JP2989838B2 - Hard coat transfer foil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a hard coat transfer foil, and more particularly, to high hardness, abrasion resistance, abrasion resistance,
The present invention relates to a hard coat transfer foil capable of easily providing a surface layer having excellent stain resistance and the like.

(Prior art) Conventionally, acrylic resins, polystyrene resins, polycarbonate resins, and other synthetic resins have various advantages such as good moldability, excellent transparency, light weight, and low cost. It is widely used as molded products such as various industrial materials, building materials, decorative materials, optical materials, light electric materials, cosmetic container materials, household materials and the like.

On the other hand, although such a resin molded article has the above-mentioned various advantages, its surface hardness is lower than that of glass, metal, etc., so that the surface is easily scratched, the transparency is reduced, and the contamination is reduced. There is a problem that the property is increased.

As a method of providing a surface protective layer having high hardness, abrasion resistance, excellent stain resistance, etc. on the surface of various resin molded articles as described above, a method of applying and curing an ionizing radiation-curable resin paint, or A method of transferring a hard coat layer made of an ionizing radiation-curable resin paint from a transfer foil is known.

The hard coat transfer foil is obtained by laminating a hard coat layer on the surface of a base material sheet via a release layer, and further laminating a pattern layer and a heat-sensitive adhesive layer as necessary. The hard coat layer is transferred on the surface and transferred by a conventional method, or the hard coat layer is transferred by an in-mold coating method in which a resin is injected and molded in a mold. In this case, peeling at the time of transfer occurs at the interface between the release layer and the hard coat layer, and the hard coat layer is located on the surface of the transferred layer.

In the case of the above-mentioned conventional hard coat transfer foil, a hard coat layer having excellent hardness can be provided on the surface of various articles by transfer, but the hard coat layer has excellent surface hardness, but the surface slip property is low. Since the stress is locally concentrated by external force, there is a problem that the scratch resistance and the impact resistance are poor.

Such problems are caused by slip agents (lubricants) in the hard coat layer.
However, when such a slip agent is added to the hard coat layer, the physical properties of the hard coat layer are reduced, the original function of the hard coat layer is reduced, and the transparency is reduced. There is a problem.

Accordingly, an object of the present invention is to solve the various problems of the prior art as described above, and to provide a hard coat transfer foil capable of easily applying a hard coat layer having excellent scratch resistance and impact resistance to various articles. To provide.

(Means for Solving the Problems) The above object is achieved by the present invention described below. That is,
The present invention provides a hard coat transfer foil provided with a hard coat layer made of an ionizing radiation-curable resin via a release layer on one surface of a base sheet, wherein the release layer is an ionizing radiation-curable resin containing a slip agent. A resin layer having a thickness of 2.0 μm or less, wherein the adhesiveness of the resin layer to the hard coat layer is greater than the adhesiveness to the substrate sheet,
A hard coat transfer foil, which is peeled off from a substrate sheet during transfer.

(Function) The release layer of the hard coat transfer foil contains a slip agent 2.
A resin layer made of an ionizing radiation curable resin having a thickness of 0 μm or less, wherein the adhesiveness of the resin layer to the hard coat layer is larger than the adhesiveness to the base sheet, and the resin layer is separated from the base sheet during transfer. By forming so that
After the transfer, even if an external force is concentrated on the transferred release layer, it exhibits excellent slip properties, so that a surface having excellent scratch resistance and impact resistance is provided. On the other hand, since the hard coat layer is formed of the ionizing radiation-curable resin containing no slip agent, the excellent physical properties inherent to the ionizing radiation-curable resin are maintained.

Preferred Embodiment Next, the present invention will be described in more detail with reference to the accompanying drawings, which show a preferred embodiment schematically.

As shown in FIG. 1, the hard coat transfer foil of the present invention has a hard coat layer 3 on one surface of a base sheet 1 via a release layer 2 made of an ionizing radiation curable resin containing a slip agent.
Is formed, and if necessary, a primer layer 4, a decorative layer 5 such as a picture layer or a metal deposition layer, and / or a heat-sensitive adhesive layer 6 can be provided on the surface thereof. The pattern layer may be any pattern such as wood pattern, stone pattern, etc. of natural products, characters, symbols, abstract patterns, and solid patterns on the whole surface.Also, the metal deposition layer may be provided on the entire surface or partially provided. Is also good.

The base sheet 1 used in the hard coat transfer foil of the present invention may be any conventionally known base sheet, for example, a polyester film such as polyethylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polybutylene terephthalate, etc. polyethylene,
Polyolefin film such as polyolefin film such as polypropylene, polymethylpentene, polyvinyl chloride film, polyvinylidene chloride film, ethylene / vinyl alcohol copolymer film, polycarbonate film, polyamide film, etc. Any of the base sheets used in conventional hard coat transfer foils, such as various processed papers such as those formed as a release layer, can be used in the present invention,
Particularly preferred is a biaxially stretched polyethylene terephthalate film having a thickness of about 10 to 100 μm.

The release layer 2 provided on the surface of the base sheet 1 mainly characterizes the present invention.
The resin having an adhesive property to the hard coat layer 3 provided thereon is larger than the adhesive property to the base sheet 1, that is, an ionizing radiation curable resin.

As the slip agent to be added to the resin, for example,
Known resins such as silicone resins, fluorine resins, ionizing radiation curable resins modified with silicon or fluorine, various waxes, stearic acid or their metallic soaps, higher fatty acid amides and the like are not particularly limited. The amount of these slip agents added to the resin is preferably about 0.1 to 10% by weight of the resin.

In order to form the release layer 2 from the resin and the slip agent, an aqueous dispersion or an organic solvent solution of the resin and the slip agent is prepared, and this coating solution is subjected to, for example, a blade coating method, a gravure coating method, and a rod coating method. It is formed by applying and drying on the above-mentioned substrate sheet by an arbitrary application method such as a coating method, a knife coating method, a reverse roll coating method, a spray coating method, an offset gravure coating method, and a moss coating method.

At this time, the thickness of the release layer 2 formed is also important. If the release layer 2 is too thick, the thick release layer 2 comes to the surface of the hard coat layer 3 after transfer. On the other hand, if it is too thin, it is difficult to impart slip properties, which is the object of the present invention. Therefore, the release layer should have a thickness of 2 μm or less, preferably 0.5 to 1.0 μm.

In particular, it is preferable that these release layers 2 are formed to have a uniform thickness. A release layer having a thickness of several μm is formed before the stretching process of the base sheet, and then the base sheet is biaxially stretched. Accordingly, the thickness of the release layer can be reduced to 2 μm or less to form a uniform thin film release layer.

In the release layer 2 formed as described above, various other additives, for example, an antistatic agent, a water repellent, an oil repellent, an ultraviolet absorber, a stabilizer, a matting agent, a conductive agent, and an antifogging agent By adding various additives such as these, various properties that cannot be exhibited by the hard coat layer alone can be imparted without impairing the various physical properties inherent to the hard coat layer.

The hard coat layer 3 provided on the release layer 2 as described above is formed from an ionizing radiation curable paint. Particularly preferred ionizing radiation curable paints are electron beam curable paints and UV curable paints.

Electron beam-curable paints and ultraviolet-curable paints are similar in composition except that the latter contains a photopolymerization initiator or a sensitizer, and generally have a structure as a film-forming component. Polymer, oligomer, monomer, etc. having a radical polymerizable double bond or epoxy group in the main component,
It contains a non-reactive polymer, an organic solvent, a wax, and other additives as necessary.

Particularly preferred for the purpose of the present invention, those in which the film-forming component has an acrylate-based functional group, for example, a polyester resin having a relatively low molecular weight, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, Spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene as reactive diluents Monofunctional monomers such as methylstyrene and N-vinylpyrrolidone and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, and tripropylene glycol (meth) acrylate Diethylene glycol (meth)
It contains relatively large amounts of acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, and the like.

By using such a polyfunctional (meth) acrylate-based ionizing radiation-curable paint, a hard coat layer excellent in surface hardness, transparency, abrasion resistance, abrasion resistance and the like can be formed.

Further, when such a hard coat layer 3 is required to have high flexibility and shrink resistance, an appropriate amount of a thermoplastic resin such as a non-reactive acrylic resin or various wax These demands can be met by adding such elements.

Further, in order to make the above-mentioned curable paint into an ultraviolet-curable paint, acetophenones, as photopolymerization initiators therein,
Benzophenone, Michler benzoyl benzoate, α
-Amyloxime esters, tetramethylthiuram monosulfide, thioxanthones, and n-butylamine, triethylamine, tri-n-butylphosphine, and the like as photosensitizers can be mixed and used.

Various types of ionizing radiation curable paints such as the above-mentioned electron beam or ultraviolet curable paints are known, and all of them are easily available from the market and can be used in the present invention.

Conventional curing methods can be used as they are, for example, in the case of electron beam curing, Cockloft-Walton type, Bandegraf type, Resonant transformation type, Insulating core transformer type, Linear type, Dynamitron type, High frequency type 50 to 1,000 KeV, preferably 10 to 10 emitted from various electron beam accelerators such as
An electron beam having an energy of 0 to 300 KeV is used, and in the case of ultraviolet curing, an ultra-high pressure mercury lamp, a high pressure mercury lamp,
Ultraviolet rays emitted from a light source such as a low-pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are used.

The curable coating as described above can be prepared by any coating method such as a blade coating method, a gravure coating method, a rod coating method, a knife coating method, a reverse roll coating method, a spray coating method, an offset gravure coating method, and a moss coating method. It is applied on the above-mentioned release layer, and particularly preferred are a gravure coating method, a gravure reverse coating method, a reverse roll coating method, an offset gravure coating method, etc., which are excellent in the accuracy of the applied thickness, the smoothness of the applied surface and the like. The hard coat layer 3 may be cured before or after the transfer or during the transfer.

Further, if the coating amount of the above-mentioned curable paint is too small, a sufficient surface hardness and a scratch-resistant hard coat layer cannot be obtained,
If the amount is too large, a decrease in the curing speed or distortion such as curling of the base sheet at the time of curing occurs, so 1 to 50 μm, particularly 1.5 to 20 μm
A thickness (dry thickness) in the range of m is preferred.

Although the hard coat transfer foil of the present invention basically has the above-described configuration, an arbitrary pattern 5 can be applied to the surface of the hard coat layer with a normal gravure ink or the like,
Further, the heat-sensitive adhesive layer 6 can be formed thereon or directly.

Adhesives used include heat-sensitive adhesives, pressure-sensitive adhesives,
Although any adhesive such as a solvent-activated adhesive and an ionizing radiation-curable adhesive can be used, a preferable adhesive is a heat-sensitive adhesive which has no tackiness at room temperature but exhibits adhesiveness when heated. The use of an adhesive is preferable from the viewpoint of productivity because the substrate sheet having the hard coat layer and the adhesive layer formed thereon can be wound into a roll or the like even when continuously produced.

The method of using the hard coat transfer foil of the present invention is performed, for example, as shown in FIG. The hard coat transfer foil of the present invention shown in FIG. 1 is overlaid with the adhesive layer 6 facing the surface of any transfer material 7, and the adhesive layer is activated by applying heat and pressure to adhere to the transfer material 7. Let it. Next, by peeling the base sheet 1, the adhesive layer 6, the picture layer 5, the primer layer 4, the hard coat layer 3 and the release layer 2 are integrally transferred to the transfer material 7.

Incidentally, the hard coat transfer foil of the present invention without an adhesive layer, if the transferred material itself has a heat-sensitive adhesive, for example, in the case of a thermoplastic resin molded article or in-mold coating method, Alternatively, it can be advantageously used when an adhesive layer is provided in advance on the transfer material.

The transfer material to which the hard coat layer is transferred by the hard coat transfer foil of the present invention is not limited at all, such as a synthetic resin molded product, metal, wood, ceramics, and glass.

(Effects) According to the present invention as described above, the release layer of the hard coat transfer foil is a resin layer made of an ionizing radiation-curable resin having a thickness of 2.0 μm or less containing a slip agent. Adhesiveness to the coat layer is greater than adhesiveness to the base sheet, and by forming so as to be separated from the base sheet at the time of transfer, excellent even if external force is concentrated on the transferred release layer after transfer. Since it exhibits slip properties, it provides a surface with excellent scratch resistance and impact resistance. On the other hand, since the hard coat layer is formed of the ionizing radiation-curable resin containing no slip agent, the excellent physical properties inherent to the ionizing radiation-curable resin are maintained.

(Examples) Next, the present invention will be described more specifically with reference to examples and comparative examples.

Example 1 A film obtained by adding 1% by weight of stearic acid to a surface of a polyethylene terephthalate film (T-60, manufactured by Toray Industries, Inc.) and adding ionizing radiation-curable resin HC-A (manufactured by Morohoshi Ink) to a thickness of 1 μm when dried. After drying at 100 ° C for 1 minute, the surface is further coated with ionizing radiation-curable resin HC-
C (made by Morohoshi Ink) to a dry thickness of 10 μm
Dry at 0 ° C. for 1 minute. Further, a primer (manufactured by Morohoshi Ink) was formed on the surface to a thickness of 1 μm.

Using a scanning type electron beam irradiator, the above coated film was accelerated at 175 KV, beam current 36 mA, and irradiation dose 10 M.
The hard coat layer was cured by irradiating an electron beam with rad.

After that, pattern printing is performed with an acrylic resin-based gravure ink (manufactured by Showa Ink Co., Ltd.), and an acrylic heat-sensitive adhesive solution (manufactured by Showa Ink Co., Ltd.) is dried on the surface to a thickness of 1 μm.
And dried at 100 ° C. for 1 minute to obtain a hard coat transfer foil of the present invention.

Examples 2 to 4 Hard coat transfer foils of the present invention were obtained in the same manner as in Example 1 except that the slip agent in Example 1 was changed as shown in Table 1 below.

Comparative Example 1 In Example 1, no release layer was formed, and the others were the same as in Example 1.
As above, a hard coat transfer foil was obtained.

Using the hard coat transfer foil of the above Examples and Comparative Examples,
The hard coat layer was transferred to the surface of the ABS molded product under the conditions of 200 ° C. × 3 m / min. × 15 kg / cm (pressure). Then, after the ABS molded product cools, the polyester film is peeled off,
The release layer and the hard coat layer were transferred to the surface of the molded article. The physical properties of the obtained transfer hard code layer are as shown in Table 2 below.

[Brief description of the drawings]

FIG. 1 schematically shows a cross section of a hard coat transfer foil of the present invention, and FIG. 2 schematically shows a transfer method using the above hard coat transfer foil. 1: Base sheet 2: Release layer 3: Hard coat layer 4: Picture layer 5: Primer layer 6: Adhesive layer 7: Transfer material

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) B44C 1/165-1/17

Claims (3)

(57) [Claims] 1. A hard coat transfer foil provided with a hard coat layer made of an ionizing radiation-curable resin on one surface of a base sheet via a release layer, wherein the release layer comprises an ionizing radiation-curable resin containing a slip agent. A resin layer having a thickness of 2.0 μm or less made of a resin, wherein the adhesiveness of the resin layer to the hard coat layer is greater than the adhesiveness to the base sheet, and is separated from the base sheet during transfer. Hard coat transfer foil. 2. The hard coat transfer foil according to claim 1, wherein the release layer has a thickness of 0.5 to 1.0 μm. 3. The hard coat transfer foil according to claim 1, wherein a decorative layer such as a picture layer or a metal deposited layer and / or a heat-sensitive adhesive layer is formed on the surface of the hard coat layer.