JP2001088245A - Abrasion-resistant decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem such that when a protective layer is formed on the surface of a decorative material with the use of a resin added with a rigid filler, notches are formed on the surface to deteriorate slidability so that an object which contacts the decorative material is damaged, and the touch of the surface is deteriorated. SOLUTION: An abrasion-resistant decorative material 1 is manufactured by a method in which a printing sheet 2 is manufactured by forming a solid printing layer 12a and a pattern layer 12 on a base material 11 such as paper and a plastic sheet by printing, etc., an uncured ionizing radiation curable resin 14a containing a scaly filler 15 and a shape-indefinite filler 16 is applied on the pattern layer 12, a protective layer 13 is formed so that the filler 15 is oriented horizontally in the coating film, the protective layer 13 is irradiated with ionizing radiation 18 to cure the curable resin 14a, and the protective layer 13 comprising the cured ionizing radiation curable resin 14b is formed on the surface of the base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a surface decoration material for interiors such as floors, walls, ceilings and the like of buildings, furniture and surface decoration materials for various cabinets, surface decoration of fittings, vehicle interiors and the like. More particularly, the present invention relates to a decorative material used for applications requiring surface abrasion resistance.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used for decorative surfaces of building interiors, furniture, cabinets, etc., a pattern or a solid printing ink layer is provided on one side of a base sheet, and this ink layer is provided. To protect, as a protective layer, apply a thermosetting urethane resin or the like, apply heat drying, heat cure to form a thermosetting resin layer, or apply an ionizing radiation curable resin, and apply ionizing radiation. There is a method in which a coating film is cured by irradiation 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.

However, if the crosslink density of the resin is increased to increase the surface hardness, the flexibility of the protective layer is impaired, and the protective layer is broken by an impact,
Further, there arises a problem that cracks are easily generated during post-processing such as lapping. 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 protective layer.

Therefore, as a method for improving abrasion resistance without lowering the flexibility of the protective layer, a method of adding an inorganic material to the resin of the protective layer has been conventionally used. For example, Japanese Patent Application Laid-Open No. 60-23642 discloses silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) having an average particle diameter of 1 to 50 μm used as an abrasive such as a sand blast method and a brush polishing method. It is disclosed that a protective layer is formed using a paint containing a natural glass powder as a main component. The protective layer formed by the above-mentioned paint had higher hardness and flexibility than conventional products, and exhibited physical properties excellent in abrasion resistance and scratch resistance.

[0005]

However, when a protective layer of a decorative material 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 a material without the inorganic filler. Although the abrasion property is improved, the addition of the inorganic filler causes the inorganic filler to protrude from the surface of the protective layer, causing roughness on the surface. In particular, when used as a flooring material, there is also a problem that, when the cosmetic material comes into direct contact with the decorative material, such as footwear, the material is worn or damaged. In addition, when the substrate is coated by the gravure roll coating method using the coating material to which the above-mentioned inorganic filler is added, the alumina or natural glass powder of the inorganic filler has a polygonal shape with sharp corners. Was worn or damaged, which was a major problem in processing.

Further, when a low viscosity coating liquid such as an ionizing radiation curable resin is applied using an impregnating base material such as paper,
The ionizing radiation-curable resin impregnates the paper and retains the inorganic filler.The amount of the ionizing radiation-curable resin decreases, and the inorganic filler is not sufficiently retained by the protective layer composed of the ionizing radiation-curable resin layer, and the abrasion resistance is sufficient. There was also a problem that it was not possible to demonstrate its properties. In addition, since the amount of the ionizing radiation-curable resin on the impregnating base material is reduced, the inorganic filler protrudes from the surface of the coating film (protective layer), causing roughness on the protective layer surface and poor slipperiness. there were. In particular, when the coating liquid is applied and then heated to dry and harden the resin, the heating reduces the viscosity of the coating liquid and penetrates into the base material. There have been problems that the force is weakened and that the inorganic filler protrudes from the surface of the protective layer.

[0007]

Therefore, in the present invention, as a filler to be added to a binder resin composed of a curable resin forming a protective layer, a hard particle harder than the cured binder resin and a flaky filler are used. Or, further select an amorphous filler together with the scaly filler,
When forming the protective layer with the scaly filler or a binder resin containing a further amorphous filler, forming the protective layer so that the scaly filler is oriented in the lateral direction of the protective layer, the above problem is solved. Worked out a solution.

[0008] That is, in the present invention, in order to solve the above problem, the configuration of the decorative material is as follows.

[0009] The wear-resistant decorative material of the present invention comprises:
In a decorative material formed with a coating film made of a binder resin containing a hard filler, the hard filler is made of a flaky filler having a hardness higher than that of the binder resin, and the binder resin is made of a cured product of a curable resin. And a wear-resistant decorative material.

[0010] As described above, the coating film serving as the protective layer is made to have abrasion resistance as well as abrasion resistance by including a flaky filler having a specific hardness in a binder resin composed of a cured product of a curable resin. And the feeling of touch becomes very soft. In addition, the surface has good slipperiness and does not wear an object in contact with the wear-resistant decorative material. Therefore, it can be used in fields where high abrasion resistance is required, such as flooring materials, and the contacting object is not damaged.

[0011] Further, the wear-resistant decorative material of the present invention may further comprise an irregular-shaped hard filler having a hardness higher than that of the binder resin, in addition to the scaly filler, in addition to the scaly filler. It also contains a filler, characterized in that the coating is formed such that the scaly filler is oriented and distributed in the lateral direction in the coating, and that the scaly filler does not protrude to the surface of the coating. And a wear-resistant decorative material.

By adopting such a configuration, it is possible to reliably obtain abrasion resistance, roughness of the surface, smoothness of the surface, and a very soft touch. Abrasion resistance, coating suitability, and the like can be appropriately adjusted to improve the properties. For example, when a pattern layer is provided on the surface of the base material, and a protective layer made of an ionizing radiation-curable resin containing a filler is formed thereon to produce a wear-resistant decorative material, the ionizing radiation-curable resin is used. As a filler to be added,
Hard particles having hardness higher than that of the cured ionizing radiation-curable resin, and flaky inorganic particles and amorphous inorganic particles are used. The flaky inorganic particles are laterally (horizontally) over the protective layer.
By forming a coating film (protective layer) so as to orient and preventing the scale-like inorganic particles from projecting to the surface of the coating film, roughness of the surface of the decorative material can be prevented.

[0013] Further, the wear-resistant decorative material of the present invention is characterized in that, in the above structure, the flaky filler is composed of flaky alumina, and the irregular filler is composed of irregular silica. A wear-resistant decorative material was used.

[0014] As described above, by using the inorganic filler of scaly alumina as the scaly filler and using the inorganic filler of amorphous silica as the amorphous filler, the above-mentioned respective effects of the present invention can be obtained. can get. That is, if a scale-like alumina particle is used as a scale-like filler, silica (SiO ₂ ) particles are used as an amorphous filler, and a binder resin such as an ionizing radiation-curable resin is used, the surface feel is good. In addition, it is possible to obtain a decorative material which is excellent in wear resistance and does not wear an object in contact therewith. For example, flaky alumina (particle size: 5 to 40 μm) is used as a flaky filler, and silica particles (particle size: 10 to 1) are used as an amorphous filler.
5 μm) and a fine powder of silica (particle diameter of 2 μm or less) prevent the amorphous silica particles from agglomerating and settling when coating a coating solution containing a filler, and provide a stable coating. And a uniform coating film (protective layer) can be obtained.

[0015]

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 wear-resistant decorative material of the present invention. FIG. 2 shows another embodiment of the abrasion-resistant decorative material of the present invention. When an impregnating base material such as paper is used as the base material, a sealer layer is provided to prevent the coating liquid from penetrating into the paper. It is a schematic sectional view at the time. FIG. 3 is an explanatory view for producing the wear-resistant decorative material of the present invention. FIG. 4 is an explanatory diagram when a wear-resistant decorative material is manufactured using paper as a base material. FIG. 5 is a perspective view showing a flow state of an uncured electron beam-curable resin when a wear-resistant decorative material is produced using paper as a base material. FIG. 6 is an explanatory diagram when a wear-resistant decorative material is manufactured according to the first embodiment. FIG. 7 is an explanatory diagram for producing a wear-resistant decorative material according to the second embodiment. FIG.
FIG. 4 is an explanatory diagram when a decorative material is manufactured according to Comparative Example 1. FIG. 9 is an explanatory diagram when a wear-resistant decorative material is manufactured according to Comparative Example 2. FIG. 10 is a perspective view showing an example of the shape of a flaky filler. FIG. 11 is a perspective view illustrating the shape of the amorphous filler.

In the case of the embodiment shown in FIG. 1, the abrasion resistant decorative material 1 of the present invention is provided with a pattern layer 12 on one side of a base material 11 and a cured curable resin on the pattern layer 12. (Used as a binder resin) A protective layer 13 made of a binder resin 14 which is a hardened curable resin containing scale-like fillers 15 and amorphous fillers 16 which are hard particles having higher hardness. . Note that the picture layer 12 is provided as needed and can be omitted if unnecessary.
The irregular-shaped filler 16 is also used as needed, if necessary, and can be omitted if unnecessary. Then, in the protective layer 13, a coating film is formed such that the flaky filler 15 is oriented and distributed in the lateral direction of the protective layer 13 (horizontal direction with respect to the base material 11). Further, the protective layer 1 is protected so that the scale-like filler 15 does not protrude from the surface of the protective layer 13.
By forming No. 3, the surface roughness was eliminated, the surface had good slipperiness, and the feel was soft. In particular, in the present invention, as the flaky filler 15, flaky alumina is preferably used. And since the scale-like alumina formed the coating film so as to be oriented in the horizontal direction of the coating film, the scale-like alumina no longer protrudes to the surface of the coating film, and the surface with a good slipperiness and soft touch was obtained. can get.

The abrasion-resistant decorative material 1 of the present invention illustrated in FIG. 2 is an example in which a paper 11a is used as a base material. After a picture layer 12 is provided, a sealer layer 17 is formed thereon. This is to prevent the binder resin 14 made of a curable resin from penetrating into the paper. That is, when the coating liquid composed of the uncured curable resin containing the flaky filler 15 and the amorphous filler 16 is coated on the paper 11a, the uncured curable resin penetrates into the paper before being cured. This prevents the amount of resin in the coating film (protective layer) from decreasing, preventing the scale-like filler and amorphous filler from protruding to the protective layer surface and preventing the binder resin from exhibiting sufficient holding power. It was done.

As the flake-like filler, flake-like alumina (particle size: 5 to 40 μm), which is an inorganic filler, is used as the amorphous filler; silica particles (particle size: 10 to 15 μm), which are inorganic fillers; By using (a particle size of 2 μm or less), when coating a coating solution containing a filler, the amorphous silica particles are prevented from agglomerating and settling, and a stable coating can be performed. A uniform coating film (protective layer) was obtained.

Hereinafter, the method for producing the wear-resistant decorative material of the present invention will be described with reference to some embodiments. In the description of the manufacturing method described below, an ionizing radiation-curable resin is used as a curable resin as a binder resin, and flaky Al and amorphous silica are used as hard fillers. The invention is not limited to this.

First, as shown in FIG.
The printed sheet 2 is produced by printing a colored and opaque solid printing layer 12a and a pattern layer 12 on the substrate 11 by gravure printing or the like using an impregnated paper or a plastic sheet. On the other hand, an ionizing radiation curable resin is used as a binder resin, and a scaly filler 15 such as alumina is added thereto.
And an irregular filler 16 such as silica are added to prepare a coating liquid (resin composition) containing the flaky filler 15 and the irregular filler 16. Next, as shown in FIG. 3B, the scale-like filler 15 and the irregular-shaped filler 16 are contained on the pattern layer 12 side of the printing sheet 2 provided with the solid printing layer 12a and the pattern layer 12. A coating film composed of an uncured ionizing radiation-curable resin 14a obtained by coating a coating liquid by a gravure roll coating method or the like, namely
Form 3 Next, as shown in FIG. 3B, the uncured ionizing radiation-curable resin 14a is irradiated with ionizing radiation 18 such as an electron beam or an ultraviolet ray from above the uncured ionizing radiation-curable resin 14a to cure the uncured ionizing radiation-curable resin 14a. Then, as shown in FIG. 3C, the wear-resistant decorative material 1 having the protective layer 13 made of the cured ionizing radiation-curable resin 14b containing the flaky filler 15 and the amorphous filler 16 is produced. .

When the above-mentioned printing sheet 2 is coated with a coating solution containing the flaky filler 15 and the amorphous filler 16 to form a coating film composed of an uncured ionizing radiation-curable resin 14a, By adding fine powder silica in the range of 0.5 to 3% by weight in the coating liquid, the viscosity of the coating liquid is increased to improve the coating suitability, and when coated by a gravure coating method or the like, The scale-like fillers 15 are oriented in the horizontal direction, and have a distribution state as shown in FIG. When the printing sheet 2 is coated with a coating liquid containing the flaky filler 15 and the amorphous filler 16 and dried with hot air or a heater, the coating film made of the uncured ionizing radiation-curable resin 14a is Since the viscosity decreases with an increase in temperature, the scale-like filler 15 and the irregular-shaped filler 16 move downward so that there is no protrusion on the surface of the coating film, and the resin layer (coating film) It also flows in the horizontal direction, and slight irregularities or undulations on the surface generated during coating become flat and smooth.

Next, the protective layer 13 having a smooth surface is
As shown in FIG. 3B, the uncured ionizing radiation-curable resin 14a is cured by irradiating with ionizing radiation 18 using an ionizing radiation irradiator (not shown). As the ionizing radiation, an electron beam or an ultraviolet ray is usually used. When the ionizing radiation-curable resin is completely cured, as shown in FIG. 3C, the flaky filler 15 and the amorphous filler 16 are fixed in the cured ionizing radiation-curable resin 14b,
The protective layer 13 having a smooth and wear-resistant surface is formed. Therefore, the abrasion-resistant decorative material 1 having no roughness on the surface, good slipperiness, and a soft touch can be obtained.

When the base material is made of a fibrous material such as paper and the coating liquid for forming the protective layer permeates the base material, it is necessary to suppress the penetration of the coating liquid into the base material. There is.
Hereinafter, a case where paper is used as the base material and an electron beam curable resin is used as the ionizing radiation curable resin will be described. First, as shown in FIG. 4A, an opaque solid printing layer 12a and a picture layer 12 which are colored and opaque on a paper 11a by gravure printing or the like.
Is provided to produce the print sheet 2. Next, as shown in FIG. 4B, a sealer layer 17 is formed by gravure printing or the like in order to prevent the uncured electron beam curable resin from penetrating into the paper. As the binder resin for forming the sealer layer 17, for example, a resin such as polyurethane, a cellulose resin, or polyester, a two-part curable resin, or an ionizing radiation curable resin is used. In addition, resins such as acrylic resins, vinyl chloride / vinyl acetate copolymer resins, chlorinated polyethylene, and chlorinated polypropylene are used for the sealer layer.

When the paper is coated with a low-viscosity uncured electron beam-curable resin, as shown in FIG. 5, the uncured electron beam-curable resin 14c moves downward (in the Z direction) and penetrates the paper. I will do it. If the permeation amount becomes too large, the uncured electron beam-curable resin layer becomes thin, and the flaky alumina and amorphous silica project on the surface of the electron beam-curable resin layer (protective layer). On the other hand, when the amount of the electron beam-curable resin is small, the effect as a binder for flaky alumina and amorphous silica is not sufficiently exhibited, and the purpose of the protective layer of the present invention cannot be achieved.

Further, even if the paper is coated with a relatively high-viscosity uncured electron beam-curable resin and does not penetrate the paper at the beginning of coating, the uncured electron beam-curable resin is heated for drying. When heated, the temperature of the uncured electron beam-curable resin rises due to heating, and the viscosity of the uncured electron beam-curable resin decreases with the rise in temperature. It becomes easier to flow and permeates the paper as described above. At this time, due to the presence of the sealer layer 17, the uncured electron beam-curable resin whose viscosity has been reduced by heating is, as shown in FIG.
Since it does not penetrate into the paper, it does not move downward (Z direction) and flows only in the X and Y directions, that is, in the horizontal direction. Therefore, slight unevenness or waving on the surface generated during coating becomes flat and smooth. Surface. Therefore, by heating the uncured electron beam-curable resin to which the flaky filler and the amorphous filler are added, the protrusion of the filler on the surface is eliminated, and a smooth flat surface can be obtained.

After forming the sealer layer 17 on the printing sheet 2 as described above, as shown in FIG. 4B, an uncured electron beam curable resin containing flaky alumina 15a and amorphous silica 16a. 14c and protective layer 1
Form 3 Since the uncured electron beam-curable resin 14c is prevented from penetrating into the paper 11a by the sealer layer 17, the uncured electron beam-curable resin 14c containing the flaky alumina 15a and the amorphous silica 16a is fixed to a predetermined layer. It can be formed to a thickness. That is, due to the formation of the sealer layer 17, the uncured electron beam curable resin 14c paper 11a is formed.
Since the permeation into the protective layer 13 is suppressed and the predetermined amount of resin is maintained, the effect of the binder resin on the flaky alumina 15a and the amorphous silica 16a can be sufficiently exhibited. In addition, the uncured electron beam-curable resin coated on the paper 11a, when heated and dried, reduces the viscosity of the uncured electron beam-curable resin due to heating, causing the scale-like alumina contained in the protective layer to be reduced. Although the 15a and the amorphous silica 16a move downward, the thickness of the protective layer does not decrease, so the uncured electron beam-curable resin layer (protective layer)
On the surface of flake-like alumina 15a and amorphous silica 16
a does not protrude. Further, the uncured electron beam-curable resin flows in the horizontal direction by heating, so that slight irregularities on the surface become smooth, and the protective layer has a surface with good slipperiness.

Next, as shown in FIG. 4C, an electron beam 18a is irradiated onto the protective layer 13 made of the uncured electron beam curable resin 14c to irradiate the uncured electron beam curable resin 14c.
Is cured to produce a wear-resistant decorative material 1 having a protective layer 13 made of a cured electron beam-curable resin 14d containing scale-like alumina 15a and amorphous silica 16a, as shown in FIG. 4 (d). I do. Obtained wear-resistant decorative material 1
Has no roughness on the surface, has good slipperiness, and has a soft feel.

As the scaly filler used in the present invention, any organic or inorganic filler can be used as long as it has a higher hardness (evaluated by Mohs hardness, Vickers hardness, etc.) than the binder resin. Organic materials include polyamide (nylon) resin, urethane resin,
Melamine resin, polycarbonate resin, crosslinked acrylic resin, urea resin and the like are used. As inorganic substances,
Alumina (such as α-alumina), mullite, silinamite, aluminosilicate, silicon carbide, boron carbide, boron nitride, borax, silica, diamond and the like are used. However, in terms of hardness, chemical durability and the like, inorganic scaly particles, especially those having a Knoop hardness of 13 GPa (about 1300 kg / mm ² in the conventional unit notation) are preferable,
Scale-like alumina (for example, scale-like α-alumina) is preferred.

The flaky filler such as flaky alumina is
A particle size (defined as the radius of the circumscribed sphere or the diagonal length of the flat surface) of 5 to 40 μm is used, and an average particle size of 20 to 30 μm is preferable. Further, the perspective view of FIG. 10 is a diagram showing an example of the particle shape of the flaky filler 15 and has a flat or substantially flat plate surface Fp and a side surface Fs. In addition, although the front view shape of the flat plate surface Fp in the figure is a hexagon, it is not limited to this.

The amount of the flaky filler added to the curable resin is 5 to 50% by weight based on the cured curable resin.
It is added so as to be in the range of about. When the content of the flaky filler relative to the curable resin cured as the cured coating film is less than 5% by weight, the wear resistance is insufficient, and the effect of adding the flaky filler is not sufficiently exhibited. Further, when the content exceeds 50% by weight, the addition amount of the entire filler including the case where the amorphous filler is added together with the flaky filler is too large, and the holding power of the binder resin with respect to the filler is reduced. At the same time, the viscosity of the coating liquid increases and coating becomes difficult.

As the amorphous filler used in the present invention, any of organic and inorganic fillers can be used as long as the filler is harder than the resin of the protective layer. For example, as the material, those exemplified for the above-mentioned scaly filler can be used. In addition, calcium carbonate, calcium phosphate, kaolinite, glass powder and the like can be used. In the present invention, amorphous silica is preferred. The perspective view of FIG. 11 is a diagram exemplifying the particle shape of the amorphous filler 16, and is composed of an aggregate of two or more kinds of polygonal particles having different shapes and dimensions. The shape is not fixed as in

The particle size of the amorphous filler such as amorphous silica is from 10 to 15 μm from fine powder having an average particle size of 2 μm or less.
Particles having a wide range of particle sizes can be used. In the present invention, it is important that the particle diameter of the amorphous filler is smaller than the thickness of the protective layer made of a curable resin. As a result, the decorative material exhibits physical properties with excellent abrasion resistance, and has no roughness on the surface, so that a decorative material with good slipperiness can be obtained. Usually, amorphous silica has an average particle size of 10 to 15 μm and an average particle size of 2 μm.
It is preferable to add two types of fine powder silica having a particle size of m or less. By adding 0.5 to 3% by weight of fine powder silica, the coating suitability of the coating liquid is improved,
The coating step is stabilized, and a stable protective layer is obtained.

When the amorphous filler is added, the amount of the amorphous filler is 5 to 50% by weight, as in the case of the flaky filler.
It is necessary to be Then, it is necessary that the total amount of the amorphous filler and the flaky filler is 60% by weight or less. When the content of the amorphous filler in the cured coating film is less than 5% by weight, the abrasion resistance of the amorphous filler is insufficient, and the effect of adding the amorphous silica is not sufficiently exhibited. On the other hand, when the content exceeds 50% by weight, the effect of the curable resin as a binder is not sufficiently exhibited, so that the flexibility of the coating film is impaired and the coating operation becomes difficult.

The scaly filler such as the scaly alumina and the irregular filler such as the irregular silica are subjected to a surface treatment in order to improve physical properties such as adhesion and dispersibility with a curable resin serving as a protective layer. Sometimes. For example, treatment with a fatty acid such as stearic acid improves dispersibility. Further, when the surface is treated with a silane coupling agent, the adhesion to a curable resin as a binder and the dispersibility of a filler are improved. Examples of the silane coupling agent include an alkoxysilane having a radical polymerizable unsaturated bond such as a vinyl group and an acryloyloxy group in the molecule and an alkoxysilane having a functional group such as an epoxy group, an amino group and a mercapto group in the molecule. Can be In the present invention, when an ionizing radiation curable resin is used as the curable resin of the binder resin, the silane coupling agent is preferably an alkoxysilane having a radical polymerizable unsaturated bond.

Specific examples of the alkoxysilane having a radical polymerizable unsaturated bond include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxy Propyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ
-(Meth) acryloxypropyltriethoxysilane,
γ- (meth) acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane and the like. Here, “(meth) acryloxy” is used to mean acryloxy or methacryloxy.

The method of treating the surface of a flaky filler such as flaky alumina and an irregular filler such as amorphous silica with a silane coupling agent is not particularly limited, and a known method can be used. For example, a method of spraying a predetermined silane coupling agent while vigorously stirring a filler as a dry method, or a method of dispersing a filler in a solvent such as toluene as a wet method, followed by adding a predetermined amount of a silane coupling agent and reacting. There is a method to make it. It is preferable that the processing amount (required amount) of the silane coupling agent with respect to the filler is such that the minimum coverage area of the silane coupling agent is 10 or more with respect to the specific surface area of the filler of 100. When the minimum coating area of the silane coupling agent is less than 10 with respect to the specific surface area of the filler of 100, there is not much surface treatment effect.

As the binder resin used in the present invention, basically, an acrylic resin, a thermoplastic polyester resin, a cellulose resin, a thermoplastic resin such as a vinyl chloride-vinyl acetate copolymer, or a two-part curable urethane resin , Epoxy resin, heat or two-component reactive curable resin such as melamine resin, ionizing radiation-curable resin can be used, but in terms of abrasion resistance, preferably heat or two-component reactive curable resin, ionizing radiation-curable resin A curable resin such as a resin is desirable, and an ionizing radiation curable resin is more preferable.

Specific examples of the ionizing radiation-curable resin include radically polymerizable unsaturated groups such as (meth) acryloyl group and (meth) acryloyloxy group, and cationic polymerizable functional groups such as epoxy group in the molecule. A composition in which a monomer, a prepolymer, an oligomer, and / or a polymer having two or more thiols is appropriately mixed, and a composition curable by ionizing radiation is used. Here, the (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group, and will be used in the same meaning hereinafter. Here, the ionizing radiation means one having an energy quantum capable of polymerizing or crosslinking a molecule in an electromagnetic wave or a charged particle beam, and usually an electron beam or an ultraviolet ray is used.

Examples of the prepolymer and oligomer include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyester (meth) acrylates, polyether (meth) acrylates, polyol (meth) acrylates, Melamine (meth) acrylate, epoxy (meth) acrylate, urethane (meth)
Examples include (meth) acrylates such as acrylates, and cationic polymerization type epoxy compounds. Here, “(meth) acrylate” is used to mean acrylate or methacrylate. The molecular weight is usually 25
Those having about 0 to 10,000 are used. As the polymer having a radical polymerizable unsaturated group, those having a polymerization degree of the above prepolymer or oligomer of about 10,000 or more are used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. No.

Examples of the monomer having a cationically polymerizable functional group include the above-mentioned prepolymeric monomer having a cationically polymerizable functional group. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate, dipentaerythritol tetrathioglycolate, and the like.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers of a (meth) acrylate compound, for example, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate and the like.

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 monomers used for the ionizing radiation-curable resin include styrene monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Methoxyethyl (meth) acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl (meth) acrylate, ethyl (meth) acrylate, propyl methacrylate, ethoxymethyl (meth) acrylate, (meth ) (Meth) acrylates such as lauryl acrylate, 2- (N, N-diethylamino) ethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, (Meth) acrylic acid-2-
Substitution of unsaturated acids such as (N, N-dibenzylamino) ethyl, (N, N-dimethylamino) methyl (meth) acrylate, 2- (N, N-didiethylamino) propyl (meth) acrylate Amino alcohol esters, unsaturated carboxylic acid amides such as (meth) acrylamide, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( Polyfunctional compounds such as (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and / or Has two or more thiol groups Richioru compounds, e.g., trimethylol propane trithioglycolate, trimethylolpropane tri thio propylate, pentaerythritol tetra thioglycolic like.

If necessary, one or two of the above compounds may be used.
The prepolymer or oligomer is used in an amount of 5% by weight or more and the monomer and / or polythiol is used in an amount of 95% by weight or less in order to impart ordinary coating suitability to the ionizing radiation-curable resin. Is preferred.

In selecting the monomer, if the flexibility of the cured product is required, the amount of the monomer may be reduced within a range that does not impair coating suitability, or a monofunctional or bifunctional acrylate monomer may be used. A structure having a relatively low crosslink density is used. In addition, when the heat resistance, hardness, solvent resistance, etc. of the cured product are required, the amount of the monomer may be increased within a range that does not hinder coating suitability,
It is preferable to use a tri- or more functional acrylate-based monomer to obtain a structure having a high crosslinking density. It is also possible to adjust the coating suitability and the physical properties of the cured product by mixing a monofunctional or difunctional monomer and a trifunctional or higher functional monomer.

The above-mentioned monofunctional (meth) acrylate monomers include 2-hydroxy (meth) acrylate, 2-hexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like. Examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate. Examples include methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

When the resin is cured by ultraviolet light or visible light as the ionizing radiation-curable resin, 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.

As the material of the substrate used in the present invention,
Any one of sheet-like materials such as paper, non-woven fabric or woven fabric, plastic sheet, metal foil, etc., or plate-like materials such as metal plate, woody plate, plastic plate, etc., can be used. However, it is preferable because continuous production is possible in a wound state in a manufacturing process. Usually, when using a sheet-like thing, the thickness of the sheet is 5 to 200 μm
Is preferred. Further, those having irregularities or three-dimensional shapes on the surface of the substrate can be used.

Examples of paper used as a substrate include thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, so-called vinyl wallpaper raw paper obtained by sol or dry laminating polyvinyl chloride resin on paper, fine paper, Coated paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper and the like can be mentioned. Further, as the non-woven fabric or woven fabric, non-woven fabric or woven fabric made of fibers such as glass fiber, asbestos, potassium titanate fiber, inorganic fiber such as alumina fiber, silica fiber, carbon fiber, etc., and synthetic resin such as polyester, vinylon, etc. Etc.

Examples of the plastic sheet used as the substrate include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer. Polymer, ethylene-vinyl alcohol copolymer, vinyl resin such as vinylon, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate
Polyester resins such as isophthalate copolymer; acrylic resins such as poly (methyl) acrylate, ethyl poly (meth) acrylate and butyl poly (meth) acrylate; polyamide resins such as nylon 6 and nylon 66; A single or laminated body of a cellulose resin such as cellulose acetate and cellophane, or a synthetic resin sheet (or film) such as polystyrene, polycarbonate, polyarylate, and polyimide can be used. Examples of the metal foil include metal foils or sheets of aluminum, iron, copper, stainless steel, and the like; and composites of the above materials.

As the board used as the base material, wood alone, wood plywood, particle board, medium density fiber board (M
DF), wood board such as wood fiber board, iron board, aluminum board, galvanized steel sheet, polyvinyl chloride sol coated steel sheet, metal sheet such as copper sheet, gypsum board, gypsum board such as gypsum slag board, calcium silicate board, Cement board such as asbestos slate board, lightweight foam concrete board, hollow extruded cement board, etc., fiber cement board such as pulp cement board, asbestos cement board, wood chip cement board, ceramics such as porcelain, porcelain, setware, earthenware, glass and enamel Plates, thermoplastic resins such as acrylic resin, polycarbonate, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyolefin, ABS resin, phenol resin, vinyl chloride resin, cellulosic resin and rubber Can be

Further, phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin,
Thermosetting resin plate such as melamine resin, phenol resin, urea resin, unsaturated polyester resin, polyurethane resin,
A resin plate such as a so-called FRP, in which a resin such as an epoxy resin, a melamine resin, or a diallyl phthalate resin is impregnated and cured into a glass fiber nonwoven fabric, cloth, paper, or other various fibrous base materials to form a composite.

Further, as the substrate used in the present invention, a composite substrate obtained by laminating two or more of the above various substrates by a known method such as an adhesive or heat fusion may be used. it can.

A pattern layer can be formed on one side of the substrate by printing or the like. As the pattern layer, there are a printed pattern by printing, an embossed pattern by embossing, and a concavo-convex pattern by hairline processing.Furthermore, the concave portion of the concavo-convex pattern may be filled with a coloring ink by a known wiping method to form a picture layer. it can. Print pattern layers include wood pattern, stone pattern, cloth pattern, leather pattern, geometric figures, characters,
There are symbols, various abstract patterns, or solid printing on the entire surface. The concealing layer of the full-area solid printing may be omitted depending on the surface condition of the adherend to which the decorative sheet (abrasion resistant decorative material) is to be attached.

The ink used for pattern printing varies depending on the material and form of the base material. In general, however, it is generally possible to use nitrified cotton, cellulose acetate, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, urethane resin, acrylic resin, polyester, and the like. A resin is used alone, or a mixture of two or more of these is used as a vehicle, and an ink composed of the vehicle and ordinary coloring agents such as pigments and dyes, extenders, curing agents, additives, solvents and the like is used.

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 by a transfer printing method from the obtained transfer sheet. In addition, instead of printing patterns, aluminum, chromium, gold, silver, copper and other metals are vacuum deposited,
A pattern layer can be formed by forming a metal thin film entirely or partially on a substrate by sputtering or the like.

After the pattern layer is formed on the surface of the base material as described above, a curable resin containing a flaky filler such as flaky alumina and, if necessary, an amorphous filler such as amorphous silica. Is used to form a protective layer by a known coating method. The curable resin to which the specific hard filler is added, if necessary, a thermoplastic resin, a filler,
A coating composition is prepared by adding a photopolymerization initiator, a solvent, and the like, and the surface of a substrate is coated with the coating composition by a direct coating method or a transfer coating method. In general, when a material that does not penetrate the coating composition is used as the material of the base material, any of a direct coating method or a transfer coating method may be used. The transfer coating method is more preferable when a substrate having an uneven surface or when it is necessary to provide a uniform coating thickness or when it is necessary to make the abrasion resistance of the protective layer uniform.

As the direct coating (coating) method, gravure roll coat, gravure reverse roll coat,
Gravure offset 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 and the like can be used. Among them, the plate surface Fp of the flaky filler is oriented so as to be parallel or substantially parallel to the surface of the coating film, and in order to prevent the protrusion of the flaky filler, the coating film is subjected to shear stress at the time of coating. The method is preferred. As such a coating method, a gravure roll coat, a gravure reverse roll coat, a roll coat, a reverse roll coat, a wire bar coat, and a comma coat are 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 lamp, a black light lamp, and a metal halide lamp is used. As the electron beam irradiation device, Cockcroft-Walton type, Van degraft type, Resonant transformer type, Insulating core transformer type, Linear type, Dynamitron type,
Various electron beam accelerators such as a high-frequency type are used.

When irradiating with an electron beam, 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. If the absorbed dose is less than 1 kGy, curing of the coating film will be insufficient, and if the absorbed dose exceeds 300 kGy, the cured coating film and substrate will turn yellow or be damaged. In the case of ultraviolet irradiation, the irradiation amount is 50 to 1
The range is preferably 000 mJ / cm ² . When the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , the curing of the coating film becomes insufficient, and when the irradiation amount exceeds 1000 mJ / cm ² , the cured coating film turns yellow. 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.

The wear-resistant decorative material of the present invention can be laminated on another adherend (or backing material). Examples of the adherend include plate materials such as flat plates and curved plates of various materials, sheets (or films), and various three-dimensionally shaped articles (molded products). The abrasion-resistant decorative material of the present invention is used for various applications by laminating on various adherends and subjecting them to a predetermined molding process. For example, interior decoration of buildings such as walls, ceilings, floors, etc., household equipment used in bathrooms, washrooms, kitchens, etc., window frames, doors, door frames, surface makeup of fittings such as handrails, desks, dining tables, chests, etc. It can be used for 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, when the wear-resistant decorative material cannot be directly adhered to the adherend, it is adhered to the adherend via a suitable easy-adhesion layer or an adhesive layer. However, when the wear-resistant decorative material can be bonded to the adherend by heat fusion or the like, the easy-adhesion layer or the adhesive layer may be omitted.

As a material to be used as an adherend, either a plate material or a sheet (film), a wood veneer,
Wood plywood, particle board, medium density fiberboard (MD
F), wood material such as wood fiber board, metal such as iron and aluminum, acrylic resin, polycarbonate resin, polyester resin, polystyrene, polyolefin resin, ABS resin, phenol resin, polyvinyl chloride, cellulose resin, rubber and other resins. Is mentioned. Examples of the material used exclusively as a plate material or a three-dimensional article as the adherend include ceramics such as glass and ceramics, cement such as ALC (foamed lightweight concrete), and non-cement ceramic materials such as calcium silicate and gypsum. . Materials used exclusively as sheets (or films) as adherends include non-woven fabrics and woven fabrics made of fibers such as high-quality paper and Japanese paper, carbon, asbestos, potassium titanate, glass, and synthetic resins. .

As a method of laminating these various adherends,
For example, the following methods (1) to (5) can be mentioned.
That is, (1) a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive layer therebetween, and (2) Japanese Patent Publication No. 50-1913.
No. 2, JP-B-43-27488, etc., a decorative sheet is inserted between the male and female molds for injection molding, the molds are closed, and the molten resin is injected from the male gate. After filling and cooling, a decorative sheet is adhered and laminated on the surface of the resin molded article at the same time as molding, so-called simultaneous injection molding laminating method. (3) JP-B-56-45768, JP-B-60-58014, etc. As described in, the decorative sheet is placed on the surface of the molded article through an adhesive, and the decorative sheet is laminated on the surface of the molded article by a pressure difference due to vacuum suction from the molded article side, so-called Vacuum forming simultaneous lamination method such as vacuum press lamination method, (4)
As described in JP-A-1-5895, JP-B-58-48348, etc., a decorative sheet is supplied in the longitudinal direction of a columnar base material such as a cylinder or a polygonal column through an adhesive layer therebetween. A so-called lapping method in which decorative sheets are successively pressed and laminated on a plurality of side surfaces constituting a columnar body by a number of rollers having different directions, so-called lapping method.
As described in JP-A-31122, JP-A-48-47972, etc., a decorative sheet is first laminated on a plate-like substrate via an adhesive layer, and then the decorative sheet is opposite to the plate-like substrate's decorative sheet. On the side surface, cut a V-shaped or U-shaped groove reaching the interface between the decorative sheet and the plate-shaped substrate, and then apply an adhesive in the groove, and then cut the groove. A so-called V-cut or U-cut processing method for forming a box, a box or a column, can be used.

[0065]

The present invention will be described below in more detail with reference to examples.

Example 1 First, as a base material, an impregnated paper 1 impregnated with an acrylic resin latex and having a basis weight of 60 g / m ² was used.
1b (“GF-601” manufactured by Kojin Co., Ltd.), solid printing and grain pattern printing by gravure printing, and as shown in FIG. 6A, colored opaque solid printing on the impregnated paper 11b. Layer 12
a and the pattern layer 12 were formed to produce a print sheet 2.
As the solid printing ink, an ink (manufactured by The Inktec Co., Ltd.) obtained by adding a pigment consisting mainly of red iron oxide, carbon black, titanium white, and graphite to a binder resin obtained by mixing an acrylic resin and a nitrified cotton. The ink used for the design was a binder resin consisting of nitrified cotton and an alkyd resin, and an ink made by adding a pigment consisting mainly of reddish carbon black.
Inktec Co., Ltd.) was used.

Next, as shown in FIG. 6 (b), on the pattern layer 12 side of the printing sheet 2, the following is obtained by adding scaly alumina 15a, amorphous silica 16a and fine powder silica 16b to an electron beam curable resin. Using a coating resin composition (A) of
25 g of coating amount composed of uncured electron beam curable resin 14c
/ M ² of the protective layer 13 was formed.

Composition of coating resin composition (A) ・ Epoxy acrylate 38 parts by weight ・ Trimethylolpropane triacrylate 38 parts by weight ・ Methacrylate-modified silicone 1 part by weight ・ Fine powdered silica (average particle size 0.1 μm) 1 part by weight Part: amorphous silica (average particle diameter: 12 μm) 8 parts by weight ・ scale alumina (average particle diameter: 25 μm) 14 parts by weight

Next, as shown in FIG. 6B, absorption was performed on the protective layer 13 made of the uncured electron beam curable resin 14c at an acceleration voltage of 175 keV using an electron beam irradiation device. The electron beam 18a is irradiated so that the dose becomes 50 kGy (kilo gray), the electron beam curable resin is completely cured, and the protective layer 13 made of the electron beam curable resin 14d cured on the surface is formed. An abrasion resistant decorative material 1 as shown in (c) was produced. The obtained wear-resistant decorative material 1 is
Since the flaky alumina and amorphous silica added to the electron beam-curable resin did not protrude from the surface of the protective layer 13, the surface was soft to the touch and excellent in abrasion resistance.

Example 2 As a substrate, a thickness of 100 μm
Gravure printing with a urethane-based ink (manufactured by Showa Ink Industries, Ltd.) using a colored polyethylene-based thermoplastic elastomer resin sheet ("Tuffer" manufactured by Tatsuno Chemical Co., Ltd.) (hereinafter referred to as a colored PO sheet 11c). And FIG.
As shown in (a), a colored opaque solid printing layer 12a and a picture layer 12 were formed on a colored PO sheet 11c to produce a printed sheet 2. Next, as shown in FIG. 7B, on the pattern layer 12 side of the print sheet 2, as in Example 1,
The coating resin composition (A) was coated by a gravure reverse method to form a protective layer 13 having a coating amount of 25 g / m ² . Further, similarly to Example 1, the uncured electron beam-curable resin 14c is cured by irradiating the electron beam 18a,
An abrasion resistant decorative sheet 1a as shown in FIG. 7 (c) was produced. Next, as shown in FIG. 7 (d), a urethane-based adhesive is applied to the colored PO sheet 11c side of the wear-resistant decorative sheet 1a to form an adhesive layer 21, and the adhesive layer 21 is removed. Through which an AB having a thickness of 200 μm
It was laminated on an S resin plate to produce a wear-resistant decorative material 1 as shown in FIG.

Example 3 As in Example 1, impregnated paper 1
A printed sheet 2 as shown in FIG. 6A was prepared by forming a colored opaque solid printing layer 12a and a picture layer 12 on 1b. Next, on the picture layer side of the printed sheet, Example 1
Means that a coating resin composition whose composition is changed as described below is coated by a gravure reverse method, and a coating amount of 25 is applied.
g / m ² of the protective layer was formed. Further, in the same manner as in Example 1, an uncured electron beam-curable resin was cured by irradiating an electron beam to produce a wear-resistant decorative material (not shown). The resin composition for coating used in Example 3 was the same as the resin composition for coating (A) used in Example 1 except that fine powdered silica (average particle diameter: 0.1 μm) was used as a filler. And amorphous silica (average particle size: 12 μm) were not used together, and the same composition was used except that only 23 parts by weight of flaky alumina (average particle size: 25 μm) was used.

(Comparative Example 1) As in Example 1, impregnated paper 1
A printed sheet 2 was prepared as shown in FIG. 8A by forming a colored opaque solid printing layer 12a and a picture layer 12 on 1b. Next, as shown in FIG. 8B, a two-part curable urethane-based top coat agent (manufactured by The Inktech Co., Ltd.) is applied by gravure printing to the entire surface of the print sheet 2 on the picture layer 12 side. By applying, an uncured top coat layer 19a having a thickness of 3 μm was formed. Further, the decorative material having the uncured top coat layer 19a formed thereon is stored at 60 ° C. for 3 days to completely cure the uncured top coat layer 19a, as shown in FIG. 8 (c). Then, a decorative material 3 having a hardened top coat layer 19b on the surface was produced.

(Comparative Example 2) As in Example 1, impregnated paper 1
A printed sheet 2 was prepared as shown in FIG. 9A by forming a colored opaque solid printing layer 12a and a picture layer 12 on 1b. Next, as shown in FIG. 9 (b), spherical alumina 20, amorphous silica 16a and fine powder silica 16b were added to the electron beam curable resin on the pattern layer 12 side of the printing sheet 2.
Was coated by the gravure reverse method using the following coating resin composition (B) to which was added, thereby forming a protective layer 13 composed of an uncured electron beam curable resin 14c and having a coating amount of 25 g / m ² . .

Composition of Coating Resin Composition (B) 50 parts by weight of bisphenol A ethylene oxide-modified diacrylate 20 parts by weight of trimethylolpropane ethylene oxide-modified triacrylate 1 part by weight of methacrylate-modified silicone at both ends 1 globular α- 20 parts by weight of alumina (average particle size: 25 μm) ・ 8 parts by weight of amorphous silica (average particle size: 1.8 μm) ・ 1 part by weight of fine powdered silica (average particle size: 0.1 μm)

Next, as shown in FIG. 9B, the protective layer 13 made of the uncured electron beam-curable resin 14c is irradiated with an electron beam 18a in the same manner as in the first embodiment. The beam-curable resin is completely cured to form a protective layer 13 made of a cured electron beam-curable resin 14d on the surface.
An abrasion resistant decorative material 1 as shown in (c) was produced. In the obtained wear-resistant decorative material, the particle diameter of the added hard spherical alumina is larger than the thickness of the protective layer, and the hard spherical alumina is hardened on the protective layer made of an electron beam curable resin. Since it protruded, the abrasion resistance was excellent, but roughness was observed on the surface and a soft touch was not obtained.

(Abrasion Resistance Test) The abrasion resistance of the abrasion-resistant decorative materials manufactured in Examples 1 to 3 and the decorative materials and the abrasion-resistant decorative materials manufactured in Comparative Examples 1 and 2 were measured in accordance with JIS K6902. The test was performed.

(Slipperiness test) A cotton cloth was applied under a load of 300 g / cm ² to the abrasion-resistant decorative materials manufactured in Examples 1 to 3 and the decorative materials and abrasion-resistant decorative materials manufactured in Comparative Examples 1 and ^2. In a state of being pressed, the cotton cloth was rubbed 10 times a distance of 10 cm, and the degree of damage of the cotton cloth was visually determined.

Table 1 shows the results of the wear resistance test and the slip test.
Shown in As can be seen from the results in Table 1, the wear-resistant decorative materials prepared in Examples 1 to 3 were all flaky alumina.
Further, the abrasion resistance was superior to the decorative material of Comparative Example 1 in which neither amorphous silica nor finely divided silica was used. In addition, the abrasion-resistant decorative materials prepared in Examples 1 and 2 had no surface roughness, smoothness and good softness because the flaky alumina, amorphous silica and fine powdered silica did not protrude on the surface of the protective layer. Feeling was obtained. In addition, the abrasion-resistant decorative material produced in Example 3 did not have flaky alumina protruding from the surface of the protective layer, so that the surface had no roughness, had a good sliding property, and had a soft touch. On the other hand, in the abrasion-resistant decorative material produced in Comparative Example 2, the diameter of the hard spherical alumina is larger than the thickness of the protective layer, and the protrusion protrudes from the surface of the protective layer. In the slip test, the cotton fabric was severely damaged.

[0079]

[Table 1]

[0080]

(1) The wear-resistant decorative material of the present invention is obtained by incorporating a flaky filler having a hardness higher than that of a binder resin made of a cured product of a curable resin into a coating film serving as a protective layer. In addition to having abrasion resistance, roughness on the surface is eliminated, and the feeling of touch becomes very soft. In addition, the wear-resistant decorative material has improved surface slipperiness, and does not wear or damage the object even when the decorative material comes into direct contact with the object. Therefore, it can be used in fields where high abrasion resistance is required, such as flooring materials, and the contacting object is not damaged. (2) Further, in addition to the flaky filler, together with an amorphous filler having a hardness higher than the binder resin, the flaky filler is oriented and distributed in the coating film in the horizontal direction, and the flaky filler By forming the coating so that the filler does not protrude to the surface of the coating, the effect of the above (1) can be reliably obtained, and the abrasion resistance, coating suitability, etc. are appropriately adjusted and properly adjusted. You can do it. (3) Further, by using flaky alumina for the flaky filler and amorphous silica for the irregular filler, the effect of the above (1) can be surely obtained. In addition, coating aptitude can be improved, and the flaky filler is easily distributed in the lateral direction.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one example of a wear-resistant decorative material of the present invention.

FIG. 2 In another embodiment of the abrasion-resistant decorative material of the present invention, when an impregnating base material such as paper is used as a base material, a sealer layer is provided in order to prevent a coating solution from penetrating into paper. FIG.

FIG. 3 is an explanatory view for producing a wear-resistant decorative material of the present invention.

FIG. 4 is an explanatory view when a wear-resistant decorative material is produced using paper as a base material.

FIG. 5 is a diagram showing a flow state of an uncured electron beam-curable resin when a wear-resistant decorative material is produced using paper as a base material.

FIG. 6 is an explanatory diagram when a wear-resistant decorative material is manufactured according to Example 1.

FIG. 7 is an explanatory view when producing a wear-resistant decorative material according to Example 2.

FIG. 8 is an explanatory diagram when a decorative material is produced according to Comparative Example 1.

FIG. 9 is an explanatory view when producing a wear-resistant decorative material according to Comparative Example 2.

FIG. 10 is a perspective view showing an example of the shape of a flaky filler.

FIG. 11 is a perspective view illustrating the shape of an amorphous filler.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Abrasion resistant decorative material 1a Abrasion resistant decorative sheet 2 Printing sheet 3 Decorative material 11 Base material 11a Paper 11b Impregnated paper 11c Colored PO sheet 12 Picture layer 12a Solid printing layer 13 Protective layer 14 Binder resin 14a Uncured ionizing radiation curing Resin 14b Cured ionizing radiation curable resin 14c Uncured electron beam curable resin 14d Cured electron beam curable resin 15 Scale-like filler 15a Scale-like alumina 16 Amorphous filler 16a Amorphous silica 16b Fine powder silica 17 Sealer layer 18 Ionizing radiation 18a Electron beam 19a Uncured top coat layer 19b Cured top coat layer 20 Spherical alumina 21 Adhesive layer 22 Adherend Fp Flat surface Fs Side surface

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) E04F 13/18 E04F 13/18 A 15/10 104 15/10 104A

Claims (3)

[Claims] 1. A decorative material in which a coating film made of a binder resin containing a hard filler is formed on a base material, wherein the hard filler comprises a flaky filler having a hardness higher than the hardness of the binder resin. A wear-resistant decorative material, wherein the binder resin comprises a cured product of a curable resin. 2. The hard filler in the coating film comprises, in addition to the flaky filler, an amorphous filler having a hardness higher than the hardness of the binder resin, wherein the flaky filler is contained in the coating film. The abrasion-resistant decorative material according to claim 1, wherein a coating film is formed so as to be oriented and distributed in a lateral direction, and that the flaky filler does not protrude to the surface of the coating film. 3. The abrasion-resistant decorative material according to claim 2, wherein the flaky filler is composed of flaky alumina, and the irregular filler is composed of irregular silica.