JP2001104874A - Surface protective transfer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface protective transfer material capable of easily attaining the interlayer adhesion property to an adhesive layer and the surface protection of a material to be transferred and excellent in scratch resistance, solvent resistance and the like. SOLUTION: In this surface protective transfer material, a layer 2 consisting essentially of a cationic polymerization based alicyclic epoxy compound is formed on the surface of a base film 1 having release characteristic and the adhesive layer 3 is formed thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to abrasion resistance of interior and exterior building materials, molded parts for interior and exterior of automobiles, miscellaneous goods, cards, cosmetic container caps, general-purpose packages, light electrical appliances, woodwork, crafts and folk crafts. In the indispensable fields such as stain resistance, solvent resistance, and water resistance, the transfer material is not damaged in the appearance and design of the transfer material, and the transfer material has scratch resistance, stain resistance, solvent resistance, water resistance, etc. The present invention relates to a transfer material for surface protection which imparts the following.

[0002]

2. Description of the Related Art Conventionally, a layer made of a radical polymerization type ionizing radiation curable resin is often used as a surface protective layer, but strong interlayer adhesion is required in laminating another layer on this radical polymerization type ionizing radiation curable resin layer. It was generally difficult to obtain sex. Therefore, when the radical polymerization-based ionizing radiation-curable resin layer is processed, the curing of the resin layer is controlled to an incomplete state, and after processing the next layer such as an adhesive layer, a method of completely curing by ionizing radiation again, a tacky adhesive, etc. For example, a method of obtaining adhesion to a radical polymerization-based ionizing radiation-curable resin layer has been performed. Recently, a first intermediate layer made of a polyurethane resin, an acrylic resin and isocyanate is provided between a radical polymerization-based ionizing radiation-curable resin and an adhesive layer, and a second intermediate layer made of an acrylic resin is provided next. Thus, a method has been proposed in which the adhesiveness between the radiation-curable resin layer and the adhesive layer is obtained.

[0003]

However, the method of controlling the degree of curing of the radical polymerizing ionizing radiation curable resin layer is difficult to control the curing, and the radical polymerizing ionizing radiation is again processed after processing the next layer such as the adhesive layer. Full curing is required. Further, the method of using the pressure-sensitive adhesive impairs the appearance and has a problem in durability after transfer. In addition, the method of using a urethane resin, an acrylic resin, or an isocyanate for the first intermediate layer generally has poor compatibility between the urethane resin and the acrylic resin, and thus causes radical polymerization such as lack of transparency. When the system ionizing radiation curable resin layer is used as the surface protective layer, various problems are likely to occur.

Accordingly, an object of the present invention is to control the curing of a radical polymerization type ionizing radiation curable resin layer in the conventional method, to re-cure by ionizing radiation after processing the next layer, and to reduce the appearance and resistance by using an adhesive. Solve the problem of
An object of the present invention is to provide a transfer material for surface protection which has excellent interlayer adhesion with an adhesive layer or the like instead of a radical polymerization type ionizing radiation curable resin.

[0005]

The transfer material for surface protection of the present invention has been made in order to solve the above-mentioned problems, and a cationically polymerizable transfer material is provided on a base film (1) having releasability. Layer mainly composed of alicyclic epoxy compound (2)
And a layer (2) containing a cationically polymerizable alicyclic epoxy compound as a main component, characterized in that the transfer material for surface protection comprises at least an adhesive layer (3) provided thereon. The transfer material for surface protection described above, which is a layer also containing a radical polymerizing ionizing radiation curable resin other than the above, and further comprises a printing layer having an arbitrary pattern or pattern and / or a metal-deposited thin film layer as described in (2) and (3) And the above-mentioned transfer material for surface protection further provided between the two.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The base film (1) having releasability used in the transfer material for surface protection of the present invention is not particularly limited, and is usually a releasable base film having sufficient self-holding properties. Any material can be used as long as it is used for a transfer foil. For example, polyethylene terephthalate film, polypropylene film, polycarbonate film, polystyrene film, polyamide film,
Polyamideimide film, polyethylene film, synthetic resin film such as polyvinyl chloride film, artificial resin film such as cellulose acetate film, cellophane paper, paper such as glassine paper, film such as Japanese paper, or composite film of these or Examples thereof include composite sheet materials and those obtained by subjecting them to release treatment.

[0007] The thickness of the base film is not particularly limited and is usually in the range of 4 to 100 µm, preferably 9 to 5 µm.
It is preferable to use a material having a thickness of 0 μm in terms of facilitating the production of a transfer material for surface protection without wrinkles or cracks. In the transfer material for surface protection of the present invention, the main resin of the layer (2) containing a cationically polymerizable alicyclic epoxy compound as a main component, which is used for imparting protection, may be a cyclic resin such as cyclohexene oxide or cyclopentene oxide. Any resin layer may be used as long as it is a resin layer made of a resin composition containing a compound in which an epoxy group is directly bonded to an aliphatic compound as a main component, and among them, a resin mainly containing an ultraviolet-curable cationically polymerizable alicyclic epoxy compound is preferable. . The content of the cationically polymerizable alicyclic epoxy compound in the resin layer (2) is at least 50% by weight,
It is preferably at least 60% by weight and there is no particular upper limit, but it is preferably at most 95% by weight and at most 90% by weight. When the amount is less than 50% by weight, the composition is often unsatisfactory, such as insufficient adhesion to the adhesive layer and insufficient hardness as a surface protective layer. There are many problems in the flexibility of (3).

The resin layer (2) containing the cationically polymerizable alicyclic epoxy compound as a main component is coated with a known aliphatic epoxy compound (eg, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether). , Trimethylolpropane triglycidyl ether, etc.), aromatic epoxy compounds, etc. may be contained within a range not to impair the object of the present invention, and further other acrylic resins, polyalkylene oxides, etc. may be added, , Photopolymerization initiator, leveling agent, solvent, titanium oxide,
It may be formed by incorporating components other than the main agent such as a pigment such as zinc oxide. The method for forming the resin layer (2) containing a cationically polymerizable alicyclic epoxy compound as a main component is not particularly limited, and its solid film thickness is preferably from 0.01 to 15 μm, more preferably from 0.1 to 15 μm. 5 μm.

In a preferred embodiment, the resin layer (2) of the present invention further comprises a radical polymerization type ionizing radiation resin in addition to the resin containing the cationic polymerization type alicyclic epoxy compound as a main component. The content thereof is preferably in a range other than the content of the above-mentioned resin containing the cationically polymerizable alicyclic epoxy compound as a main component. The radical polymerization type ionizing radiation resin is not particularly limited, and examples thereof include urethane acrylate and polyester acrylate.
Acrylates, epoxy acrylates, unsaturated polyesters, silicone acrylates, and other special acrylates alone or as a mixture thereof.

The adhesive layer (3) used in the transfer material for surface protection of the present invention is not particularly limited, and may be appropriately selected from the resins used for ordinary transfer materials. For example, acrylic resin, vinyl acetate, vinyl chloride, styrene butadiene, vinyl chloride-vinyl acetate, ethylene-vinyl acetate, polyester, chloride rubber, chlorinated polypropylene, urethane resin alone or these It is appropriately selected and adopted from emulsion resins, organic solvent-type resins, and water-soluble resins containing a mixture as a main component. Adhesive layer
(3) is formed by applying a coating solution obtained by diluting the resin with water or an organic solvent by using a gravure printing method, a screen printing method, or an offset printing method, or by applying the coating solution on a printed layer and drying. The thickness of the adhesive layer is not particularly limited.
It is appropriately selected and adopted from the range of about 20 μm depending on the surface condition of the transfer object.

In the present invention, a printing layer and a metal-deposited thin film layer may be appropriately provided between the resin layer (2) containing the cationically polymerizable alicyclic epoxy compound as a main component and the adhesive layer (3). It is practically preferable. Examples of the metal used for the metal-deposited thin film layer include metals such as aluminum, chromium, gold, silver, tin, indium, titanium, and copper. Is preferably formed in the range of 10 to 100 nm. The transfer material for surface protection obtained in this way solves the problems of the surface protection transfer material having the conventional radical polymerization-type ionizing radiation-curable resin layer, that is, problems such as interlayer adhesion and workability, and provides scratch resistance. It has excellent effects on properties, solvent resistance and the like.

[0012]

The present invention will be described in detail below with reference to examples. Hereinafter, all parts in Examples are parts by weight. ** Example 1 Biaxially oriented polypropylene film having a thickness of 12 μm (1)
Above, celloxide 202 as an alicyclic epoxy compound
1 (manufactured by Daicel) 75 parts (hereinafter, similarly, parts by weight),
A coating comprising 3 parts of 1,4-cyclohexane dimethylol divinyl ether, 15 parts of phenol novolak epoxy resin (manufactured by Asahi Ciba) and 4 parts of a cationic photopolymerization initiator (manufactured by Union Carbide) is applied, and a high-pressure mercury lamp is applied. , And post-cured to form a resin layer (2) having a thickness of 5 μm. Then, an acrylic resin 20 is formed on the layer (2).
, 60 parts of toluene and 30 parts of MEK were applied by a reverse coating method and dried to a thickness of 1.0 μm.
Was formed to obtain a transfer material for surface protection of the present invention.

** Example 2 Biaxially oriented polypropylene film having a thickness of 12 μm (1)
Above, celloxide 202 as an alicyclic epoxy compound
1 (manufactured by Daicel) 75 parts (hereinafter, similarly, parts by weight),
1,4-cyclohexane dimethylol divinyl ether 3 parts, photocationic polymerization initiator (manufactured by Union Carbide) 3 parts, urethane acrylate 10 parts, epoxy acrylate 5 parts, radical polymerization initiator 1 part , And a solvent were applied, cured with a high-pressure mercury lamp, and post-cured to form a resin layer (2) having a thickness of 5 μm.
Thereafter, a solution consisting of 20 parts of acrylic resin, 60 parts of toluene and 30 parts of MEK is applied on the layer (2) by a reverse coating method and dried to form an adhesive layer having a thickness of 1.0 μm. Was obtained.

** Comparative Example On a biaxially stretched polypropylene film having a thickness of 12 μm,
Urethane acrylate 20 parts, epoxy acrylate 1
A solution consisting of 0 parts, 40 parts of toluene, 20 parts of MEK, and 10 parts of IPA is applied by a reverse coating method, dried,
The resin was cured by ionizing radiation to form a radical polymerization type ionizing radiation resin layer having a thickness of 3.5 μm. 20 parts of acrylic resin, 60 parts of toluene, MEK3
A solution consisting of 0 parts is applied by a reverse coating method,
After drying, an adhesive layer having a thickness of 1.0 μm was formed to obtain a transfer material for surface protection.

<Evaluation Method> The transfer material for surface protection obtained in each example was transferred to a vinyl chloride resin sheet, and the transferability, surface hardness and solvent resistance were evaluated. Each property evaluation was as follows. <Transferability>: When the transfer surface after transfer was visually checked, the transfer surface was evaluated as が な い if there was no problem as a uniform surface, 場合 if the transfer surface was slightly non-uniform, △. Was evaluated as x. <Surface hardness>: Measured according to JIS K5400. <Solvent resistance>: A rubbing test was carried out using methyl ethyl ketone, and no change was evaluated as 、, slight change in surface turbidity or the like was rated as Δ, and change in surface turbidity or the like was marked as x.

The evaluation results were as follows. In Example 1, <transferability> was ○, <surface hardness> was H, and <solvent resistance> was ○. In Example 2, <transferability> was good, <surface hardness> was 2H, and <solvent resistance> was good. In Comparative Example 1, <transferability> was x, and both <surface hardness> and <solvent resistance> could not be evaluated.

[0017]

The transfer material for surface protection according to the present invention uses a resin layer mainly composed of a cationically polymerizable alicyclic epoxy compound as a surface protective layer, thereby making it difficult to obtain interlayer adhesion. It is excellent in property and can easily provide a surface protective layer to a material to be transferred.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B44C 1/165 B44C 1/165 K F term (Reference) 3B005 EA01 EA04 EB01 EC01 EC02 EC04 FA02 FA04 FA08 FA12 FB02 FB12 FB22 FB42 FB53 FC07Y FC20Y GA01 GB01 4D075 AE03 BB41Y BB85Y CA02 CA34 CA38 CA44 DA04 DB31 EA35 EB33 4F100 AA07 AB01D AK01B AK25 AK33 AK53B J00G BAJB11 J04B07 J04 JL14A JM02D

Claims (3)

[Claims] 1. A layer (2) containing a cationically polymerizable alicyclic epoxy compound as a main component is provided on a base film (1) having releasability, and at least an adhesive layer (3) is provided thereon. A transfer material for surface protection. 2. The surface protecting composition according to claim 1, wherein the layer (2) containing a cationically polymerizable alicyclic epoxy compound as a main component is a layer containing a radically polymerizable ionizing radiation curable resin other than the epoxy compound. Transfer material. 3. The transfer material for surface protection according to claim 1, further comprising a printing layer having an arbitrary pattern or pattern and / or a metal-deposited thin film layer provided between (2) and (3).