acrylic urethane resin and vinyl chloride acrylic urethane resin. A coating of an organic polymer such as aluminum oxide, titanium oxide, silicon oxide, zirconium oxide, aluminum nitride, titanium nitride, zirconium nitride, magnesium fluoride, tin oxide, bismuth oxide, zinc sulfide, or the like. An inorganic compound thin film such as a mixture is used.

To form such an inorganic protective layer, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method (PV
D) method or direct thin film forming method such as chemical vapor deposition (CVD) method, or after forming a thin film of a metal or an organic compound or an inorganic compound of a metal, a compound such as an oxide by a reaction such as oxidation or hydrolysis A method of forming a thin film is appropriately used.

Although the thickness of the transparent anchor layer (5) depends on the material and properties of the transparent anchor layer itself and the material and properties of the transferred material, it is usually 0.
It is selected from the range of 005 to 5 μm. If the thickness is less than 0.005 μm, a sufficient adhesive effect cannot be obtained. On the other hand, if the thickness exceeds 5 μm, not only is the transparent anchor layer too thick to make it difficult to transfer and form a delicate pattern, but it is also not economically preferable. . The transparent anchor layer may be appropriately colored so long as it is transparent or translucent.

Next, the present invention will be described with reference to examples.

[Example] Example 1 A 25 μm thick biaxially stretched polyester film was coated with a 25% solid content acrylic resin, a mixed solution of toluene and methyl ethyl ketone, and then the solvent was evaporated by hot air drying at 100 ° C. To form a treatment layer having a thickness of about 1 μm. Next, acrylic modified resin coating of silicon-based hard coating agent obtained by hydrolyzing triethoxysilane with ethyl alcohol on the treated layer (Formulation Example 1) Silicon-based hard coating agent 20 parts (heavy weight ratio) Acrylic resin 4 A protective layer was formed by applying 0.4 parts of stabilizer 0.4 parts of catalyst 0.1 part of solvent 75.5 parts to about 3 μm. Further, a mixed solvent solution of acrylic resin and ethylene / vinyl acetate resin in toluene and ethyl acetate was applied on the protective layer to form an adhesive layer having a thickness of about 2 μm to obtain a transfer foil of the present invention.

Using this transfer foil, transfer was performed on an ABS resin molded product at 180 ° C. for 2 seconds.

As a result, it was possible to obtain a transfer molded article for exterior use with good weather resistance of 2000 hours and abrasion resistance (traverse method) of 100,000 times and good durability.

Example 2 A substrate having a thickness of 38 μm and made of biaxially stretched polyester film was coated with a mixed solution of an acrylic resin having a solid content of 25%, toluene and methyl ethyl ketone, and then dried at 100 ° C. in a hot air to evaporate the solvent to a thickness of about 2. A 1 μm treated layer was formed. Then, an acrylic-modified resin coating of a silicon-based hard coating agent obtained by hydrolyzing triethoxysilane with ethyl alcohol on the treated layer (Formulation Example 2) Silicon-based hard coating agent 15 parts (heavy weight ratio) Acrylic resin 5 A protective layer was formed by applying 0.4 parts of stabilizer, 0.1 part of catalyst and 79.6 parts of solvent to about 3 μm. Further, a mixed solvent solution of a vinyl chloride / acrylic urethane copolymer of ethyl acetate and isopropyl alcohol was applied on the protective layer to form a transparent anchor layer having a thickness of about 1 μm. Further, a vinyl chloride / vinyl acetate copolymer and an acrylic resin mixed solvent solution of toluene, ethyl acetate and methyl ethyl ketone is applied on the transparent anchor layer to form an adhesive layer having a thickness of about 3 μm, and the transfer foil of the present invention is obtained. Obtained.

By setting this transfer foil in an injection molding die and simultaneously molding it, an acrylic resin molded article having a surface excellent in weather resistance and abrasion resistance could be produced.

Example 3 30 parts of a methacrylic acid / 2.hydroxyethyl methacrylate / butyl methacrylate / acrylamide / butyl acrylate copolymer and a melamine prepolymer having a solid content of 60% were formed on a substrate made of a biaxially stretched polyester film having a thickness of 25 μm. 15 parts, paratoluenesulfonic acid 10 parts, toluene,
25% solids with a composition of 45 parts mixed solvent of methyl ethyl ketone, isobutyl alcohol, cellosolve acetate
After applying the solution of, volatilize the solvent by hot air drying at 80 ℃,
Further, the same protective layer was formed in the same manner as in Example 1 except that the treatment layer was cured at 160 ° C. for 1 minute to form a treatment layer having a thickness of about 1 μm. Then, a transparent anchor layer and an adhesive layer were sequentially formed to obtain a transfer foil of the present invention.

Using this transfer foil, transfer was performed on an ABS resin molded product at 180 ° C. for 2 seconds.

As a result, it was possible to obtain a transfer molded article for exterior use with good weather resistance of 2000 hours and abrasion resistance (traverse method) of 100,000 times and good durability.

Example 4 Instead of the base material made of the biaxially stretched polyester film of Example 2, a base material made of a biaxially stretched polypropylene film having a thickness of 20 μm was used, and on the base material (without providing a treatment layer). Directly in the same manner as in Example 2, the same protective layer, transparent anchor layer and adhesive layer were sequentially formed to obtain a transfer foil of the present invention.

Using this transfer foil, transfer was performed on an ABS resin molded product at 180 ° C. for 2 seconds.

As a result, it was possible to obtain a transfer molded article for exterior use with good weather resistance of 2000 hours and abrasion resistance (traverse method) of 100,000 times and good durability.

[Effects of the Invention] The resin molded articles obtained by using the transfer foils of the present invention obtained in Examples 1 to 4 were all tested and found to have weather resistance of 2000 hours and abrasion resistance (traverse method) of 100,000. It was possible to obtain a transfer molded article for exterior with excellent durability and no abnormalities during rotation.

[Brief description of drawings]

 FIG. 1 is a sectional view showing the structure of the transfer foil of the present invention. (Symbols in Drawings) (1): Base Material (2): Treatment Layer (3): Protective Layer (4): Adhesive Layer (5): Transparent Anchor Layer

Claims (3)

[Claims] 1. A treatment layer (2) directly or on a substrate (1).
In a transfer foil in which at least a protective layer (3) and an adhesive layer (4) are sequentially formed through a protective layer (3), the protective layer (3) is obtained by hydrolysis of alkylalkoxysilane. A transfer foil comprising a coating film of a modified silicone hard coat agent. 2. The transfer foil according to claim 1, wherein the protective layer (3) has a thickness in the range of 0.5 to 10 μm. 3. The transfer foil according to claim 1, wherein a transparent anchor layer (5) is provided between the protective layer (3) and the adhesive layer (4).