JPH08192598A - Transfer foil - Google Patents

Abstract

PURPOSE: To permit the formation of a film, excellent in weatherability and scratch resistance, by a method wherein a resin, whose glass transition point and weight-average molecular weight are specified values, is used for the resin of an acrylic resin layer, in a transfer foil, in which a siloxane resin layer and the acrylic resin layer are formed sequentially on the mold releasing surface of a substrate sheet. CONSTITUTION: A transfer foil 2, employed for an external cladding material for building, a surface material for automobile lamp, a sound-shielding material for a highway and the like, is constituted of a substrate sheet 11, a siloxane resin layer 12, an acrylic resin layer 13, a figure pattern layer 14 and a bonding agent layer 15. A resin, having a glass transition point of 80 deg.C or more and a weight-average molecular weight of 50000 or more, is employed for the resin of the acrylic resin layer. A silane coupling agent is added into at least one of the siloxane resin layer or acrylic resin layer by 0.1-5wt.% and, further, a resin layer, into which at least one kind of inorganic compound powder of aluminum, silicon, titanium, magnesium, zirconium and the like is added, is employed as the siloxane resin layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer foil used as a building material exterior member, an automobile lamp surface material, a highway sound insulation material, etc. The transfer foil has weather resistance and high surface hardness. The present invention aims to obtain a product having improved scratch resistance and wear resistance.

[0002]

2. Description of the Related Art Various transfer foils having a transfer layer laminated on the surface of a base material sheet are known, and these transfer foils are heated from the base material sheet side to bond the transfer layer to a transfer target. After that, the base material sheet is peeled off to transfer the transfer layer to the transfer target. Among them, a transfer foil in which an ultraviolet curable resin or an electron beam curable resin is used on the surface of the transfer layer has been proposed as an attempt to improve the surface strength. Further, as a method of providing a cured coating layer on a product, a spray coating method, a dipping coating method, a method of simultaneously coating at the time of molding a resin plate, and the like are performed.

[0003]

However, in the method of using the ultraviolet curable resin or the electron beam curable resin on the surface of the transfer layer, these resins are excellent in scratch resistance, but the weather resistance is not high. On the contrary, there is a drawback that the scratch resistance decreases when the weather resistance is increased.

Further, in the spray coating method and the dipping coating method, the composition for forming a cured coating is a solution, and this solution is adhered to a molded product to form a coating, so that the work efficiency is poor, environmental pollution and molding are performed. There is a problem such as dust adhering to the product surface. Further, there is a problem that a cleaning step for removing dust and oil adhering to the surface of the molded product is required, resulting in a decrease in work efficiency.

Further, in order to prevent the liquid treatment liquid from sagging, tampering, etc., the shape of the molded product is restricted, and there is a problem in workability. In addition, the method of coating the ultraviolet curable resin at the time of molding the resin plate is limited to a flat molded product, and then a step of cutting to a desired dimension is required.

The present invention solves these problems and provides a transfer foil excellent in weather resistance and scratch resistance, which is not found in conventional transfer foils. By using the transfer foil, weather resistance,
It is intended to obtain a high-performance exterior transfer material having excellent scratch resistance.

[0007]

[Means for Solving the Problems] On the release surface of the base sheet,
A transfer foil having a siloxane-based resin layer and an acrylic-based resin layer formed in this order, wherein the resin of the acrylic-based resin layer has a glass transition point (hereinafter referred to as Tg) of 80 ° C. or higher and a weight average molecular weight (hereinafter referred to as Mw). Is 50000 or more. The siloxane-based resin layer and the acrylic-based resin layer are resin layers obtained by adding 0.1 to 5% by weight of a silane coupling agent to at least one of the resin layers, and the siloxane-based resin layer is the resin layer. Was used as a transfer foil, which is a resin layer in which at least one kind of inorganic compound powder such as aluminum, silicon, titanium, magnesium, and zirconium is added. Then, the siloxane-based resin layer and the acrylic-based resin layer are transfer foils which are resin layers obtained by adding an ultraviolet absorber, a stabilizer, and an antioxidant to at least one of the resin layers.

[0008]

According to the present invention, the siloxane-based resin layer and the acrylic-based resin layer formed on the base sheet have excellent weather resistance and scratch resistance. It is possible to easily form a coating film having excellent weather resistance and scratch resistance on the surface of. Therefore, building material exterior members,
It is possible to efficiently manufacture automobile lamp surface materials, highway sound insulation materials, etc. without problems such as environmental pollution by only a transfer process.

[0009]

The present invention will be described in detail below with reference to the drawings based on the embodiments. FIG. 1 is an enlarged sectional view showing an example of the transfer foil of the present invention, and FIG. 2 is an enlarged sectional view of a transfer foil having an adhesive layer. FIG. 3 is an enlarged cross-sectional view when the transfer foil of the present invention is used for transferring to a transfer target, and FIG. 4 is an enlarged sectional view when the transfer foil having an adhesive layer is used for transfer. is there. FIG. 5 is an explanatory diagram when the transfer foil produced in Example 1 is transferred to a polycarbonate plate,
FIG. 6 is an explanatory diagram when the transfer foil produced in Example 3 is transferred to a polycarbonate plate.

The transfer foil 1 of the present invention, as shown in FIG.
Basically, the base sheet 11 and the siloxane resin layer 1
2. It is composed of the acrylic resin layer 13. Also, FIG.
As shown in FIG. 1, the transfer foil 1 is provided with a pattern layer 14 and an adhesive layer 1.
5 is provided to form the transfer foil 2.

With the above-mentioned structure, when the transfer foil is used for transfer to a molded article or the like, a coating film of an acrylic resin layer and a siloxane resin layer is formed in this order on the surface of the transfer target, and the siloxane-based resin layer is formed. The resin layer becomes the outermost surface. Therefore, as a result of various studies on the compositions of these resins, it was possible to obtain a transferred material having a surface excellent in weather resistance and scratch resistance by setting the resin composition and layer constitution as shown below. .

The method of manufacturing the transfer foil of the present invention and the material of each layer of the transfer foil will be described in more detail below. As a material for the base sheet, a sheet or film having heat resistance and good dimensional stability is used. For example, polyester such as polyethylene terephthalate, polyamide such as nylon, acrylic resin such as polyvinyl chloride and polymethyl methacrylate, polypropylene, cellulose triacetate, plastic film or sheet such as cellophane,
Alternatively, a metal foil of copper, iron, aluminum or the like, paper, or the like can be given.

As the resin for the surface layer, a siloxane resin having high hardness is used. The coating amount is 0.1-6 g /
can be used in the range of m ^2, 2~5g / m ² is preferred. Acrylic resin has excellent weather resistance and heat resistance,
In the present invention, since it is necessary to further improve weather resistance and heat resistance, a glass transition point of 80 ° C. or higher and a weight average molecular weight of 50,000 or higher are used. Cracks may occur in the siloxane resin layer having high hardness, and in order to prevent this, it is necessary for the acrylic resin to relieve the stress applied to the siloxane resin, the hardness is appropriate, and there is some flexibility. Resin is selected. Therefore, it is desirable that the coating amount be slightly larger than that of the siloxane resin, and the range of 0.5 to 6 g / m ² is appropriate. The ratio of the coating amount of the siloxane resin to the acrylic resin is preferably 1/1 to 1/3.

A silane coupling agent is added to both resins in order to increase the adhesive strength between the siloxane resin and the acrylic resin. Considering the reaction between the silane coupling agent and the siloxane resin, the curing period of the transfer foil is 6
It requires at least 3-5 days at 0 ° C.

Further, by adding an inorganic compound powder to the siloxane resin, it is possible to improve abrasion resistance and weather resistance. The appropriate amount of addition is 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin. As the inorganic compound, oxides of aluminum, silicon, titanium, magnesium, zirconium or the like or other compounds are used.

Further, in order to improve weather resistance, an ultraviolet absorber may be added to the siloxane resin. The addition amount is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin. In addition, the weather resistance can be improved by adding a stabilizer or an antioxidant to the siloxane resin and the acrylic resin to stabilize the resin.

Examples of the UV absorber include benzotriazole-based, benzophenone-based, triazine-based, anilide nitrate-based, cyanoacrylate-based compounds and the like. Examples of the light stabilizer include compounds such as hindered amine compounds and amino ether compounds. Examples of the antioxidant include phenol-based compounds, sulfur-based compounds, phosphorus-based compounds and the like.

The pattern of the transfer foil can be formed by various printing methods using ordinary printing ink. As the ink binder, a thermoplastic resin is generally used, and vinyl chloride-vinyl acetate copolymer, polyamide, polyester, polyacrylate, polymethacrylate, polyurethane, polyvinyl acetate, polyester urethane, chlorinated rubber, chlorinated polyethylene, polypropylene chloride, styrene. -Based resins and styrene-based copolymers, cellulose derivatives, rosin ester resins, polyvinyl acetate resins,
It is possible to use one kind or a mixture of two or more kinds of polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, coumarone resin, vinyltoluene resin, butyral resin, shellac, gum arabic, acaloid, mastic and the like.

The adhesive layer is necessary for transferring the transfer layer to the transfer-receiving member, and the material thereof is the adhesive used for ordinary transfer foils. For example, acrylic resin,
Examples thereof include styrene resin, vinyl chloride-vinyl acetate copolymer, butyral resin, polyurethane resin, polyester resin and epoxy resin.

Hereinafter, the present invention will be described in more detail with reference to specific examples. (Example 1) As shown in FIG. 1, a polyethylene terephthalate (hereinafter referred to as PET) film having a thickness of 50 μm (“T-60” manufactured by Toray Industries, Inc.) was used as a base material 11 and a siloxane resin having the following composition. A siloxane-based resin layer 12 and an acrylic-based resin are applied so that the siloxane-based resin and the acrylic-based resin are applied in this order by an gravure coating method using an acrylic-based resin and dried so that each applied amount is 2 g / m ^2. Transfer foil 1 was prepared by forming layer 13.

Siloxane-based resin composition 100 parts by weight of siloxane-based resin (NSC-2319 manufactured by Nippon Seika Co., Ltd.) 5 parts by weight of silane coupling agent (γ-aminopropyltriexisilane 12 manufactured by Toshiba Silicon Co., Ltd.) ) Acrylic resin composition-Acrylic resin (Tg: 105 ° C Mw: 67,000) 100 parts by weight (Mitsubishi Rayon Co., Ltd. LR-1065) -Silane coupling agent 5 parts by weight (Toshiba Silicon Co., Ltd.) γ-aminopropyltriexisilane 12)

As described above, a transfer foil as shown in FIG. 1 was produced, and then the transfer foil was completed by storing it at 60 ° C. for 5 days as a curing period.

Next, polycarbonate resin (hereinafter referred to as PC) (Made by Mitsubishi Kasei Co., Ltd., Novalex 7022L)
I) in injection molding at a molding temperature of 280 ° C.
A C plate was produced. As shown in FIG. 5A, the resin foil 16a is heated at 230 ° C. by using the transfer foil and a heat roll.
Transfer was performed at a transfer speed of 2 m / s, and then the base material sheet 11 was peeled off to fabricate a PC board 3 having a transfer layer on the surface as shown in FIG. 5B.

(Example 2) A resin having the following composition was used as a siloxane-based resin, and the same acrylic resin as in Example 1 was used. In the same manner as in Example 1, a siloxane-based resin layer and an acrylic resin were formed on a PET film. 2 g / m for each resin layer
² (as a dry matter) to form a transfer foil. ☆ Siloxane-based resin composition ・ Siloxane-based resin 100 parts by weight (NSC-2319 manufactured by NIPPON SEISAKA Co., Ltd.) ・ Silane coupling agent 5 parts by weight (γ-aminopropyltriexisilane 12 manufactured by Toshiba Silicon Co., Ltd.) ・ Silica 5 parts by weight (Aerosil manufactured by Nippon Aerosil Co., Ltd.) In the same manner as in Example 1, the transfer foil was transferred to a PC plate to prepare a PC plate as shown in FIG. 5 (b).

(Example 3) Similar to Example 1, after forming a siloxane-based resin layer and an acrylic-based resin layer at 2 g / m ² each, the acrylic resin-based ink (Showa Showa) was further formed thereon by gravure printing. A pattern layer 14 and an adhesive layer 15 were formed using an acrylic resin adhesive by using Ink Kogyo Co., Ltd., and a transfer foil 2 as shown in FIG. 6A was produced.
This is transferred to a PC board in the same manner as in Example 1, and the result is shown in FIG.
A PC decorative board 4 as shown in (b) was produced.

(Example 4) A resin having the following composition was used as the siloxane-based resin, the same resin as in Example 1 was used as the acrylic-based resin, and the siloxane-based resin layer and the acrylic-based resin layer were used in the same manner as in Example 1. 2 g / m ² each, and a pattern layer and an adhesive layer are further formed thereon in the same manner as in Example 3,
A transfer foil 2 as shown in FIG. 6A was produced. ☆ Siloxane-based resin composition-Siloxane-based resin 100 parts by weight (NSC-2319 manufactured by Nippon Seika Co., Ltd.)-Silane coupling agent 5 parts by weight-UV absorber (Tinubin P manufactured by Ciba-Geigy) 3 parts by weight 6 in the same manner as in Example 3.
A PC decorative board as shown in (b) was produced.

(Example 5) Using the same siloxane resin and acrylic resin as in Example 1, in the same manner as in Example 1, a siloxane resin layer 1 g / m ² and an acrylic resin layer 2 g / m were formed on a PET film. m ² formed, then Example 3
Similarly to the above, a transfer foil 2 was prepared by providing a pattern layer and an adhesive layer as shown in FIG. 6 (a). With this transfer foil,
It was transferred to a PC board in the same manner as in Example 1 to prepare a PC decorative board 4 as shown in FIG. 6 (b).

Example 6 The siloxane resin (NSC-2319 manufactured by Nippon Seika Co., Ltd.) and the acrylic resin (LR-106 manufactured by Mitsubishi Rayon Co., Ltd.) used in Example 1 were used.
Using a resin containing no silane coupling agent in 5), a siloxane-based resin layer and an acrylic-based resin layer of 2 g / m ² each were formed in the same manner as in Example 1, and further formed thereon by a gravure printing method. A pattern layer 14 is formed using an acrylic resin ink (manufactured by Showa Ink Industry Co., Ltd.) and an adhesive layer 15 is formed using an acrylic resin adhesive, and a transfer foil 2 as shown in FIG. It was made. This was transferred to a PC board in the same manner as in Example 3 to prepare a PC decorative board 4 as shown in FIG. 6 (b).

(Example 7) Using the same siloxane resin and acrylic resin as in Example 1, a PET film was coated in the same manner as in Example 1 to give 1 g of siloxane resin layer /
A transfer foil was prepared by forming m ² and an acrylic resin layer of 0.5 g / m ² . Further, using this transfer foil, it was transferred to a PC plate in the same manner as in Example 1 to prepare a PC plate having a transfer layer.

(Comparative Example) Instead of the siloxane resin,
A resin having the following composition was used as the resin for the surface layer, the same resin as in Example 1 was used as the acrylic resin, and in the same manner as in Example 1, the PET film was provided with 2 g / m ² for each of the surface layer and the acrylic resin layer. A transfer foil was prepared by forming (as a dry matter).
Further, using this transfer foil, it was transferred to a PC plate in the same manner as in Example 1 to prepare a PC plate having a transfer layer. ☆ Resin composition of surface layer-Acrylic resin (Tg: 105 ° C Mw: 40,000) 100 parts by weight (Mitsubishi Rayon Co., Ltd., Dinal R-83) -Urethane resin 50 parts by weight (Mitsui Toatsu Chemicals, Inc.) Olestar Q176) · Electron beam curable resin 80 parts by weight (NMP, TMPTA)

Table 1 shows the results of measuring the surface hardness and the weather resistance of the PC board and the PC decorative board having the transfer layer prepared in Examples 1 to 7 and Comparative Example. The surface hardness was measured by pencil hardness under a load of 500 g and scratch resistance by rubbing steel wool. The weather resistance was observed with a weatherometer for 1000 hours and 3000 hours and then observed for surface crackle, interlayer adhesion and the like.

[0032]

[Table 1] (Note) ○: Good △: Somewhat bad ×: Poor 1): Poor interlayer adhesion 2): Cracking

As can be seen from the results of the examples in Table 1, the surface hardness is obtained by using a siloxane resin as the surface layer and an acrylic resin as the next layer, and adding a silane coupling agent to both of them. And has excellent scratch resistance,
Moreover, it was possible to obtain a transferred material having good weather resistance. On the contrary, as shown in Example 6, when the silane coupling agent was not added, the adhesion between the siloxane-based resin and the acrylic-based resin was poor after the weatherometer was exposed for 3000 hours, and the weather resistance was sufficient. It wasn't. Further, as shown in Example 7, even when the silane coupling agent was added, the coating amount of the acrylic resin was 0.5 g / m ²
If the number is too small, cracks will occur in the siloxane resin layer on the surface after 3000 hours of weatherometer exposure,
Again, it was not possible to obtain the desired transferred material having good weather resistance. Furthermore, as shown in Comparative Examples, when the conventional electron beam curable resin was used, both the surface hardness and the weather resistance were poor, and it was extremely inferior to the transfer foil of the present invention.
Therefore, it has been clarified that the transfer foil of the present invention is very effective for obtaining a molded product having excellent scratch resistance and weather resistance.

[0034]

According to the present invention, since the siloxane-based resin layer and the acrylic-based resin layer formed on the transfer foil have excellent weather resistance and scratch resistance, they can be transferred to a molded article,
It is possible to easily form a coating having excellent weather resistance and scratch resistance on the surface of a molded product or the like. Therefore, a building material exterior member having excellent weather resistance and scratch resistance, an automobile lamp surface material, a sound insulation material for a highway, etc. can be efficiently manufactured without problems such as environmental pollution only by a transfer process. Therefore, since the conventional spray coating method and dipping method use a solvent, the work environment and environmental pollution have been serious problems. Since a film having excellent scratch resistance can be formed, problems of working environment and environmental pollution can be solved, and working efficiency can be improved and manufacturing cost can be reduced.

[Brief description of drawings]

FIG. 1 is an enlarged sectional view showing an example of a transfer foil according to the present invention.

FIG. 2 is an enlarged sectional view of a transfer foil having an adhesive layer of the present invention.

FIG. 3 is an enlarged cross-sectional view of the transfer foil of the present invention transferred to a transfer target.

FIG. 4 is an enlarged sectional view of a transfer foil having an adhesive layer, which is used for transfer to a transfer target.

FIG. 5 is an explanatory diagram when the transfer foil produced in Example 1 is transferred to a PC board, and (a) is a sectional view when the transfer foil is attached to the PC board. (B) A cross-sectional view of the PC plate after transfer to the PC plate and peeling of the base material sheet.

FIG. 6 is an explanatory view when the transfer foil prepared in Example 3 is transferred to a PC board, and (a) a cross-sectional view when a transfer foil having a pattern is attached to the PC board. (B) A cross-sectional view of the PC decorative board after transfer to the PC board and peeling of the base material sheet.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transfer foil 2 Transfer foil having an adhesive layer 3 PC board having a transfer layer 4 PC decorative board having a transfer layer 11 Base sheet 12 Siloxane resin layer 13 Acrylic resin layer 14 Picture layer 15 Adhesive layer 16 Transferred layer Body 16a PC board

Claims (4)

[Claims] 1. A transfer foil in which a siloxane-based resin layer and an acrylic-based resin layer are formed in this order on a release surface of a substrate sheet, and the resin of the acrylic-based resin layer has a glass transition point of 8 or less.
A transfer foil having a temperature of 0 ° C. or higher and a weight average molecular weight of 50,000 or higher. 2. The siloxane-based resin layer and the acrylic-based resin layer are resin layers obtained by adding 0.1 to 5% by weight of a silane coupling agent to at least one of the resin layers. Transfer foil as described. 3. The resin layer according to claim 1, wherein the siloxane resin layer is a resin layer obtained by adding at least one kind of inorganic compound powder such as aluminum, silicon, titanium, magnesium and zirconium to the resin layer. Item 2. The transfer foil according to item 2. 4. The siloxane-based resin layer and the acrylic-based resin layer are resin layers obtained by adding an ultraviolet absorber, a stabilizer, and an antioxidant to at least one of the resin layers. The transfer foil according to claim 2 or claim 3.