JPH11309998A - Manufacture of decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To transfer a resin transfer layer to become a hard surface protective layer or the like and a design transfer layer to a base material only by one step. SOLUTION: The method for manufacturing a decorative material comprises the steps of transferring a design transfer layer 4 from a design transfer sheet S2 having at least a design layer 5 as a desing transfer layer 4 on a releasable support sheet 1a to an intermediate sheet S1 having a resin transfer layer 2 made of an uncured material of thermoplastic ionizing radiation curable resin of a non-flowing state at the ambient temperature in an uncured state on a releasable support sheet 1 to a surface of the layer 2 to an integral transfer sheet S, then transferring the layer 2 and the layer 4 to a base material at the integral transfer sheet, and then emitting an ionizing radioactive ray to crosslink to cure the layer 2 to the decorative material D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative material used for exterior and interior materials of a house, furniture, home electric appliances and the like. Specifically, the present invention relates to a method for producing a decorative material such as an inorganic decorative plate having a resin layer serving as a surface protective layer or the like.

[0002]

2. Description of the Related Art Conventionally, various decorative materials such as decorative boards have been manufactured by decoration using a transfer method to a substrate. And, in order to improve surface physical properties such as scratch resistance, for example, a surface protective layer made of a hard resin layer, etc.
It is provided by the following method. A method of forming a decorative layer that also serves as a surface protective layer by spray-coating an ultraviolet-curable resin paint on a base material to form a decorative material. Alternatively, a method in which a pattern layer is formed on a substrate by a transfer method or the like, and a surface protective layer is further formed thereon with an ultraviolet-curable resin paint or the like. Alternatively, as described in Japanese Patent Publication No. 5-57120,
As a transfer layer on a release support sheet, a protective layer consisting of an uncured resin layer of a non-adhesive solid UV curable resin or an electron beam curable resin at room temperature even in an uncured state, and a transfer sheet having a picture layer And transferring the protective layer and the picture layer to the base material, and then irradiating ultraviolet rays or electron beams to crosslink and cure the transferred protective layer.

[0003]

However, in the above method, since the spray coating is used, there are many coating defects such as unevenness and omission, and the productivity is inferior. In addition, 1
Although surface makeup only by color is possible, it is impossible to make a picture with a pattern, and a cosmetic material with an excellent design feeling cannot be obtained. In addition, the above method requires two steps, such as a pattern transfer step and a surface protection layer coating step, so that the working efficiency is inferior. Further, in the above method, in order to increase the crosslink density of the cured coating film in order to improve the surface properties such as the hardness after curing of the protective layer, it is generally necessary to use a low molecular weight monomer as a main component. However, in such a case, the solvent resistance of the uncured protective layer becomes insufficient, and when printed thereon, the protective layer dissolves and swells with the solvent in the printing ink,
The pattern layer cannot be printed on the uncured resin layer because the protective layer made of the uncured resin layer is adhered to the plate side at room temperature. For this reason, when the surface protective layer and the picture layer were simultaneously transferred to the substrate in one step, a material having excellent surface properties could not be obtained as the surface protective layer.

[0004]

In order to solve the above-mentioned problems, a method for producing a decorative material according to the present invention comprises the steps of: providing a first release support sheet on an uncured state at room temperature in a non-flowable state; And, for an intermediate sheet having a resin transfer layer made of an uncured material of a thermoplastic ionizing radiation-curable resin, at least a picture layer as a picture transfer layer on a second release support sheet. By transferring the pattern transfer layer to the resin transfer layer surface using a pattern transfer sheet having a resin transfer layer and a pattern transfer layer on the first release support sheet, in this order. After the integrated transfer sheet is laminated, the resin transfer layer and the pattern transfer layer are transferred to the substrate using the integrated transfer sheet, and then the resin transfer layer transferred and irradiated with ionizing radiation is cross-linked and cured. Let's make it a cosmetic material. As a result, the resin transfer layer serving as a surface protective layer and the picture transfer layer can be simultaneously transferred to the base material in one step to produce a decorative material, thereby improving the working efficiency. Moreover, the resin transfer layer serving as a surface protective layer and the like, in order to have a high cross-linking density, poor solvent resistance, also tends to stick at room temperature when uncured, even when using a large amount of low molecular weight monomers, Since the formation of the picture transfer layer on the (integral type) transfer sheet is performed by a transfer method instead of direct printing, the picture can be formed on the resin transfer layer without any problem.

[0005] In the above-mentioned production method, a thermoplastic acrylic resin having no polymerizable unsaturated group and a monomer having a polymerizable unsaturated group may be further used as the main components of the ionizing radiation-curable resin of the resin transfer layer. And / or by using a prepolymer, after the transfer, the crosslinked and cured resin transfer layer,
In addition to the surface properties such as abrasion, it gives a moderate flexibility to give a tough surface which is hard to crack. Even when the uncured resin transfer layer in the intermediate sheet contains many monomer components and becomes liquid or sticky, it can be adjusted to a non-adhesive non-flowable state.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the method for producing a decorative material according to the present invention will be described below.

[Outline] FIG. 1 is an explanatory view conceptually illustrating a method of manufacturing a decorative material according to the present invention. First, FIG. 1A is a cross-sectional view illustrating a configuration of the intermediate sheet. Intermediate sheet S1
Is basically a configuration in which an uncured resin transfer layer 2 made of the above-described specific material is laminated as a transfer layer on a first release support sheet 1. When the resin transfer layer 2 has an adhesive property and the handling is hindered, as shown in the intermediate sheet S1a on the left side of FIG. When the layer is transferred, the separator 3 is peeled off and the intermediate sheet S
1 may be used. Picture transfer sheet S2
FIG. 1B shows a configuration in which at least a picture layer 5 is laminated as a picture transfer layer 4 on a second release support sheet 1a as exemplified in the cross-sectional view of FIG. In the case of (1), a primer layer 6 for improving the adhesion between the pattern layer and the resin transfer layer 2 is provided on the pattern layer 5 as a part of the pattern transfer layer. The second in the picture transfer sheet S2
The releasable support sheet 1a is separate from the first releasable support sheet 1 of the intermediate sheet S1, but a sheet of the same material may of course be used.

[0008] In the method for producing a decorative material according to the present invention,
The pattern transfer layer 4 including the pattern layer 5 is transferred from the pattern transfer sheet S2 to the surface of the resin transfer layer 2 of the intermediate sheet S1 (or the sheet after the separator of the intermediate sheet S1a), and FIG. ) Is an integrated transfer sheet S as shown in FIG. Since the transfer in this case is both sheet-like, for example, as shown in FIG. 1 (C), as a roller transfer method, the intermediate sheet S1 and the picture transfer sheet S2 pass between two appropriately heated rollers. If S1 and S2 are adhered so that the transfer layer side faces each other, and then only the second release support sheet 1a is peeled off, it can be performed continuously. The releasable support sheet 1 in the obtained integrated transfer sheet S is the first releasable support sheet 1 used for the intermediate sheet S1 or S1a. In this way, as shown in FIG. 1 (D), the integrated transfer sheet S is formed on the first release support sheet 1 with the resin transfer layer 2 and the picture transfer layer 4 (in this case, the primer layer 6). And a pattern layer 5) are laminated in this order.

Then, when the transfer material is transferred to the base material B using the integrated transfer sheet S and then irradiated with ionizing radiation, the decorative material D as illustrated in FIG. 1E can be obtained in one step. The configuration of the decorative material D illustrated in the figure includes a base material B, a pattern transfer layer 4 (a pattern layer 5 and a primer layer 6 on the base material B side) and a resin transfer layer 2 as a surface layer in order from the base material side. It becomes a laminated structure. The resin transfer layer is used not only as a surface protective layer for protecting the surface and improving surface properties such as scratch resistance and water resistance, but also as a functional layer for forming a design feeling such as a coating feeling by transfer. When the pattern transfer layer itself does not work as an adhesive layer at the time of transfer, an adhesive layer is provided on the substrate side to transfer.

[0010] The resin constituting the resin transfer layer is
In the uncured state is a non-fluid state at normal temperature, and, as an uncured product of a thermoplastic ionizing radiation-curable resin,
Its main component is composed of a thermoplastic acrylic resin having no polymerizable unsaturated group and a monomer and / or prepolymer having a polymerizable unsaturated group, so that the surface properties are excellent. It is preferable to improve it. By having a configuration having a thermoplastic acrylic resin having no polymerizable unsaturated group, the resin transfer layer after crosslinking and curing, in addition to surface properties such as abrasion, moderate flexibility can be obtained, Be tough.
Further, even when a large amount of a monomer component is added to the resin of the resin transfer layer at the time of uncuring to become liquid or sticky, it can be adjusted to a non-adhesive and non-flowable state.

[Releaseable Support Sheet] A releasable support sheet 1 used as an intermediate sheet (a sheet that becomes the releasable support sheet 1 of an integrated transfer sheet) and a releasable support sheet used for a picture transfer sheet As 1a, the same sheet may be used, or different sheets may be used. The release support sheets 1 and 1a are not particularly limited, and various types of conventionally known sheets may be used as general transfer sheets according to the intended use. For example, the resin in the case of a resin sheet (film) includes polyolefin resins such as polypropylene, polyethylene, and olefin-based thermoplastic elastomers; thermoplastic polyesters such as polyethylene terephthalate, ethylene terephthalate / isophthalate copolymer polyester, and polybutylene terephthalate. Resin, vinyl chloride resin and the like are used. In addition to the resin sheet, paper subjected to a release treatment or the like is also used. In particular, a laminate obtained by laminating a polyolefin resin such as polypropylene as a release layer on a high-quality paper as a release treatment is preferable in terms of excellent transferability and low cost.
The thickness of the release support sheet is usually about 20 to 200 μm.

If necessary, the release support sheet may be provided with a release layer as a component of the support in order to improve the releasability from the transfer layer on the transfer layer side as described above. good.
Further, in order to adjust the releasability, the surface of the releasable support sheet on the transfer layer side may be subjected to corona treatment, ozone treatment, or the like.
In the case of the releasable support sheet used for the intermediate sheet, if an irregular pattern is provided on the surface on the transfer layer side, an irregular pattern such as grain, pear, wood grain can be formed on the surface of the decorative material. The uneven pattern is formed by a known method such as embossing.

[Resin Transfer Layer] The resin transfer layer 2 in the intermediate sheet and the integrated transfer sheet is in a non-flowing state at room temperature in an uncured state, and is not formed of a thermoplastic ionizing radiation-curable resin. It is configured as a layer made of a cured product. Uncured is a state before complete curing. Here, the ionizing radiation is not particularly limited as long as it has an energy capable of crosslinking and polymerizing the molecule, but usually, an ultraviolet ray or an electron beam is used. Such a resin is a resin having a polymerizable unsaturated group such as a radical polymerizable group or a cationic polymerizable functional group. Examples of the polymerizable unsaturated group include a (meth) acryloyl group and a (meth) acryloyloxy group,
Moreover, an epoxy group etc. are mentioned as a cationic polymerizable functional group. For example, the following resin (composition) can be used. The “normal temperature” in the present invention refers to an indoor (or outdoor) room where the resin layer transfer sheet and the integrated transfer sheet are manufactured and stored, and the release support sheet of the integrated transfer sheet is peeled off. Means ambient temperature. The specific value is
Depending on the climate and working environment, it is usually in the range of 10 to 40C, more usually in the range of 15 to 25C. or,
Room temperature is also the lowest temperature at which the support is peeled off. Also,
The non-fluid state referred to in the present invention includes both an adhesive (agent) state and a touch-dry state (non-adhesive state).

(I) having a radically polymerizable unsaturated group,
The following two types of resins (prepolymers) of thermoplasticity (1) or (2). (1) Those having a radical polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C. More specifically, a polymer obtained by polymerizing or copolymerizing the following can be used by introducing a radical polymerizable unsaturated group by methods (a) to (d) described below. In the following, for example, (meth) acrylate is used to mean acrylate or methacrylate. A monomer having a hydroxyl group; N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. Monomers having a carboxyl group; (meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate and the like. Monomers having an epoxy group; glycidyl (meth) acrylate and the like. Monomers having an aziridinyl group; 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, and the like. Monomer having an amino group; (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like. A monomer having a sulfone group; 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like. A monomer having an isocyanate group; an adduct of a diisocyanate and a radical polymerizable monomer having active hydrogen, such as an adduct of 1 to 1 mol of 2,4-toluene diisocyanate and 2-hydroxyethyl (meth) acrylate; A monomer copolymerizable with the above-mentioned monomers and other than the above-mentioned monomers; this monomer is used as a copolymer component for controlling the glass transition temperature and physical properties of the obtained copolymer.
For example, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate,
Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

Next, the polymer or copolymer obtained as described above is reacted by the following methods (a) to (d) to introduce a radical polymerizable unsaturated group. (a) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as the aforementioned (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 sulfone 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 the above-described 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, the monomer having the epoxy group or the monomer having the aziridinyl or the diisocyanate compound and the hydroxyl group-containing acrylate monomer A monomer having an isocyanate group such as 1 mole to 1 mole of an adduct is
Addition reaction is performed. In order to carry out the above reaction, it is desirable to add a trace amount of a polymerization inhibitor such as hydroquinone and to carry out the reaction while sending dry air.

(2) A compound having a melting point of 20 ° C. to 250 ° C. and having a radically polymerizable unsaturated group. Specific examples include stearyl (meth) acrylate, triacryl isocyanurate, cyclohexanediol di (meth) acrylate, spiroglycol diacrylate, spiroglycol (meth) acrylate, and the like.

Further, the above (1) and (2) can be used as a mixture. Furthermore, the above (1) or (2), or (1) and
A radical polymerizable monomer can be added as a reactive diluent to the mixture of (2). This radical polymerizable monomer increases the crosslink density by irradiation with ionizing radiation such as ultraviolet rays or electron beams, and improves heat resistance. As the monomer, for example, in addition to the above-mentioned monomers,
Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (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 Rate, and sorbitol tetraglycidyl ether tetra (meth) acrylate can be used. The amount is 0.1 to 100 parts by weight of the resin (1) or (2) alone or as a mixture with respect to 100 parts by weight of the resin.
It is preferably used in parts by weight.

(II) Alternatively, a monomer and / or prepolymer having a radically polymerizable unsaturated group and a thermoplastic acrylic resin having no polymerizable unsaturated group as main components. Here, as the monomer,
The compounds listed in the above (I) are used, and as the prepolymer, radicals such as polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, silicone (meth) acrylate and the like are used. A prepolymer having a polymerizable unsaturated group is used. Incidentally, as the prepolymer, a prepolymer having a cationically polymerizable functional group,
For example, bisphenol-type epoxy resin, novolak-type epoxy resin, vinyl ether-based resin and the like can be used.
The molecular weight of the prepolymer is from 250 to 100,00
Use something about 0. In addition, a monomer and / or a prepolymer mean any of a monomer and a prepolymer, a monomer, and a prepolymer.

By adding a thermoplastic acrylic resin having no polymerizable unsaturated group as a non-crosslinkable resin, after the transfer, the crosslinked and cured resin transfer layer has an appropriate surface property such as abrasion resistance and the like. To provide a tough surface that is less prone to cracking. Even when the uncured resin transfer layer in the intermediate sheet contains many monomer components and becomes liquid or sticky, it can be adjusted to a non-adhesive non-flowable state. The acrylic resin includes, as monomers, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth)
Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate , Alkyl (meth) acrylates such as lauryl (meth) acrylate, 2-chloroethyl (meth) acrylate, (meth)
Alkyl (meth) acrylates such as 3-chloropropyl acrylate, 2-hydroxyethyl (meth) acrylate, and (meth) acrylates having a hydroxyl group such as 2-hydroxypropyl (meth) acrylate ,
halogenated (meth) acrylates such as methyl α-chloro (meth) acrylate, ethyl α-chloro (meth) acrylate, (meth) acrylic acid-1-chloro-2-
An α-alkyl (meth) acrylate having a hydroxyl group such as hydroxyethyl and a (meth) acrylic monomer such as glycidyl (meth) acrylate are used, and the acrylic resin is one or more of the above. Or a homopolymer or copolymer consisting of

In addition, these acrylic resins are particularly non-adhesive to the resin transfer layer in a non-flowing state when not cured (ie,
In the case of a dry state to the touch, the average molecular weight is 50,000.
0-600,000 and a glass transition temperature of 50-130.
C, preferably 80 to 110C. When the average molecular weight is less than 50,000, the abrasion resistance of the resin transfer layer after crosslinking and curing is extremely reduced. On the other hand, when the average molecular weight exceeds 600,000, the resin transfer layer becomes difficult to stretch at the time of transfer.
Cracks are easily generated in the resin transfer layer. When the glass transition temperature is lower than 50 ° C., the abrasion resistance of the resin transfer layer after crosslinking and curing is extremely reduced. On the other hand, when the glass transition temperature is 13
When the temperature exceeds 0 ° C., the resin transfer layer at the time of transfer becomes difficult to elongate.

In the case of an ultraviolet curable resin cured by ultraviolet light, a known photopolymerization initiator is further added to the above resin. As the photopolymerization initiator, in the case of a radical polymerization type resin, acetophenones, benzophenones, and thioxanthones are used alone or in combination. In the case of a cationic polymerization type resin, an aromatic diazonium salt, an aromatic iodonium salt, a metallocene, or the like is used alone or in combination.

In the above ionizing radiation curable resin,
Furthermore, various additives can be added as needed. As these additives, for example, extenders (fillers) composed of fine powders such as calcium carbonate, barium sulfate, silica, and alumina, waxes, resin beads, dyes,
Coloring agents such as pigments;

In order to form such a resin transfer layer composed of an uncured ionizing radiation-curable resin on the first release support sheet, a resin-free resin composition melt or A solution diluted with a solvent may be applied by a conventionally known coating method. Examples of the coating method include gravure coat, gravure reverse coat, roll coat, reverse roll coat, knife coat, wire bar coat, flow coat, comma coat and the like. The thickness of the resin transfer layer depends on the application, but is usually about 1 to 100 μm.

[Separator] Separator (release sheet)
3 is not particularly limited, and a conventionally known one can be used. For example, a resin film such as a biaxially stretched polyethylene terephthalate film, paper, or the like as a base material, and the surface of which is subjected to release treatment by coating with a silicone resin, polymethylpentene, or the like can be used. The thickness is usually about 50 to 200 μm.

[Picture Transfer Layer] The pattern transfer layer 4 comprises at least a picture layer 5. Further, in addition to the picture layer, as described above, a primer layer or a release layer may be a component of the picture transfer layer.

(Pattern Layer) The pattern layer 5 may be a conventionally known one and is not particularly limited. For example, when a picture layer is formed by printing, as a resin used as a binder of the ink for forming the picture layer, alkyd resin, urethane resin, vinyl chloride-vinyl acetate copolymer, acrylic resin such as acrylic polyol, polyester resin, etc. Is used alone or as a mixture. Further, as the pigment used for the colorant of the ink, for example,
Inorganic pigments such as titanium white, carbon black, red iron oxide, graphite, and ultramarine blue, and organic pigments such as aniline black, quinacridone, isoindolinone, and phthalocyanine blue are used.
The printing method may be a known means such as gravure printing, silk screen printing, offset printing and the like. In addition, the pattern of the pattern layer is a wood grain pattern, a stone grain pattern, a cloth grain pattern, a tile pattern, a brick pattern, a leather pattern, a character, a geometric pattern, a solid pattern, or the like.

(Primer Layer) The primer layer 6 is provided on the pattern transfer sheet so as to be between the resin transfer layer and the pattern layer, if necessary, in order to improve the adhesion between the resin transfer layer and the pattern layer. If it is provided on the pattern transfer sheet side, a primer layer can be used even if the resin transfer layer on the intermediate sheet has adhesiveness. As such a primer layer, 2
Liquid-curable resins are preferred. A urethane resin or the like is used as the two-component curable resin. Acrylic polyol or the like is used as a main component of the urethane resin. Specifically, an acrylic polyol composed of a copolymer or the like containing methyl methacrylate and β-hydroxyethyl methacrylate as main components is a preferable main agent. On the other hand, as the isocyanate, non-yellowing isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate are preferable from the viewpoint of weather resistance. In the case where the resin transfer layer on the intermediate sheet has no tackiness or the like, a primer layer may be provided on the resin transfer layer of the intermediate sheet, and finally the same can be achieved in the configuration of the integrated transfer sheet. . The primer layer is formed by a known printing method or coating method similarly to the picture layer.

(Release Layer) The release layer is a layer provided on the second releasable support sheet 1a side of the pattern transfer layer in the pattern transfer sheet. In the final integrated transfer sheet,
This is the outermost layer of the transfer layer of the transfer sheet. Therefore, when the adhesive layer is not provided on the base material side and the picture layer itself does not become the adhesive layer, the adhesive layer is also used as a heat-sealing adhesive layer to the base material, and is provided as necessary. Further, the release layer is interposed between the pattern transfer layer and the second release support sheet in the pattern transfer sheet, and is also used for adjusting the releasability of these pattern transfer layers. As the release layer, a non-adhesive solid resin at normal temperature, for example, a thermoplastic acrylic resin, vinyl chloride-
A simple substance such as a vinyl acetate copolymer, a thermoplastic polyester resin, or a cellulose resin, or a mixture of two or more thereof is used. The release layer is formed by a known printing method or coating method similarly to the pattern layer.

[Transfer from Picture Transfer Sheet to Intermediate Sheet] The transfer method for transferring the picture transfer layer 4 from the picture transfer sheet S2 to the resin transfer layer 2 of the intermediate sheet S1 is not particularly limited. What is necessary is just to carry out by the conventionally well-known transfer method. In terms of productivity, since both sheets are usually processed in a continuous belt shape, a roller transfer method in which pressure is applied by two rollers as exemplified in FIG. 1C is preferable. These rollers are made of metal or have a metal core covered with rubber. Further, if necessary, it is used by heating to an appropriate temperature.

[Substrate] The material of the substrate B, which is the object to be transferred, is not particularly limited. For example, asbestos cement, asbestos calcium silicate, gypsum, calcium silicate, wood chip cement, A
Non-ceramic ceramics-based inorganics such as LC (lightweight foamed concrete), GRC (glass fiber reinforced concrete), other inorganics such as ceramics such as ceramics and glass, metals such as iron, stainless steel, and aluminum; Wood materials such as wood plywood, particle board, laminated wood, medium-density fiberboard (MDF), or resins such as polypropylene, vinyl chloride resin, and ABS resin can be used. The shape of the substrate is a plate, a sheet, a three-dimensional object, or the like.

A base coat layer is provided on the transfer surface of the base material as necessary. The base coat layer prevents the bleeding of an alkali component (in the case of an alkaline substrate) from the inside of the substrate, and prevents irregularities and holes on the surface of the substrate, etc. It is provided to impart surface properties suitable for transferability to the substrate. As the resin for forming the base coat layer, a two-component curable urethane resin, a one-component moisture-curable urethane resin, an acrylic resin, a vinyl acetate resin, an epoxy resin, a polyester resin, or the like is used. In particular, when the base material is an alkali base material such as calcium silicate or cement, a resin having excellent alkali resistance is preferable. The resin is preferably an acrylic urethane resin obtained from an acrylic polyol and an isocyanate. The base coat layer may be formed of a paint containing these resins by a known coating method such as spray coating.

[Transfer to base material using integrated transfer sheet]
The transfer method for transferring the integrated transfer sheet to the substrate is not particularly limited, and may be a conventionally known transfer method such as the following. Among them, the roller transfer method is preferable as a simple transfer method capable of transferring even a small uneven surface by making the elastic roller soft. Alternatively, the transfer may be performed by a transfer method utilizing solid particle collision pressure. In this method, transfer can be performed even on a large surface unevenness which has been impossible in the past.

As described in JP-B-60-59876, JP-A-5-270199 and JP-A-5-139097, the transfer sheet is placed on the support with the transfer layer facing the substrate side. A so-called roller transfer method in which a rubber roller is used as an elastic roller serving as a transfer roller, and the support is peeled off after the transfer layer is pressed against the base material. JP-B-56-45768 (overlay method),
As described in Japanese Patent Publication No. 60-58014 (vacuum pressing method) and the like, a transfer sheet is placed on a surface of a three-dimensional substrate such as a molded article facing or placed with the transfer layer side facing the substrate side. ,
A transfer method using a so-called vacuum forming and laminating method in which a transfer layer of a transfer sheet is transferred to the base material surface by a pressure difference caused by at least vacuum suction from the base material side, and further, pressurized pressure from the support sheet side as appropriate (vacuum forming) Transfer method). JP-B-2-42080, JP-B-4-19924
Injection molding simultaneous painting transfer method as described in Japanese Patent Application Publication No.
This involves placing a transfer sheet in an injection mold in advance so that the transfer layer faces the injection resin side, performing injection molding, and simultaneously forming a base material (molded product) made of resin with the transfer sheet. This is a method of transferring a transfer layer to a surface. Or, JP-B-59-51900, JP-B-61
-5895, JP-B-3-2666, and the like.

As disclosed in Japanese Patent Application Laid-Open No. 9-315095, as a novel transfer method, the transfer pressure pressing means itself uses a solid particle collision pressure as the transfer pressure. This transfer method is suitable for transferring a surface unevenness such as a large three-dimensional shape to a base material, which is impossible with the above-mentioned conventional various transfer methods. In this method, a transfer layer side of a transfer sheet is opposed to a base material side, and a large number of solid particles are made to collide with the release support sheet side of the transfer sheet, and the collision pressure is used to apply the solid particles to the base material. The transfer method is to transfer the transfer layer to the substrate by pressure-contacting the transfer sheet and peeling off the releasable support sheet after the transfer layer is adhered to the substrate. As the solid particles, inorganic particles such as glass beads, metal particles such as zinc and iron, and the like are used. The shape of the solid particles is spherical or the like, and the particle size is usually 10 to 1000 μm.
m. The solid particles are typically ejected from an ejector using an impeller or an ejection nozzle to collide with a transfer sheet. Sandblasting, shot blasting, shot peening and the like used in the blasting field can be used as the ejector. For example, the impeller is a centrifugal blast device or the like.

[Cross-Linking and Curing of Resin Transfer Layer] In order to cross-link and cure the resin transfer layer after transfer to the substrate, the resin used is irradiated with ultraviolet rays if it is an ultraviolet-curable resin, and if it is an electron beam-curable resin, it is irradiated with ultraviolet rays. Irradiation with a line is sufficient. The cross-linking and curing may be performed after the release support sheet is separated from the uncured resin transfer layer, as long as the release support sheet can be separated from the resin transfer layer. I do. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp is used. As the electron beam source, various electron beam accelerators such as a Cockcroft-Walton type, a Van degraft type, a resonance transformer type, an insulating core transformer type, or a linear type, a dynamitron type, and a high frequency type are used.
To 1000 keV, preferably 100 to 300 keV
A device that irradiates an electron having an energy of?

[Use of Cosmetic Material] The cosmetic material obtained by the present invention can be used for various uses. For example, exteriors such as siding, exterior walls such as fences, roofs, gates, and gable boards, interiors of buildings such as walls, ceilings, floors, etc. Furniture, etc., surface makeup of cabinets for light electric / OA equipment such as TV receivers, automobiles,
Vehicle interior materials such as trains, aircraft, and ships. Among them, the cosmetic material obtained by the present invention is excellent in surface physical properties, and therefore, it is suitable for use as a cosmetic material for soft materials such as resins or porous materials such as cement and calcium silicate. The shape of the decorative material is a plate, a stick, a three-dimensional object, a sheet, or the like.

[0037]

Next, the present invention will be further described with reference to Examples and Comparative Examples.

[Example] Substrate: Flexible board (Portland cement:
A base material B (asbestos = 65: 35 weight ratio) was prepared, the surface of which was dust-removed, and then used as a sealer treatment for sealing.
After spray-coating a sealant made of a liquid-curable acrylic urethane resin, the sealant was dried in an oven at 80 ° C. for 10 minutes to form a base coat layer having a coating amount of 80 g / m ² (solid basis).

Adhesive: Next, an adhesive composed of a two-component curable polyurethane resin is applied to the sealer-treated substrate with a roll coater, and dried in an oven at 80 ° C. for 90 seconds. An adhesive layer having a coating amount of 5 g / m ² (based on solid content) was formed.

Intermediate sheet: A UV-curable resin (urethane acrylate, pentaerythritol tetraacrylate using pentaerythritol triacrylate, and photopolymerization) on a 50 μm-thick polyethylene terephthalate film as the first release support sheet 1. 1-hydroxycyclohexyl phenyl ketone as an initiator and a methyl methacrylate acrylic resin having a glass transition temperature of 105 ° C. as a thermoplastic acrylic resin having no polymerizable unsaturated group.
A non-flowable resin transfer layer 2 in an uncured state was formed by coating with μm. Then, a polyethylene film was laminated thereon as a separator 3 to form an intermediate sheet S1a (FIG. 1A, right).

Picture transfer sheet: A 25 μm-thick release layer made of polypropylene (manufactured by Mitsubishi Chemical Corporation, part number FL25R) was extruded on thin paper having a basis weight of 40 g / m ² as the second release support sheet 1a. A sheet having a thickness of 60 μm having a configuration of being laminated by a coating method was prepared.
An 8: 2 weight ratio mixture of a urethane resin composed of polycarbonate diol and isophorone diisocyanate and having a urea bond introduced thereto, and a vinyl chloride-vinyl acetate copolymer, is formed on the release layer surface of the second release support sheet. A color ink obtained by using a resin as a binder and adding a pigment thereto was gravure printed to form a picture layer. Furthermore, on the picture layer,
Acrylic polyol (a copolymer having methyl methacrylate and β-hydroxyethyl methacrylate as main components monomers, a glass transition temperature of 99 ° C. and a hydroxyl value of 30
), A primer layer is formed with a urethane resin ink obtained by adding 7 parts by weight of a hexamethylene diisocyanate-based curing agent to 100 parts by weight of the main agent of The pattern transfer sheet S2 on which the layer 4 was formed was obtained [FIG. 1 (B)].

Transfer: First, a pattern transfer layer was transferred from the pattern transfer sheet to the intermediate sheet S1 (a) (after the separator was peeled off) to obtain an integrated transfer sheet S. The transfer is performed by placing the pattern transfer sheet on a flat table with the pattern transfer layer facing upward, and then directing the resin transfer layer downward from above the transfer roller (the iron core is JIS rubber hardness of 60 °). Roller coated with silicone rubber). Roller surface temperature is heated to 120 ° C, transfer speed is 3
m / min. The roller surface temperature is low (60 ° C)
If the pattern transfer layer does not adhere to the resin transfer layer,
(° C. or more), the resin transfer layer itself peeled off from the release support sheet, and could not be laminated as an integral transfer sheet. Next, the resin transfer layer and the pattern transfer layer were transferred to the above-mentioned base material B on which the adhesive layer was formed, which was preheated to 60 ° C. with the integrated transfer sheet S obtained above. The transfer was performed by a roller transfer method. Roller is made of iron core with JIS rubber hardness of 60 °
Coated with silicone rubber, with a surface temperature of 180 ° C
And used. The transfer speed was 3 m / min.

Ultraviolet irradiation: Then, ultraviolet rays are irradiated from an ultraviolet irradiation device (a mercury lamp having an output of 80 W / cm) through the first release support sheet 1 to crosslink and cure the resin transfer layer. The mold support sheet was peeled off to obtain a decorative material D [FIG. 1 (E)]. In the obtained decorative material, the resin transfer layer serves as a hard surface protective layer, is excellent in scratch resistance, etc., has a moderate flexibility, is hard to crack, and has tough surface properties, and is coated with a pattern transfer layer. The decoration with the impossible pattern was made, and the design became excellent.

Comparative Example 1 The pattern transfer layer was directly transferred to the substrate (with the adhesive layer formed thereon) used in the example preheated to 60 ° C. using the pattern transfer sheet used in the example. Next, using the intermediate sheet used in the example as a transfer sheet, the resin transfer layer was transferred onto the pattern transfer layer transferred to the base material. These transfer methods and conditions are the same as in the transfer of the integrated transfer sheet in the examples. Then, as in the example, the resin transfer layer is irradiated with ultraviolet rays to crosslink and cure the resin transfer layer,
A cosmetic material was obtained. Although there was no problem in each transfer step, two steps were required for on-site transfer in which the substrate was handled, resulting in reduced workability.

[Comparative Example 2] Intermediate sheet S used in Example
An image transfer layer was directly formed by gravure printing on the two resin transfer layers of FIG. 1A, and an attempt was made to form an integrated transfer sheet having the same layer configuration as in the example. However, since the resin transfer layer is an uncured layer, first, during printing of the primer layer in the picture transfer layer, the first release support sheet 1 of the intermediate sheet is not used.
The resin transfer layer 2 was peeled off from the plate, causing poor printability such that the resin transfer layer 2 adhered to the plate surface. As a result, an integrated transfer sheet was not obtained.

[0046]

According to the present invention, a decorative material can be manufactured by simultaneously transferring a resin transfer layer serving as a surface protective layer and the like and a picture transfer layer to a base material in one step, and can be used at a site where the base material is handled. Work efficiency is improved. Moreover, in order to make the resin transfer layer serving as a surface protective layer and the like have a high crosslinking density, a large amount of a low-molecular-weight monomer which is easily tacky at room temperature when uncured and has low solvent resistance is used in the resin transfer layer. However, since the formation of the pattern transfer layer on the (integral type) transfer sheet is performed by a transfer method instead of direct printing, the pattern can be formed on the resin transfer layer without any problem. In addition, by incorporating the ionizing radiation-curable resin of the resin transfer layer also with a thermoplastic acrylic resin having no polymerizable unsaturated group, the surface of the resin transfer layer, which has been cross-linked and cured after the transfer, has abrasion resistance and the like. In addition, it provides a moderate degree of flexibility and a tough surface property that is not easily cracked. Even when the uncured resin transfer layer in the intermediate sheet contains many monomer components and becomes liquid or sticky, it can be adjusted to a non-adhesive non-flowable state.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram illustrating a method for manufacturing a cosmetic material of the present invention.

[Explanation of symbols]

 Reference Signs List 1 first releasable support sheet 1a second releasable support sheet 2 resin transfer layer 3 separator 4 picture transfer layer 5 picture layer 6 primer layer B base material D cosmetic material S1 intermediate sheet S1a intermediate sheet (separator Attached) S2 Picture transfer sheet S Integrated transfer sheet

Claims (2)

[Claims] 1. A resin transfer layer formed of an uncured material of a thermoplastic ionizing radiation-curable resin that is in a non-flowable state at room temperature in an uncured state and is uncured on a first release support sheet. For an intermediate sheet having, by using a pattern transfer sheet having at least a pattern layer as a pattern transfer layer on the second release support sheet, by transferring the pattern transfer layer to the resin transfer layer surface, On the first releasable support sheet, a resin transfer layer and a pattern transfer layer are integrally laminated in this order to form an integrated transfer sheet, and then, using the integrated transfer sheet, A method for manufacturing a decorative material, comprising transferring a resin transfer layer and a pattern transfer layer, and then irradiating ionizing radiation to crosslink and cure the transferred resin transfer layer to form a decorative material. 2. A thermoplastic acrylic resin having no polymerizable unsaturated group, a monomer having a polymerizable unsaturated group, and / or a thermoplastic acrylic resin having no polymerizable unsaturated group as main components of the ionizing radiation-curable resin of the resin transfer layer.
The method for producing a decorative material according to claim 1, wherein the method uses a prepolymer.