JPH01216900A - Transfer sheet - Google Patents

Abstract

PURPOSE:To obtain a transfer sheet having excellent rubbing resistance, mar resistance and chemical resistance, by composing a releasable protective layer of a hardened layer 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, and providing a combination of a colored layer with a vapor-deposited metallic layer to provide a metallic color. CONSTITUTION:A transfer sheet comprises a base sheet 1, a releasable protective layer 2 provided on one side of the base sheet 1, a colored layer 3 and a vapor- deposited metallic layer 2. The protective layer 2 is composed of a hardened layer 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. A desired metallic color can be obtained by the combination of the colored layer 3 with the metallic layer 4. The protective layer 2 is hardened by irradiation with inonizing radiations, so that the transfer sheet is excellent in mar resistance, rubbing resistance, chemical resistance or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transfer sheet having a metallic color such as gold or silver and having excellent abrasion resistance, scratch resistance and chemical resistance.

[Conventional technology and problems]

Transfer sheets with metallic colors such as gold or silver are generally made by laminating a releasable protective layer on a base sheet, and then laminating an adhesive layer through a colored layer, a metal vapor deposited layer, etc., and then attaching the adhesive layer to the object to be transferred. The base sheet is peeled off after being adhered to the base sheet by thermocompression bonding or the like.

By the way, in conventional metallic color transfer sheets, the releasable protective layer, colored layer, and adhesive layer are all made of solvent-type paint or printing ink obtained by dissolving resin in a solvent, so they have poor durability. There were problems with poor solvent resistance, scratch resistance, abrasion resistance, etc.

Therefore, in recent years, the transferred surface is required to have solvent resistance, scratch resistance, abrasion resistance, etc., and methods such as applying a coating generally called a hard coat to the transferred 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, it has been attempted to provide a cured protective layer on the transfer layer in advance so as to increase the surface hardness and then transfer the layer, but there is a problem that the surface hardness as a metallic color transfer sheet is not necessarily sufficient.

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

[Means for Solving the Problems] In view of the above problems, as a result of intensive research, the present inventors developed a hardening method consisting of an ionizing radiation-curable compound and a filler whose surface was treated with an alkoxysilane having a radically polymerizable unsaturated bond. The inventors have discovered that a transfer sheet exhibiting a desired metallic color can be obtained by using a protective layer and providing various colored layers and metal vapor deposited layers thereon, and have conceived the present invention.

That is, the transfer sheet of the present invention includes a base sheet, a releasable protective layer laminated on one side of the base sheet, a colored layer,
the releasable protective layer comprises (a) a curable compound having two or more acryloyl groups or methacryloyl groups in the molecule; and (b) a radically polymerizable unsaturated bond in the molecule. It is composed of a cured layer of a composition containing a filler surface-treated with an alkoxysilane having
Further, it is characterized in that it has a desired metallic color due to the combination of the colored layer and the metal vapor deposited layer.

The present invention will be explained in detail below.

Constituting the releasable protective layer in the transfer sheet of the present invention (
As the component a), a curable compound having two or more acryloyl 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, propylene glycol diglycidyl ether di Examples of polyfunctional (meth)acrylates include (meth)acrylate, polypropylene glycol diglycidyl ether di(meth)acrylate, sorbitol tetraglycidyl ether tetra(meth)acrylate, polyurethane (meth)acrylate, and melamine (meth)acrylate. However, others 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 T-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, T-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ
-methacryloxypropyldimethylethoxysilane, T
-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, T-acryloxypropyldimethylmethoxysilane, T-acryloxypropyltriethoxysilane, T-acryloxypropylmethyljethoxysilane, γ-acryloxypropyl Examples include dimethylethoxysilane and vinyltriethoxysilane.

Examples of fillers include Sin, (silica), and Al2O.
, (alumina), etc. powder particle size is 10 mm ~ 10 μm
Commercially available products such as "Aerosil" manufactured by Nippon Aerosil ■, "Aluminum Oxide-〇", and "Syroid" manufactured by Fuji Davison ■ are suitable. In particular, SiO□ (silica) powder and A1□03 (alumina) powder are preferred because they 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 in which a predetermined amount of silane coupling agent is sprayed while stirring the filler vigorously, and a wet method in which a predetermined amount of silane coupling agent is sprayed after dispersing the filler in a solvent such as toluene. Although there are methods of adding and reacting, etc., the latter wet method is preferred in order to uniformly perform surface treatment.

The amount (required amount) of the silane coupling agent to be treated with respect to the filler is preferably such that the minimum covered area of the silane coupling agent is 10 or more with respect to the specific surface area of 100 of the filler. 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 polyfunctional (meth)acrylate and surface-treated filler,
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.

The base sheet is for providing the above-mentioned releasable protective layer, and may be made of any material as long as it can improve adhesion to the releasable protective layer.

Specific examples include polyester film, polyamide film, cellophane film, acetate film, polypropylene film, etc. In addition, the above-mentioned film may be laminated onto paper, metal foil, or the like.

After a releasable protective layer is provided on the base sheet, a transparent thermoplastic resin layer (ink adhesive layer) is provided if necessary, and then a colored layer, a metal vapor deposition layer, etc. are laminated.

The type of ink in the colored layer is determined by considering the metallic color of the transfer sheet. The ink for the colored layer is prepared by adding and kneading a coloring agent consisting of a dye, a plasticizer, a stabilizer, other additives, and a solvent or diluent to a vehicle.

Binters (vehicles) related to adhesion among ink components include homopolymers of acrylic or methacrylic monomers, such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate, or these monomers. There are preferably alcohol-insoluble resins such as styrene resins and styrene copolymer resins such as polystyrene and polyα-methylstyrene, cellulose acetate, nitrocellulose, vinyl chloride, and polyester resins. Select and use one or more types.

Further, in addition to the colored layer, a burl layer containing a pearl pigment may be provided. Furthermore, by adding a pearl pigment to the colored layer, a pearl-like colored layer may be obtained. Moreover, metal powders such as aluminum powder, bronze powder, etc. can also be used instead of pearlescent pigments.

The thickness of the colored layer is generally about 0.5 to 10 μm.

In order to give a metallic appearance or pattern to the surface of the transferred object,
A metal vapor deposition layer is provided. Materials for forming the metal vapor deposition layer include aluminum, chromium, tin, silver, copper, and gold, but from an economical point of view, it is preferable to produce a desired metal color by combining with a colored layer. For example, gold color can be produced by providing a yellow colored layer on the aluminum vapor deposited layer. Moreover, in the case of silver color, it can be produced by making the colored layer transparent or by omitting it.

The thickness of the metal vapor deposition layer is generally about 400 to 1000 layers. The metal vapor deposited layer can be made into a pattern or letter shape as required. For this purpose, a method is adopted in which a water-soluble pattern is provided, a metal thin film is applied, and then water is applied, or a metal thin film is first provided and then water is applied. A method is used in which a resist pattern is provided and then an acid or alkal is applied. Note that before forming the metal vapor deposition layer, a vapor deposition anchor layer may be provided so that the metal atoms are smoothly attached. This vapor deposition anchor layer is also formed by printing or coating.

Such a colored layer is preferably placed between the releasable protective layer and the metal vapor deposited layer. Further, the ink adhesive layer coated after the releasable protective layer may be a colored layer, or the colored layer may be provided via a transparent ink adhesive layer. Furthermore, the vapor-deposited anchor layer may be a colored layer.

The transfer sheet of the present invention may have an adhesive layer in order to improve adhesion to the object to be transferred.

The composition of the adhesive layer may generally be the same as the binder used for the colored layer. The thickness of the adhesive layer is 0.5 to 10 μm; if it is less than 0.5 μm, the adhesive force is insufficient;
If it exceeds this, the interlayer strength of the adhesive layer will decrease.

The structure of the above transfer sheet will be explained with reference to the attached drawings.

FIG. 1 shows a typical example of the transfer sheet described above, in which 1 is a base sheet, 2 is a releasable protective layer, 3 is a colored layer, and 4 is a transfer sheet.
indicates a metal deposited layer. As described above, an ink adhesive layer may be formed before the colored layer is formed, and a vapor deposition anchor layer may be formed before the metal vapor deposition layer. Furthermore, an adhesive layer may be provided after the metal vapor deposition layer.

Regarding the curing of the releasable protective layer in the transfer sheet of the present invention, there are two cases: (i) irradiation with ionizing radiation after formation on the base sheet and before the formation of the colored layer, and (ii) irradiation with ionizing radiation after the formation of the colored layer, etc. It depends.

Ru. In either case, it is preferable to use electron beams or ultraviolet rays as the ionizing radiation.

In the case of electron beam irradiation, 50 to 1000 KeV emitted from various electron beam accelerators such as Kotscroft Walton type, bump graph 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 example, the transfer method using the transfer sheet of the present invention is as follows:
■Thermal transfer method, in which the adhesive layer (or other layers layered on top of the adhesive layer in some cases) is thermally bonded to the object to be transferred by heating. An example is a solvent activated transfer method in which an activation liquid consisting of a solvent or a solution of a resin is interposed.

Further interesting methods that can be used as transfer methods using the transfer sheet of the present invention include press molding, vacuum forming, pressure forming, vacuum pressure forming, injection simultaneous molding, etc., in which the transfer sheet is There is an advantage that the transfer can be performed at the same time as the molding by placing the mold in advance. Further, in extrusion molding or calendar molding, the transfer can be similarly performed at the same time as the molding, and furthermore, press molding, vacuum forming, pressure forming, vacuum pressure forming, etc. may be performed as a second forming after the transfer.

In the transfer sheet of the present invention, a curable compound having two or more acryloyl groups or methacryloyl groups in the molecule is used as the compound constituting the releasable layer, and this is cured to form the releasable protective layer. It has superior physical and chemical properties compared to conventional mold release layers made of thermoplastic resin. Therefore, the metal color such as gold or silver does not change.

〔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 (8) was prepared using this.

Mixture (a) Silica powder: 500 parts by weight (manufactured by Nippon Aerosil, Aerosil #200) T-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., K
BM503)...420 parts by weight diluted hydrochloric acid (adjusted to pH=3)...70 parts by weight toluene...3000 Heavy I I! Denatured ethanol・・・・・・・・・100 parts by weight of treated silica (
b) 25 parts by weight Dipentaerythritol hexaacrylate 25 parts by weight Polymethyl methacrylate 50 parts by weight Toluene
・・・・・・・・・250 1 part heavy Methyl ethyl ketone・
...250 parts by weight 25 μm thick as base sheet
polyester film (east side, Lumirror T-60
), the coating agent (8) obtained above 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 120°C. Dry the layer to the touch, thickness 3-20μ
A releasable protective layer of m was obtained.

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 with a thickness of 3 to 120 μm.

Polymethyl methacrylate: 30 parts by weight Methyl ethyl ketone, a@φ・, 85 parts by weight Toluene...
...85x115 Then, the releasable protective layer was crosslinked and cured by irradiating the coated surface side with an electron beam accelerated to 175 kV at 5 Mrad in a nitrogen gas atmosphere.

Next, a gravure ink of the following composition (e) was printed on the entire surface of the ink adhesive layer using a halftone gravure plate, and 1
A colored layer for gold color was formed by passing through a drying hood at 20°C.

Composition (N) Polymethyl methacrylate...20 parts by weight Yellow dye...0.4 parts by weight Methyl ethyl ketone...63 parts by weight Toluene... ...
...17.6 layers of 1iH was further coated with the following composition to form a vapor deposition anchor layer.

Composition (f) Polymethyl methacrylate polyol 25 parts by weight Nitrified cotton 5 parts by weight xamethylene diisocyanate ......13 parts by weight Ethyl acetate...80 parts by weight An aluminum vapor-deposited layer was formed to a thickness of 500 μm on the formed vapor-deposited anchor layer with a thickness of 1 μm. Formed.

The following compositions (g) and (h) were applied in order on the aluminum vapor deposited layer to form an adhesive layer with a thickness of about 1 μm to obtain a transfer sheet.

Composition (1.) Vinyl chloride/vinyl acetate copolymer resin...20 parts by weight Ethyl acetate...40 parts by weight Toluene...・・・・・・・・・40118B Composition (H) Acrylic resin・・・・・・・・・20 parts by weight L・Luene・・・・・・・・・・・・40 Heavy I II Methyl ethyl ketone・・・・・・・40 parts by weight of the obtained adhesive layer of the transfer sheet was brought into close contact with an AS resin plate, and the surface temperature was maintained at 20%.
With a silicone rubber roller at 0℃, pressure 6.5kg/
It was heated under pressure at CI+f and a running temperature of 15 mm/sec, and then the polyester base sheet of the transfer sheet was peeled off. The transfer layer thus obtained had a beautiful golden color and good abrasion resistance and scratch resistance.

Example 2 In the same manner as in Example 1, a releasable protective layer and an ink adhesive layer were applied using the coating agent (c) and anti-mold coating agent (d), and the mold was released by irradiating with an electron beam under the same conditions. The protective layer was cured.

Next, a gravure ink of the following composition (i) was coated on the ink adhesive layer to form a vapor deposition anchor layer and colored layer.

Composition (January Polymethyl methacrylate polyol...25 parts by weight Nitrified cotton...5 parts by weight xamethylene diisocyanate... ......13 parts by weight Yellow dye...0.4 parts by weight Ethyl acetate...80 parts by weight Formed thickness 1
An aluminum vapor deposition layer was formed to a thickness of 500 μm on the vapor deposition anchor layer.

The same composition as in Example 1 (g) on the aluminum vapor deposited layer,
(H) was applied in order to form an adhesive layer with a thickness of about 1 μm to obtain a transfer sheet.

When the obtained transfer sheet was transferred onto an AS resin plate under the same conditions as in Example 1, a transfer layer having a beautiful golden color and excellent abrasion resistance and scratch resistance was obtained.

Example 3 Coating agent (c) was applied in the same manner as in example 1, and the following composition (v) was coated on the surface of the obtained releasable protective layer to form an ink adhesive layer and colored layer. did.

Composition (nu) Polymethyl methacrylate...30 parts by weight Yellow dye...0.4 parts by weight Methyl ethyl ketone...85 parts by weight Toluene...・・・・・・
...85111% Next, the releasable protective layer was crosslinked and cured by irradiating 5 Mrad of electron beam accelerated to 175 kV from the coated surface side in a nitrogen gas atmosphere.

Furthermore, the composition of Example 1 was coated on the ink adhesive layer/colored layer to form a vapor deposition anchor layer.

50 μm thick on the formed 1 μm thick vapor deposition anchor layer.
An aluminum vapor deposition layer was formed so that there were no people.

The compositions (g) and (h) of Example 1 were sequentially applied on the aluminum vapor deposited layer to form an adhesive layer with a thickness of about 1 μm,
A transfer sheet was obtained.

When the obtained transfer sheet was transferred onto an AS resin plate under the same conditions as in Example 1, a transfer layer having a beautiful golden color and excellent abrasion resistance and scratch resistance was obtained.

Comparative Example 1 Transfer painting was carried out on an AS resin board using a transfer sheet in the same manner as in Example 1 except that the releasable protective layer was formed of polymetal methyl gyrate resin.

The AS resin plates with transfer decoration obtained in Examples 1 to 3 and Comparative Example 1 were subjected to the following tests.

(1) Scratch resistance test Apply the transferred painted surface using a friction tester [manufactured by Suga Test Instruments ■,
FR-2 type] steel wool 00 under a load of 500g
A reciprocating test was conducted 100 times using No. 00 (manufactured by Yamazaki Sangyo ■).

(2) Solvent resistance test: Ethyl alcohol (EtOH)
), methyl ethyl ketone (MEK), and toluene were added dropwise to the sample, covered with a watch glass, and allowed to stand for 20 hours while preventing evaporation. Changes in appearance were then examined.

(3) Moisture and heat resistance test The AS resin board with the transfer painting was tested at a temperature of 60°C and a humidity of 9.
After being left in a 0% atmosphere for 24 hours, changes in appearance were examined.

(4) Chemical resistance test A 10% aqueous hydrochloric acid solution and a 10% aqueous sodium hydroxide solution were each dropped onto the surface of the transfer layer, covered with a watch and allowed to stand for 20 hours, then washed with water and dried to examine changes in appearance.

(5) Wear resistance test RCAIi! Using an abrasion tester, abrasion paper (computer tape, puff color, oil-free product 11/
An abrasion test was conducted using a 16-inch width) to determine the number of times the paint film peeled off.

The results of the above tests are shown in Table 1 below.

Table 1 [Effects of the Invention] In the transfer sheet of the present invention, the releasable protective layer is formed from an ionizing radiation-curable composition containing a filler whose surface is treated with an alkoxysilane having a radically polymerizable unsaturated bond. , and has a colored layer and a metal vapor deposited layer. Therefore, a desired metallic color can be produced by combining the colored layer and the metal vapor deposited layer, and since the releasable protective layer is hardened by irradiation with ionizing radiation, it has excellent scratch resistance, abrasion resistance, and chemical resistance. Excellent in etc.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of a transfer sheet according to an embodiment of the present invention. 1...Base sheet 2...Release protection layer 3...Colored layer 4...Metal deposited layer

Claims (3)

[Claims] (1) In a transfer sheet having a base sheet, a releasable protective layer laminated on one side of the base sheet, a colored layer, and a metal vapor-deposited layer, the releasable protective layer (a) is in the molecule. Consisting of a cured layer of a composition containing a curable compound having two or more acryloyl groups or methacryloyl groups, and (b) a filler surface-treated with an alkoxysilane having a radically polymerizable unsaturated bond in the molecule. A transfer sheet having a desired metallic color due to the combination of the colored layer and the metal vapor deposited layer. (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. (3) The transfer sheet according to claim 1 or 2, wherein the colored layer is yellow and the metal vapor deposited layer is made of aluminum, so that it appears golden.