JPH09239908A - Precoated decorative paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide precoated decorative paper having good interlayer strength between a top coat layer and resin-impregnated paper, surface abrasion resistance, and work efficiency in production. SOLUTION: A resin for making a coating film which is nonfluid and nonsticky at room temperature by drying or cooling in a state in which an impregnation resin is uncured is used, a decorative paper substrate is impregnated with the resin, after a coating composition for a top coat layer composed of a curing resin 31 and spherical particles 32 having higher hardness than the resin 31 being applied on the surface of the impregnation resin in a state in which the resin is uncured and dried or cooled, the resin of impregnated paper 2 and the resin of the top coat layer 3 are cured together to obtain precoated decorative paper 1. In this process, the impregnation resin and the curing resin 31 have reactive groups which react with each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative paper used for producing a decorative board or the like by sticking it to a base material such as plywood, and a top coat layer having excellent abrasion resistance on the surface of the decorative paper in advance. The present invention relates to a pre-coated decorative paper that is provided with, and is particularly used for a horizontal surface such as a floor surface or a desk surface, and is most suitable for applications where durability is important.

[0002]

2. Description of the Related Art Conventionally, melamine decorative boards, dup decorative boards, polyester decorative boards, etc. have been used as materials for decorating the interiors of buildings, furniture, cabinets, etc., especially those having excellent surface durability. Decorative boards using various curable resins are used. These decorative boards are made by impregnating a paper having a pattern such as a pattern on the surface with a curable resin, and laminating a base material of the decorative board on the back side of the impregnated paper with an adhesive or the like, heating the whole, It is formed by being pressed and integrated. Therefore, these decorative boards have to be manufactured in a single-wafer manner, cannot be continuously manufactured, and have low production efficiency.

On the other hand, a decorative sheet such as a vinyl chloride decorative sheet in which a pattern layer such as a picture is formed on the surface of a flexible vinyl chloride sheet has been widely used. This decorative sheet can be continuously manufactured as a web and can be wound into a roll, which has a very high productivity. This decorative sheet can be laminated on the surface of plywood or the like using an adhesive or the like to form a decorative sheet. The decorative sheet obtained by laminating this vinyl chloride decorative sheet is impregnated with the above curable resin. It was inferior in surface physical properties such as abrasion resistance and hardness to a melamine decorative board made of impregnated paper.

A curable resin is impregnated in place of the vinyl chloride sheet in order to maintain the same productivity as a decorative sheet made by adhering a vinyl chloride decorative sheet to plywood and improve surface properties such as abrasion resistance. A decorative board is known in which a resin-impregnated paper used as a resin is used and the impregnated paper is attached as a decorative paper to a substrate such as plywood. The above decorative paper is, for example, one obtained by impregnating a thermosetting resin with titanium paper or the like to allow the above resin to penetrate into the interior of the paper and hardened, or the Japanese Patent Publication No. 63- An impregnated paper obtained by impregnating and curing the electron beam-curable composition described in Japanese Patent No. 52580 is known. This impregnated paper has remarkably excellent surface properties as compared with a decorative sheet made of a thermoplastic resin such as a vinyl chloride decorative sheet.

However, when a resin layer is further provided as a top coat layer on the surface of the resin-impregnated paper, there is a problem that the peel strength between the top coat layer and the impregnated paper is poor. That is, the surface of the resin-impregnated paper is in a state of being covered with the cured resin, the crosslinking reaction does not occur between the resin forming the topcoat layer and the resin of the impregnated paper, and the topcoat layer is removed from the surface of the impregnated paper. Easy to peel off. In particular, when an ionizing radiation curable resin is used as the resin forming the top coat layer, the surface of the ionizing radiation curable resin is likely to be formed smoothly, and so on. Poor adhesion.

As one of means for solving such a problem, Japanese Patent Laid-Open No. 60-75697 discloses an electronic device having an ethylenic double bond in a molecule on a paper (or printing paper) having a good permeability. An impregnating agent containing a ray-curable mixture as a main component is impregnated, and a coating agent containing an electron beam-curable mixture having a higher viscosity than the impregnating agent as a main component is applied to the surface of the impregnated paper, and then an electron is applied. There is disclosed a method of irradiating a ray to cure an impregnating agent and a coating agent at the same time to obtain a precoated decorative paper having a top coat layer made of an electron beam curable resin formed on the surface of impregnated paper (Patent Claim) Range).

[0007]

However, in the above method, the coating agent for the top coat layer is applied to the impregnated paper and cured while the impregnated resin is in an uncured state. The amount of impregnation fluctuates as it drips from the paper or flows too much to penetrate. Further, there is a problem that the manufacturing line of the decorative paper is contaminated if the impregnated resin drips between the impregnation of the curable resin and the coating of the coating agent to cure the resin.

The present invention has been made in order to solve the above-mentioned drawbacks of the prior art, and is more excellent in abrasion resistance as compared with the conventional impregnated paper, and the adhesion between the top coat layer and the impregnated resin layer is improved. It is an object of the present invention to provide a precoated decorative paper which has a good interpenetration strength, a high inter-paper strength of impregnated paper, and is free from problems such as staining the surroundings during the production of the precoated decorative paper.

[0009]

The present invention provides (1) a resin-impregnated paper in which a decorative paper base material is impregnated with a curable impregnating resin, and a curable resin is formed on the surface of the resin-impregnated paper. In the pre-coated decorative paper consisting of the above-mentioned top coat layer, a coating film that is non-fluid and non-adhesive at room temperature by drying or cooling in a state that is not completely cured as an impregnating resin for the decorative paper base material. Using the resin to be provided, the coating composition for the topcoat layer is applied onto the resin-impregnated paper in which the impregnated resin is not completely cured and is in a dried or cooled state, and the impregnated resin and the curable resin for the topcoat layer are Pre-coated decorative paper, characterized in that the impregnated resin and the curable resin of the top coat layer have a reactive group that reacts with each other when cured together, and (2) the top coat layer has a reactive group more than the curable resin of the layer. High hardness Precoated cosmetic paper according to the above (1) containing spherical particles, (3) Precoated decorative paper according to the above (2) wherein the average particle diameter of the spherical particles is 0.1 to 30 μm, and (4) Topcoat. The precoated decorative paper according to any one of (1) to (3) above, wherein the curable resin of the layer has an average molecular weight between crosslinks of 100 to 1000.
Is the gist.

[0010]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a longitudinal sectional view showing an example of the precoated decorative paper of the present invention, and FIG. 2 is a process diagram showing an example of a method for producing the precoated decorative paper. As shown in FIGS. 1 and 2, a precoated decorative paper 1 of the present invention is provided with a resin-impregnated paper 2 in which a decorative paper base material 21 is impregnated with a curable impregnating resin 22, and a surface of the impregnated paper 2. And a top coat layer 3 made of a curable resin 31. Further, it is preferable in terms of the design of the decorative paper to form the printing layer 4 on the surface of the impregnated paper 2.

The decorative paper base material 21 is only required to be able to penetrate the impregnating resin, and specifically, thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, and polyvinyl chloride resin sol on paper. Examples include so-called vinyl wallpaper stock coated or dry laminated, fine paper, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper and the like. Further, a paper-like sheet can also be used as a decorative paper substrate if the impregnating resin can penetrate. Examples of the paper-like sheet include glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, inorganic fibers such as carbon fibers, polyester, woven or non-woven fabric using organic resin such as vinylon, and the like. . Particularly preferably as a decorative paper base, paper called "titanium paper" mixed with a masking pigment such as titanium oxide is suitable for impregnation with an impregnating resin liquid,
Also, it is most suitable because of its excellent concealing property of the decorative plate base material to which the precoated decorative paper is attached. Decorative paper base material 21 having a basis weight 20g / m ² ~120g / m ² is preferred.

The curable resin (impregnated resin 22) for impregnated paper is
Although it is solid at room temperature in an uncured or semi-cured state that is not completely cured, and has thermoplasticity and solvent solubility, it is apparently or touched by drying or cooling after coating. At times, a resin that gives a coating film that is non-fluid (dry to the touch) and is non-adhesive (hereinafter, referred to as a resin that is solid at room temperature when not completely cured) is used.
This impregnated resin is, for example, a solvent-free composition, which has fluidity when heated and has curability such that it becomes solid at room temperature when cooled, or a composition containing a solvent, which contains a solvent. Although it has fluidity in the above state, it is a resin or the like having curability, which becomes solid when the solvent is volatilized.

Incidentally, FIG. 2 (c) shows a state in which the impregnating resin 22 is impregnated in the decorative paper base material 21, but the resin is in a non-curing state and is completely uncured (not cured at all), or It is a partially cured semi-cured state. Decorative paper base 1
The impregnated amount of the impregnated resin is 50% to 200% by weight with respect to the decorative paper base material 21, and if it is less than 50%, the entire impregnated paper may not be impregnated.
If it exceeds 0%, excessive impregnation may occur.

In the present invention, even if the amount of the impregnated resin is a little large, since it has a touch-drying property after drying or cooling, there is no risk of contaminating the guide roll or the like in the production line. Further, when the impregnated amount of the impregnated resin is slightly small, even if a coating composition for the topcoat layer having a low viscosity is applied, the impregnated resin is formed into a solid state in a state where it is not completely cured. The engineering composition penetrates and reaches the back surface of the impregnated paper and falls off,
There is no risk that the impregnated resin and the coating composition for the top coat layer are mixed.

In the present invention, it is important to use, as the above-mentioned impregnating resin, a resin which is solid at room temperature in a state where it is not completely cured. By using the above-mentioned resin as the impregnating resin 22, the impregnating resin of the resin-impregnated paper has a solid state when the topcoat layer 3 is coated, so that the coating composition of the topcoat layer 3 has a stable film thickness. Can be formed, and the top coat layer can be coated with good workability.

In the present invention, a curable resin is used as the impregnating resin 22 in order to improve the inter-paper strength, and the preferable impregnating resin 22 includes an ionizing radiation curable resin and a thermosetting resin. By adjusting the melting point, crystallinity and the like of these resins based on the molecular weight, molecular structure and the like of the resin before curing, it is possible to obtain a solid resin at room temperature in the uncured state. Particularly preferable as the impregnating resin is a solid-phase reaction type ionizing radiation curable resin, and specifically, the following two types of resins (a) and (b) can be mentioned.

(A) A resin having a radically polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C. Specifically, a radical copolymerizable unsaturated group is introduced by the methods (a) to (d) described below to the one obtained by polymerizing or copolymerizing the following.

Monomers having hydroxyl groups: N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3. Monomers having carboxyl groups such as phenoxypropyl (meth) acrylate: (meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate, etc. Monomers having epoxy groups: Glycidyl (meth) acrylate, aziridinyl groups Monomers having: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, etc. Monomers having amino groups: (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (Meth) acrylate, diet Aminoethyl (meth)
Monomers having a sulfone group such as acrylate: 2-
Monomers having an isocyanate group such as (meth) acrylamido-2-methylpropanesulfonic acid: 2,4-
Addition of 1 mol to 1 mol of a toluene diisocyanate and 2-hydroxyethyl (meth) acrylate such as an adduct of a diisocyanate and a radical-polymerizable monomer having active hydrogen, and the glass transition point of the above copolymer. In order to adjust or adjust the physical properties of the entire impregnated paper, the above compound and the following monomer copolymerizable with this compound can be copolymerized.

Examples of the monomer copolymerizable with the above compounds (1) to (3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate.
Acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate and the like can be mentioned.

The method of introducing a radically polymerizable unsaturated group into the polymer obtained as described above is (a) in the case of a polymer or copolymer of a monomer having a hydroxyl group, (meth) In the case of (b) a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, a condensation reaction of a monomer having a carboxyl group such as acrylic acid is carried out, and the monomer having a hydroxyl group described above. In the case of (c) a polymer or copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, a monomer having a hydroxyl group or a monomer having a carboxyl group described above In the case of a polymer or copolymer of (d) a monomer having a hydroxyl group or a carboxyl group, it is a monomer having an epoxy group or a monomer having an aziridinyl group. There are methods such as addition reaction of 1-to-1 mole of adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer.

(B) A compound having a melting point of normal temperature (20 ° C.) to 250 ° C. and having a radical-polymerizable unsaturated group. Specific examples thereof include stearyl acrylate, stearyl (meth) acrylate, triacryl isocyanurate, cyclohexanediol di (meth) acrylate, cyclohexanediol di (meth) acrylate, spiroglycol diacrylate, and spiroglycol (meth) acrylate.

Further, the compounds of the above (1) and (2) can be mixed and used, and a radical-polymerizable unsaturated monomer can be added to them. This radically polymerizable unsaturated monomer increases the crosslink density and improves heat resistance upon irradiation with ionizing radiation. In addition to the above-mentioned monomers, ethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, polyethylene glycol diglycidyl ether di (meth) acrylate, propylene glycol diglycidyl ether di (meth) It is possible to use acrylate, polypropylene glycol diglycidyl ether di (meth) acrylate, sorbitol tetraglycidyl ether tetra (meth) acrylate, etc., in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin. It is preferable to use. Further, as the sensitizer, benzoin ethers such as benzoquinone, benzoin, and benzoin methyl ether, halogenated acetophenones, and biacetyls that generate radicals upon irradiation with ultraviolet rays can be added to the above composition.

As the impregnating resin 22 which is solid at room temperature in a state where it is not completely cured, a composition prepared by mixing a thermoplastic resin and a reactive plasticizer and diluting it with a solvent or the like can be used.

As the thermosetting resin used as the impregnating resin 22, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin. , Melamine-urea co-condensation resin, silicon resin, polysiloxane resin and the like.

The impregnating resin 22 is used as the top coat layer 3
Top coating layer 3 after being completely cured before being applied, or after being partially cured by adjusting irradiation conditions of ionizing radiation and heating conditions. May be applied.

Further, in addition to the curable resin which is solid in the uncured state as described above, even if the resin has fluidity in the uncured state, it may be irradiated with ionizing radiation or heated. When adjusting the conditions and partially curing it to a semi-cured state, use a resin that gives a coating that is non-fluid and non-adhesive when touched by hand or by hand. be able to. If necessary, a sensitizer, a cross-linking agent, a polymerization initiator, a solvent, a viscosity modifier, an extender pigment, etc. may be added to the impregnated resin to be used as an impregnated resin composition.

As the impregnating resin, a mixed resin prepared by mixing resins having different curing conditions can be used. This mixed resin does not cure the other resin under the curing conditions of one resin, and when it is cured under either one of the curing conditions, it is non-adhesive at room temperature and gives a non-fluid coating film. . Examples of the above-mentioned mixed resin include a mixed resin of an ionizing radiation curable resin such as an ultraviolet ray and an electron beam and a thermosetting resin.

Further, as the impregnating resin, a bireactive resin having reactive groups having different curing means in one molecule can be used. One of the reactive groups may be a radically polymerizable unsaturated group, and the other may be one or more reactive groups such as a carboxyl group, a hydroxyl group and an amino group. The bireactive resin is, for example, a resin having an acrylate and a reactive hydroxyl group, and is used by mixing a resin having an isocyanate group. The above resin is a state in which a hydroxyl group and an isocyanate group are reacted in a state of being impregnated, and is formed in a non-adhesive and non-fluid state at room temperature, and an acrylate is in an unreacted state. After working, the acrylate can be reacted with a curing means such as irradiation of ionizing radiation to be completely cured.

The bireactive resin has the following advantages. When the impregnating resin is a resin that is cured by the same curing reaction as that of the top coat layer, it is necessary to form the resin with a high molecular weight in order to form the resin so as to be in a non-fluid and non-adhesive state. However, this may make it difficult for the resin to be impregnated into the base material such as paper. On the other hand, when the impregnated resin has reactivity by a curing means different from the curing means for the topcoat layer, or when a bireactive resin is used, a curing means different from the curing means for the topcoat layer is used. Since it can be used to increase the viscosity by reacting after impregnation of the resin and to eliminate the fluidity, the resin before impregnation may have a considerably low molecular weight, and it is easy to impregnate the paper with the impregnated resin. It can be carried out.

As means for impregnating the decorative paper base material 21 with the solid impregnating resin 22 in an uncured or semi-cured state at room temperature, a decorative paper base is contained in an impregnated resin composition prepared by dissolving the impregnating resin 22 in a solvent or the like. After dipping the material 21, the solvent is volatilized and dried under the condition that the impregnating resin 22 is not cured, or the impregnating resin 22 is dissolved in the solvent or is heated (in a range where the resin is not cured). After impregnating the impregnated resin composition in a state of being coated on the surface of the decorative paper base material 21 to permeate the interior, it is heated (in the range where the impregnated resin does not cure) to dry or cool the solvent to form a solid state. There are ways. A particularly preferable impregnation method is a method of coating the surface of the decorative paper base material 21 with the composition of the impregnating resin 22 to impregnate it, and is most preferable from the viewpoint of high productivity.

When the surface of the decorative paper base material 21 is coated with the impregnated resin 22 and impregnated, the impregnated resin composition penetrates into the back surface of the decorative paper base material 21 before the impregnated resin is dried or cooled. It is preferable to coat so as not to do so. To this end, the viscosity and temperature of the impregnated resin composition, the drying or cooling speed of the line, etc. can be appropriately adjusted to control the amount of impregnation for coating.

When the composition of the impregnated resin 22 is applied to the decorative paper base material 21 for impregnation, the coating method is gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll. Coat, knife coat, kiss coat, wheeler coat,
Dip coat, silk screen solid coat,
Wire bar coating, flow coating, comma coating, pouring coating, brush coating, spray coating and the like can be mentioned. A particularly preferable coating method is dip coating from the viewpoint of easy impregnation.

The top coat layer 3 of the pre-coated decorative paper 1 of FIG. 1 is formed from a coating composition in which a binder made of a curable resin 31 and spherical particles 32 having a hardness higher than that of the curable resin are contained. ing. The top coat layer 3 is
It is located on the outermost surface of the precoated decorative paper 1 and functions as a surface protection and abrasion resistant layer. By incorporating spherical particles 32 having a hardness higher than that of the curable resin 31 of the layer in the top coat layer 3, more excellent abrasion resistance can be obtained.

The spherical particles 32 may have a surface surrounded by a smooth curved surface, such as a true sphere, an elliptic sphere having a flattened sphere, a shape close to the true sphere or an ellipsoid. The spherical particles 32 have no protrusions or corners on the particle surface,
A so-called spherical shape without a cutting edge is preferred.

The spherical particles 32 greatly improve the abrasion resistance of the top coat layer 3 itself as compared with the irregular particles of the same material, and wear the coating device when the top coat layer 3 is coated. When the coating film is cured, the coating film is cured, and other objects that come into contact with the coating film are not abraded, and the transparency of the coating film is increased. The effect is particularly great when there is no cutting edge. The spherical particles 32 are contained in the top coat layer 3 in such an amount that the binder component 1 made of a curable resin after curing is used.
It is preferable to adjust the coating composition so as to be 5 to 20 parts by weight with respect to 00 parts by weight.

The particle size of the spherical particles 32 is 0.1 to 100.
The average particle size can be used, and it is appropriately selected depending on the thickness of the top coat layer 3, but is preferably 0.1 to 30 μm. When the particle size of the spherical particles 32 is small, the wear resistance is reduced, while when the particle size is large, the wear resistance is improved, but when the particle size is too large, it is difficult to perform uniform coating during coating. Become. For example, when forming the thickness of the top coat layer to 10 to 30 μm, the particle diameter of the spherical particles 32 is preferably in the range of 10 to 50 μm.

The material of the spherical particles 32 is not particularly limited as long as it is harder than the curable resin 31, and both inorganic particles and organic resin particles can be used. The hardness of the curable resin, which is compared with the hardness of the spherical particles, refers to the hardness when cured with only the resin. The difference in hardness between the spherical particles 32 and the curable resin 31 is measured by a method such as Mohs hardness or Vickers hardness. For example, when expressed in Mohs hardness, the hardness is preferably 1 or more.

The material of the spherical particles 32 is, specifically, α-
Examples thereof include inorganic particles such as alumina, silica, chromium oxide, iron oxide, diamond and graphite, and organic resin particles such as synthetic resin beads such as crosslinked acrylic. A particularly preferable spherical particle 32 is spherical α-alumina because it has a very high hardness and a large effect on wear resistance, and spherical particles are relatively easy to obtain.

Spherical α-alumina is disclosed in JP-A-2-552.
As disclosed in Japanese Patent Publication No. 69, an alumina hydrate,
Mineralizers or crystallization agents such as halogen compounds and boron compounds are added in small amounts to crushed products of fused alumina or sintered alumina, and heat-treated at a temperature of 1400 ° C or higher for 2 hours or more, the cutting edge in alumina is The number is reduced and at the same time the shape is spherical. Such spherical alumina is available from Showa Denko KK as “spherical alumina (S
physical Alumina) AS-10, AS
-20, AS-30, AS-40, AS-50 "having various average particle sizes are commercially available.

The spherical particles 32 can be treated on the surface thereof. For example, treatment with a fatty acid such as stearic acid improves dispersibility. Further, by treating the surface with a silane coupling agent, the adhesion with the curable resin used as a binder and the dispersibility of particles in the coating composition are improved. The silane coupling agent, an alkoxysilane having a radical polymerizable unsaturated bond such as vinyl and methacryl in the molecule, epoxy, amino in the molecule,
An alkoxysilane having a functional group such as mercapto can be used.

As the silane coupling agent, an alkoxysilane having a radical-polymerizable unsaturated bond is used depending on the kind of the curable resin 31 of the binder, for example, in the case of an ionizing radiation curable resin such as (meth) acrylate. In the case of a two-component curing type urethane resin, it is preferable to select the type of radical-polymerizable unsaturated bond or functional group so that an alkoxysilane having an epoxy group or an amino group is used.

Specific examples of the alkoxysilane having a radical-polymerizable unsaturated bond include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane and γ-methacryloxy. Propyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane , Γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, and other alkoxysilanes having a radical-polymerizable unsaturated bond in the molecule, and epoxies, aminos, and mercuras in the molecule. There are alkoxysilanes having a functional group bets like.

The method of treating the surface of the spherical particles 32 with the silane coupling agent is not particularly limited, and a known method can be used. For example, a method in which a predetermined amount of a silane coupling agent is sprayed while vigorously stirring spherical particles as a dry method, or a method in which a predetermined amount of a silane coupling agent is dispersed after dispersing spherical particles in a solvent such as toluene as a wet method. A method of adding and reacting is given.

The amount (required amount) of the silane coupling agent to be treated on the spherical particles 32 is preferably such that the minimum coverage area of the silane coupling agent is 10 or more with respect to 100 of the specific surface area of the spherical particles 32. When the minimum covering area of the spherical particles is less than 10 with respect to the specific surface area of the spherical particles of 100, the effect is not so large.

The curable resin 31 used as the binder of the top coat layer 3 is a conventionally known cosmetic material such as an ionizing radiation curable resin or a thermosetting resin (including a room temperature curable resin and a two-component reaction curable resin). The resin used as the crosslinkable resin can be used. Among them, the ionizing radiation curable resin has a high curing speed and good workability, and the physical properties of the resin such as flexibility and hardness can be adjusted by mixing several kinds of components having different molecular weights and functional groups. It is easy and preferable because it can be performed. Further, the selection of the above resin can be appropriately selected depending on the application of the decorative paper.

As the crosslink density of the curable resin 31 increases, its wear resistance improves, but its flexibility decreases. Therefore, it is preferable that the crosslink density of the curable resin is appropriately selected depending on the wear resistance and flexibility. The crosslink density of a curable resin formed by mixing components having different molecular weights and the number of functional groups can be represented by, for example, the average molecular weight between crosslinks shown in the following formula 1.

[0047]

## EQU00001 ## Average molecular weight between crosslinks = total molecular weight / number of crosslink points ... [1]

In the above formula [1], the total molecular weight is Σ (the number of moles of each component blended × the molecular weight of each component), and the number of crosslinking points is Σ [{(number of functional groups of each component− 1) ×
2} × the number of moles of each component].

Table 1 below shows an experimental example showing the relationship between abrasion resistance and flexibility when the average molecular weight between crosslinks of the curable resin 31 is changed. Table 1 shows that urethane acrylate oligomer and two types of acrylate monomers were used as each component of the curable resin, and the average cross-linking molecular weight was adjusted by changing the mixing ratio of the components, and spherical particles were added. It is a comparison of abrasion resistance and flexibility when a composition coated with the composition at a coating amount of 25 g / m ² is cured.

The spherical particles A are spherical α-alumina particles having an average particle diameter of 30 μm in an amount of 1 per 100 parts by weight of the curable resin.
1 part by weight is added, and B is an amorphous α having an average particle size of 30 μm.
-Alumina was added in the same amount, and no spherical particles were added at all.

The abrasion resistance test of Table 1 is based on JIS K690.
The number of times until the thickness of the resin layer is reduced to half is shown according to 2. Further, the flexibility is ◎ when the cured curable resin is very soft, ◯ is good, Δ is slightly less flexible,
Those with considerably low flexibility are indicated by x.

In the resin system of Table 1, the average molecular weight between crosslinks is 10.
It can be used in the range of 0 to 1000, more preferably 100 to 700. When a flexible substrate is used, the average molecular weight between crosslinks is 300 to 700.
It is more preferable to use the above-mentioned one, and in the above range, a topcoat layer having both excellent flexibility and abrasion resistance can be obtained.

[0053]

[Table 1]

The experimental results shown in Table 1 above show that when the curable resins are the same, the smaller the average molecular weight between crosslinks (that is, the higher the crosslink density), the more curable resin the binder holds the spherical particles. This shows that the wear resistance is further improved. Therefore, the abrasion resistance can be further improved by adjusting the average molecular weight between crosslinks of the curable resin to be small within a range that does not impair the flexibility.

The ionizing radiation curable resin used as the curable resin 31 of the top coat layer 3 is specifically a prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond or an epoxy group in the molecule. A composition which is curable by ionizing radiation and is appropriately mixed is 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 ultraviolet ray or an electron beam is used.

Examples of the above prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, methacrylates such as polyester methacrylates, polyether methacrylates, polyol methacrylates and melamine methacrylates, polyester acrylates, Examples thereof include acrylates such as epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

Examples of the above monomers include styrene and α
Styrene-based monomers such as methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, acrylates such as phenyl acrylate, methacrylic acid Methacrylic acid esters such as methyl, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, memethacryl 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dibenzylamino) methyl acrylate, 2- (N, N-diethylamino) propyl acrylate Substituted amino alcohol ester , Acrylamide, unsaturated carboxylic acid amides such as methacrylamide, ethylene glycol diacrylate, dipropylene glycol diacrylate,
Compounds such as propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6 hexanediol diacrylate, triethylene glycol diacrylate, and other compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate. Functional compounds and / or polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like can be mentioned.

Usually, one kind or a mixture of two or more kinds of the above compounds is used as necessary. In order to impart ordinary coating suitability to the ionizing radiation curable resin, 5 parts of the above prepolymer or polythiol is used. It is preferable that the amount of the monomer and / or the polythiol is 95% by weight or more and the amount of the monomer and / or polythiol is 95% by weight or less.

In selecting the monomer, when flexibility of the cured product is required, the amount of the monomer may be reduced within a range that does not hinder coating suitability, or a monofunctional or bifunctional acrylate monomer may be used. The structure has a relatively low crosslinking density. When the cured product is required to have abrasion resistance, heat resistance, solvent resistance, etc., increase the amount of the monomer or use a trifunctional or higher functional acrylate monomer within a range that does not hinder the coating suitability. It is possible to obtain a structure having a high crosslink density. It is also possible to mix a mono- or di-functional monomer and a tri- or more-functional monomer to adjust the coating suitability and the physical properties of the cured product.

Examples of the monofunctional acrylate monomer as described above include 2-hydroxy acrylate, 2-hexyl acrylate and phenoxyethyl acrylate. Further, as the bifunctional acrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, etc., and as the trifunctional or higher functional acrylate, trimethylolpropane triacrylate, pentaerythritol tri (tetra) acrylate, dipentaerythritol hexaacrylate. Acrylate etc. are mentioned.

Furthermore, an ionizing radiation non-curable resin may be added to the ionizing radiation curable resin for adjusting the physical properties such as flexibility and surface hardness of the cured product. The ionizing radiation non-curable resin may be a thermoplastic resin such as urethane type, fibrin type, polyester type, acrylic type, butyral type, polyvinyl chloride, polyvinyl acetate, etc. , Butyral type is preferable from the viewpoint of flexibility.

When ultraviolet rays are irradiated to cure the ionizing radiation curable resin having the above composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-aminoxime ester are used as photopolymerization initiators. , Tetramethylthiuram monosulfide,
Thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes, and photopolymerization accelerators (sensitizers)
As n-butylamine, triethylamine, tri-n
-Butylphosphine or the like can be further mixed and used.

The thermosetting resin used as the curable resin 31 of the top coat layer 3 is specifically a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin. Resins, epoxy resins, aminoalkyd resins, melamine-urea co-condensation resins, silicone resins, polysiloxane resins and the like. If necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, etc. may be added and used. As the above curing agent, isocyanates or organic sulfonates are usually used in unsaturated polyester resins or polyurethane resins, amines are used in epoxy resins, peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutyl nitrile are used. Often used for saturated polyesters.

As the above-mentioned isocyanate, an aliphatic or aromatic isocyanate having a valence of 2 or more can be used, but an aliphatic isocyanate is preferable from the viewpoint of thermal discoloration prevention and weather resistance. Specific isocyanates include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like.

The coating composition for forming the top coat layer 3 includes, in addition to the curable resin 31 and the spherical particles 32, colorants such as dyes and pigments, and other known CaCO ₃ , BaSO ₄ , nylon resin beads and the like. Fillers such as matting modifiers and bulking agents, and other additives can be added.

In the present invention, the impregnating resin of the resin-impregnated paper and the curable resin of the top coat layer are selected so that both resins have a reactive group that reacts with each other.

The method for producing the precoated decorative paper of the present invention will be described below with reference to FIG. First, as shown in FIG. 2A, a decorative paper base material 21 is prepared. Then, FIG. 2 (b)
As shown in FIG. 3, gravure printing, offset printing, and the like on the surface side of the decorative paper base material 21 with known printing ink for forming a pattern,
Alternatively, the pattern layer 4 is provided by using a known printing means such as silk screen printing.

The pattern layer 4 may be partially provided in a pattern (for example, a pattern pattern such as wood grain, cloth grain, figure, and letter), or may be provided on the entire surface. For example, the pattern is partially provided when a part of the pattern (for example, the shining part of the wood grain pattern) is particularly emphasized, and the entire pattern is provided in a solid pattern with a pearly feeling or This is the case when the interference appearance is brought out.

In the present invention, although not shown in the drawing, it is also possible to use a decorative paper base material in which the decorative paper base material 21 itself is colored or a pattern is formed without forming the pattern layer 4 as described above.

Next, as shown in FIG. 2 (c), the decorative paper base material 21 provided with the pattern layer 4 is impregnated with the impregnating resin 22 made of a curable resin, and then the resin is dried or cooled to make it non-conductive. It is in a tacky, non-fluidic, uncured or semi-cured state that is not completely cured.

After forming the resin-impregnated paper 2 in which the decorative paper base material 21 is impregnated with the impregnated resin 22, as shown in FIG.
The top coat layer 3 is formed on the surface of the resin-impregnated paper 2. The top coat layer 3 is formed by applying the coating composition for forming the top coat layer 3 on the surface of the resin-impregnated paper 2 in which the impregnated resin is uncured,
And to cure the coating composition.

In the present invention, the coating (impregnation) of the impregnating resin 22 and the coating of the curable resin 31 of the top coat layer 3 are carried out.
The impregnating resin is applied first, and the top coat layer is applied thereafter. Then, both of them are cured, but the timing of the curing may be any of the following three types (a) to (c). Among the following curing times, a preferred embodiment is, for example, a method of simultaneously curing the top coat layer 3 and the resin-impregnated paper 2 of (c) below when both are ionizing radiation curable resins. Can be mentioned.

(A) First, the top coat layer 3 is cured,
After that, the resin-impregnated paper 2 is cured. (A) The resin-impregnated paper 2 is cured first, and then the top coat layer 3 is cured. (C) The top coat layer 3 and the resin-impregnated paper 2 are simultaneously cured.

When the resin-impregnated paper 2 and the top coat layer 3 are cured, when an ionizing radiation-curable resin is used as the coating composition or the impregnating resin, an ionizing radiation irradiation device is used. Specifically, when the apparatus irradiates ultraviolet rays as ionizing radiation, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp,
Light sources such as carbon arc, black light lamps, metal halide lamps are used, and when irradiating with an electron beam, Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, or linear type, Various electron beam accelerators such as dynamitron type and high frequency type are used.

When irradiating with an electron beam, it is usually 100-
It is preferable to irradiate with an electron having an energy of 1000 keV, preferably 100 to 300 keV at an irradiation dose of about 0.1 to 30 Mrad to cure.

When a thermosetting resin is used as the coating composition or the impregnating resin, a heating means is used, for example, known methods such as infrared irradiation, warm air blowing, and heat conduction from a heating roller. Is used.

The precoated decorative paper 1 of the present invention is suitable for various uses, and is useful for, for example, surface decoration of buildings, vehicle ships, furniture, musical instruments, cabinets, etc., and decoration of packaging materials. Most suitable for floors, desks, etc. where sex is required. The precoated decorative paper 1 of the present invention can be easily attached to the surface of another substrate by using a known adhesive or the like to easily obtain various decorative boards having excellent surface physical properties.

To obtain a decorative board, precoated decorative paper 1
Other base materials to be attached include wood veneer, wood plywood,
Particle board, wood board such as MDF (medium density fiber board), gypsum board such as gypsum board, gypsum slag board, calcium silicate board, asbestos slate board, lightweight expanded concrete board, cement board such as hollow extruded cement board, pulp cement Board, fiber cement board such as asbestos cement board, wood chip cement board, ceramics board such as pottery, magnetism, stoneware, earthenware, glass, enamel, iron plate, galvanized steel plate, polyvinyl chloride sol coated steel plate, aluminum plate, copper plate, etc. Metal plate, polyolefin resin plate, acrylic resin plate, ABS plate, thermoplastic resin plate such as polycarbonate plate, phenol resin plate, urea resin plate, unsaturated polyester resin plate, polyurethane resin plate,
Thermosetting resin plate such as epoxy resin plate and melamine resin plate,
Phenolic resin, urea resin, unsaturated polyester resin,
A resin plate such as a so-called FRP plate obtained by impregnating and curing a resin such as polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin into glass fiber non-woven fabric, cloth, paper or other various fibrous base materials to form a composite . Also,
As the base material, a composite base material obtained by laminating two or more of the above various base materials by a known means such as an adhesive or heat fusion may be used.

[0079]

EXAMPLES The present invention will be described in more detail below by showing specific examples of the present invention. Examples 1 to 4, Comparative Examples 1 to 4 Decorative paper base material having a wood grain pattern printed (grammage: 50 g / m ² ).
To form a resin-impregnated paper by impregnating the impregnated resin composition shown in Table 2 with an impregnation dip coater, and applying the top coat layer coating composition shown in Table 2 on the pattern surface in a state where the impregnated resin is uncured. After working, irradiate with electron beam (175kv, 5Mr
Ad) The impregnated resin and the coated material were cured to obtain a precoated decorative paper.

In Examples 1 to 4, after impregnation with the impregnating resin,
After heating and drying to solidify the resin, the coating composition for the top coat layer was applied and cured. In addition, Comparative Examples 1 to
In No. 3, immediately after the impregnation with the impregnating resin, the coating composition for the top coat layer was applied and cured. In Comparative Example 4, the resin composition impregnated with the resin is dried, and then the resin is impregnated with ionizing radiation to completely cure the impregnated resin. Cured.

Table 2 shows the evaluation of the interlaminar strength, abrasion resistance and workability of the obtained precoated decorative paper. The evaluation method is as follows. The interlayer strength was measured by a cellotape peel test. The abrasion resistance test was performed in the same manner as the method shown in Table 1. The workability was rated as ◯ when the impregnated resin did not drip during the work, and rated as x when the impregnated resin dripped.

[0082]

[Table 2]

* 1 [Impregnating resin composition] (A) Ionizing radiation curable resin that is solid at room temperature-Ester acrylate polymer (melting point 50 ° C, molecular weight 20,000, 2-3 functional groups in one molecule) 40 Parts by weight Toluene 60 parts by weight

(B) Thermosetting resin that is solid at room temperature 40 parts by weight of diallyl phthalate polymer (molecular weight: 60,000 to 70,000) 2 parts by weight of peroxide 58 parts by weight of toluene / xylene

(C) Ionizing radiation curable resin that is fluid at room temperature-Ester acrylate oligomer (molecular weight: 20,000) 30 parts by weight-Bifunctional monomer (molecular weight: 300) 30 parts by weight-Toluene 40 parts by weight

* 2 [Composition composition of topcoat layer] (D) -Urethane acrylate oligomer (molecular weight: 2000, number of functional groups: 2) 40 parts by weight-Bifunctional acrylate monomer (molecular weight: 510) 50 parts by weight-2 Functional acrylate monomer (molecular weight: 300) 10 parts by weight Silicone acrylate 2 parts by weight Average molecular weight between crosslinks 330

(E) • Urethane acrylate oligomer (molecular weight: 2000, number of functional groups: 2) 100 parts by weight • Bifunctional monomer (molecular weight: 300) 30 parts by weight • Bifunctional monomer (molecular weight: 510) 40 parts by weight • Silicon acrylate 2 parts by weight

* 3: After impregnating the impregnated resin, the resin was completely cured and then the top coat layer was applied and cured.

As a reference example, the results of an abrasion resistance test of various commercially available general decorative materials as in the example of Table 2 are shown in Table 3 below.

[0090]

[Table 3]

[0091]

The reason why the precoated decorative paper of the present invention has excellent abrasion resistance is as follows. In the present invention, the top coat layer is applied to the impregnated paper in which the impregnated resin is in an uncured or semi-cured state, and the resins in the impregnated resin and the pre-coat layer are cured, so Since the resin of the top coat layer comes into contact with each other, the two become entangled with each other, and a precoated decorative paper excellent in strength between the two is obtained. Furthermore, since the impregnating resin and the resin of the precoat layer have a reactive group that reacts with each other, a strong bond is formed between the two,
Excellent interlaminar strength between impregnated paper and precoat layer.

Further, since the top coat layer and the impregnated resin are both cured, the resins react with each other and bond firmly. Moreover, since the impregnated resin is a resin that gives a coating film that is non-fluid and non-adhesive when dried in an uncured state, until the top coat layer is coated and cured after impregnation with the impregnated resin, There is no risk of the impregnating resin dripping and contaminating the manufacturing equipment. Moreover, since the resin of the top coat layer is applied in a state where the impregnated resin is dried, the top coat layer is uniformly and stably formed on the surface of the impregnated paper.

This has the following differences when compared with the conventional precoated decorative paper. For example, JP-A-60-
In the decorative paper described in Japanese Patent No. 759667, the viscosity of the coating agent is higher than that of the impregnated resin. However, since the coating agent has fluidity, the impregnated resin drips from the paper and the impregnated amount varies. Inevitably, it is difficult to uniformly apply the coating agent to the surface of the uncured impregnated paper. Furthermore, as the viscosity of the coating agent is increased in order to prevent the coating agent from penetrating into the impregnated paper, uniform coating becomes more difficult. Also,
If the viscosity of the coating agent changes due to temperature changes, etc., the permeation amount into the impregnated paper will change immediately, so it will take a great deal of time and effort to control the viscosity and temperature in the production line. On the other hand, in the pre-coated decorative paper of the present invention, since it is non-fluid and non-adhesive at room temperature in a state where it is not completely cured as an impregnating resin, there is no such possibility, and therefore the pre-coated decorative paper is stable. It became possible to manufacture it.

Further, conventionally, when the coating agent has a high viscosity and it is difficult to obtain smoothness, the release film is laid on the coated surface after coating and irradiated with an electron beam to remove the film after curing. Then, there is an attempt to prevent the coating agent from flowing, but the method of curing the coating agent by using a film on the surface of the coating agent uses a film, which complicates the work and is economically disadvantageous.

The effect of including the spherical particles of the invention of claim 2 in the top coat layer is as follows. In the field of paints, transfer sheets and the like, addition of hard particles to the surface resin layer in order to improve wear resistance has been conventionally performed as shown below.

Using a coating material containing a powder of natural glass containing SiO ₂ and Al ₂ O ₃ having an average particle diameter of about 1 to 50 μm, which was used as an abrasive in the sand blasting method, brush polishing method, etc. Constitution of surface resin layer
0-23462). In the case of a transfer sheet, an ionizing radiation curable resin is added to the resin 100 for the purpose of improving the abrasion resistance and scratch resistance of the surface of the transfer target after transfer.
10 to 30 parts by weight per part by weight of particle size 1 to 5 μm α-
The applicant of the present application has previously filed a transfer sheet in which a resin layer formed by adding alumina powder is formed as a surface protective layer positioned on the surface of a transfer target after the transfer of the transfer sheet (Japanese Patent Laid-Open No. Hei. 76698).

However, when a coating material containing an inorganic material such as α-alumina or powder of natural glass is used as a decorative material, the abrasion resistance of the decorative material is improved, but its effect is not sufficient. Absent. Further, when forming the surface resin layer, if the gravure roll or the doctor blade comes into direct contact with the coating containing α-alumina or natural glass, these powders may wear or scratch the gravure roll or the doctor blade. There is a problem in that the formed coating film has a rough feel to the touch, and the shoes are worn when walking on the coating film. On the other hand, the precoated decorative sheet according to the second aspect does not have such a fear as described in detail below.

FIG. 3 is a cross-sectional view showing a state in which an object is in contact with the surface of the decorative paper and stress is applied to explain the action of the precoated decorative paper, and FIG. 3 (a) shows spherical particles in the top coat layer. FIG. 2B shows the case where amorphous particles are used in the top coat layer. FIG.
As shown in (a), when stress is applied to the top coat layer on the surface of the decorative paper of the present invention by the contact substance 9, even if the spherical particles 32 of the top coat layer are partially exposed on the surface,
Since the portion is slippery, the stress is dispersed. Therefore, the possibility that the spherical particles 32 will fall off from the curable resin 31 as a binder is extremely small.

On the other hand, when the irregular-shaped particles 32 are used, the contact substance 9 is caught by the protrusion-shaped portion of the surface of the particles 32, and stress is applied to the interface with the curable resin holding the particles. Is more likely to be added, and the amorphous particles 10 are likely to fall off the crosslinkable resin 4. Therefore, the surface resin layer of the decorative material of the present invention has a good slip and abrasion resistance is remarkably improved. In addition, the spherical particles 5 on the surface are less likely to be caught at the time of scooping or the like as compared with the irregular particles 10 and do not damage or abrade the surface of other contact objects.

Further, a soft resin, which is a non-crosslinking resin such as a thermoplastic resin, has particles significantly harder than that (hard particles).
When added and dispersed, when the external force of the particles is applied, the resin is destroyed by the hard particles and falls off, or it is dragged by the abrasion material and has the effect of damaging the resin surface like a hoe plowing the field, Abrasion does not improve as expected. On the other hand, when a curable resin is used as the binder resin, since the strength of the resin is high, the hard particles do not fall off or are scratched, and thus the abrasion resistance of the coating film can be significantly improved. .

Further, as shown in FIG. 10B, when the conventional amorphous particles 10 are used, the voids 11 and the like tend to exist between the curable resin 31 and the amorphous particles 10. ,
In the case of the present invention, such voids are unlikely to occur because the particles are spherical particles. Therefore, it is difficult to form an air layer in the top coat layer and the surface is not whitened, so that the designability is not deteriorated. In addition, the absence of the gap also increases the bonding strength of the binder with the curable resin and contributes to the improvement of the wear resistance.

[0102]

As described above, in the precoated decorative paper of the present invention, the coating composition for the top coat layer is applied in a state where the impregnated resin of the resin-impregnated paper is not completely cured, and the impregnated resin and the top coat layer are applied. As a result of being cured, the adhesion between the top coat layer and the resin-impregnated paper is good, the inter-paper strength of the impregnated paper is high, and a pre-coated decorative sheet excellent in abrasion resistance is obtained, By simply sticking the decorative sheet of the present invention to a substrate, a decorative plate having high wear resistance and high durability can be easily obtained.

Further, the precoated decorative paper of the present invention is a resin which gives a coating film which is non-fluid and non-adhesive at room temperature when dried or cooled as an impregnating resin for resin-impregnated paper when it is not completely cured. By using, when applying the impregnated resin and the topcoat layer, there is no risk of the impregnated resin dripping or contaminating the surroundings, and there is no problem that the topcoat layer becomes non-uniform, and uniform coating and Stable manufacturing is possible, and pre-coated decorative paper with excellent inter-paper strength can be easily and inexpensively supplied. Further, since the impregnated resin and the top coat layer are resins having a reactive group that reacts with each other, the resin-impregnated paper and the top coat layer are firmly bonded to each other, and excellent adhesion can be obtained.

In the precoated decorative paper of the present invention, when the topcoat layer contains spherical particles having a hardness higher than that of the curable resin of the layer, the abrasion resistance of the topcoat layer is further improved. Especially spherical particles 0.1 to 30 μm
In this case, the effect of improving wear resistance can be reliably obtained. Moreover, the spherical particles are less likely to wear the doctor knife, roll, etc. of the coating apparatus when manufacturing the top coat layer, as compared with the conventional amorphous particles.

As the curable resin for the top coat layer,
When the average molecular weight between crosslinks is 100 to 100, the wear resistance is excellent, and particularly when the spherical particles are used, good wear resistance is obtained.

[Brief description of drawings]

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

FIG. 2 is a process drawing showing an example of a method for producing a precoated decorative paper of the present invention.

FIG. 3 is a view for explaining the action of the precoated decorative paper of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Pre-coated decorative paper 2 Resin-impregnated paper 3 Top coat layer 21 Decorative paper base material 22 Impregnated resin 31 Curable resin 32 Spherical particles having a hardness higher than that of a curable resin

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 7/18 C08K 7/18 C08L 67/06 MSE C08L 67/06 MSE

Claims (4)

[Claims] 1. A precoated decorative paper comprising a resin-impregnated paper in which a decorative paper base material is impregnated with a curable impregnating resin, and a topcoat layer formed on the surface of the resin-impregnated paper using a curable resin. In the above, as the impregnating resin for the decorative paper base material, a resin that gives a coating that is non-fluid and non-adhesive at room temperature by being dried or cooled in a state where it is not completely cured is used. The coating composition for the top coat layer is applied onto the resin-impregnated paper that has not been cured and is in a dried or cooled state, and the impregnated resin and the curable resin for the top coat layer are both cured. A precoated decorative paper characterized in that it has a reactive group that reacts with the curable resin of the coating layer. 2. The precoated decorative paper according to claim 1, wherein the topcoat layer contains spherical particles having a hardness higher than that of the curable resin of the layer. 3. The spherical particles have an average particle size of 0.1 to 30 μm.
The precoated decorative paper according to claim 2. 4. The precoated decorative paper according to claim 1, wherein the curable resin of the top coat layer has an average molecular weight between crosslinks of 100 to 1000.