JPH082717B2 - Transfer sheet - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a transfer sheet, and more specifically, to a release sheet having a resin that is apparently dry but can be crosslinked and cured by irradiation with ionizing radiation. The present invention relates to a transfer sheet having a crosslinked cured layer.

(Prior Art) Conventionally, in order to protect the surfaces of various articles and patterns on articles, protective layers made of various synthetic resins are formed on these surfaces.

These protective layers are formed by a method of applying a transparent coating on the surface of the pattern of the article and drying, or a method of laminating a transparent film.

As a method of providing a protective layer on a design or the like, a method of previously forming a protective layer on a transfer sheet for transferring the design is also used.

In the case of this transfer sheet, a crosslinked cured layer made of a thermoplastic resin or a thermosetting resin is provided on the release sheet,
Further, a transfer sheet provided with a pattern layer and the like are already widely known.

However, in the case of the coating method, laminating method or transfer method as described above, whichever method is used,
Since the protective layer itself is not so excellent in physical and chemical properties, the physical and chemical properties of the surface of the product provided with the protective layer are not sufficient, and scratch resistance, solvent resistance and stain resistance Etc. are only unsatisfactory.

In recent years, ionizing radiation-curable coatings of the type that are cured by irradiation with ionizing radiation, particularly ultraviolet rays or electron beams, have attracted attention due to their high solvent-free curing speed, and these coatings are cross-linked by the method as described above. Some attempts have been made to utilize it for forming a hardened layer.

However, since these coatings retain fluidity or adhesiveness when they are not exposed to ionizing radiation after application, it is necessary to apply ionizing radiation after coating in any of the above methods, which is a Even if there is no particular problem in mass production, it is difficult to perform such irradiation of ionizing radiation outside the factory each time.

In particular, in the case of a transfer sheet, it is impossible to form such a paint layer on the release sheet and then directly provide a picture layer and other layers.

Therefore, after performing transfer using a transfer sheet having no protective layer, the above-mentioned ionizing radiation-curable coating material is applied onto the transfer pattern, and then cross-linking is cured by irradiation with ionizing radiation. Since the transfer method itself is mainly used as a printing method for a small lot, it is almost impossible industrially to apply a liquid ionizing radiation curable coating material to the transfer surface and to crosslink and cure it at each transfer. is there.

(Problems to be solved by the invention) Accordingly, an object of the present invention is to provide various physical properties on various articles and patterns, such as scratch resistance and resistance, even outside of factories, small factories, etc. or even general stores and homes. It is an object of the present invention to provide a transfer sheet capable of forming a protective layer excellent in stain resistance and the like.

(Means for Solving Problems) That is, the present invention provides a release surface of a release sheet, a crosslinked cured layer of an ionizing radiation curable resin which is solid at room temperature in an uncured state, and a thermoplastic resin layer. , A pattern layer, a concealing layer, and an adhesive layer are sequentially laminated, which is a transfer sheet.

The present invention will now be described in more detail with reference to the accompanying drawings showing an example of the present invention.

FIG. 1 shows a basic structure of a transfer sheet 10 of the present invention, and shows a state in which a specific cured resin layer 2 is laminated on a release surface of a release sheet 1.

FIG. 2 shows one of the embodiments of the transfer sheet 10 of the present invention. In addition to the structure of FIG.
Is provided.

The above-mentioned embodiment is suitable for transferring a protective layer made of a cured resin layer on the surface of an article, not for transferring a pattern layer or the like.

FIG. 3 shows one of further embodiments of the transfer sheet 10 of the present invention, in which a pattern layer 4 is further provided on the structure of FIG.

FIG. 4 shows another embodiment, which has a structure in which a concealing layer 5 is added to the structure shown in FIG. This concealing layer has a function of concealing the hue of the transferred material when the transfer sheet 10 is used for transfer.

FIGS. 5 and 6 show an additional adhesive layer 6, the one of FIG. 5 corresponding to that of FIG. 3 and the one of FIG. 6 corresponding to that of FIG.

The above embodiment is mainly for transferring the pattern layer 4 to the article (material to be transferred) together with the protective layer (crosslinked cured layer 2).

Of course, the adhesive layer 6 as described above may be provided also in FIGS. 1 and 2.

The releasable sheet 1 holds a layer transferred by transfer until the time of transfer. For example, a film or sheet of synthetic resin such as polyethylene terephthalate, polyamide, polypropylene or polyethylene, or paper or synthetic paper is used. To do. The releasable sheet 1 may be a laminate of the above materials.

The releasable sheet 1 may be a single material or a laminate of the above-mentioned materials, but if necessary, a releasable substance such as wax or silicone is used as an appropriate vehicle (vehicle) in order to further ensure the releasability. In the above example, a release layer (not shown) may be formed by applying a release coating obtained by dissolving an ordinary ink composition as a vehicle (described later) with a solvent and the like. Good.

The releasable sheet 1 may have its release surface subjected to a mat treatment by various methods in the sense of adjusting the gloss of the surface of the crosslinked cured layer 2 after transfer. Matting treatment includes kneading of matting agent, application of paint containing matting agent, sandblasting, chemical etching, etc.
Patterned matting treatment may be appropriately performed by these methods. Alternatively, a convex portion may be formed on the release surface by printing or the like in order to form a concave portion on the surface of the crosslinked cured layer 2 after transfer.

The above releasable sheet 1 may have any thickness as long as it has a certain level of strength, but generally 10 to
It is about 500 μm.

The crosslinked cured layer 2 is one characteristic part of the present invention,
It is solid at room temperature in the uncured state, and has solvent solubility. When a solution of an organic solvent is applied and dried,
It is formed by cross-linking and curing an ionizing radiation-curable resin that gives a coating that is non-fluid and non-tacky when it is apparently or to the touch.

Such an ionizing radiation curable resin has a relatively high molecular weight, is a solid at room temperature in a state where it is not dissolved in a solvent, and has a polymerizable group, any conventionally known ionizing radiation curable resin. Although it can be used as a resin, the following two types are particularly preferable in the present invention from the viewpoints of curing speed, various physical properties of a crosslinked cured product, adhesion to other layers, and the like.

(I) A polymer having a glass transition temperature of 0 to 250 ° C. and having a radically polymerizable unsaturated group.

More specifically, as a polymer, a radically polymerizable unsaturated group is introduced by a method (a) to (d) described below with respect to a polymer obtained by polymerizing or copolymerizing the following monomers (1) to (8). Any thing can be used.

(1) Monomer having hydroxyl group: N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy. Propyl (meth) acrylate and the like.

(2) Monomer having carboxyl group: (meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate and the like.

(3) Epoxy group-containing monomer: Glycidyl (meth) acrylate and the like.

(4) Monomer having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate and the like.

(5) Monomer having amino group: (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like.

(6) Monomer having sulfonic acid group: 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like.

(7) Monomer having isocyanate group: Diisocyanate such as 1 mol to 1 mol adduct of 2,4-toluene diisocyanate and 2-hydroxyethyl (meth) acrylate and a monomer having a radically polymerizable unsaturated group having active hydrogen Additions etc.

(8) Further, in order to control the glass transition point of the above copolymer or the physical properties of the crosslinked cured film, the above monomer and the following monomer copolymerizable with this monomer are added. It can also be copolymerized.

Examples of such a copolymerizable monomer include, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, isobutyl (meth) acrylate, t-
Butyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-
Examples thereof include ethylhexyl (meth) acrylate.

Next, the polymer obtained as described above is reacted by the following methods (a) to (d) to introduce a radically polymerizable unsaturated group, whereby the crosslinked cured layer 2 of the present invention is obtained.
It is possible to obtain an ionizing radiation-curable resin useful for forming

(A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as (meth) acrylic acid is subjected to a condensation reaction.

(B) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfonic acid group, the above-mentioned monomer having a hydroxyl group is subjected to a condensation reaction.

(C) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or a monomer having a carboxyl group is subjected to an addition reaction.

(D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a 1: 1 ratio of a monomer having an epoxy group, a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester monomer A mole of the adduct is added.

In order to carry out the above reaction, it is preferable to add a trace amount of a polymerization inhibitor such as hydroquinone and to carry out the reaction while sending dry air.

(II) A relatively high molecular weight polymerizable compound having a melting point of 0 to 250 ° C. and a radically polymerizable unsaturated group.

Specific examples include stearyl (meth) acrylate, tri (meth) acrylic isocyanurate, cyclohexanediol di (meth) acrylate, spiroglycol di (meth) acrylate, and the like.

Further, in the present invention, the above-mentioned (I) and (II) may be mixed and used, and further, a reactive diluent having a radically polymerizable unsaturated group may be added thereto.

This reactive diluent having a radically polymerizable unsaturated group improves the crosslink density of the crosslinked cured product upon irradiation with ionizing radiation, and has various physical properties such as film strength, hardness, scratch resistance, stain resistance, and heat resistance. In addition to the above-mentioned monomers, ethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (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 (meth) acrylate, polypropylene glycol diglycidyl ether di (meth ) Acrylate, sorbitol tetraglycidyl ether tetra (meth) acrylate, etc. can be used 100 parts by weight of the solid content of the above-described ionizing radiation-curable resin, it is preferably used in an 0.1 parts by weight.

Further, although the above can be sufficiently cured by electron beam as it is, when cured by irradiation with ultraviolet rays, benzoquinone as a sensitizer, benzoin, benzoin ethers such as benzoin methyl ether, halogenated acetophenones, It is also possible to use those such as biacetyls that generate radicals by irradiation with ultraviolet rays.

In the present invention, a cured resin layer 2 which is transparent or colored and transparent from the ionizing radiation curable resin as described above on the release surface of the release sheet 1 (needs to be transparent in the embodiment of FIGS. 1 and 2). Do not form). Since these resins themselves are solid at room temperature, they are heated to a liquid state, or preferably in a highly volatile organic solvent, preferably with a solid content of 10%.
Dissolve in a concentration of about 60% by weight to prepare a coating solution, and apply it to the release surface of the release sheet by any coating method as described below, and evaporate and dry the solvent. Layer 2 that is solid at room temperature and is not tacky (uncured)
Is formed. The thickness of this layer 2 is not particularly limited and varies according to desired surface characteristics, but generally 0.5 to 100 μm.
About m is preferable.

The layer 2 thus formed is crosslinked and cured by a method described below to form the transfer sheet 10 of the present invention shown in FIG.
The transfer sheet 10 can be transferred as it is onto various articles and patterns to form a protective layer having excellent surface characteristics.

However, if the layer 2 is cured as it is, the curing of the layer 2 may be hindered by oxygen in the air if there is a time before curing, or it may be difficult to transfer to another article when a separate adhesive is not used at the time of transfer. In some cases, the protective layer 2 may be easily peeled off even after transfer, and when the pattern of the transfer sheet 10 shown in the first illustration is provided, the adhesion to the ink forming the pattern is insufficient. There are cases.

Such a point is that after the next thermoplastic resin layer 3 is formed on the layer 2, the uncured layer 2 is cross-linked and cured by irradiating with ionizing radiation from the thermoplastic resin layer 3 side or the release sheet 1 side. By doing so, the above problem can be solved.

In the second illustrated embodiment of the invention, layer 2 formed as described above.
The thermoplastic resin layer 3 is formed on the surface of the. The thermoplastic resin layer 3 may be provided after the cross-linking and curing of the layer 2, but it is preferable to provide it before the curing.
Of adhesiveness at the time of transferring, and further the cross-linking cured layer 2 and the pattern layer 4
It has the purpose of increasing the adhesiveness with and is preferably transparent or colored transparent like the cross-linked cured layer 2, but may be opaque in the embodiment of FIGS. 1 and 2.

As a material for forming the thermoplastic resin layer 3, a material having good adhesiveness to the material to be transferred or the pattern layer 4 is selected from various resins for an ink vehicle as described below and a resin for an adhesive described later. Can be used. However, since the ionizing radiation curable resin used for forming the crosslinked cured layer in the present invention is a resin mainly in the acrylic group, the most preferable resin for forming the thermoplastic resin layer 3 is an acrylic resin, An acrylic resin such as a thermoplastic acrylic resin such as a polymerized acrylic resin, an acrylic modified epoxy resin, an acrylic modified urethane resin, an acrylic modified polyester resin, a urethane modified acrylic resin or an epoxy modified acrylic resin is most suitable.

The thermoplastic resin layer 3 is formed by preparing a coating liquid or ink with the resin for the thermoplastic resin layer 3 as described above, and coating and drying the coating liquid or ink on the surface of the layer 2 (preferably before curing). The coating method and the drying may be the same as those in the prior art. The thickness of the thermoplastic resin layer 3 may be any thickness, but generally 0.5 to 20 μm is sufficient. When the layer 2 is in an uncured state, after the thermoplastic resin layer 3 is formed, the uncured cross-linked cured layer 2 can be cross-linked and cured by irradiation with ionizing radiation. Since the layer 2 is cross-linked and cured while the resin layer 3 is in contact with the layer 2, the thermoplastic resin layer 3
The cross-linked cured layer 2 is preferable because it can give a very excellent adhesiveness by being partially cross-linked or reacted between the layers.

Electron beams or ultraviolet rays are preferable as the ionizing radiation used for crosslinking and curing the layer 2, and the electron beams include Cockroft-Walton type, Van de Graaff type, resonant transformer type, insulating core transformer type, linear type, It is emitted from various electron beam accelerators such as dynamitron type and high frequency type,
An electron beam having an energy in the range of 1000 KeV, preferably 100 to 300 KeV is used, and as the ultraviolet ray, an ultraviolet ray using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp. Use what comes from the source.

By further providing the pattern layer 4, the concealing layer 5, and the adhesive layer 6 on the thermoplastic resin layer 3, the transfer sheet 10 of the present invention shown in FIGS. 3 to 6 can be formed. Each of these layers can be formed by using the same ordinary ink and paint as those used in the conventional ordinary transfer sheet.

Usual inks and paints used for forming the pattern layer 4 are those obtained by kneading a vehicle with a colorant such as a pigment or a dye, a plasticizer, a stabilizer, other additives, a solvent or a diluent. As the vehicle, for example, ethyl cellulose, ethyl hydroxyethyl cellulose,
Cellulose acetate propionate, cellulose derivatives such as cellulose acetate, polystyrene, styrene resin such as poly α-methylstyrene and styrene copolymer resin, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc. , Acrylic or methacrylic resin homopolymer or copolymer resin, rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin, coumarone resin, vinyltoluene resin, vinyl chloride resin, polyester One or more of resins, polyurethane resins, butyral resins, shellac, gum arabic, acaloids, mastics, etc. are selected and used.

Further, these pattern layers 4 are not limited to the above-mentioned printed patterns, and may be patterns composed of a vapor deposition layer of a metal such as aluminum, tin, gold, silver and copper having an arbitrary thickness, and these metal vapor deposition layers and the above Any combination of patterns, characters, symbols and the like used in the conventional transfer sheet, such as a combination with a printed pattern, is not particularly limited.

As the ink or paint used to form the concealing layer 5, it is preferable to use the above-mentioned ordinary ink or paint prepared by adding and kneading titanium white, rouge and the like having particularly high concealing properties.

The adhesive layer 6 may be formed of any adhesive, but it is preferable to form the adhesive layer 6 from a heat-sensitive adhesive that has a relatively high softening point and is not tacky at room temperature and exhibits tackiness when heated. .

As a preferable heat-sensitive adhesive for forming the adhesive layer 6,
Any of the adhesives used in conventionally known thermal transfer sheets can be used. For example, rubber resins such as polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, and (meth) acrylate resin Adhesion of any of polyvinyl ether resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, polystyrene resin, polyester resin, polyamide resin, polychlorinated olefin resin, polyvinyl butyral resin, etc. Agents, and if necessary, various additives such as a tackifier, a softener, a filler, an antioxidant and the like.

The layers 2, 3, 4, 5 and 6 are formed by printing the solution of the ionizing radiation-curable resin, ink or paint as described above with a printing method such as gravure, offset gravure or silk screen, or roll coating or gravure coating. It can be appropriately provided by coating by a coating method such as the above and drying if necessary.

Next, the transfer method using the transfer sheet 10 of the present invention will be described. As the transfer method itself, various known methods can be appropriately selected and used. Examples of the transfer method include (a) thermocompression bonding of the crosslinked cured layer 2 of the transfer sheet 10 (in some cases, the thermoplastic resin layer 3, the pattern layer 4, the hiding layer 5 or the adhesive layer 6) to the transfer target. And (b) a thermal transfer method for transferring the cross-linked cured layer 2 (or the layer formed on the layer 2), (b) activation of a solvent or a solvent solution of a resin between the transfer sheet 10 and the transfer target. An example is a solvent-activated transfer method that is performed with a liquid interposed.

In the transfer method described above, the crosslinked cured layer 2 is a thermal transfer sheet.
Since it has already been cross-linked and cured in any step of the preparation step of 10, the cross-linked cured layer 2 of the transfer sheet 10 (thermoplastic resin layer 3, pattern layer 4 depending on the transfer sheet 10) is formed on the transfer surface of the transfer body. , The concealing layer 5 or the adhesive layer 6) are brought into contact with each other, and the transfer is performed as described above.
Can be peeled off.

For example, the following materials can be used as the transferred material when transferring using the transfer sheet 10 of the present invention.

Bleached kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, polycarbonate,
Nylon, polystyrene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, plastic film or sheet of ionomer, wood, plywood,
Wood base material such as particle board, gypsum board such as gypsum board and gypsum slag board, fiber cement board such as pulp cement board, asbestos cement board, wood chip cement board, metal foil such as GRC and concrete, iron, aluminum, copper Alternatively, a sheet, a composite of the above base materials, and the like.

Further, various molded products can also be used as the transferred material, and as the material of the molded product, the following materials can be exemplified although they overlap with the above-mentioned base material.

AAS resin, ABS resin, ACS resin, amino resin, cellulose acetate, cellulose butyrate, cellulose resins such as ethyl cellulose, allyl resin, ethylene-α-olefin copolymer, ethylene-vinyl acetate-vinyl chloride copolymer,
Ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer, MBS resin, methacryl-styrene copolymer, nitrile resin, phenol resin, polyamide resin, polyarylate resin, polycarbonate resin, polybutadiene resin, polybutylene terephthalate Resin, polyethylene resin, polyethylene terephthalate resin, polypropylene resin, polyphenylene oxide resin, polystyrene resin, AS resin, polyurethane resin, polyvinyl chloride resin, acrylic modified polyvinyl chloride resin,
Plastic moldings such as unsaturated polyester resin, iron,
Extruded products of metals such as aluminum, copper and stainless steel.

If necessary, the transfer surface of these transfer members may be subjected to pretreatment or the like according to the material of the transfer member surface.
Pretreatment for improving adhesiveness such as primer treatment and corona treatment, adjustment of base color by painting or the like, sealing treatment, and alkali leaching prevention treatment for alkaline base materials such as cement.

(Operation / Effect) According to the present invention as described above, the following operation / effect is achieved.

(1) Since a layer that has been crosslinked and cured in advance is transferably formed on the release sheet 1, when a protective layer is formed on various articles as in the prior art, a coating process or a curing process of a liquid coating material. Is unnecessary, and a protective layer having excellent scratch resistance and stain resistance can be easily provided on any article or pattern anytime and anywhere. Further, in a preferred embodiment, the thermoplastic resin layer 3 is formed on the layer 2, so that transfer and adhesion to other articles are easy. Further, by curing the layer 2 after forming the layer 3, the adhesiveness between the layer 2 and the layer 3 or the pattern layer 4 is improved.

(2) When the transfer sheet 10 is formed, the crosslinked cured layer 2 is solid even in an uncured state and has no tackiness, so that the next layer can be continuously formed as it is, which is advantageous in the manufacturing process. .

(3) A conventional transfer sheet having a crosslinked cured layer formed of an ionizing radiation curable resin has various problems due to poor adhesion to a picture layer formed thereon, but the transfer of a preferred embodiment of the present invention In the sheet 10, the thermoplastic resin layer 3 is formed between the crosslinked cured layer 2 and the pattern layer 4, and this layer acts as a primer layer. Therefore, when the pattern layer 4 is formed thereon, the crosslinked cured layer is formed. The adhesiveness between 2 and the pattern layer 4 was sufficiently improved.

(4) Further, in the uncured state of the crosslinked cured layer 2, the thermoplastic resin layer 3 is formed thereon, and then the crosslinked cured layer 2 is cured, whereby the curability of the layer 2 and the crosslinked cured layer 2 are improved. The adhesiveness with the thermoplastic resin layer 3, that is, the adhesiveness with the pattern layer 4 was significantly improved.

As described above, according to the present invention, a very high surface property, that is, the crosslinked cured layer 2 having excellent scratch resistance, solvent resistance, stain resistance, etc. can be transferred onto any article or pattern,
Further, by forming the pattern layer 4, the transfer image having the above surface characteristics can be easily transferred onto an arbitrary article.

 Next, the present invention will be described more specifically with reference to examples.

Example 1 A 25 μm-thick polyethylene terephthalate film (Lumirror T60 manufactured by Toray) was used as a releasable seal 1, and a melamine acrylate UV curable resin (manufactured by Mitsubishi Yuka Fine, Yupimer LZ-07) was used on one side of this film.
5) was dissolved in methyl ethyl keto to a solid content of 40% by weight and applied by a gravure coating method, and dried with hot air at 100 ° C. to form an uncured layer 2 having a thickness of 5 μm. This layer 2 was solid at room temperature and did not exhibit tackiness.

Then, place the sheet under a high pressure mercury lamp (160 W / cm) for 5 mm
The layer 2 was sufficiently crosslinked and cured at a speed of / min. 10 times to obtain a transfer sheet 10 (first illustrated) of the present invention.

Using the transfer sheet 10 of the present invention obtained above, a decorative acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd.) having a 1.5 μm adhesive layer formed on the surface of the transfer sheet 10 on the side of the crosslinkable resin 2 And a pressure-sensitive rubber roller having a surface temperature of 200 ° C., and the release sheet was peeled off.

The surface of the decorative acrylic resin plate thus obtained does not change even after rubbing 50 times with a cotton cloth impregnated with methyl ethyl ketone, and the scratch resistance, solvent resistance and stain resistance are extremely excellent. Further, there was no possibility that the crosslinked cured layer 2 would be delaminated from the decorative surface.

Example 2 An acrylic resin coating material (GG, manufactured by Showa Ink Co., Ltd.) was further applied to the surface of the layer 2 before crosslinking and curing in Example 1 and dried to form a thermoplastic resin layer 3 having a thickness of 2 μm.

Then, the sheet was passed under a high pressure mercury lamp (160 W / cm) 10 times at a speed of 5 mm / min.
Was sufficiently crosslinked and cured to obtain a transfer sheet 10 (second shown) of the present invention.

Using the transfer sheet 10 of the present invention obtained above, the thermoplastic resin layer 3 side of the transfer sheet 10 and the decorative surface of a decorative acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd.) are overlapped, and the surface temperature is 200 ° C.
The release sheet was peeled off by pressing with a heating rubber roller.

The surface of the decorative surface of the thus-prepared decorative acrylic resin plate did not change even after rubbing 50 times with a cotton cloth impregnated with methyl ethyl ketone, and its scratch resistance, solvent resistance, and stain resistance were outstanding. It was excellent, and there was no risk of delamination of the crosslinked cured layer 2 from the decorative surface.

Example 3 On the surface of the transfer sheet 10 of Example 2, a gravure ink using an acrylic resin as a vehicle (Showa Ink, TACS)
Is used to print the pattern layer 4 by a silk screen method, and the same white ink (containing titanium white) is mainly used to form a concealing layer 5. On the concealing layer 5, an acrylic heat-sensitive adhesive (Showa Ink) is used. R-5) was applied over the entire surface to form an adhesive layer 6 having a thickness of 10 μm to obtain a transfer sheet 10 (sixth illustration) of the present invention.

Using the transfer sheet 10 of the present invention obtained above, the adhesive layer 6 side of the transfer sheet 10 and an acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd.) are overlaid, and pressure-bonded with a heating rubber roller having a surface temperature of 200 ° C. The sex seal was peeled off.

The surface of the pattern layer 4 of the thus-obtained decorative acrylic resin plate does not change even after being rubbed 50 times with a cotton cloth impregnated with methyl ethyl ketone, and has no scratch resistance, solvent resistance or stain resistance. It was remarkably excellent, and there was no risk of delamination of the crosslinked cured layer 2 from the pattern layer 4.

Example 4 A release sheet 1 was obtained by extrusion-coating a thin paper (basis weight: 30 g / m ² ) with a polyethylene resin on one side thereof to a thickness of 30 μm.

An ultraviolet curable resin (made by Mitsubishi Yuka Fine, triazine acrylate, LZ) is applied to the release surface of the release sheet 1 described above.
-075) methyl ethyl ketone / cyclohexanone = 2/1
(Weight ratio) Gravure coating the solution to a thickness of 5 μm
Layer 2 of was formed.

Epoxy-modified acrylic resin coating (solid content on layer 2)
35%) was applied and dried to form a thermoplastic resin layer 3 having a thickness of 5 μm.

Then, using a high pressure mercury lamp (80 W / cm), the layer 2 was irradiated with ultraviolet rays for 2 seconds to crosslink and cure the layer 2.

Next, the picture layer 4 is gravure-printed using a gravure ink for vinyl chloride printing using a vinyl chloride / vinyl acetate copolymer resin as a vehicle, and a pattern of joint tiles is printed to transfer the transfer sheet 10 of the present invention (shown in FIG. 3). And

On the other hand, as an object to be transferred, prepare an asbestos slate plate on the surface of which the joints of tiles have been previously formed on the surface by pressing using a metal mold, and apply a polyurethane sealer on the surface to carry out alkali exudation prevention treatment and base masking It was

The pattern surface 4 of the transfer sheet 10 of the present invention obtained above was brought into contact with the treated surface of the treated asbestos slate plate, and the temperature was adjusted to 14
Pressed by a flatbed press under the conditions of 0 ° C., pressure of 20 kg / cm ² and pressure time of 2 minutes to transfer the pattern layer, the thermoplastic resin layer 3 and the crosslinked cured layer 2, and then the release sheet 1 was peeled and removed. .

The decorative asbestos slate plate thus obtained has excellent scratch resistance, solvent resistance and stain resistance on the surface of the pattern layer 4, and
The joint portion is mat-like, while the tile portion has a gloss-like surface condition, and the cross-linked cured layer 2
There was no possibility of delamination from the pattern layer 4.

Example 5 The same transfer sheet 10 as that used in Example 4 was used as the transfer sheet 10 (however, the layer 2 was crosslinked by electron beam irradiation of 150 Kev, 15 mA and 5 Mrad in a nitrogen atmosphere after the formation of the thermoplastic resin layer 3). (Cured) was prepared.

An unplasticized polyvinyl chloride extruded product in which voids are filled with a foamed polyurethane resin is prepared as a transfer target, and the activation liquid having the following composition is wetted on the surface of the pattern layer 4 of the transfer sheet 10 by a roll coating method. The application amount of 5 g / m ² is applied, and immediately after application, the activation liquid application surface of the transfer sheet 10 is aligned with the surface of the molded product, and the linear pressure is applied by a rubber roll.
Pressurization was applied under the condition of 2 Kg / cm, and the release sheet 1 was peeled off after pressurization.

Composition of activating liquid Polyvinyl chloride resin 15 parts by weight Acrylic resin 5 parts by weight Ethyl acetate 60 parts by weight Toluene 10 parts by weight Methyl ethyl ketone 10 parts by weight The cosmetic molding thus obtained has very excellent scratch resistance and stain resistance on the surface. It was excellent, and there was no fear of delamination between the crosslinked cured layer 2 and the pattern layer 4.

[Brief description of drawings]

1 to 6 are all diagrams schematically showing a cross section of the transfer sheet 10 of the present invention. 1 ... Releasable sheet 2 ... Cross-linking cured layer 3 ... Thermoplastic resin layer 4 ... Picture layer 5 ... Hiding layer 6 ... Adhesive layer 10 ... Transfer sheet

Claims (1)

[Claims] 1. A crosslinked cured layer of an ionizing radiation curable resin which is solid at room temperature in an uncured state on the release surface of a release sheet.
A transfer sheet comprising a thermoplastic resin layer, a pattern layer, a hiding layer and an adhesive layer, which are sequentially laminated.