JP2002036446A - Decorative paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable use of an inter-sheet reinforcing sheet as a paper base and to upgrade a cellophane tape resistance and a wear resistance. SOLUTION: The decorative paper 10 comprises a sealer resin layer 2 of an ionizing radiation curable resin provided near at least a surface of a paper base 1, a coloring ink layer 3 containing a binder resin of the ionizing radiation curable resin and a surface protective layer 4 of a transparent ionizing radiation curable resin laminated on a surface of the paper base so that the resins of these three layers are crosslinked cured and adhesively integrated. In this paper 10, it is preferred that the paper base is at least partly impregnated with the sealer resin layer, its resin has an acryloyl group as an ionization radiation reactive functional group, a hydroxyl group or an isocyanate group as a functional group having affinity with a cellulose, further has an ordinary temperature solid thermoplastic urethane resin and a silica powder, and it is preferred that an uncured state is ordinary temperature non-adhesive solid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to decorative paper used for interior materials of buildings such as walls, doors and other fittings, and surface materials of furniture and the like. In particular, the present invention relates to a decorative paper in which a paper between sheets can be used as a paper base material and has excellent cellophane tape resistance and abrasion resistance.

[0002]

2. Description of the Related Art Conventionally, in the above surface decoration applications, surface strength such as abrasion resistance is required, and adhesion in a decorative paper layer is also required. For this reason, for example, Japanese Patent Application Laid-Open
Japanese Patent No. 58631 discloses a method in which a solid layer (solid printing layer) and a picture layer serving as a colored ink layer are formed by printing on a paper base material and a surface protective layer is further provided. By using an ionizing radiation-curable resin for the layers and laminating these three layers in an uncured state, and then irradiating with ionizing radiation to cure the three layers, the adhesion between the surface protective layer, the pattern layer and the solid layer over the entire surface is improved. Are disclosed.

[0003]

However, in the decorative paper as described above, the adhesion between the surface protective layer, the picture layer and the solid layer is certainly improved, but the adhesion between the solid layer and the paper substrate is improved. The adhesion was insufficient. For this purpose, cellophane tape resistance (adhesion of decorative paper evaluated by the presence or absence of peeling of decorative paper when peeling after applying cellophane adhesive tape to the surface of decorative material with decorative paper adhered to the substrate to be adhered) ), The abrasion resistance was still insufficient. In particular, the tendency is recognized in a paper-to-paper reinforced paper in which a resin having insufficient adhesion with an ionizing radiation-curable resin such as styrene-butadiene rubber (SBR) or an acrylic resin is previously added between paper fibers. Was.

[0004] Therefore, an object of the present invention is to provide a decorative paper that can use a paper-reinforced paper that could not be used conventionally as a paper base material, and that also has good cellophane tape resistance and abrasion resistance. is there.

[0005]

In order to solve the above-mentioned problems, the decorative paper of the present invention has a sealer resin layer of an ionizing radiation-curable resin at least near the surface of a paper substrate. On the surface of the sealer resin layer, a colored ink layer in which a binder resin is composed of an ionizing radiation-curable resin, and a surface protective layer of a transparent ionizing radiation-curable resin are laminated in this order. The radiation-curable resin was cross-linked and cured and bonded and integrated. By adopting such a configuration, the adhesion between the three layers of the paper base material, the colored ink layer and the surface protection layer can be improved. Can,
Cellophane tape (adhesion) resistance and abrasion resistance are also good.

Further, the decorative paper of the present invention is configured such that at least a part of the sealer resin layer is impregnated in a paper base material. With such a configuration,
Adhesion between the paper substrate and the colored ink layer via the sealer resin layer or between the paper substrate and the surface protective layer is further improved. As a result, cellophane tape resistance and abrasion resistance can be further improved.

Further, in the decorative paper of the present invention, the ionizing radiation-curable resin constituting the sealer resin layer may further comprise an acryloyl group as an ionizing radiation-reactive functional group, And a resin having a hydroxyl group or an isocyanate group as a functional group having an affinity for the resin. With such a configuration, the adhesion between the sealer resin impregnating the paper base and the paper base is further improved. As a result, cellophane tape resistance and abrasion resistance can be further improved.

Further, in the decorative paper of the present invention, the ionizing radiation-curable resin constituting the sealer resin layer further contains a thermoplastic urethane resin which is solid at room temperature and silica powder. In this state, it is a non-adhesive solid at room temperature. With such a configuration, the paper base material coated with the sealer resin is once wound up and stored, and thereafter, at a desired time, the paper base material coated with the sealer resin layer by a desired coating amount is used. Since decorative paper can be manufactured by rewinding, printing and coating, the degree of freedom in the preparation of the manufacturing process and the production plan can be increased.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The decorative paper of the present invention is described below.
An embodiment will be described.

First, FIG. 1 is a cross-sectional view illustrating an embodiment of the decorative paper of the present invention through its manufacturing process. That is, the decorative paper of the present invention has a paper base 1 as shown in FIG.
On the other hand, as shown in FIG. 1B, a sealer resin layer 2A of an ionizing radiation-curable resin is formed (however, at this stage, the sealer resin layer 2A is in an uncured state). As shown in C), on the surface on which the sealer resin layer 2A is formed, a colorant 3 is contained in a binder resin 3a made of an ionizing radiation-curable resin.
The colored ink layer 3A containing b is formed (however, the colored ink layer 3A is also in an uncured state at this stage), and then, as shown in FIG. A surface protection layer 4A made of a transparent ionizing radiation-curable resin (this surface protection layer 4A is also in an uncured state at this stage) is formed, and then, as shown in FIG. Then, the ionizing radiation-curable resin of the sealer resin layer 2A, the colored ink layer 3A, and the surface protective layer 4A is cross-linked and cured.
As a result, the uncured sealer resin layer 2A becomes the crosslinked and cured sealer resin layer 2, the uncured colored ink layer 3A becomes the crosslinked and cured colored ink layer 3, and the uncured surface protection layer 4A becomes the crosslinked and cured surface protection. The decorative paper 10 of the present invention has a configuration in which the three layers are bonded and integrated as the layer 4.

FIG. 1 is a view for explaining one embodiment of the decorative paper of the present invention, and the sealer resin layer 2 is an example in which the paper base material 1 is not impregnated. 2
It is better to at least partially impregnate the paper base material 1,
The resin that forms the sealer resin layer 2 penetrates into the fibers that form the paper base material 1 and becomes entangled with the fibers, and the adhesion between the paper base material 1 and the sealer resin layer 2 is further improved by the anchoring effect. It is preferred in that respect. For example, the sealer resin layer 2 may impregnate a part of the layer of the paper substrate 1 while leaving a part thereof (see FIG. 2), or the sealer resin layer 2 may leave a part of the paper substrate 1 All layers are impregnated (see FIG. 3 (A)), or the sealer resin layer 2 and the paper substrate 1 are impregnated so as to completely overlap (see FIG. 3 (B)). . Further, in order to improve the adhesion between the sealer resin and the paper base material and to further improve the cellophane tape resistance, when the paper base material is impregnated with an ionizing radiation-curable resin serving as a sealer resin layer, the ionizing radiation The curable resin is also preferably a resin having an acryloyl group as an ionizing radiation reactive functional group and a hydroxyl group or an isocyanate group as a functional group having an affinity for cellulose. In this case, the ionizing radiation-curable resin preferably contains a thermoplastic urethane resin which is solid at room temperature and silica powder, and is a non-adhesive solid at room temperature in an uncured state.

Hereinafter, each of these layers will be described in more detail.

[Paper Base] Paper base 1 includes thin paper, kraft paper, woodfree paper, linter paper, baryta paper, parchment paper,
Paper such as Japanese paper is used. The basis weight is usually 20-100g /
m ² . Further, the paper base material, between the fibers of the paper base or between the other layer and the paper base to enhance the interlaminar strength, to prevent fluff, paper base, further acrylic resin, styrene butadiene rubber, A resin to which a resin such as a melamine resin or a urethane resin is added (the resin is impregnated after paper-making or filled in during paper-making) may be used. In particular, in the decorative paper of the present invention, the inter-paper reinforced paper internally containing a resin that does not have sufficient adhesion to an ionizing radiation-curable resin such as styrene-butadiene rubber (SBR) or an acrylic resin does not lose cellophane tape resistance. It can be used as a paper base. In addition, as pulp constituting paper,
N-wood (coniferous) pulp, L-wood (hardwood) pulp, or pulp obtained by mixing these materials is used. In general, paper formation,
When importance is attached to surface smoothness and formation, L pulp is used.
When importance is placed on the strength of paper, N-pulp is mainly used.

[Sealer Resin Layer] The sealer resin layer 2 is used for forming a colored ink layer and a surface protective layer formed thereon by printing or coating when an uncured liquid ink or coating liquid is applied to the inside of a paper substrate. In order to prevent the film thickness from being absorbed and the film thickness from being reduced, and the unevenness in the formation of the paper base material from becoming uneven in gloss, the adhesion between the paper base material, the colored ink layer and the surface protective layer It is formed in order to enhance the properties and improve cellophane tape resistance and abrasion resistance.

The sealer resin layer 2 is formed by applying a liquid ionizing radiation curable resin by gravure coating, roll coating, or the like to form an uncured sealing resin layer 2A. It is formed by crosslinking and curing. The sealer resin layer may be formed by solid printing on the entire surface by gravure printing or the like. The coating amount depends on the basis weight of the paper base material, the presence or absence of impregnation into the paper base material and the degree of impregnation when present, but usually 0.5 to 10 g / m ² (solid basis).
It is about.

The ionizing radiation-curable resin used as the sealer resin can be basically selected from known ionizing radiation-curable resins according to the intended use, required physical properties, and the like.

That is, as the ionizing radiation-curable resin, specifically, a prepolymer (including a so-called oligomer) and / or a monomer having a radical polymerizable unsaturated bond or a cation polymerizable functional group in a molecule. Preferably, a composition curable by ionizing radiation, which is appropriately mixed with, is used. Here, the term “ionizing radiation” means an electromagnetic wave or a charged particle having energy capable of cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used.

The above-mentioned prepolymer or monomer specifically has a radical polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, a cationic polymerizable functional group such as an epoxy group in the molecule. Consisting of a compound having These prepolymers and monomers may be used alone or as a mixture of two or more. Here, for example, the (meth) acryloyl group means an acryloyl group or a methacryloyl group. As the ionizing radiation-curable resin, a polyene / thiol-based prepolymer obtained by combining a polyene and a polythiol is also preferably used.

Examples of the prepolymer having a radical polymerizable unsaturated group in the molecule include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. And silicone (meth) acrylate. A molecular weight of about 250 to 100,000 is usually used.

Examples of monomers having a radically polymerizable unsaturated group in the molecule include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Further, among the polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate And dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Examples of the prepolymer having a cationically polymerizable functional group in the molecule include epoxy resins such as bisphenol type epoxy resin and novolak type epoxy compound.
There are prepolymers of vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those obtained by adding allyl alcohol to both ends of a polyurethane made of a diol and a diisocyanate.

In the ionizing radiation-curable resin, the functional group capable of undergoing a cross-linking reaction by ionizing radiation, that is, the ionizing radiation-reactive functional group is a radical polymerizable group such as a (meth) acryloyl group and a (meth) acryloyloxy group. Unsaturated groups, cationic polymerizable functional groups such as epoxy groups, or vinyl groups, but particularly preferred as the ionizing radiation-curable resin used for the sealer resin have good adhesion between the paper substrate and the sealer resin. Acryloyl group as an ionizing radiation reactive functional group and (constituting paper base material)
It is a resin having a hydroxyl group, an isocyanate group, a carboxyl group, an amino group, an ether group (ether bond) or the like as a functional group having an affinity for cellulose. Among them, a hydroxyl group or an isocyanate group is preferable as the functional group having an affinity for cellulose from the viewpoint of the adhesion.

The ionizing radiation-curable resin as described above is preferably a resin containing a compound having both an ionizing radiation-reactive functional group and a functional group having an affinity for cellulose in one molecule. However, since the ionizing radiation-curable resin is generally a composition containing a plurality of types of compounds, a compound having an ionizing radiation-reactive functional group in its molecule (but not having a functional group having an affinity for cellulose) An ionizing radiation-curable resin comprising a composition comprising a compound having a functional group having an affinity for cellulose in a molecule (but not having an ionizing radiation-reactive functional group) can also be used. In this case, the compound having a functional group having an affinity for cellulose in the molecule does not participate in the crosslinking reaction by ionizing radiation irradiation, but in the sealer resin layer after crosslinking and curing, the former polymer molecule and the latter molecule are This is because a similar effect can be obtained as in the case where both molecules are present in one molecule, for example, by entanglement.

Specific examples of the compound having both an ionizing radiation-reactive functional group and a functional group having an affinity for cellulose in one molecule include polyethylene glycol di (meth) acrylate and diisocyanate di (meth) acrylate. In addition to acrylates and the like, there are the following compounds.

(1) a monomer having a hydroxyl group;
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. [Here, (meth) acrylate means acrylate or methacrylate. (2) a monomer having a carboxyl group; (meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate and the like. (3) Monomer having amino group; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate and the like. (4) Monomer having isocyanate group; 2,4-tolylene diisocyanate and 2-hydroxyethyl (meth)
Adducts of diisocyanates such as 1 mol to 1 mol of acrylate adducts with radically polymerizable monomers having active hydrogen.

In order to adjust the glass transition temperature of the homopolymer or copolymer of the monomers (1) to (4) or to adjust the physical properties of the cured product,
This monomer can be copolymerized with the following copolymerizable monomers. Such copolymerizable monomers 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-ethylhexyl (meth)
Acrylate or ethylene glycol di (meth)
Acrylate, polyethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and the like.

Alternatively, the homopolymer or copolymer obtained by using the above-mentioned monomer is added to the following methods (a) to (a).
According to (d), a compound into which a radically polymerizable unsaturated group serving as an ionizing radiation reactive functional group has been introduced can also be used.

(A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, the (meth)
A monomer having a carboxyl group such as 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 (1) 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, add the monomer having a hydroxyl group described in (1) above or the monomer having a carboxyl group described in (2) above. Let react. (d) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group or a monomer having an aziridinyl described below, or a diisocyanate compound of the above (4) and a hydroxyl group-containing acrylate ester A monomer having an isocyanate group such as an adduct of 1 mol to 1 mol with the monomer is subjected to an addition reaction. 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.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate. Examples of the monomer having an aziridinyl include 2-aziridinylethyl (meth) acrylate and allyl 2-aziridinylpropionate. And the like.

As the ionizing radiation-curable resin, any of acrylate and methacrylate can be used. In general, acrylate is preferable to methacrylate because it has a higher reaction rate.

Further, various additives may be added to the ionizing radiation-curable resin, if necessary. As these additives, for example, thermoplastic urethane resin, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, thermoplastic resin such as cellulose resin, silica,
They are extenders such as calcium carbonate, coloring agents, and solvents.
The addition of extenders such as thermoplastic resins and silica makes it easier to adjust the ionizing radiation-curable resin to a non-adhesive solid at room temperature in an uncured state. As the solvent, an organic solvent such as methyl ethyl ketone, ethyl acetate, toluene and isopropyl alcohol, or water is selected according to the type of resin, coating suitability, drying ability and the like. When water is used, any of an aqueous dispersion emulsion and an aqueous solution may be used.

The sealer resin layer 2 is formed by applying a sealer resin on a paper base by a roll coater, a gravure roll coater, a comma coater, a spray (spraying) coater or the like to form a sealer resin layer. As described above, it may be impregnated or filled during papermaking. As the sealer resin, preferably, after drying the (diluted) solvent, a resin that is in a non-adhesive thermoplastic solid state even at an uncured state at room temperature is preferably selected. Select such a resin and apply it to the paper substrate surface,
Since the front side (back side) of the paper base material coated by impregnation etc. by drying the solvent becomes non-adhesive, the coated paper base material is mass-produced, and once wound up and stored. Thereafter, at desired times, the paper base material coated by a desired quantity can be rewound, and further printed and coated to produce decorative paper, so that the degree of freedom in the preparation of the manufacturing process and the production plan can be increased. In particular, after all these layers are once formed in an uncured state as an uncured sealer resin layer 2A, an uncured colored ink layer 3A, and an uncured surface protective layer 4A, these three layers are simultaneously irradiated with ionizing radiation. In order to crosslink and cure and bond and integrate, ionizing radiation curable resin to be used (same for colored ink layer)
However, a resin that becomes a non-adhesive thermoplastic solid even in an uncured state at room temperature is preferable because it is easy to handle.

If the surface of the paper substrate coated with the sealer resin is in an adhesive state, the paper substrate adheres to the plate or the coating head. A printing or coating method for contact cannot be adopted. For this reason, only non-contact printing or coating methods such as spray coating and ink jet printing can be adopted, making it difficult to apply a uniform and reproducible coating, and problems such as scattering of paint mist. There is a problem that printing speed is slow and high-speed mass production cannot be performed. On the other hand, as described above, in the uncured state, an ionizing radiation-curable resin that becomes a non-adhesive thermoplastic solid at room temperature is applied to the paper base, so that the coated paper base is non-adhesive. This is because the plate can adopt a coating or printing method in which a coating head is brought into contact, and the above problem is solved.

In order to make the ionizing radiation-curable resin into a non-adhesive thermoplastic solid at room temperature after drying the solvent in an uncured state, it is necessary to: A prepolymer having a large (degree of polymerization) is selected, and its melting point or melting temperature is set to room temperature or higher. (2) Thermoplastic acrylic resin [polymethyl (meth) acrylate, polybutyl (meth) acrylate, styrene-methyl (meth) acrylate copolymer, etc.] in a monomer or prepolymer of an ionizing radiation-curable resin liquid at room temperature A thermoplastic resin such as a thermoplastic urethane resin and a thermoplastic polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.) which becomes a non-adhesive solid at room temperature is added. Addition amount is monomer or prepolymer 1
The amount is usually about 100 to 300 parts by mass in 00 parts by mass.

More preferably, in addition to this, silica,
A powder having a particle size (average) of about 0.1 to 10 μm of an inorganic substance such as calcium carbonate, alumina, barium sulfate, and talc is added. The amount of addition is usually about 10 to 50 parts by mass per 100 parts by mass of the monomer or prepolymer.

Here, the normal temperature is an ambient temperature at which the paper base material coated with the sealer resin is stored, transported, and further subjected to printing and coating. Depending on the season, region, etc., usually,
It is about 5 to 40 ° C.

When the ionizing radiation-curable resin is cured by ultraviolet rays, a photopolymerization initiator is added. In the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoinsulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. In addition, the addition amount of these photopolymerization initiators is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation-curable resin.

As a source of ionizing radiation, an ultraviolet 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, a metal halide lamp or the like is used. The wavelength of the ultraviolet light is usually 190
The wavelength range of ３380 nm is mainly used. Also, as the electron beam source, Cockcroft-Walton type, Van degraft type, Resonant transformer type, Insulated core transformer type, or
Using various types of electron beam accelerators such as a linear type, a dynamitron type and a high frequency type, 100 to 1000 keV, preferably 1 to 1000 keV.
A device that emits electrons having an energy of 00 to 300 keV is used. The irradiation amount (absorbed dose) of the electron beam is usually about 20 to 150 kGy (2 to 15 Mrad).

The sealer resin layer is formed by coating a part of the coated sealer resin layer 2 near the surface of the paper substrate 1 as shown in FIG. And may be impregnated. Alternatively, the sealer resin may be further impregnated in the entire thickness direction from the front surface to the back surface of the paper base material, as shown in FIGS. 3A and 3B.
In this case, impregnation by dipping, and a sealer resin may be mixed with the pulp and mixed. In this way, by impregnating the inside of the paper base with the sealer resin layer, the adhesion between the colored ink layer and the paper base via the sealer resin layer can be further enhanced. In addition, since the strength of the paper itself consisting of the paper base material and the sealer resin can be enhanced, the cellophane tape resistance and abrasion resistance of the decorative paper can be further improved.

[Colored ink layer] Colored ink layer 3 or 3
A is a binder resin 3 composed of an ionizing radiation curable resin.
a contains a coloring agent 3b. As the ionizing radiation-curable resin used as the binder resin, the ionizing radiation-curable resin as described above for the sealer resin layer can be used. Therefore, further description is omitted. However, a resin having an acryloyl group as an ionizing radiation reactive functional group and a hydroxyl group or an isocyanate group as a functional group having an affinity for cellulose may not be used. However, in order to form the three layers of the sealer resin layer, the colored ink layer and the surface protective layer once in an uncured state and then simultaneously cross-link and cure by irradiation with ionizing radiation to bond and integrate, as in the case of the aforementioned sealer resin layer, If the colored ink layer is also a non-adhesive solid at room temperature in the uncured state, the handling of the paper substrate after the formation of the uncured colored ink layer is easy, and the flexibility of the production process setup and production planning can be increased. .

As the coloring agent, known dyes and pigments can be used. For example, titanium white, carbon black,
Inorganic pigments such as graphite, red iron oxide, ultramarine blue, aluminum foil powder, titanium dioxide coated mica foil powder, isoindolinone yellow,
Organic pigments such as quinacridone red and phthalocyanine blue. These colorants are used alone or in a mixture of two or more.

As shown in FIG. 2, the colored ink layer 3 has
There is an entire solid layer 31 formed over the entire surface and a pattern layer 32 formed in a pattern. These are usually combined so that the pattern layer 32 comes on the entire solid layer 31 as shown in FIG. used. The patterns of the pattern layer formed in a pattern form include a wood pattern, a stone pattern, a cloth pattern, characters, a geometric pattern, and the like. The color ink layer may be formed by a known printing method such as gravure printing, letterpress printing, offset printing, silk screen printing, and ink jet printing.
In the case of a solid layer on the entire surface, it can be formed by a known coating method such as roll coating.

[Surface Protective Layer] The surface protective layer 4 is formed of a transparent ionizing radiation curable resin. The surface protective layer may be colored as long as it is transparent enough to see the lower colored ink layer. For coloring the surface protective layer, known coloring agents such as those described above for the colored ink layer can be used. As the ionizing radiation-curable resin used for the surface protective layer, the ionizing radiation-curable resin as described above for the sealer resin layer can be used. Therefore, further description is omitted. However, a resin having an acryloyl group as an ionizing radiation reactive functional group and a hydroxyl group or an isocyanate group as a functional group having an affinity for cellulose may not be used. The surface protective layer may be formed by a known coating method such as roll coating. The coating amount is usually about 1 to ²⁰ g / m ² (solid basis).

In the transparent ionizing radiation-curable resin serving as the surface protective layer, calcium carbonate,
Various additives such as an extender such as barium sulfate and a fine powder such as a lubricating agent, a filler such as a silicone resin and a wax may be added.

When the wear resistance is required to be improved, hard inorganic particles are used as the lubricant. Examples of the material of the inorganic particles include alumina (such as α-alumina), silica, glass, silicon carbide, and diamond.
The shape of the inorganic particles is a sphere, a polygon, a scale, an irregular shape, or the like. The average particle size of the inorganic particles is preferably about 3 to 30 μm. If the average particle size is too small, the effect of improving the wear resistance is reduced, and if it is too large, the surface smoothness is reduced. The amount of the lubricant added is about 5 to 30% by mass based on the total amount of the resin.

The ionizing radiation-curable resin of the surface protective layer is formed by the above-mentioned sealer resin layer (rather than by crosslinking and curing the ionizing radiation-curable resin each time the sealer resin layer, the colored ink layer, and the surface protective layer are formed). By simultaneously irradiating ionizing radiation with the ionizing radiation-curable resin of the colored ink layer and cross-linking and curing the three layers, these three layers can be more firmly bonded and integrated, resulting in a better cellophane tape. This is preferable in that the properties and abrasion resistance can be obtained.

[Coated Substrate] The decorative paper of the present invention is used as a surface decorative material by adhering to the surface of various coated substrates.

The substrate to be adhered is not particularly limited. For example, the material of the substrate to be adhered is an inorganic nonmetal-based, metal-based, wood-based, plastic-based, or the like. Specifically, in the case of inorganic nonmetals, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC
(Glass fiber reinforced concrete), non-ceramic ceramic materials such as pulp cement, wood chip cement, asbestos cement, calcium silicate, gypsum, gypsum slag; There are materials. In the case of metal, for example, iron, aluminum,
There is a metal material such as copper. In the wood system, for example,
There are veneers made of cedar, cypress, oak, lauan, teak, etc., plywood, particle board, fiber board, laminated wood and the like. In the case of plastics, for example, there are resin materials such as polypropylene, ABS resin, and phenol resin. The shape of the adhered substrate is arbitrary such as a flat plate, a curved plate, a polygonal column, and the like.

[Use] The decorative paper of the present invention is adhered to the surface of a substrate to be adhered as described above, and is used for building interior materials such as walls and ceilings.
It is used as a surface material for fittings such as doors, door frames and window frames, a surface material for construction members such as rims and skirting boards, and a surface material for furniture such as chests and cabinets.

[0050]

EXAMPLES The present invention will be further described below with reference to examples.

Example 1 As shown in the sectional view of FIG. 2, a decorative paper 11 in which the sealer resin layer 2 is partially impregnated in a part of the paper substrate 1 except for a part is produced as follows. did. As a paper base material 1, a building material paper made from L material (hardwood) cellulose pulp having a basis weight of 30 g / m ² was coated with a sealer resin composed of an ionizing radiation-curable resin having the following composition A1 by a roll coater at 5 g / m ^2. After application, the entire surface solid layer 31 as a colored ink layer 3 with a coloring ink of the following composition B1 using an ionizing radiation-curable resin as a binder resin, and coloring of the following composition B2 using an ionizing radiation-curable resin as a binder resin After the gravure printing of a wood pattern pattern layer 32 as a colored ink layer 3 with ink in this order, a transparent coating made of an ionizing radiation curable resin having the following composition C1 as a surface protective layer 4 is coated thereon by gravure roll coating. After applying 10 g / m ² at
An electron beam was irradiated under the conditions of 175 keV and 50 kGy (5 Mrad) to simultaneously crosslink and cure the sealer resin layer, the colored ink layer, and the surface protective layer to bond and integrate them to obtain the desired decorative paper 11.

Composition A1 (for sealer resin layer) Polyethylene glycol diacrylate 8 parts by mass Thermoplastic urethane resin 12 parts by mass Silica powder 20 parts by mass Ethyl acetate (diluent solvent) 30 parts by mass Toluene (diluent solvent) 30 parts by mass

Composition B1 (for solid layer of colored ink layer) Thermoplastic urethane resin 10 parts by mass Unsaturated polyester resin prepolymer 10 parts by mass Trimethylolpropane triacrylate 2 parts by mass Titanium oxide (colored pigment) 20 parts by mass Iron oxide (Coloring pigment) 2 parts by mass Ethyl acetate (diluent solvent) 28 parts by mass Toluene (diluent solvent) 28 parts by mass

Composition B2 (for design layer of colored ink layer) Thermoplastic urethane resin 10 parts by mass Unsaturated polyester resin prepolymer 10 parts by mass Trimethylolpropane triacrylate 2 parts by mass Iron oxide (colored pigment) 20 parts by mass Carbon black ( Color pigment) 2 parts by mass Ethyl acetate (diluent solvent) 28 parts by mass Toluene (diluent solvent) 28 parts by mass

Composition C1 (for surface protective layer) Bisphenol A diacrylate prepolymer 60 parts by mass Trimethylolpropane triacrylate 30 parts by mass Silica powder (matting agent) 7 parts by mass Fine powder silica 1 part by mass Silicone acrylate 2 parts by mass

Example 2 A decorative paper was obtained in the same manner as in Example 1, except that the composition A1 of the sealer resin was changed to the following composition A2.

Composition A2 (for sealer resin layer) diisocyanate diacrylate 8 parts by mass thermoplastic urethane resin 12 parts by mass silica powder 20 parts by mass ethyl acetate (diluent solvent) 30 parts by mass toluene (diluent solvent) 30 parts by mass

Example 3 A decorative paper 13 having the structure shown in FIG. 3B was produced as follows. As the paper substrate 1, a basis weight 3 obtained by making an L-material cellulose pulp with the following composition D1
In the same manner as in Example 1, a colored ink layer 3 composed of a solid layer 31 of the entire composition B1 and a picture layer 32 of the composition B2, and a surface protective layer of the composition C1 were coated on a base paper containing a sealer resin of 0 g / m ^2. After forming No. 4, each ionizing radiation-curable resin was simultaneously cross-linked and cured by electron beam irradiation to obtain decorative paper.

Composition D1 (for paper substrate filled with sealer resin) Chemical pulp 85 parts by mass Rosin size 1 part by mass Aluminum sulfate 1 part by mass Anionic acrylamide 3 parts by mass Cationic starch 5 parts by mass Polyethylene glycol diacrylate 5 parts by mass

Example 4 In Example 3, the composition D1
Example 3 except that the polyethylene glycol diacrylate in the above was changed to diisocyanate diacrylate.
A decorative paper was obtained in the same manner as described above.

Comparative Example 1 In Example 1, the composition A1
Decorative paper was obtained in the same manner as in Example 1, except that the formation of the sealer resin layer was omitted.

[Comparative Example 2] In Example 3, the composition D1
A decorative paper was obtained in the same manner as in Example 3 except that anionic acrylamide was added instead of polyethylene glycol diacrylate in the inside.

[Evaluation of Physical Properties] The decorative paper was laminated on a 25 mm-thick particle board as a substrate to be adhered using a urea resin-based adhesive to prepare a decorative board. Cellophane tape properties (adhesion A and adhesion B) and abrasion resistance were evaluated. Table 1 shows the results
Shown in

(1) Cellophane tape resistance: A cut is made on the surface of the decorative plate to reach the paper substrate with a cutter knife, and a total of 100 grids of 10 mm in length and width are formed in a grid pattern, each of which is 10 pieces in length and width. Then, a cellophane adhesive tape (Nichiban Co., Ltd., registered trademark “Cellotape”, 24
mm width, industrial), the cellophane adhesive tape was peeled off by hand, and the number of cells remaining without peeling was evaluated. 1
When the cell was also peeled (99/100 or less), it was determined to be defective, and when all cells were not peeled (100/100), it was rated good. This operation was repeated up to 10 times in the case of good (100/100). The above evaluation was regarded as adhesion A, and the adhesion B was evaluated after removing the release silicone on the surface of the decorative board with an eraser. However, the adhesion B is
It was determined to be good when the number of remaining meshes was 50/100 or more.

(2) Abrasion resistance: Evaluation was made by the number of revolutions in a test method according to JIS K 6902. 30 times or more was regarded as good.

[0066]

[Table 1]

[Consideration of evaluation results]
In Example 1, even if the adhesion A was repeated 10 times, the residual mesh was 1
00/100, which was good, and the adhesion B was peeled off in the paper base material at 50/100 after the repetition of three times, but it was judged to be good at a usable level. On the other hand, the wear resistance of Example 1 was as good as 40 times. In Examples 2 and 3, the adhesion A was at the same level as in Example 1, but the adhesion B was further improved to 5 repetitions. Further, the wear resistance of Examples 2 and 3 was further improved to 50 times. In Example 4, the number of repetitions was 1 until the adhesion B was the same as the adhesion A.
Even at 0 times, the residual mesh was further improved to 100/100, and the wear resistance was further improved to 60 times.

On the other hand, in Comparative Examples 1 and 2, the adhesion A was good, but the adhesion B was poor. That is, in the first test (the first test), the remaining cells in Comparative Example 1 were 20 /
At 100, delamination occurred between the paper substrate and the colored ink layer (solid layer on the entire surface). Further, in Comparative Example 2, the value was 0/100 in the first peeling, and the interlayer peeled between the paper substrate and the colored ink layer (solid layer on the entire surface). Moreover, the abrasion resistance of Comparative Examples 1 and 2 was as poor as 20 times. As described above, only the examples had good cellophane tape resistance and abrasion resistance.

[0069]

(1) According to the decorative paper of the present invention, a paper base material,
Since the adhesion between the three layers of the colored ink layer and the surface protective layer can be improved, a type of paper-reinforced paper that could not be used conventionally as a paper base material can be used, and cellophane tape resistance and abrasion resistance Is also good. (2) Furthermore, if at least a part of the sealer resin layer is configured to be impregnated in the paper base material, the sealer resin layer is formed by the anchoring effect due to the entanglement of the sealer resin and the paper fibers that have entered the paper base material. Adhesion between the paper substrate and the colored ink layer or between the paper substrate and the surface protective layer via the interlayer is further improved. As a result, cellophane tape resistance and abrasion resistance can be further improved. (3) In addition, the ionizing radiation-curable resin impregnating the paper base,
An acryloyl group as an ionizing radiation-reactive functional group, and a resin composition having a hydroxyl group or an isocyanate group as a functional group having an affinity for cellulose, a sealer resin and a paper base to be impregnated into a paper base. Is further improved. As a result, cellophane tape resistance and abrasion resistance can be further improved. (4) Further, in addition to the constitution of the above (3), the ionizing radiation-curable resin impregnating the paper base contains a thermoplastic urethane resin which is solid at room temperature and silica powder, and is in an uncured state. If the composition is a non-adhesive solid at room temperature, the coated paper base is mass-produced, once wound up and stored, and then, at a desired time, the desired amount of coated paper base is rewound. Moreover, since decorative paper can be manufactured by printing and coating, the degree of freedom in the preparation of the manufacturing process and the production plan can be increased.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating one embodiment of the decorative paper of the present invention in a manufacturing process.

FIG. 2 is a cross-sectional view illustrating another embodiment of the decorative paper of the present invention.

FIG. 3 is a cross-sectional view illustrating another impregnated state of a sealer resin layer in the decorative paper of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Paper base material 2A Sealer resin layer (unhardened state) 2 Sealer resin layer 3A Colored ink layer (unhardened state) 3 Colored ink layer 3a Binder resin 3b Colorant 4 Surface protective layer 4A (unhardened state) Surface Protective layer 10 Decorative paper 11-13 Decorative paper 31 Solid layer (colored ink layer) 32 Picture layer (colored ink layer) R Ionizing radiation

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 75/04 C08L 75/04 F term (Reference) 4F100 AA20B AA20H AK01B AK01C AK01D AK25 AK44 AK51B BA04 BA07 BA10A BA10D CA23B CB02C DG10A EC18 EJ05 EJ08 EJ64B EJ82B GB08 GB81 HB00C HB01 HB31 JB14B JB14C JB14D JB16B JK06 JK09 JL00 JL10C JL13B JN01D 4J002 CK021 DJ016 FA086 GK00

Claims (4)

[Claims] 1. A sealer resin layer of an ionizing radiation-curable resin is provided at least near the surface of a paper substrate, and a binder resin is formed of an ionizing radiation-curable resin on the surface of the sealer resin layer of the paper substrate. A colored ink layer, and a surface protective layer of a transparent ionizing radiation-curable resin are laminated in this order,
Further, decorative paper formed by crosslinking and curing these three layers of ionizing radiation-curable resin and bonding and integrating them. 2. The decorative paper according to claim 1, wherein at least a part of the sealer resin layer is impregnated in a paper base material. 3. The ionizing radiation-curable resin constituting the sealer resin layer is a resin having an acryloyl group as an ionizing radiation-reactive functional group and a hydroxyl group or isocyanate group as a functional group having an affinity for cellulose. The decorative paper according to claim 1 or 2. 4. The ionizing radiation-curable resin constituting the sealer resin layer contains a thermoplastic urethane resin solid at room temperature and silica powder, and is a non-adhesive solid at room temperature in an uncured state. 3. The decorative paper according to 3.