JPH03130200A - Hard coating transfer foil - Google Patents

Abstract

PURPOSE:To improve scratch resistance, impact resistance by forming a peeling layer of a resin layer having a thickness of 2.0mum or lower including a slipping agent, increasing the adhesive properties of the resin layer to the hard coating layer as compared with those to a base material sheet, and peeling it from the sheet at the time of transferring. CONSTITUTION:A peeling layer 2 of a hard coating transfer foil is formed of a resin layer having a thickness of 2.0mum or lower including a slipping agent, the adhesive properties of the resin layer to a hard coating layer 3 is increased larger than those to a base material sheet 1, and peeled from the sheet at the time of transferring. Thus, after transferring, even if an external force is concentrated at the transferred layer 2, excellent slipping property is exhibited. Accordingly, excellent scratch resistance and impact resistance are imparted to the surface. Since the layer 3 is formed of ionizing radiation curable resin including no slipping agent, the original excellent physical properties of the resin is maintained.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a hard coat transfer foil, and more specifically, a hard coat transfer foil that has high hardness, scratch resistance, abrasion resistance, stain resistance, etc. on the surface of various resin molded products. This invention relates to a hard coat transfer foil that can easily provide an excellent surface layer.

(Prior art) Acrylic resins, polystyrene resins, polycarbonate resins, and other synthetic resins have traditionally had various advantages such as good moldability, excellent transparency, light weight, and low cost. It is widely used as molded products for various industrial materials, building materials, decorative materials, optical materials, weak electrical materials, cosmetic container materials, household materials, etc.

On the other hand, although such resin molded products have various advantages as mentioned above, their surface hardness is lower than that of glass, metal, etc., so the surface is easily scratched (and transparency is reduced). There are problems such as increased contamination.

Methods for imparting surface protection M with excellent hardness, abrasion resistance, stain resistance, etc. to the surfaces of various resin molded products as described above include methods of applying and curing ionizing radiation-curable resin paints;
Alternatively, a method is known in which a hard coat layer made of an ionizing radiation-curable resin paint is transferred from a transfer foil.

The above-mentioned hard coat transfer foil is made by laminating a hard coat layer on the surface of a base sheet via a release layer, and further laminating a pattern layer and a heat-sensitive adhesive layer as necessary. The hard coat layer is either placed on the surface and transferred by a conventional method, or placed in a mold and transferred by an in-mold coating method in which a resin is injected into the mold. In this case, peeling during 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 with excellent hardness can be applied to the surface of various articles by transfer, but although the hard coat layer has excellent surface hardness, it has poor surface slipperiness. Since stress is locally concentrated due to external force, there is a problem that scratch resistance and impact resistance are poor.

Such problems can be improved by adding a slip agent (lubricant) to the hard coat layer, but adding such a slip agent to the hard coat layer causes a decrease in the physical properties of the hard coat layer, causing the hard coat layer to deteriorate. There are problems in that the original function is degraded and the transparency is degraded.

Therefore, 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 that can easily apply a hard coat layer with excellent scratch resistance and impact resistance to various articles. It is to provide.

Measures to solve problem C) The above objects are achieved by the present invention as described below.

That is, the present invention provides a hard coat transfer foil in which a hard coat layer made of an ionizing radiation curable resin is provided on one surface of a base sheet via a release layer, wherein the release layer has a thickness of 2.0 μm containing a slip agent. A resin layer having a thickness of:
The hard coat transfer foil is characterized in that the adhesiveness of the resin layer to the hard coat layer is greater than the adhesiveness to the base sheet and is peeled off from the base sheet during transfer.

(Function) The release layer of the hard coat transfer foil is coated with 2. containing a slip agent.
A resin layer having a thickness of 0 μm or less, the adhesiveness of the resin layer to the hard coat layer is greater than the adhesiveness to the base sheet, and the resin layer is formed so as to be peeled from the base sheet during transfer. After transfer, the transferred release layer exhibits excellent slip properties even when external force is concentrated, providing a surface with excellent scratch resistance and impact resistance. On the other hand, since the hard coat layer is formed from an ionizing radiation-curable resin that does not contain a slip agent, the excellent physical properties inherent to the ionizing radiation-curable resin are maintained.

(Preferred Embodiments) The present invention will now be described in more detail with reference to the accompanying drawings which schematically show preferred embodiments.

As shown in the first diagram, the hard coat transfer foil of the present invention has a hard coat layer 3 formed on one side of a base sheet 1 via a release layer 2 made of a resin containing a slip agent,
Further, if necessary, a brimer M4, a decorative layer 5 such as a pattern layer or a metal vapor deposition layer, and/or a heat-sensitive adhesive layer 5 can be provided on the surface. The pattern layer can be any pattern, such as natural patterns such as wood grain or stone grain, letters, symbols, abstract patterns, solid patterns on the entire surface, etc. You can.

The base sheet used in the hard coat transfer foil of the present invention may be any conventionally known base sheet, such as polyester films of polyethylene terephthalate, polyethylene terephthalate/isophthalate copolymer, polybutylene terephthalate, etc. Single layer or laminate of polyolefin film such as polyethylene, polypropylene, polymethylpentene, polyvinyl chloride film, polyvinylidene chloride film, ethylene/vinyl alcohol copolymer film, polycarbonate film, polyamide film, etc., on high quality paper. Any base material sheet used for conventional hard coat transfer foils, such as various processed papers such as those formed with polyolefin as a release layer, can be used in the present invention, but particularly preferred ones are 10 to 1100 LL. 2 degrees of thickness
It is an axially stretched polyethylene terephthalate film.

The present invention is mainly characterized by the release layer 2 provided on the surface of the base sheet 1, and the adhesiveness of the release layer 2 to the hard coat layer 3 provided thereon is higher than the adhesiveness to the base sheet 1. It is preferable to use a resin having a high temperature, such as a crosslinked polyurethane resin such as a thermosetting type, a catalyst curing type, or an ionizing radiation curing type, an acrylic resin, a melamine resin, or an epoxy resin. Particularly preferred is an ionizing radiation-curable resin for forming the hard coat layer described below.

Examples of slip agents to be added to the resin include silicone resins, fluorine resins, silicone-modified or fluorine-modified ionizing radiation-curable resins, various waxes, stearic acid or their metal soaps, higher fatty acid amides, and other known slip agents. There are no particular limitations. The amount of these slip agents added to the resin is preferably about 0.1 to 10% by weight of the resin.

To form the release layer 2 from the above resin and slip agent,
An aqueous dispersion or an organic solvent solution of the above resin and slip agent is prepared, and this coating liquid is applied to, for example, 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, It is formed by coating on the above base sheet by any coating method such as an offset gravure coating method or a moss coating method and drying it.

The thickness of the release layer 2 formed at this time is also important; if the release layer 2 is too thick, the thick release layer 2 will be on the surface of the hard coat layer 3 after transfer, so On the other hand, if it is too thin, it becomes difficult to impart slip properties, which is the objective 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 to form these peeling layers H2 to a uniform thickness, by forming a peeling layer several μm thick before stretching the base sheet, and then biaxially stretching the base sheet. By setting the thickness of the release layer to 2 μm or less, the release layer can be a uniform thin film.

The release layer 2 formed as described above may contain various other additives, such as antistatic agents, water repellents, oil clarifying agents, ultraviolet absorbers, stabilizers, matting agents, conductive agents, and antifogging agents. By adding various additives such as additives, various performances that cannot be exhibited by the hard coat layer alone can be imparted without impairing the various physical properties originally possessed by the hard coat layer.

The hard coat layer 3 provided on layer 2 as described above is formed from an ionizing radiation curable coating. Particularly preferred ionizing radiation curable coatings are electron beam curable coatings and ultraviolet ray curable coatings.

Electron beam-curable paints and ultraviolet-curable paints are similar in composition, except that the latter contains a photopolymerization initiator and a sensitizer, and generally their structure is the film-forming component. The main component is a polymer, oligomer, monomer, etc. that has a radically polymerizable double bond or epoxy group, and contains non-reactive polymers, organic solvents, wax, and other additives as necessary. be.

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

By using such a polyfunctional (meth)acrylate-based ionizing radiation-curable paint, surface hardness, transparency,
A hard coat layer with excellent abrasion resistance, scratch resistance, etc. can be formed.

Furthermore, if such hard coat layer 3 is required to have high flexibility and shrinkage resistance, an appropriate amount of thermoplastic resin, such as non-reactive acrylic resin or various waxes, may be added to the above-mentioned curable paint. These demands can be met by adding the following.

In addition, in order to convert the above-mentioned curable paint into an ultraviolet curable paint,
These include acetophenones, benzophenone, Michler's benzoyl benzoate, a-amyloxime ester, tetramethylthiuram monosulfide, thioxanthone as photopolymerization initiators, and n-butylamine, triethylamine, tri-n-butylphosphine as photosensitizers. etc. can be used in combination.

Various grades of ionizing radiation curable coatings such as electron beam or ultraviolet ray curable coatings as described above are known, all of which are readily available on the market and can be used in the present invention.

In addition, the conventional technology can be used as is for those curing methods.
For example, in the case of electron beam curing, 50 to An electron beam or the like having an energy of 1,0OOKeV, preferably 100 to 300 KeV is used, and in the case of ultraviolet curing, an ultra-high pressure mercury lamp,
Ultraviolet rays emitted from light sources such as high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, xenon arcs, and metal halide lamps are used.

The above-mentioned curable paints include, for example, 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, a moss coating method, etc.
Coated on the above release layer by any coating method,
In particular, gravure coating methods, gravure reverse coating methods, reverse roll coating methods, offset gravure coating methods, etc., which are excellent in coating thickness accuracy, coating surface smoothness, etc., are suitable. Further, the hard coat layer 3 may be cured before or after the transfer or during the transfer.

In addition, if the amount of the above-mentioned curable paint is too small, it will not be possible to obtain a hard coat layer with sufficient surface hardness and scratch resistance, and if it is too large, the curing speed will decrease and the base sheet may curl during curing. 1 to 50 μm, especially 1.5 to 2 μm.
A thickness (dry thickness) in the range of 0 μm is suitable.

The hard coat transfer foil of the present invention basically has the above structure, but any pattern 5 can be applied to the surface of the hard coat layer using ordinary gravure ink, etc.
A heat-sensitive adhesive layer 6 can be formed thereon or directly.

Any adhesive can be used, including heat-sensitive adhesives, pressure-sensitive adhesives, solvent-activated adhesives, and ionizing radiation-curable adhesives, but preferred adhesives are those that are not tacky at room temperature, but It is preferable to use a heat-sensitive adhesive that shows adhesive properties when heated. By using such a heat-sensitive adhesive, it is possible to continuously produce a base sheet on which a hard coat layer and an adhesive layer are formed, without winding it into a roll or the like. This is preferable from the viewpoint of productivity.

The method of using the hard coat transfer foil of the present invention is carried out, for example, as shown in the second figure. The hard coat transfer foil of the present invention shown in the first figure is stacked on the surface of any transfer material 7 with adhesive M6 facing the surface, and heat and pressure are applied to activate the adhesive layer and adhere to the transfer material 7. . Next, by peeling off the base sheet 1, the adhesive layer 6, the pattern layer 5, and the brimer layer 4 are removed.
, the hard coat layer 3 and the release layer 2 are integrated into the transferred material 7.
transcribed into.

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

The materials to which the hard coat layer is transferred by the hard coat transfer foil of the present invention include synthetic resin molded products, metals, wood,
It is not limited to ceramics, glass, etc.

(Effects) According to the present invention as described above, the release layer of the hard coat transfer foil is made of 2. ozm or less in thickness, the resin layer has greater adhesion to the hard coat layer than to the base sheet, and is formed so as to peel off from the base sheet during transfer. Therefore, even if an external force is concentrated on the transferred release layer after transfer, it exhibits excellent slip properties, providing a surface with excellent scratch resistance and impact resistance. On the other hand, the hard coat layer is made of an ionizing radiation-curable resin that does not contain a slip agent.
The inherent excellent physical properties of the ionizing radiation-curable resin are maintained.

(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples.

Example 1 Ionizing radiation curing resin HC-A (
(manufactured by Moroboshi Ink) to which 1% by weight of stearic acid was added was gravure coated to a dry thickness of 1 μm, and after drying at 100°C for 1 minute, the surface was coated with ionizing radiation curing resin HC-C (manufactured by Moroboshi Ink). ) was applied to a dry thickness of 10 μm and dried at 100° C. for 1 minute. Furthermore, a brimer (manufactured by Moroboshi Ink) was formed on the surface to a thickness of 1 μm.

The hard coat layer was cured by irradiating the coated film with an electron beam using a scanning type electron beam irradiation machine at an acceleration voltage of 175 KV, a beam current of 36 mA, and an irradiation dose of 10 Mrad.

After that, acrylic resin gravure ink (Showa Ink)
The hard coat transfer foil of the present invention was prepared by printing a pattern on the surface of the hard coat transfer foil by gravure coating the surface with an acrylic heat-sensitive adhesive solution (manufactured by Showa Ink ■) to a dry thickness of 1 μm and drying at 100 °C for 1 minute. I got it.

Examples 2 to 4 The slip agent in Example 1 was modified as shown in Table 1 below.
A hard coat transfer foil of the present invention was obtained in the same manner as in Example 1 except for the following changes.

Comparative Example 1 A hard coat transfer foil was obtained in the same manner as in Example 1 except that no release layer was formed.

Using the hard coat transfer foils of the above examples and comparative examples, 2
00℃ x 3m/min, X 15Kg/cm (pressure)
A hard coat layer was transferred to the surface of an ABS molded product under the following conditions. Thereafter, after the ABS molded product had cooled down, the polyester film was peeled off, and the release layer, hard coat layer, etc. were transferred to the surface of the ABS molded product. The physical properties of the obtained transfer hard code layer were as shown in Table 2 below.

n1≦ζjma 4: Picture layer 5 Niburima single layer 6: Adhesive layer 7: Transferred material 1. Pencil hardness; evaluated under a load of 500 g.

2. Scratch resistance: evaluated by rubbing lightly (10 times) using #0O00 steel wool.

○: Whitening is not noticeable.

△: Whitening is noticeable.

[Brief explanation of the drawing]

FIG. 1 schematically shows a cross section of the hard coat transfer foil of the present invention, and FIG. 2 is a diagram schematically explaining a transfer method using the hard coat transfer foil. 1: Base sheet 2: Release layer 3 Nihard coat layer

Claims (4)

[Claims] (1) In a hard coat transfer foil in which a hard coat layer made of an ionizing radiation curable resin is provided on one surface of a base sheet via a release layer, the release layer has a thickness of 2.0 μm or less and contains a slip agent. 1. A hard coat transfer foil characterized in that the resin layer has a higher adhesiveness to the hard coat layer than the adhesiveness to the base sheet, and is peeled from the base sheet during transfer. (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) Claim 1 in which the release layer is made of an ionizing radiation curable resin.
Hard coat transfer foil described in . (4) The hard coat transfer foil according to claim 1, wherein a decorative layer such as a pattern layer or a metal vapor deposition layer and/or a heat-sensitive adhesive layer are formed on the surface of the hard coat layer.