JP2000238196A - Decorative paper having wear resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain decorative paper excellent in wear resistance and weatherability by forming an ionizing radiation curable resin layer having high hardness without damaging flexibility on the surface of a permeable fibrous base material such as paper or the like. SOLUTION: Decorative paper 1 excellent in wear resistance is produced by forming a pattern layer 12 on a fibrous base material 11 and coating this fibrous base material with a mixture of a two-pack type curable urethane resin and a butyral resin or a coating soln. comprising an acrylic resin in order to suppress the penetration of an ionizing radiation curable resin into the fibrous base material 11 to form a sealer layer 13 and coating the sealer layer 13 with the ionizing radiation curable resin containing spherical alumina 15 and irradiating the coating layer with ionizing radiation to cure the same to form a cured ionizing radiation curable resin layer 14.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to be used as interior decoration of floors, walls, ceilings, etc. of buildings, surface decoration materials such as furniture and various cabinets, surface decoration of fittings, interior decoration of vehicles, etc. More particularly, the present invention relates to decorative paper used for applications requiring surface abrasion resistance and weather resistance.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used for decorative surfaces of building interiors, furniture, cabinets, etc., a printing ink layer such as a pattern layer or a solid printing layer is provided on one side of a base sheet. In order to protect the ink layer, as a top coat layer, a thermosetting urethane resin or the like is applied, and then dried and thermally cured to form a thermosetting resin layer, or an ionizing radiation-curable resin is applied. There is a method in which a coating film is cured by irradiating with ionizing radiation to form a cured ionizing radiation-curable resin layer on the surface. In particular, an ionizing radiation-curable resin layer cured using an ionizing radiation-curable resin having a high crosslinking density has excellent physical properties such as surface hardness, chemical resistance, and stain resistance.

[0003] By using a hard resin as the binder resin as described above, the wear resistance is certainly improved. Therefore, in the case of a decorative material using a hard base material, such as a melamine decorative board, the flexibility of the surface resin layer does not matter so much. As a method of improving abrasion resistance, a hard resin is used on the surface. Doing so is an effective means. However, when using a flexible base material such as thin paper or plastic sheet as the base material, if the cross-linking density of the resin is increased, the flexibility of the resin layer will be impaired, and the surface resin layer will have an impact. This causes problems such as cracks and cracks. Therefore, there is a limit in the case where flexibility is required even if an attempt is made to improve the abrasion resistance by increasing the crosslink density of the surface resin.

[0004] Therefore, as a method of improving abrasion resistance without reducing the flexibility of the resin layer, a method of adding an inorganic material to the resin layer has been conventionally performed. For example, Japanese Patent Application Laid-Open No. 60-23642 discloses that the average particle size used as an abrasive such as a sand blast method or a brush polishing method is 1%.
Silica (SiO ₂ ) and alumina (Al ₂
It is disclosed that a surface resin layer is formed using a paint containing a powder of natural glass containing O ₃ ) as a main component. The surface protective layer formed by the above-mentioned paint had higher hardness and flexibility than conventional products, and exhibited physical properties with excellent wear resistance and scratch resistance.

Further, in the case of a transfer sheet, in order to improve abrasion resistance and abrasion resistance of the surface of the transfer-receiving body after transfer,
To the ionizing radiation-curable resin forming the surface protective layer, an alumina powder having an average particle size of 1 to 5 μm is added in an amount of 10 to 30 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin. It is disclosed that a protective layer of a transfer sheet is formed using a resin.

[0006]

However, when a protective layer of a decorative sheet is formed using a coating material to which an inorganic filler such as alumina or natural glass powder is added, the resistance of the decorative material is higher than that of the case where no inorganic material is added. Although the abrasion is improved, when an impregnable substrate such as paper is used as the substrate sheet, there is a problem that the coating liquid impregnates the paper and a required coating film cannot be obtained.

That is, in order to obtain an ionizing radiation-curable resin layer having a high hardness without impairing flexibility, it is necessary to increase the crosslink density of the ionizing radiation-curable resin, and to obtain a polyfunctional ionizing radiation-curable resin having a small molecular weight. You need to use However, since the ionizing radiation-curable resin having a small molecular weight has a low viscosity, when it is applied to paper, it is impregnated into the paper, and a coating film of a required thickness cannot be obtained on the surface of the paper. Also, when an ionizing radiation-curable resin to which spherical alumina is added is applied, the ionizing radiation-curable resin impregnates the paper to reduce the amount of ionizing radiation-curable resin holding the spherical alumina, and the spherical alumina is cured by ionizing radiation. Is not sufficiently retained by the conductive resin layer,
Sufficient wear resistance cannot be exhibited.

Therefore, when an ionizing radiation-curable resin layer is formed on the surface using an impregnating substrate such as paper, it is necessary to increase the thickness of the ionizing radiation-curable resin layer in order to stably obtain predetermined physical properties. there were. However, increasing the application amount of the ionizing radiation-curable resin also increases the amount of expensive spherical alumina used, which increases the manufacturing cost. In addition, when the amount of the ionizing radiation-curable resin applied is increased, the decorative paper curls intensely due to shrinkage that occurs when the ionizing radiation-curable resin is cured. Therefore, in the post-processing of decorative paper,
Workability deteriorates, leading to an increase in production cost, which is a major problem.

Further, when a substrate is coated by a gravure roll coating method using a coating liquid containing an inorganic filler, alumina or natural glass powder of the inorganic filler has a polygonal shape with sharp corners. The roll and the doctor blade were worn or damaged, which was a serious problem in processing. Further, a coating film formed by using a coating liquid to which a hard, sharp-pointed polygonal powder is added has a poor touch feeling and cannot be used for a touch-sensitive one.
In addition, when used as a flooring material, there is another problem that, when the decorative material comes into direct contact with the decorative material, such as footwear, the object is worn.

[0010]

Means for Solving the Problems In order to solve the above problems, the configuration of the decorative paper is as follows. For fibrous base materials,
A decorative paper was obtained by laminating a picture layer, a sealer layer and a cured ionizing radiation-curable resin layer in this order.
Further, the decorative paper is characterized in that the sealer layer is made of a resin composition using an acrylic resin or a blend resin of a butyral resin and a urethane resin as a binder.
Further, the decorative paper is characterized in that the ionizing radiation-curable resin layer contains 15 to 20% by weight of alumina, and the applied amount is 10 to 22 g / m ² as a cured resin composition. did. The sealer layer suppresses the penetration of the ionizing radiation-curable resin composition into the impregnating substrate when the ionizing radiation-curable resin composition is applied to an impregnating substrate such as a fibrous substrate. It means a coating film formed in order to perform coating.

That is, on the surface of the impregnated fibrous base material,
When producing a decorative paper by laminating a pattern layer, a sealer layer and a cured ionizing radiation curable resin layer, by using an acrylic resin as a binder resin of the sealer layer, or a blend resin of a butyral resin and a urethane resin, The application amount of the ionizing radiation-curable resin containing alumina is 10
２２22 g / m ² , which solved the problem of curling of decorative paper. Further, the amount of expensive spherical alumina added to the ionizing radiation-curable resin is 15 to 20.
% By weight, and the production cost could be reduced. And by making the decorative paper into the above configuration, a decorative paper excellent in wear resistance and weather resistance was obtained.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the decorative paper of the present invention. FIG. 2 is a schematic cross-sectional view of a decorative paper according to another embodiment of the present invention when spherical ionizing alumina is contained in the ionizing radiation-curable resin layer. FIG. 3 is an explanatory diagram for producing the decorative paper of the present invention. FIG. 4 is an explanatory diagram for producing a decorative paper containing spherical alumina in the ionizing radiation-curable resin layer. FIG. 5 is an explanatory diagram when producing decorative paper according to the first embodiment, and FIG. 6 is an explanatory diagram when producing decorative paper according to the fifth embodiment. FIG. 7 is an explanatory diagram for producing a decorative paper according to Comparative Example 1.

As shown in FIG. 1, the decorative paper of the present invention basically comprises an impregnable fibrous base material 11, a picture layer 12,
Sealer layer 13 and cured ionizing radiation curable resin layer 1
4 As shown in FIG. 2, spherical alumina 15 is contained in the cured ionizing radiation-curable resin layer 14.
And further improved abrasion resistance. That is, the feature of the present invention is that after forming a picture layer 12 on a permeable fibrous base material 11 such as paper by printing or the like, a sealer layer 13 is formed on the When the curable ionizing radiation-curable resin is applied, by suppressing the penetration into the fibrous base material 11, the amount of the ionizing radiation-curable resin applied is reduced, which occurs when the ionizing radiation-curable resin is cured. This prevents curling of decorative paper. In particular, by forming a thin ionizing radiation-curable resin layer containing spherical alumina, it is possible to prevent decorative paper from curling and to produce decorative paper excellent in wear resistance and weather resistance. In addition, by reducing the thickness of the ionizing radiation-curable resin layer containing spherical alumina, the amount of expensive spherical alumina used is reduced, and the production cost can be reduced.

In order to increase the hardness of the ionizing radiation-curable resin layer forming the surface protective layer without impairing flexibility, the ionizing radiation-curable resin has a higher crosslink density when cured by irradiation with ionizing radiation. Thus, it is necessary to use a polyfunctional ionizing radiation-curable resin having a small molecular weight. However, the ionizing radiation-curable resin with a small molecular weight has a low viscosity, so when it is applied to a permeable substrate such as paper, it penetrates into the substrate and has the required thickness on the surface of the substrate. It was difficult to form a coating. Therefore, it was necessary to increase the coating amount to form a wear-resistant ionizing radiation-curable resin layer, but when the coating amount of the ionizing radiation-curable resin is increased,
Due to the shrinkage that occurs when the ionizing radiation-curable resin is cured, curling of the decorative paper becomes severe, and in post-processing of the decorative paper, workability has become a serious problem.

Therefore, in the present invention, after forming a picture layer on a permeable fibrous base material, the purpose is to prevent the uncured ionizing radiation-curable resin from penetrating into the fibrous base material. By forming a sealer layer using an acrylic resin or a blend resin of a butyral resin and a urethane resin, a required coating film can be formed even with an ionizing radiation curable resin having a small molecular weight and a low viscosity. Further, when forming the ionizing radiation-curable resin layer containing spherical alumina, by forming the spherical alumina content in the range of 15 to 20% by weight and applying the spherical alumina in the range of 10 to 22 g / m ² , the cosmetic is formed. The curl of the paper was reduced, the productivity was improved, and the production cost was able to be reduced.

Further, by using scale-like alumina, titanium dioxide-coated mica, fish scale foil or other scale-like particles as a filler instead of spherical alumina, a coating liquid for a permeable base material such as paper is used. Therefore, it is possible to form a coating film made of an ionizing radiation-curable resin containing a flaky filler, thereby producing a decorative paper having excellent wear resistance.

Hereinafter, a method for producing a decorative paper according to the present invention will be described. First, as shown in FIG. 3A, an impregnating paper or a synthetic paper is used as the fibrous base material 11, and the fibrous base material 11 is coated on the fibrous base material 11 by gravure printing or the like.
2a and a picture layer 12 such as a wood grain pattern are formed. Next, as shown in FIG. 3B, in order to reduce the amount of the ionizing radiation-curable resin penetrating into the fibrous base material 11, the fibrous base material 1
A sealer layer 13 is formed on the side of the first pattern layer 12 with a thickness of 2 to 5 μm using a coating liquid composed of a blended resin of a two-component curable urethane resin and a butyral resin. In addition, as a sealer layer 13, a coating liquid using an acrylic resin is used.
It may be formed with a thickness of 30 to 150 μm.

Next, as shown in FIG. 3C, a polyfunctional ionizing radiation-curable resin having a small molecular weight is applied to form an uncured ionizing radiation-curable resin layer 14a. In the present invention, even if the ionizing radiation-curable resin having a low viscosity and being permeable, the penetration into the fibrous base material is suppressed by the sealer layer 13, so that the uncured ionizing radiation-curable resin can be coated with a relatively small coating amount. Layer 14a can be formed.
Next, as shown in FIG. 3D, the uncured ionizing radiation-curable resin layer 14a is irradiated with ionizing radiation 16 such as an electron beam or an ultraviolet ray to crosslink and cure the ionizing radiation-curable resin. The decorative paper 1 having the ionizing radiation curable resin layer 14 cured on the surface is produced. Since the decorative paper 1 thus obtained has a highly protective ionizing radiation curable resin layer having a high crosslinking density and a high hardness as a surface protective layer, it has flexibility and excellent abrasion resistance.

Further, by using a coating liquid obtained by adding spherical alumina to an ionizing radiation-curable resin to form an ionizing radiation-curable resin layer containing spherical alumina on the surface, a cosmetic with more excellent wear resistance can be obtained. You can get paper. Also in this case, similarly to the above, as shown in FIGS. 4A and 4B, the solid printed layer 12a and the picture layer 12
After printing, the sealer layer 13 is formed.

Next, a coating liquid was prepared by adding 15 to 20% by weight of spherical alumina having an average particle diameter of 10 to 30 μm to the ionizing radiation-curable resin, and using this coating liquid, a coating liquid was prepared as shown in FIG.
As shown in (1), an uncured ionizing radiation-curable resin layer 14a containing spherical alumina 15 is formed by coating on the sealer layer 13. In this case, since the uncured ionizing radiation-curable resin is prevented from penetrating into the fibrous base material by the sealer layer 13, the spherical alumina 15 maintains the state held by the uncured ionizing radiation-curable resin layer 14a. I do.

Next, as shown in FIG. 5 (d), the uncured ionizing radiation-curable resin layer 14a containing the spherical alumina 15 is irradiated with ionizing radiation 16 such as an electron beam or ultraviolet ray to cure the ionizing radiation. The decorative paper 1 is produced by crosslinking and curing the reactive resin to form a cured ionizing radiation-curable resin layer 14 containing spherical alumina 15 on the surface. In the decorative paper 1 obtained, an ionizing radiation-curable resin layer having a high crosslinking density is formed as a surface protective layer, and the spherical alumina is firmly fixed to the ionizing radiation-curable resin. It exhibits sufficient wear properties, has flexibility, and has extremely excellent wear resistance.

The cured ionizing radiation-curable resin layer 14 containing the spherical alumina 15 has an average particle diameter of 10 to 30.
It contains 15 to 20% by weight of a spherical alumina having a particle size of 15 to 20 g / m ² , and the content of the spherical alumina and the amount of the applied spherical alumina are smaller than before. That is, conventionally, it was necessary to increase the coating amount in consideration of the amount of the ionizing radiation-curable resin impregnating the paper. Therefore, the addition amount of spherical alumina was 21 to 25% by weight, and the coating amount was 23 to 3%.
Although it was 0 g / m ² , in the present invention, about 20% of expensive spherical alumina was used, and its coating amount was 22 to 25%.
Could be reduced. As the spherical alumina used in the present invention, those having an average particle size of 5 to 50 μm can be used. In the present invention, the coating amount is 18 to 22 g / m ^2.
Since the coating film is relatively thin, the average particle diameter of the spherical alumina is preferably 10 to 30 μm.

In the present invention, when an ionizing radiation-curable resin is coated on a permeable fibrous base material, a flaky filler is used as a filler in order to suppress impregnation into the fibrous base material. Sometimes. The coating liquid in which the flaky filler is dispersed in the ionizing radiation-curable resin, when coated on a permeable fibrous base material, because the flaky filler is flat, the flaky filler fills the voids of the fibrous base material. The plugging and the penetration of the coating liquid into the fibrous base material are suppressed. As the flaky filler, flaky alumina, mica coated with titanium dioxide, fish scale foil, natural pearl foil, metal foil pieces and the like are used. The average particle size is preferably from 0.1 to 5 μm.

The ionizing radiation-curable resin used in the present invention is a resin which is applied in an uncured state and then irradiated with ionizing radiation such as an electron beam or ultraviolet ray to cure the coating film.
The physical properties of the cured coating film change depending on the crosslinking density. That is, the higher the crosslink density, the higher the hardness of the cured coating film and the higher the abrasion resistance, but the lower the flexibility. Therefore, in order to obtain a surface coating film having flexibility and excellent wear resistance, it is necessary to add a filler such as spherical alumina to the ionizing radiation-curable resin, and to improve the wear resistance by the filler.

When a coating film is formed by adding a filler such as spherical alumina to an ionizing radiation-curable resin, it is general to use an electron beam having a large transmitting power to the coating film as the ionizing radiation. When the spherical alumina particles become large in the ultraviolet ray, the transmission of the ultraviolet ray is hindered, so that a sufficient irradiation amount to the ultraviolet curable resin cannot be obtained, and the curing of the ultraviolet curable resin becomes insufficient. Further, in order to sufficiently cure the ultraviolet curable resin, the irradiation time of the ultraviolet ray becomes too long, which causes a practical problem such as a decrease in production efficiency.

In the present invention, when an ionizing radiation-curable resin is coated on a permeable fibrous base material, a sealer layer is formed to suppress penetration into the fibrous base material. As a liquid resin, a mixture of a urethane resin and a butyral resin, or an acrylic resin was selected.
As the urethane resin, use a two-component curable urethane resin,
As the butyral resin, a polyvinyl butyral resin is used. By forming a coating film composed of a mixture of a two-component curable urethane resin and a polyvinyl butyral resin as a sealer layer, even if an uncured ionizing radiation-curable resin is applied on this coating film, the coating film will not be exposed to ionizing radiation. Since it is resistant to the constituent components (monomer and the like) of the curable resin and does not dissolve or break, the penetration of the ionizing radiation-curable resin into the fibrous base material is suppressed.

For this reason, even if the thickness of the coating film is relatively thin, 2 to 5 μm, penetration of the ionizing radiation-curable resin into the fibrous base material is suppressed. Further, the polyvinyl butyral resin has a strong adhesive strength to the resin of the picture layer and the cured ionizing radiation-curable resin, and the delamination of the ink is eliminated. No trouble is caused by bending or the like.

As the two-part curable urethane resin used in the present invention, a urethane resin containing a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) is used. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, and polycarbonate polyol. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4 tolylene diisocyanate, xylene diisocyanate, aromatic isocyanate such as 4,4 diphenylmethane diisocyanate, or hexamethylene diisocyanate, isophorone diisocyanate,
Aliphatic or alicyclic isocyanates such as hydrogenated tolylene diisocyanate and hydrogenated diphenylmethane diisocyanate are used. Alternatively, these isocyanate adducts or multimers may be used. For example, there are an adduct of tolylene diisocyanate and a trimer of tolylene diisocyanate.

The sealer layer 13 may be formed by applying a coating liquid using an acrylic resin. In this case, the coating of the sealer layer is relatively thick, and
It is formed with a thickness of 0 μm. Since the uncured ionizing radiation-curable resin does not penetrate into the fibrous base material by increasing the thickness of the sealer layer made of an acrylic resin, the application amount of the ionizing radiation-curable resin is reduced to about 10 to 15 g / m ^2. Even so, a surface protective layer having excellent wear resistance can be formed. That is, by increasing the thickness of the sealer layer and preventing the penetration of the uncured ionizing radiation-curable resin into the fibrous base material, the ionizing radiation-curable resin layer containing expensive spherical alumina can be thinned. And the production cost can be reduced.

Examples of the acrylic resin used for the sealer layer include polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and methyl (meth) acrylate-styrene ( Acrylic resin such as (meth) acrylate copolymer (provided that (meth) acrylate means acrylate or methacrylate) alone or as a mixture of two or more, or methyl (meth) acrylate, ethyl (meth) Acrylate,
Alkyl (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate; 2-hydroxybutylethyl (meth) acrylate; An acrylic polyol obtained by copolymerizing a (meth) acrylate having a hydroxyl group in a molecule such as -hydroxy-3-phenoxypropyl (meth) acrylate can also be used.

As the ionizing radiation-curable resin used in the present invention, a prepolymer having a polymerizable unsaturated bond or a cationically polymerizable functional group in a molecule (including a so-called oligomer) and / or a composition obtained by appropriately mixing a monomer. And those curable by ionizing radiation are used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, an electron beam or an ultraviolet ray is used.

Specific examples of the ionizing radiation curable resin include a radical polymerizable unsaturated group such as a (meth) acryloyl group and a (meth) acryloyloxy group, a cationic polymerizable functional group such as an epoxy group, and the like in the molecule. It consists of a monomer or a prepolymer having two or more thiol groups.
These monomers or prepolymers may be used alone or
Alternatively, a mixture of several types may be used. Here, the (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group, and the following (meth) is used in the same meaning.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate,
Epoxy (meth) acrylate, urethane acrylate, polyether acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone (meth) acrylate and the like can be used. A molecular weight of about 250 to 100,000 is usually used.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Examples of the monomer having a thiol group include:
There are trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, dipentaerythritol tetrathioglycolate and the like.

When the ionizing radiation-curable resin is cured by ultraviolet light or visible light, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like 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 metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to.
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin.

Various additives may be added to the ionizing radiation-curable resin as required. As these additives, for example, vinyl chloride-vinyl acetate copolymer,
Extender (filler) consisting of thermoplastic resin such as polyvinyl acetate, acrylic resin, and cellulosic resin; fine powder such as calcium carbonate, barium sulfate, silica, and alumina;
There are coloring agents such as dyes and pigments.

As the coating method of the ionizing radiation curable resin, gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, dip coat, solid coat by silk screen coat, wire bar coat, Comma coat, spray coat, float coat, pouring coat, brush coating, spray coat and the like can be used. Among them, a gravure coat is preferable.

As the ionizing radiation irradiating device for curing the ionizing radiation curable resin, an ultraviolet irradiating device or an electron beam irradiating device is used. As the ultraviolet irradiation device, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, and a metal halide lamp is used. The wavelength of the ultraviolet light is usually 19
The wavelength range from 0 to 380 nm is mainly used. As the electron beam irradiator, various electron beam accelerators such as a Cockloft-Wald type, a Bande graph type, a resonance transformer type, an insulating core transformer type or a linear type, a dynamitron type, and a high frequency type are used.

When the electron beam is applied, the acceleration voltage is 100 to 1000 KeV, preferably 100 to 300 KV.
Irradiation at eV, the absorbed dose is usually 1 to 300 k
It is about Gy (kilo gray). If the absorbed dose is less than 1 kGy, curing of the coating film will be insufficient, and
If it exceeds 0 kGy, the cured coating film and the fibrous base material turn yellow or are damaged. In the case of ultraviolet irradiation, the irradiation amount is preferably in the range of 50 to 1000 mJ / cm ² . When the irradiation amount of the ultraviolet ray is less than 50 mJ / cm ² , the curing of the coating film is insufficient, and the irradiation amount is 1000 mJ / c.
If it exceeds m ² , the cured coating film will turn yellow. Also,
As a method of irradiating ionizing radiation, a method of first irradiating ultraviolet rays to cure the ionizing radiation-curable resin to at least the extent that the surface is dry to the touch, and then irradiating with an electron beam to completely cure the coating film There is also.

As the permeable fibrous base material used in the present invention, a sheet-like material such as paper, synthetic paper, and nonwoven fabric is used. As paper used as a fibrous base material,
Thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, so-called vinyl wallpaper raw paper in which polyvinyl chloride resin is sol- or dry-laminated with paper, fine paper, coated paper, sulfuric acid paper, glassine paper, parchment paper, Examples include paraffin paper and Japanese paper. Further, as the paper-like sheet, glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber, etc., inorganic fiber sheet-like, polyester, vinylon, polyethylene,
A nonwoven fabric or woven fabric made of synthetic resin fibers such as polypropylene is used.

A pattern layer is formed on the fibrous base material by printing or the like. The picture layer can be formed on one side or both sides of the substrate. Before providing the picture layer, a solid printing layer may be provided on the surface of the base material. As the pattern layer, there are a printed pattern by printing, an embossed pattern by embossing, a concavo-convex pattern by hairline processing, and the like. Further, the concave portion of the concavo-convex pattern is filled with a coloring ink by a known wiping method to form a pattern layer. Can also. Print pattern layers include wood pattern, stone pattern, cloth pattern, leather pattern, geometric figure,
There are characters, symbols, various abstract patterns, or solid printing on the entire surface. The concealing layer of the full solid printing may be omitted depending on the surface condition of the adherend to which the decorative paper is to be attached.

The ink for pattern printing varies depending on the material and form of the substrate, but is generally chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene.
A vehicle comprising a single or a mixture of two or more resins such as nitrified cotton, cellulose acetate, vinyl chloride, vinyl acetate, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, urethane resin, acrylic resin, polyester resin, etc. And an ordinary ink containing a coloring agent such as a pigment and a dye, an extender pigment, a curing agent, an additive, a solvent and the like.

As coloring agents, titanium white, zinc white, red petals,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black, etc .; organic pigments such as isoindolinone, Banzai yellow A, quinacridone, permanent red 4R, phthalocyanine blue or the like; and metals composed of foil powders such as aluminum and brass A pearlescent pigment made of a foil powder of pigment, mica coated with titanium dioxide, basic zinc carbonate or the like is used. If necessary, an inorganic filler may be added, and examples thereof include powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide). Addition amount is usually 5
６０60% by weight.

As the printing of the picture, a normal printing method such as gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, and ink jet printing can be used. Alternatively, a transfer pattern may be formed by forming a pattern once on a release sheet, and transferring the pattern printing by a transfer printing method from the transfer sheet obtained.

Instead of a printed pattern, a metal layer such as aluminum, chromium, gold, silver, copper or the like may be vacuum-deposited, sputtered, or the like to form a picture layer by forming a metal thin film entirely or partially on a substrate. it can. In addition, as the embossing, the base sheet is heated and softened, and the embossing plate is pressed,
It is formed by shaping and solidifying by cooling, and a known single-wafer or rotary embossing machine is used. As the uneven shape, the woodgrain pipe groove, stone plate surface unevenness (granite cleavage surface etc.),
Textile surface texture, satin finish, grain, hairline, line and groove, etc.

In order to improve the adhesive strength between the printing ink and the ionizing radiation-curable resin layer, an easy-adhesion layer may be provided on the picture layer. As the easily adhesive layer (also referred to as a primer layer or an anchor layer), resins such as acrylic resin, urethane resin, vinyl chloride / vinyl acetate copolymer resin, polyester resin, polyurethane resin, chlorinated polyethylene and chlorinated polypropylene are used. Although a coating solution dissolved in a solvent is used, a coating solution using a mixture of a two-component curable urethane resin and a butyral resin is particularly preferable. A coating solution obtained by dissolving the resin in a solvent is applied by a known method and dried to form an easily adhesive layer.

The decorative paper of the present invention is laminated on various adherends,
It can be used for various purposes after performing a predetermined molding process. For example, the interior of buildings such as walls, ceilings, floors, window frames,
It can be used for surface decoration of fittings such as doors and handrails, surface decoration of furniture or cabinets of light electric / OA equipment, interior of vehicles such as automobiles and trains, interior of aircraft, makeup of window glass, and the like. Therefore, if the decorative paper cannot be directly bonded to the material,
It adheres to the adherend via a suitable easy-adhesion layer or an adhesive layer. However, when the decorative paper can be bonded to the adherend by heat fusion or the like, the easy-adhesion layer or the adhesive layer may be omitted.

Examples of the adherend include flat materials of various materials, plate materials such as curved plates, sheets (or films), and various three-dimensionally shaped articles (molded products). For example, the decorative paper of the present invention can be bonded to a molded product having a curved surface such as an injection molded product.

The material used for the three-dimensional object, plate material or sheet (film) as the adherend includes:
Wood material such as wood veneer, wood plywood, particle board, wood fiber board such as medium density fiber board (MDF), metal such as iron and aluminum, acrylic resin, polycarbonate resin,
Resins such as ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester resin, polystyrene, polyolefin resin, ABS, phenol resin, polyvinyl chloride, cellulose resin, and rubber are exemplified.

[0051]

The present invention will be described below in more detail with reference to examples. (Example 1) First, solid printing and wood pattern by gravure printing were performed using an impregnated paper (manufactured by Kojin Co., Ltd.) having a basis weight of 50 g / m ² impregnated with an acrylic resin latex as the fibrous base material 11. 5A, the solid printed layer 12a having a thickness of 2 μm and the pattern layer 1 are formed on the fibrous base material 11 as shown in FIG.
2 was formed. Next, as shown in FIG. 5B, a two-part curable gravure ink (a gravure ink composed of a blend resin of a two-part curable urethane resin and a butyral resin) is applied to the fibrous base material 11 on the pattern layer 12 side. (With Showa Ink Industry Co., Ltd.) was applied by a gravure printing method and dried to form a sealer layer 13 having a thickness of 4 g / m ² .

Next, using the following electron beam-curable resin composition (A) (manufactured by Sanyo Chemical Industry Co., Ltd.), the fibrous material was roll-coated as shown in FIG. The surface of the sealer layer 13 of the base material 11 is coated, and the coating amount is 20
An uncured electron beam-curable resin layer 14b containing g / m ² (as dry matter) spherical alumina 15 was formed.

Composition of electron beam-curable resin composition (A) 50 parts by weight of bisphenol A ethylene oxide-modified diacrylate 20 parts by weight of trimethylolpropane-modified triacrylate 17 parts by weight of spherical alumina (average particle size 25 μ) 17 parts by weight Treated silica 12 parts by weight-Both ends methacrylate-modified silicone 1 part by weight

Next, as shown in FIG. 5D, the absorbed dose is reduced on the uncured electron beam-curable resin layer 14b at an acceleration voltage of 175 keV using an electron beam irradiation apparatus.
An electron beam 16a is irradiated so as to be 0 kGy (kilo gray) to completely cure the electron beam-curable resin, and a cured electron beam-curable resin layer 14c containing spherical alumina 15
Was formed, and a decorative paper 1 was produced.

(Example 2) As the fibrous base material 11,
60g / m basis weight impregnated with a lylic resin latex ^TwoIncluding
As in the case of Example 1 by using dip paper (made by Kojin Co., Ltd.)
As shown in FIG. 5 (a), a fibrous base material is formed by gravure printing.
11 has a 2 μm thick solid printing layer 12 a and a pattern layer 12 formed thereon.
Done. Then, using a diagonal engraving plate with a plate depth of 150 μm
Acrylic ink (ethyl methacrylate and hydroxy
A copolymer of ethyl ethyl methacrylate and an aliphatic
Two-part curable acrylic ink composed of cyanate)
Gravure printing, and as shown in FIG.
70 g / m^TwoWas formed.

Next, using the following electron beam-curable resin composition (B) (manufactured by Sanyo Chemical Industry Co., Ltd.), a gravure roll coating method was used, as shown in FIG. The surface of the sealer layer 13 of the porous substrate 11 was coated to form an uncured electron beam curable resin layer 14b containing spherical alumina 15 at a coating amount of 10 g / m ² (as dry matter).

Composition of electron beam-curable resin composition (B): bisphenol A ethylene oxide-modified diacrylate 59 parts by weight trimethylolpropane-modified triacrylate 20 parts by weight Spherical alumina (average particle size 25 μ) 20 parts by weight Terminal methacrylate-modified silicone 1 part by weight

Next, as shown in FIG. 5D, the absorbed dose is reduced to 5 on the uncured electron beam-curable resin layer 14b at an acceleration voltage of 175 keV using an electron beam irradiation apparatus.
An electron beam 16a is irradiated so as to be 0 kGy (kilo gray) to completely cure the electron beam-curable resin, and a cured electron beam-curable resin layer 14c containing spherical alumina 15
Was formed, and a decorative paper 1 was produced.

(Example 3) As the fibrous base material 11,
60g / m basis weight impregnated with a lylic resin latex ^TwoIncluding
As in the case of Example 1 by using dip paper (made by Kojin Co., Ltd.)
As shown in FIG. 6A, a fibrous base material is formed by gravure printing.
11 has a 2 μm thick solid printing layer 12 a and a pattern layer 12 formed thereon.
Done. Next, engrave a pattern synchronized with the print pattern
Plate height plate (plate depth of the raised portion 100μm, bank width
Acrylic embossing using 15μm line engraving)
Ink (Ethyl methacrylate and hydroxyethyl methacrylate
Ethyl acrylate copolymer and aliphatic isocyanate
Extruded part with a two-component curable acrylic ink)
Was gravure printed in a pattern. Then hot air dried
Thus, as shown in FIG.^Twoof
A raised sealer layer 13a was formed.

Next, using the following resin composition (B) (manufactured by Sanyo Chemical Industries, Ltd.) as an electron beam-curable resin, a gravure roll coating method was used, as shown in FIG.
The surface of the raised sealer layer 13a of the fibrous base material 11 was coated to form an uncured electron beam-curable resin layer 14b containing 15 g / m ² (as dry matter) of spherical alumina 15.

Composition of electron beam curable resin composition (B) Bisphenol A ethylene oxide-modified diacrylate 59 parts by weight Trimethylolpropane-modified triacrylate 20 parts by weight Spherical alumina (average particle size 25 μ) 20 parts by weight Terminal methacrylate-modified silicone 1 part by weight

Next, as shown in FIG. 6D, the absorbed dose is reduced to 5 on the uncured electron beam-curable resin layer 14b at an acceleration voltage of 175 keV by using an electron beam irradiation apparatus.
An electron beam 16a is irradiated so as to be 0 kGy (kilo gray) to completely cure the electron beam-curable resin, and a cured electron beam-curable resin layer 14c containing spherical alumina 15
Was formed, and a decorative paper 1 was produced.

Comparative Example 1 As in Example 1, as shown in FIG. 7, a fibrous base material 11 (impregnated paper having a basis weight of 50 g / m ² ) and a solid printed layer 12 a having a thickness of 2 μm and a picture layer were formed. No. 12 was formed. Next, without providing the sealer layer 13, the electron beam-curable resin composition (A) was applied onto the pattern layer 12 of the fibrous base material 11 in the same manner as in Example 1, and FIG. As shown in (), an uncured electron beam-curable resin layer 14b containing spherical alumina 15 was formed. Next, the uncured electron beam-curable resin layer 14b is irradiated with an electron beam to cure the coating, and as shown in FIG. 7C, a cured electron beam-curable resin layer containing spherical alumina 15 is formed. A decorative paper 1a having 14c was produced.

(Comparative Example 2) Basis weight 6 as fibrous base material 11
Using a 0 g / m ² impregnated paper, a solid printed layer 12 a and a picture layer 12 having a thickness of 2 μm were formed in the same manner as in Example 1. Next, the following electron beam-curable resin composition (C) was applied to the surface of the picture layer 12 of the fibrous base material 11 by the gravure roll coating method in the same manner as in Example 1, and the coating film was applied to As shown in FIG. 7C, a decorative paper having a cured electron beam curable resin layer 14c containing spherical alumina 15 was prepared.

Composition of electron beam-curable resin composition (C): Bisphenol A ethylene oxide-modified diacrylate 50 parts by weight Trimethylolpropane-modified triacrylate 20 parts by weight Spherical alumina (average particle size 25 μ) 20 parts by weight Organic 9 parts by weight of treated silica 1 part by weight of methacrylate-modified silicone at both ends

Comparative Example 3 In the same manner as in Example 2, a 2 μm-thick solid printed layer 12 a and picture layer 12 were formed on a fibrous base material 11 (impregnated paper having a basis weight of 60 g / m ² ). Next, the electron beam-curable resin composition (B) was applied onto the pattern layer 12 of the fibrous base material 11 without providing the sealer layer 13 in the same manner as in Example 2, and irradiated with an electron beam. 7 to cure the coating,
As shown in (c), a decorative paper 1a having a cured electron beam curable resin layer 14c containing spherical alumina 15 was produced.

Comparative Example 4 In the same manner as in Example 3, a 2 μm-thick solid printing layer 12 a and a pattern layer 12 were formed on a fibrous base material 11 (impregnated paper having a basis weight of 60 g / m ² ). Next, the electron beam-curable resin composition (B) was applied onto the pattern layer 12 of the fibrous base material 11 without providing the sealer layer 13 in the same manner as in Example 3, and irradiated with an electron beam. 7 to cure the coating,
As shown in (c), a decorative paper 1a having a cured electron beam curable resin layer 14c containing spherical alumina 15 was produced.

(Abrasion Resistance and Weather Resistance Test)
The decorative papers prepared in 2, 3 and Comparative Examples 1, 2, 3, and 4 were tested for abrasion resistance and weather resistance by the following methods. Abrasion Resistance Test The initial point (the number of rotations at which the picture layer starts to be removed) of each sample was measured using a Taber abrasion tester in accordance with the JAS abrasion A test. Weather resistance test Carbon arc FOM FM-0 manufactured by Suga Test Machine Co., Ltd.
Using a 02-type machine, each sample was exposed for 500 hours under conditions of a black panel temperature of 63 ° C. and an environmental humidity of 40% RH, and the fading state of the picture layer was observed.

Examples 1, 2, 3 and Comparative Examples 1, 2, 3,
Table 1 shows the test results of the abrasion resistance and weather resistance of the decorative paper prepared in Example 4.

[0070]

[Table 1]

As shown in Table 1, the decorative papers produced in Examples 1, 2, and 3 were different from the decorative papers produced in the comparative examples.
Both wear resistance and weather resistance are excellent, and the effect of the sealer layer is remarkably exhibited. That is, a fibrous base material such as paper is provided with a sealer layer using a blend of a urethane resin and a butyral resin, or an acrylic resin, so that the electron beam-curable resin applied thereon penetrates the paper. Is suppressed, and a predetermined cured electron beam curable resin layer is formed on the surface, so that the cured electron beam curable resin layer containing spherical alumina exhibits excellent wear resistance and weather resistance. It is considered something.

[0072]

According to the present invention, an ionizing radiation-curable resin layer having a high hardness is formed on the surface of a permeable fibrous base material such as paper without impairing the flexibility. A decorative paper having excellent properties and weather resistance can be obtained. Conventionally, in order to form a resin layer having high hardness with an ionizing radiation-curable resin, it was necessary to use a polyfunctional ionizing radiation-curable resin having a small molecular weight in order to increase the crosslinking density of the ionizing radiation-curable resin. . The ionizing radiation-curable resin with a low molecular weight has low viscosity, so when it is applied to paper, it is impregnated into the paper, and the required physical properties are stable because a coating film of the required thickness cannot be obtained on the paper surface. In order to obtain this, it was necessary to increase the thickness of the ionizing radiation-curable resin layer. However, increasing the application amount of the ionizing radiation-curable resin increases the amount of expensive spherical alumina to be added to the ionizing radiation-curable resin, increases the manufacturing cost, and cures the ionizing radiation-curable resin. Due to the shrinkage that occurs at the time, curling of the decorative paper becomes severe, and workability in post-processing deteriorates, leading to an increase in production cost.

Therefore, in the present invention, after forming a picture layer on a permeable fibrous base material, an acrylic resin,
Or, by forming a sealer layer using a blended resin of butyral resin and urethane resin, even with a low molecular weight, low-viscosity ionizing radiation-curable resin, penetration into a fibrous base material is suppressed, and a required coating film Can be formed. As a result, when a blended resin of butyral resin and urethane resin is used for the sealer layer, the content of expensive spherical alumina is reduced to 15 to 20% by weight, and the coating amount is also reduced to 18 to 22 g / m ^2. Becomes possible,
Production costs could be reduced. The acrylic resin is used for the sealer layer, and the thickness of the sealer layer is 30 to 1.
When the thickness was increased to 50 μm, sufficient wear resistance and weather resistance could be obtained even when the coating amount of the ionizing radiation-curable resin containing alumina was reduced to 10 to 15 g / m ² . Furthermore, by forming the ionizing radiation-curable resin layer containing spherical alumina thinly, curling of the decorative paper can be prevented, so that the productivity was improved and the production cost was reduced. In addition, when the obtained decorative paper is applied to an adherend and subjected to post-processing, it is excellent in V-cut suitability and bending workability.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of the decorative paper of the present invention.

FIG. 2 is a schematic cross-sectional view of another embodiment of the decorative paper of the present invention when spherical alumina is contained in an ionizing radiation-curable resin layer having a cured surface.

FIG. 3 is an explanatory diagram for producing the decorative paper of the present invention.

FIG. 4 is an explanatory view of another embodiment of the decorative paper of the present invention when producing a decorative paper in which the ionizing radiation-curable resin layer contains spherical alumina.

FIG. 5 is an explanatory diagram when the decorative paper of the present invention is produced according to Example 1.

FIG. 6 is an explanatory diagram when a decorative paper of the present invention is manufactured according to Example 3.

FIG. 7 is an explanatory diagram for producing a decorative paper according to Comparative Example 1.

[Explanation of symbols]

 Reference Signs List 1 decorative paper 1a decorative paper (produced in Comparative Example) 11 fibrous base material 12 picture layer 12a solid printing layer 13 sealer layer 13a raised sealer layer 14 cured ionizing radiation curable resin layer 14a uncured ionizing radiation curable Resin layer 14b Uncured electron beam curable resin layer 14c Cured electron beam curable resin layer 15 Spherical alumina 16 Ionizing radiation 16a Electron beam

Continued on the front page F-term (reference) 4F100 AA19B AA19H AA20B AA20H AK01B AK23G AK25B AK25G AK51G AL05G BA02 BA10A BA10B CC00B DE01B DE01H DG00A DG10A GB08 GB33 GB81 GB90 HB00A JA13B JL01 J13B JB01B

Claims (3)

[Claims] 1. A decorative paper comprising a fibrous base material, a pattern layer, a sealer layer and a cured ionizing radiation-curable resin layer laminated in this order. 2. The decorative paper according to claim 1, wherein the sealer layer is made of a resin composition using an acrylic resin or a blend resin of a butyral resin and a urethane resin as a binder. 3. The method according to claim 2, wherein the ionizing radiation-curable resin layer has a thickness of 15 to 15.
3. The decorative paper according to claim 1, wherein the decorative paper contains 20% by weight of alumina and has a coating amount of 10 to 22 g / m ² as a cured resin composition. 4.