JPH01257087A - Transfer sheet - Google Patents

Abstract

PURPOSE:To provide a hairline form or matted transfer layer having satisfactory scratch resistance and wear resistance by providing a releasable protective layer comprising a hardenable resin, and providing a base sheet with hairline or matted patterns, in a transfer sheet. CONSTITUTION:A transfer sheet comprises a base sheet and a releasable protective layer provided on one side of the base sheet. The protective layer is formed of a composition comprising a hardenable compound having at least two acryloyl or methacryloyl groups in the molecule thereof and a filler surface- treated with an alkoxysilane having a radical-polymerizable unsaturated bond in the molecule thereof. One side of the base sheet has a hairline or matted feeling. Upon transferring, a hairline form or matted surface having scratch resistance and wear resistance can be obtained. The quantity of the silane coupling agent applied to the filler is preferably so set that the minimum coating area of the silane coupling agent is at least 10 per 100 of the specific surface area of the filler. If the minimum coating area is less than 10, the effect of the agent is not obtained.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a transfer sheet that can easily produce a desired hairline or matte feel and has excellent scratch resistance, abrasion resistance, and chemical resistance. .

[Conventional technology and problems]

Transfer sheets are widely used to impart a hairline or matte feel to the surface of a molded article from a design standpoint.

Such transfer sheets are generally made by laminating a releasable protective layer on a base sheet, and then laminating an adhesive layer via a colored layer, a metal vapor deposited layer, etc., and the adhesive layer is bonded to the transferred object by thermocompression bonding, etc. After that, the base sheet is peeled off.

By the way, conventional transfer sheets for giving a hairline or matte feel include a releasable protective layer, a temporary layer, and an adhesive layer, all of which are solvent-type paints or printing inks obtained by dissolving resin in a solvent. Since it is made of aluminum, there is a problem that it has poor scratch resistance, abrasion resistance, etc.

Therefore, in recent years, hairline or matte surfaces have been required to have scratch resistance and abrasion resistance, and methods such as applying a coating generally called a hard coat to the transfer surface after transfer have been adopted.

However, this method has the problem that it requires one more step and requires painting and drying equipment, which has many disadvantages in terms of cost.

Therefore, an object of the present invention is to provide a transfer sheet that has a hairline or matte feel and is excellent in abrasion resistance, scratch resistance, chemical resistance, etc.

[Means for solving problems]

In view of the above problems, as a result of intensive research, the present inventors used a curable protective layer consisting of an ionizing radiation curable compound and a filler surface-treated with an alkoxysilane having a radically polymerizable unsaturated bond, and The inventors have discovered that by using a base sheet having a matte pattern, it is possible to provide a hairline or matte surface having scratch resistance and abrasion resistance after transfer, and have conceived the present invention.

That is, the transfer sheet of the present invention includes a base sheet and a releasable protection layer 1 stacked on one side of the base sheet, and the releasable protective layer includes (a) 2 (amount of snow) in the molecules; A composition comprising a curable compound having an acryloyl group or a methacryloyl group, and (b) a filler surface-treated with an alkoxysilane having a radically polymerizable unsaturated bond in the molecule, and the base sheet The one side of the sheet has a hairline texture or a matte texture.

The present invention will be explained in detail below.

Constituting the releasable protective shoulder in the transfer sheet of the present invention (
As component a), a curable compound having two or more acryloyl groups or methacryloyl groups in the molecule is used. Specific examples of component (a) include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate. meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, polyethylene glycol diglycidyl ether di(meth)acrylate , brobylene glycol diglycidyl ether di(meth)acrylate, polypropylene glycol diglycidyl ether di(meth)acrylate, sorbitol tetraglycidyl ether tetra(meth)acrylate, polyurethane(meth)acrylate, melamine(meth)acrylate, etc. Examples include (meth)acrylates, but other materials can also be used.

In order to obtain good scratch resistance, among the above-mentioned polyfunctional (meth)acrylates, (meth)allyl equivalents of 90
~200 is preferred.

In component (b), alkoxysilanes having radically polymerizable unsaturated bonds in their molecules for surface treatment of fillers are generally called silane coupling agents, such as r-methacryloxypropyltrimethoxysilane, T-methacryloxypropylmethyldimethoxysilane, T-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, T
-methacryloxypropyldimethylethoxysilane, γ
-Acryloxypropyltrimethoxysilane, T-acryloxypropylmethyldimethoxysilane, T-acryloxypropyldimethylmethoxysilane, r-acryloxypropyltriethoxysilane, T-acryloxypropylmethyljethoxysilane, γ-acryloxypropyl Examples include dimethylethoxysilane and vinyltriethoxysilane.

Examples of fillers include 5i02 (silica) and A120.
Powder particle size of 3 (alumina) etc. is 10 mm to 10 μm
Commercially available products such as "Aerosil" manufactured by Nippon Aerosil, "Aluminum Oxide-〇", and "Siroid" manufactured by Fuji Davison can be used. Especially 5102 (silica) powder and A1□03 (
Alumina) powder is preferred because it can maintain the transparency of the releasable protective layer.

There is no particular restriction on the method of treating the filler with the above-mentioned silane coupling agent, and any known method can be used.

For example, a dry method involves spraying a predetermined amount of a silane coupling agent while stirring the filler vigorously, or a wet method involves dispersing the filler in a solvent such as toluene and then spraying a predetermined amount of a 7-rank cassoplating agent. There are methods such as adding and reacting, but the latter wet method is preferable in order to uniformly perform surface treatment.

The treatment amount (required amount) of the silane coupling agent for the filler is such that the minimum coverage area of the silane coupling agent is 10 or more per 100 of the specific surface area of the filler.
is preferred. Here, if the minimum covered area is less than 10, there is no effect.

The blending ratio of the above-mentioned polyfunctional (meth)acrylate and surface-treated filler may be such that the polyfunctional (meth)acrylate does not become sticky.
It is preferable that the surface-treated filler be used in an amount of 10 to 200 parts by weight per 100 parts by weight of meth)acrylate. To use polyfunctional (meth)acrylate and surface-treated filler as a coating agent, add a solvent as necessary to a predetermined amount of surface-treated filler such as polyfunctional (meth)acrylate,
It may be kneaded using a dispersing machine such as a sand mill or a roll.

Further, in order to improve storage stability, it is preferable to add a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether to this coating agent.

Furthermore, in order to improve coating suitability, the coating agent may contain cellulose resins such as ethyl cellulose and nitrocellulose, rubber resins such as polyester resin, polyurethane resin, rosin ester resin, cyclized rubber, and chlorinated polyolefin. Polymers such as resins and allyl resins can be added. Further, coloring agents such as pigments and paints may be added as appropriate.

In order to form a releasable protective layer on the surface of the base sheet using the coating agent, general coating agent application methods can be used, such as roll coating method, gravure coating method, screen coating method, Coating methods such as fountain coating methods can be used.

After laminating an ink adhesive layer as necessary on the releasable protective layer,
After laminating the pattern layer, colored layer, metal vapor deposited layer, etc., an adhesive layer is provided.

The adhesive layer has a thermoplastic resin as its main component, and adheres to the transfer target by heat-pressing.

The adhesive layer is necessary to ensure good adhesion of the transfer layer to the transfer target, and is made of acrylic or methacrylic materials such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate. Homopolymers of monomers or copolymers containing these monomers, styrene resins such as polystyrene, polyα-methylstyrene, styrene copolymer resins, cellulose acetate, cellulose nitro, vinyl chloride, polyester resins, etc. have good adhesive properties. It can be molded from resin.

The thickness of the adhesive layer is 0.5-15 μm, 0.5 μm
If it is less than m, the adhesive strength will not be sufficient, and if it exceeds 15 μm, the interlayer strength of the adhesive layer will decrease.

The base sheet is for providing the above-mentioned releasable protective layer, and may be made of any material as long as it can impart a hairline or cloak feel to the releasable protective layer. Specifically, polyester film, polyamide film,
Examples include cellophane film, acetate film, polypropylene film, etc. In addition, the above films may be laminated on paper, metal foil, etc.

The ink adhesive layer can be formed by coating or the like using the adhesive resin described above, and its thickness is 0.5
It is about 10 μm. In addition, the colored layer and the pattern layer can be printed by printing means such as gravure, screen printing, offset,
It is formed by coating or the like using an ink suitable for each method.

After applying the releasable protective layer to the base sheet, or after further applying an adhesive layer, etc., the releasable protective layer is cured by irradiation with Hn radiation or heating. Irradiation with ionizing radiation is preferable in terms of short-time curing. An electron beam or ultraviolet light is used as the ionizing radiation.

In the case of electron beam irradiation, 50 to 1000 KeV is emitted from various electron beam accelerators such as Cockroft-Walton type, bumpgraph type, resonant transformer type, insulated core transformer type, linear type, dynamidron type, and high frequency type.

Preferably, an electron beam having an energy in the range of 100 to 300 KeV is used. Further, in the case of ultraviolet irradiation, ultraviolet rays emitted from an ultraviolet source using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc metal halide lamp, etc. are used.

[For production]

In the transfer sheet of the present invention, the releasable protective layer is formed of an ionizing radiation-curable or heat-curable compound containing a filler whose surface is treated with an alkoxysilane having a radically polymerizable unsaturated bond, and the base sheet A hairline or matte pattern is formed in advance. Therefore, a hairline or matte pattern is formed on the surface of the releasable protective layer (the surface in contact with the base sheet), and the curing treatment provides high scratch resistance and abrasion resistance.

〔Example〕

The present invention will be explained in further detail by the following examples.

Example 1 The following mixture (a) was heated under reflux for 10 hours to surface-treat the silica powder to obtain treated silica (b). A coating agent (c) was prepared using this.

Mixing example (a) Silica powder: 500 parts by weight (manufactured by Nippon Aerosil ■, Aerosil #200) r-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical ■, K
BM503) 420 parts by weight Dilute hydrochloric acid (adjusted to pH=3) 70 parts by weight Modified ethanol 100 parts by weight Toluene
・・・・・・・・・3000 heavy! +9 Coating agent (c) Treated silica (b) 35 parts by weight Dipentaerythritol hexaacrylate 35 parts by weight Polymethyl methacrylate 50 parts by weight toluene····
・・・・・・・・・250 heavy 1 l methyl ethyl ketone・
...250 parts by weight polyethylene wax...
- 3 parts by weight A 25 μm thick polyester film with a hairline surface pattern was used as the base sheet.■
The above coating agent (c) was applied uniformly over the entire surface using a gravure diagonal plate with a plate depth of 140 μm, and the solvent was evaporated by passing it through a drying hood at 80°C to remove the applied coating agent layer. was dried to the touch to obtain a releasable protective layer.

On the surface of the obtained releasable protective layer, a coating agent having the following composition (d) was applied uniformly over the entire surface using a gravure diagonal plate with a plate depth of 140 μm, and the solvent was evaporated by passing it through a drying hood at 140 ° C. The applied coating agent was dried to form an ink adhesive layer.

Coating agent (d) Polymethyl methacrylate...30 parts by weight Methyl ethyl ketone...85 parts by weight Toluene...
......1 part of 85t Then, the coated surface side was irradiated with 5 Mrad of electron beam accelerated to 175 kV in a nitrogen gas atmosphere to crosslink and harden the releasable protective layer.

An adhesive (e) having the following composition was applied thereon to form an adhesive layer.

Adhesive (e) Acrylic resin 20 parts by weight Toluene 40 parts by weight 1 l Methyl ethyl ketone 40 parts by weight 1 part The resulting transfer sheet was brought into close contact with a transparent AS resin plate, and the pressure was 6.5° using a silicone rubber roller with a surface temperature of 200°C.
kg/ant and heating under pressure at a running temperature of 15 mm/sec, and then the polyester base sheet of the transfer sheet was peeled off.

The resulting transfer material had a hairline texture and was not scratched even by nail scrunch.

Example 2 A matte-like 25 μm thick polyester film (X-44 manufactured by Toshi) was used as a base sheet in the same manner as in Example 1.
After coating with the coating agent (c) in the same manner, apply the coating agent (d) and irradiate the layer of the coating agent (c) with a 5 Mrad electron beam to cure the layer of the coating agent (c), then apply the adhesive (e). Coating was performed.

When the obtained transfer sheet was transferred to an AS plate in the same manner as in Example 1, a matte transfer body with an uneven shape having good scratch resistance and abrasion resistance was obtained.

Although the obtained transfer sheet did not have a colored layer, a colored or patterned layer may be provided.

Example 3 In the same manner as in Example 1, a matte-like 25 μm thick polyester film (X-
43) was used, and the rest was carried out in the same manner.

(manufactured by)) and the rest was done in the same way.

The resulting hairline and matte molded bodies (AS
It shows the glossiness and haze of resin plate).

Glossiness Haze (%) Example 1 - Example 2 60 20 Example 3
40 25 Example 4 20
60 Reference Example 1405 The substrate base of the reference example was Lumirror T-60 (Toshiba Co., Ltd.) with a smooth surface.

Glossiness is based on JIS 2-8741.

The haze level is based on ^5 THD-1003 (Example 1 was not measured due to hairline tone) [Effects of the Invention] As detailed above, in the transfer sheet of the present invention,
A hairline or matte transfer that has a releasable protective layer made of a curable resin and has sufficient scratch resistance and abrasion resistance because the base sheet has a hairline or matte pattern in advance. Give layers.

By variously changing the hairline or matte pattern of the base sheet, various hairline or matte effects can be easily imparted.

Claims (2)

[Claims] (1) In a transfer sheet including a base sheet and a releasable protective layer laminated on one side of the base sheet, the releasable protective layer (a) has two or more acryloyl groups or methacryloyl groups in the molecule; and (b) a filler surface-treated with an alkoxysilane having a radically polymerizable unsaturated bond in the molecule, and the one side of the base sheet has a hairline or A transfer sheet characterized by having a matte pattern. (2) The transfer sheet according to claim 1, wherein the curable compound in the releasable protective layer is crosslinked and cured by irradiation with ionizing radiation.