JP2002036484A - Decorative paper and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the generation of coating nonuniformity and the cutting of decorative paper of a paper base material during lamination caused by the deterioration of processability by the decrease of the strength of the paper base material by ionizing radiation even when the surface resin layer of the decorative paper which is incorporated with inorganic particles is crosslinked by being irradiated with the ionizing radiation to improve surface properties such as abrasion resistance. SOLUTION: In the decorative paper S, a highly-elastic resin layer sealer layer 2 of at least 40 MPa tensile strength is formed on the paper base material 1, and a surface resin layer 4 of a crosslinked ionizing radiation curable resin containing the inorganic particles a is formed as the surface layer. A pattern layer 3, etc., can be provided. A decorative material such as a decorative plate is obtained by sticking the decorative paper on a base material by using an adhesive. The gas permeability of a laminate comprising at least the paper base material and the resin sealer layer before forming the surface resin layer is preferably 5,000 s or above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD 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.
The present invention relates to a decorative material that is attached to a base material. In particular, the present invention relates to a decorative paper which has no surface unevenness such as abrasion resistance, has no coating unevenness, has good workability, and is not easily broken at the time of sticking to an adherend substrate, and a decorative material stuck thereto.

[0002]

2. Description of the Related Art Conventionally, decorative paper used for the above-mentioned applications usually requires surface properties such as abrasion resistance and stain resistance. For example, Japanese Patent Publication No. 49-31033 discloses After printing and forming a pattern layer on a paper base, as the outermost layer,
Disclosed is a decorative paper in which an ionizing radiation-curable resin coating material of an unsaturated polyester prepolymer is applied to the surface to form a coating film, and the coating film is cross-linked with an electron beam to form a cured surface resin layer. .

As described above, when a surface resin layer obtained by crosslinking and curing an ionizing radiation-curable resin composed of a monomer, a prepolymer, or the like with an ionizing radiation such as an electron beam is provided on the outermost surface layer of the decorative paper, the high cross-linking is obtained. Thus, a decorative paper having improved surface properties such as abrasion resistance and stain resistance can be obtained.

[0004]

However, in the decorative paper as described above, the cellulose molecules of the parf in the paper base material are cut off with irradiation of ionizing radiation at the time of crosslinking the surface resin layer,
A carboxyl group or a carbonyl group is generated at the cut end. As a result, the strength of the paper substrate deteriorated, and the workability of the decorative paper was reduced. For this reason, when the decorative paper is bonded to an adherend such as a wooden plywood by pressing with a roller through an adhesive between the decorative paper and the decorative paper, the decorative paper is cut due to an increase in tension applied to the decorative paper, mechanical vibration, or the like. There was it. In particular, using a wrapping process or the like to apply decorative paper to the curved surface portion of the adhered substrate,
In the case where the decorative paper is adhered to the corners of the adhered base material of the polygonal prism, there is a problem that the decorative paper is easily broken because local stress is concentrated on the decorative paper.

[0005] In addition, since the paper base material generally has permeability, when the surface resin layer is formed by coating, the coating liquid in a fluid state before complete curing may penetrate into the paper base material. Coating unevenness (permeation unevenness) in which the surface gloss (even high gloss or low gloss) becomes non-uniform may occur. This coating unevenness often occurred particularly when inorganic particles such as silica and alumina were contained in the surface resin layer in order to further improve the surface properties such as abrasion resistance of the surface resin layer. That is, when these inorganic particles are contained in the surface resin layer, it is necessary to use a coating liquid diluted with a solvent to form a solution from the viewpoint of the dispersion stability of the inorganic particles in the coating liquid. This is because such a solvent-diluted coating liquid permeates the paper substrate quickly. For this reason, conventionally, impregnated paper having a high cost but low permeability has been used as a paper base material or a base material in which coating unevenness is unlikely to occur.

Accordingly, an object of the present invention is to provide a paper base material having a surface resin layer formed of a crosslinked product of an ionizing radiation curable resin containing inorganic particles in order to impart excellent surface properties such as abrasion resistance. Even if a low-cost permeable paper base material such as a paper-to-paper reinforced paper is used for paper, the unevenness of the surface resin layer is eliminated, and the processability as decorative paper is improved. It is an object of the present invention to provide a decorative material on which such decorative paper is stuck.

[0007]

Means for Solving the Problems In order to solve the above problems, the decorative paper of the present invention is provided on a paper base material according to JIS K630.
1, a high elastic resin sealer layer having a tensile strength of 40 MPa or more was formed, and a surface resin layer formed of a crosslinked product of an ionizing radiation-curable resin containing inorganic particles was formed as the outermost surface layer.

By providing such a high elastic resin sealer layer and then forming a surface resin layer composed of a crosslinked product of an ionizing radiation curable resin containing inorganic particles, the coating liquid is formed when the surface resin layer is formed. Prevents application unevenness on the surface by penetrating into the paper base material, and furthermore, cellulose molecules of the pulp of the paper base material are cut by irradiation with ionizing radiation when forming the surface resin layer,
Even if the strength of the paper substrate deteriorates, it can compensate for the deterioration and maintain the strength of the decorative paper as a whole. As a result, in addition to having excellent surface properties such as excellent wear resistance by the surface resin layer,
In addition, a decorative paper having good workability can be obtained. Therefore, at the time of laminating, in which the decorative paper is attached to the substrate to be adhered by a roll laminator or the like, every time the mechanical vibration of the processing machine or the continuous band-shaped decorative paper is adhered to the (sheet-fed) substrate, it is transported. It is possible to prevent the decorative paper from being cut due to mechanical shock (momentary increase in tension) when stopping and cutting. In addition, low cost paper between paper sheets or the like can be used as a paper base material.

In the decorative paper according to the present invention, the laminated body comprising at least the paper base material and the highly elastic resin sealer layer before forming the surface resin layer has an air permeability of 5,000. Seconds or more.

By providing at least a highly elastic resin sealer layer on a paper base so as to achieve such air permeability, the sealer effect of the layer can be reliably obtained. Therefore, at the time of forming the surface resin layer, the coating liquid can be prevented from penetrating into the paper base material and causing uneven coating on the surface, and the surface resin layer can more reliably impart surface properties such as excellent wear resistance. .

Further, the decorative material of the present invention has a configuration in which any of the decorative papers described above is bonded to a substrate to be adhered with an adhesive. By making the decorative material such a configuration, there is no coating unevenness, and it has excellent surface properties such as abrasion resistance, and also, since the decorative paper can be prevented from breaking when it is adhered to the base material, It becomes a cosmetic material that can be manufactured with good yield.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the decorative paper and the decorative material of the present invention will be described.

FIG. 1 is a sectional view showing an embodiment of the decorative paper according to the present invention. The decorative paper S of FIG.
A high elastic resin sealer layer 2, a pattern layer 3, and a surface resin layer 4 having specific mechanical properties are sequentially laminated, and the surface resin layer 4
In this configuration, inorganic particles a are included. Also,
FIG. 2 is a cross-sectional view showing one embodiment of the decorative material of the present invention. The decorative material D shown in FIG. 2 is such that the decorative paper S as shown in FIG. 1 has an adhesive layer 5 between the paper substrate 1 side and the adhered substrate 6 side.
, And is laminated on the adherend base material 6 via.

As shown in FIG. 1, the decorative paper S of the present invention has a paper substrate 1
A high elastic resin sealer layer 2 is formed thereon, and a surface resin layer 4 containing inorganic particles a as a surface layer is formed as a surface layer on the surface side of the decorative paper. Often provided. The high elastic resin sealer layer 2
When the surface resin layer 4 is formed into a crosslinked material, the strength of the paper base material due to ionizing radiation is compensated for. Further, the high elastic resin sealer layer 2 is interposed between the paper base material 1 and the surface resin layer 4 to prevent the coating liquid for forming the surface resin layer from penetrating into the paper base material and causing uneven coating. In addition, in terms of this sealer function, the coating amount of the coating liquid for forming the high elastic resin sealer layer is at least a paper substrate to be coated with the surface resin layer forming coating liquid and the high elastic resin sealer layer. It is preferable that the air permeability of the laminate (which may have a picture layer) is 5000 seconds or more, since the effect can be surely obtained. Of course, of these layers, the picture layer 3 is a layer provided as needed, and the picture layer can be omitted as appropriate if there is no problem in design. Further, other layers such as providing a primer layer between the picture layer 3 and the surface resin layer 4 may be appropriately provided as necessary in terms of physical properties, production suitability, and the like.

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

[Paper Base] As the paper base 1, known base paper for decorative paper such as impregnated paper or non-impregnated paper is used. In particular, an object of the present invention is that cellulose molecules of the pulp are cut by ionizing radiation (especially electron beams) penetrating into the paper substrate during crosslinking and curing of the surface resin layer serving as the surface layer,
As a result, carboxyl groups or carbonyl groups are formed at the cut ends, and the pulp is made of pulp whose strength is deteriorated. Specific examples of the paper base material include thin paper, paper between sheets, kraft paper, woodfree paper, linter paper, baryta paper, parchment paper, Japanese paper, and the like. Among them, in the present invention, since a highly elastic resin sealer layer is provided, an inexpensive but permeable inter-sheet reinforced paper or the like is preferable. Further, the basis weight of the paper base material is usually 20 to 150.
g / m ² , and preferably about 20 to ²⁰⁰ μm in terms of thickness. Further, as a measure for improving the coating unevenness by the paper base material itself, the degree of shouting may be improved, and the numerical value of the air permeability may be increased (permeability reduced) by a super calendar or the like. As the pulp type, it is preferable to use hardwood (L material) pulp from the viewpoints of printability of a pattern layer and the like, uniformity of formation, and the like. In addition, softwood (N material) pulp is suitable for printing,
Although it is inferior to hardwood pulp in terms of formation uniformity, it is stronger in terms of pulp strength, so it compensates for the decrease in pulp strength due to ionizing radiation (especially electron beam) and raises pulp strength. preferable. In order to compensate for the deterioration in printability and formation uniformity of the N-material pulp, calendering, addition of a coloring pigment, or the like may be used.

[High elastic resin sealer layer] The high elastic resin sealer layer 2 exhibits high elasticity such that the tensile strength of the layer according to JIS K6301 becomes 40 MPa (corresponding to about 400 kgf / cm ² ) or more. To compensate for the decrease in strength of
It is a resin layer that also has a sealer function. The resin forming such a resin layer is basically not particularly limited as long as the resin satisfies at least the above mechanical properties and the sealer function. For example, a thermoplastic resin, a thermosetting resin, or the like can be used. Specifically, the high elastic resin sealer layer, polyester polyol resin, acrylic urethane resin by acrylic polyol and isocyanate, or a resin such as urethane resin, if appropriately selected from those satisfying the above mechanical properties, if used. good. The high elastic resin sealer layer
A coating solution composed of such a resin may be formed on a paper substrate by a known coating method such as roll coating. A solvent such as an organic solvent or water is appropriately used for the coating liquid. The coating amount depends on the original strength of the paper base material, the amount of ionizing radiation when the surface resin layer is crosslinked, the permeability of the paper base material, the application, and the like.
g / m ² (based on solid content).

By forming such a high elastic resin sealer layer on a paper base, cellulose molecules on the paper base are irradiated by ionizing radiation (especially electron beam) during crosslinking and curing of the surface resin layer formed as the surface layer. It is possible to compensate for the strength deterioration due to the cutting and prevent the coating unevenness. In order to improve the processability as decorative paper due to the strength deterioration, the tensile strength of the high elastic resin sealer layer is preferably set to 40 MPa or more. By the way, there is no particular upper limit of the tensile strength, but since the tensile strength of ordinary resin is 80 to 90 MPa, the upper limit is naturally about this (maximum about 90 MPa).
Becomes The tensile strength is a characteristic value of only the high elastic resin sealer layer, not the strength of the high elastic resin sealer layer integrated with other decorative paper constituent layers such as a paper base, that is, the decorative paper. . The tensile strength is a value obtained by forming a single layer of only the high elastic resin sealer layer and performing a tensile test on the single layer. In order to form a high elastic resin sealer layer as a single layer, a release sheet such as a polyethylene terephthalate film or a silicone resin, the surface of which has been treated with a release agent such as wax, not on a paper base, is used. After applying a coating liquid on a release sheet such as a coated release paper to form a high elastic resin sealer layer (the thickness may be thicker than that of an actual decorative paper), a high elastic resin sealer It can be obtained by peeling off only the layer. In the present invention, JIS K6
The tensile strength according to 301 (Vulcanized rubber physical test method)
It is a value measured according to the standard.

The high elastic resin sealer layer may contain a known extender, a coloring agent, or the like, as needed, for adjusting physical properties such as coating suitability, or expressing a design. If a coloring agent is contained, all of the following solid layers of the picture layer can be used. Further, the high elastic resin sealer layer may be a layer integrated with the paper base as a layer in the paper base by impregnating (permeating) all into the paper base, or a part of the paper base. It may be in a state of being impregnated therein, and the high elastic resin sealer layer and the paper substrate may be overlapped and integrated near the interface.

The amount of the high elastic resin sealer layer to be applied is determined as follows. Before forming the surface resin layer, the air permeability of at least the laminate composed of the paper substrate and the high elastic resin sealer layer is 5000 seconds or more. It is preferable to make That is, when a surface resin layer is formed on a laminate composed of a paper base material and a high elastic resin sealer layer without providing a picture layer, the air permeability in the laminate may be 5000 seconds or more. .
When a surface resin layer is formed on a printing paper on which a picture layer is formed by printing, the air permeability of the printing paper may be 5000 seconds or more. In addition, the air permeability of the printing paper after the formation of the picture layer is usually higher than the air permeability of the laminate composed of the paper base material and the highly elastic resin sealer layer. The air permeability can be measured with a pressurized smoothness / air permeability tester or the like. The measurement may be performed according to JIS P8117. In the case of decorative paper base paper which is conventionally used for decorative paper and has uneven coating, such as ordinary paper and paper between sheets, the air permeability is at most about 100 seconds even if the numerical value is high.

[Pattern Layer] The pattern layer 3 is a layer for expressing a pattern or the like, and is usually provided, but may be omitted when unnecessary. When a picture layer is provided, there is no particular limitation on the contents of the picture layer, such as the method of forming the picture layer, the material, and the picture.
The pattern layer is usually formed by a conventionally known printing method such as gravure printing, silk screen printing, offset printing, gravure offset printing, and ink jet printing using ink. The pattern is, for example, wood pattern, stone pattern, cloth pattern, tile pattern, brick pattern, leather pattern,
Characters, geometric patterns, solid colors, etc. When the entire surface is solid, it can be formed by coating with a coating solution. The ink (or coating liquid) used to form the picture layer includes a vehicle such as a binder, a coloring agent such as a pigment or a dye, and various additives such as an extender pigment, a stabilizer, a plasticizer, a catalyst, and a curing agent, which are appropriately added thereto. The binder resin may be appropriately selected from a thermoplastic resin, a thermosetting resin, an ionizing radiation-curable resin, and the like according to required physical properties, printability, and the like. For example, cellulosic resins such as nitrocellulose, cellulose acetate, cellulose acetate propionate, poly (methyl) acrylate, poly (butyl methacrylate), methyl (meth) acrylate-
Use of an acrylic resin such as butyl (meth) acrylate-dihydroxyethyl (meth) acrylate copolymer, a urethane resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, an alkyd resin, or a mixture containing these. . In addition, as the coloring agent, titanium white, carbon black, red iron oxide, graphite, inorganic pigments such as ultramarine blue, aniline black, quinacridone red, isoindolinone yellow,
Organic pigments such as phthalocyanine blue, glitter pigments such as titanium dioxide-coated mica, foil powder such as aluminum, and other dyes are used.

When a colorant is added to the high elastic resin sealer layer itself or the paper substrate itself and the design expression by the layer is sufficient, the pattern layer may be omitted.

[Surface Resin Layer] The surface resin layer 4 is a surface layer on the outermost surface of the decorative paper, and is composed of a crosslinked product of an ionizing radiation-curable resin (composition) containing inorganic particles. The surface resin layer is a liquid ionizing radiation curable resin (composition)
Is applied by gravure coating, roll coating or the like, and the coating film is crosslinked by irradiation with ionizing radiation to form a crosslinked product containing inorganic particles. In addition, you may form by full solid printing by gravure printing etc. Coating amount is 1 to 30 g / m ²
(Based on solid content).

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 cationic polymerizable functional group in a molecule is appropriately mixed. A composition which can be cross-linked and cured by ionizing radiation is preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle having an energy capable of polymerizing or cross-linking a molecule, and is generally an electron beam (EB) or an ultraviolet ray (UV). However, electron beams are more susceptible to strength degradation due to cellulose molecule fragmentation of the paper substrate than ultraviolet rays,
Since the purpose of the present invention is to compensate for this strength deterioration, an ionizing radiation-curable resin of the type utilizing electron beam irradiation for crosslinking is particularly suitable.

The above-mentioned prepolymer or monomer specifically has a radically polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, a cationically 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. Etc. can be used.
A molecular weight of about 250 to 100,000 is usually used. In addition, (meth) acrylate means acrylate or methacrylate.

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 resins and novolak type epoxy compounds.
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.

When crosslinking with ultraviolet rays, a photopolymerization initiator is added to the ionizing radiation-curable resin. 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.

On the other hand, the inorganic particles to be contained in the ionizing radiation-curable resin are, of course, inorganic particles harder than the cured product of the ionizing radiation-curable resin in order to further improve surface properties such as abrasion resistance. used. Examples of the material of such inorganic particles include alumina (such as α-alumina), aluminosilicate, silica, glass, silicon carbide, boron nitride, and diamond. The shape of the inorganic particles is a sphere, a polygon (a cube, a regular octahedron, another polyhedron, or the like), 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. For example, specifically, the average particle size 2
Α-alumina particles having a size of about 5 μm, silica particles having a mean particle size of about 5 μm, and the like are used. The average particle size is preferably in the range of 0.3 to 2.0 times the thickness of the surface resin layer. If it is less than this range, it is difficult to obtain a sufficient effect of improving abrasion resistance, and if it exceeds this range, the surface becomes rough or the feel to the touch deteriorates. In addition, the addition amount of the inorganic particles,
It is about 5 to 30% by mass relative to the total amount of the resin.

Incidentally, various additives may be added to the ionizing radiation-curable resin, if necessary. As these additives, for example, extender (filler) composed of fine powders such as thermoplastic resin such as vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin and cellulose resin, calcium carbonate and barium sulfate ), Lubricants such as silicone resin and wax, and coloring agents such as dyes and pigments.

As the electron beam source of ionizing radiation, various electron beam accelerators such as Cockcroft-Walton type, Van degraft type, Resonant transformer type, Insulating core transformer type, Linear type, Dynamitron type, High frequency type, etc. Using 100
-1000 keV, preferably 200-300 keV
A device that irradiates an electron having an energy of?
Ultraviolet light sources, ultra-high pressure mercury lamps, high pressure mercury lamps,
Light sources such as a low-pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp are used. As a wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm is usually mainly used.

[Cosmetic Material] The decorative material of the present invention can be obtained by applying the above-described decorative paper of the present invention to the surface of the substrate to be adhered with an adhesive. The decorative material D shown in the cross-sectional view of FIG. 2 is one form thereof. In the decorative material D shown in the figure, the decorative paper S of the present invention having the structure as illustrated in FIG.
It is a configuration stuck to.

[Deposited Substrate] The substrate to be deposited 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. In particular,
Inorganic nonmetals include, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium silicate, gypsum, gypsum slag, etc. Non-ceramic ceramic materials, earthenware,
There are inorganic materials such as ceramics such as pottery, porcelain, setware, glass, and enamel. In the case of metallic materials, for example, iron,
There are metal materials such as aluminum and copper. In the wood system, for example, there are a veneer, a plywood, a particle board, a fiber board, a laminated wood and the like made of cedar, cypress, oak, lauan, teak 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.

[Adhesive] The adhesive for bonding the decorative paper and the adherend substrate as the adhesive layer 5 is not particularly limited. An appropriate adhesive may be selected and used from known adhesives according to the material, application, required physical properties, and the like of the substrate to be adhered. For example, an adhesive made of a thermoplastic resin such as a polyamide resin, an acrylic resin, or a vinyl acetate resin, or a curable resin such as a thermosetting urethane resin is used as the adhesive. The adhesive may be applied by a known coating method such as roll coating.
Note that the adhesive is applied to the adherend, the decorative paper, or both, and then the decorative paper is bonded to the adherend.

[Applications] The applications of the decorative paper and the decorative material of the present invention are not particularly limited, but include interior materials for buildings such as walls, floors, and ceilings, doors, door frames, window frames and other fittings, rims, and the like. Used for building members such as skirting boards, furniture such as chests and cabinets.

[0037]

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

[First Embodiment] A decorative paper S having a structure as shown in FIG.
(Decorative paper) was produced as follows. A paper base material 1 is a building material base paper made of L-material pulp (hardwood pulp) having a basis weight of 50 g / m ² , and the entire surface of one side is subjected to gravure printing to obtain an average molecular weight of 2 as a polyester-based thermoplastic resin.
A high elastic resin sealer layer 2 (tensile strength: 40 MPa) using 0000 polyester polyol was formed so as to have a coating amount of 1.5 g / m ² on a solid content basis.

Next, on the high elastic resin sealer layer, a colored solid layer and a wood pattern pattern layer were sequentially formed as a picture layer 3 by gravure printing to obtain a printing paper. For the colored solid layer, a mixed resin of an acrylic resin and nitrocellulose was used as a binder, and as a coloring agent, an ink mainly containing titanium white, graphite and red iron oxide was used. Further, for the pattern pattern layer, a mixed resin of nitrocellulose and alkyd resin was used as a binder, and as the coloring agent, a red ink was used, which was mainly composed of a red pattern and carbon black. The air permeability of the printing paper measured with a pressurized smoothness / air permeability tester was 5,000 seconds.

On the pattern layer of the printing paper, 60 parts by mass of a polyester acrylate prepolymer, 10 parts by mass of trimethylolpropane triacrylate,
It contains 29 parts by mass of 6-hexanediol diacrylate, 1 part by mass of silicone acrylate, and 20 parts by mass of spherical α-alumina particles having an average particle size of 25 μm as inorganic particles, and is diluted with ethyl acetate so as to have a solvent content of 50% by mass. The applied ionizing radiation (electron beam) curable resin paint is applied by a roll coating method so as to have a coating amount of 25 g / m ² (based on solid content), dried, and then irradiated with an electron beam (175 keV, 5
The surface resin layer 4 containing the inorganic particles a was formed as a crosslinked product by applying 0 kGy (5 Mrad) to obtain a decorative paper S.

Next, after applying the vinyl acetate-based adhesive to the decorative paper S on an MDF (medium fiber board) having a thickness of 3 mm as the substrate 6 to be adhered, the paper substrate side of the decorative paper is adhered to the substrate. The decorative material (decorative board) of the present invention as shown in FIG. 2 was obtained by sticking with a roll laminator so as to face the material. That is, the decorative material D shown in FIG. 2 includes a paper substrate 1, a highly elastic resin sealer layer 2, a picture layer 3, and inorganic particles on the adhered substrate 6 via the adhesive layer 5 from the adhered substrate side. Surface resin layer 4 containing a
Is a configuration in which decorative paper S made of is adhered and laminated.

Example 2 In Example 1, the coating amount (solid basis) of the high elastic resin sealer layer having a tensile strength of 40 MPa was changed to 2.3 g / m ² , and A decorative paper was obtained in the same manner as in Example 1 except that the air permeability was 7,500 seconds. A decorative material was obtained using this decorative paper in the same manner as in Example 1.

Example 3 In Example 1, a polyester thermoplastic resin having a tensile strength of 55 MPa was used as the resin of the high elastic resin sealer layer, and the coating amount (based on solid content) of the high elastic resin sealer layer was used. Was changed to 3.2 g / m ² and the air permeability of the printing paper was set to 10,000 seconds, except that a decorative paper was obtained in the same manner as in Example 1. A decorative material was obtained using this decorative paper in the same manner as in Example 1.

Comparative Example 1 A decorative paper Sa as shown in FIG. 4 was obtained in the same manner as in Example 1 except that the formation of the high elastic resin sealer layer was omitted. A decorative material was obtained using this decorative paper in the same manner as in Example 1. The air permeability of the printing paper was 300 seconds.

Comparative Example 2 In Example 1, the coating amount (solid basis) of the high elastic resin sealer layer having a tensile strength of 40 MPa was changed to 0.7 g / m ² , and A decorative paper was obtained in the same manner as in Example 1 except that the air permeability was changed to 1000 seconds. A decorative material was obtained using this decorative paper in the same manner as in Example 1.

Comparative Example 3 In Example 1, the coating amount (solid basis) of the high elastic resin sealer layer having a tensile strength of 40 MPa was changed to 1.0 g / m ² , and A decorative paper was obtained in the same manner as in Example 1 except that the air permeability was set to 4000 seconds. A decorative material was obtained using this decorative paper in the same manner as in Example 1.

[Comparative Example 4] In Example 1, the resin of the high elastic resin sealer layer was a polyester-based thermoplastic resin having a tensile strength of 30 MPa, and the applied amount (solid basis) was 1.5 g. / M ² , and a decorative paper was obtained in the same manner as in Example 1, except that the air permeability of the printing paper was changed to 5000 seconds. A decorative material was obtained using this decorative paper in the same manner as in Example 1.

[Evaluation of Performance] In each of Examples and Comparative Examples, coating unevenness and workability were evaluated by the following evaluation methods.
The results are summarized in Table 1.

(1) Uneven coating: The occurrence of uneven coating on the surface of the surface resin layer was visually observed and evaluated.

(2) Workability: A roll laminator was used to evaluate the occurrence of paper breakage when a continuous strip of decorative paper was bonded to an adherend with an adhesive. Good if no paper breaks,
If it occurred, it was regarded as defective.

[0051]

[Table 1]

[Consideration of Results] First, as shown in Table 1, the coating unevenness was evaluated by providing a highly elastic resin sealer layer and having an air permeability of 5000.
Seconds or more, and the resin has a (high elasticity) resin sealer layer with a tensile strength of less than 40 MPa and an air permeability of 500
No occurrence occurred in Comparative Example 4, which was 0 seconds or longer. However, Comparative Example 1 in which the high elastic resin sealer layer was not provided and Comparative Examples 2 and 3 in which the layer was provided but the air permeability was less than 5000 seconds occurred.

The workability was determined in each of the examples and comparative example 2.
In Nos. 1 to 3, the workability was all good because a high elastic resin sealer layer having a tensile strength of 40 MPa or more was provided. However, Comparative Example 1 in which the high elastic resin sealer layer was omitted, and
(High elasticity) 40M tensile strength even with resin sealer layer
In Comparative Example 4, which was less than Pa, paper breakage occurred and was poor.

[0054]

(1) According to the decorative paper of the present invention, a surface resin comprising a crosslinked product of an ionizing radiation-curable resin containing inorganic particles, after providing a high elastic resin sealer layer with specific mechanical properties. Since the layer is formed, it is possible to prevent the coating liquid from penetrating into the paper base material during the formation of the surface resin layer, thereby preventing the occurrence of coating unevenness on the surface. Moreover, even if cellulose molecules of the pulp of the paper substrate are cut by irradiation with ionizing radiation during the formation of the surface resin layer and the strength of the paper substrate deteriorates, the strength of the decorative paper as a whole can be maintained by supplementing it. it can. As a result, in addition to having excellent surface properties such as abrasion resistance by the surface resin layer, the processability of the decorative paper is also improved. Therefore, at the time of laminating, in which the decorative paper is attached to the substrate to be adhered by a roll laminator or the like, every time the mechanical vibration of the processing machine or the continuous band-shaped decorative paper is adhered to the (sheet-fed) substrate, it is transported. It is possible to prevent the decorative paper from being cut due to mechanical shock (momentary increase in tension) when stopping and cutting. In addition, low cost paper between paper sheets or the like can be used as a paper base material. (2) Further, before forming the surface resin layer, the high elastic resin sealer layer is provided so that the air permeability of the laminate composed of at least the paper base material and the high elastic resin sealer layer is 5000 seconds or more. In this way, it is possible to reliably obtain the sealing effect of the layer. Therefore, at the time of forming the surface resin layer, the coating liquid can be prevented from penetrating into the paper base material and causing uneven coating on the surface, and the surface properties such as excellent abrasion resistance by the surface resin layer can be improved.
It can be provided more reliably.

(3) According to the decorative material of the present invention, due to the effect of the decorative paper, there is no coating unevenness, excellent surface properties such as abrasion resistance, and good workability. Since the paper is adhered to the adhered substrate, it is possible to prevent the paper from being broken at the time of adhering and to provide a cosmetic material that can be manufactured with a high yield.

[Brief description of the drawings]

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

FIG. 2 is a cross-sectional view illustrating one embodiment of the cosmetic material of the present invention.

FIG. 3 is a cross-sectional view showing an example of a conventional decorative paper.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Paper base material 2 High elastic resin sealer layer 3 Picture layer 4 Surface resin layer 5 Adhesive layer 6 Adhered base material a Inorganic particle D Cosmetic material S Decorative paper Sa Conventional decorative paper

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AA01C AK01C AK80B AR00D BA03 BA05 BA07 BA10A BA10C BA10D CB00 DE01C DG10A EJ05C EJ52C GB07 GB81 HB00D JK02B JK09 JL14C YY00 YY00B 4J002 AA021

Claims (3)

[Claims] 1. A highly elastic resin sealer layer having a tensile strength of 40 MPa or more according to JIS K6301 is formed on a paper base material, and then a crosslinked product of an ionizing radiation curable resin containing inorganic particles as an outermost surface layer. Decorative paper with a surface resin layer formed. 2. The decorative paper according to claim 1, wherein the air permeability of the laminate comprising at least the paper base and the high elastic resin sealer layer before forming the surface resin layer is 5000 seconds or more. 3. A decorative material obtained by bonding the decorative paper according to claim 1 or 2 to an adherend substrate with an adhesive.