JP2000211092A - Decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material always having more excellent abrasion resistance even if a base material is thin paper or paper good in permeability, having good design effect, not abrading the roll or doctor knife of a coating apparatus when a surface resin layer is formed, improved in the abrasion resistance of its surface resin layer having a flexible base material and having abrasion resistance but hard to abrade other thing. SOLUTION: In a decorative material obtained by providing an abrasion- resistant resin layer formed from a coating compsn. containing a binder comprising a crosslinkable resin and spherical particles harder than the crosslinkable resin on the surface of a base material and having abrasion resistance satisfying formula 0.3 t<=d<=2.0 t [wherein the abrasion-resistant resin layer is t(mm) and the mean particle size of sherical particles is d(mm)], a penetration suppressing coating film having a property suppressing the penetration of the abrasion-resistant coating compsn. is provided between the base material and the abrasion-resistant resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative material used as a surface decoration material for interiors such as floors, walls, ceilings and the like of buildings, furniture and various cabinets. The present invention relates to a cosmetic material used for various purposes.

[0002]

2. Description of the Related Art Various decorative materials such as melamine veneer, dup veneer, polyester veneer, printed plywood, and vinyl chloride veneer have been used as materials for decorating the interior of buildings, furniture, cabinets, and other surfaces. Is used. Various attempts have been made to improve the wear resistance of the surface of such a decorative material. As described in, for example, Japanese Patent No. 2740943, the applicant of the present application also discloses that (1) a coating composition containing a binder composed of a crosslinkable resin and spherical particles having a higher hardness than the crosslinkable resin. When the formed wear-resistant resin layer is provided on the surface of the base material, the average thickness of the wear-resistant resin layer is t (mm), and the average particle size of the spherical particles is d (mm), A decorative material having wear resistance, characterized by satisfying the following expression (1). 0.3t ≦ d ≦ 2.0t (1) (2) The above (1) in which the spherical particles are spherical α-alumina.
(1) The base material is in the form of a sheet having flexibility.
Alternatively, a cosmetic material having the wear resistance described in (2) has been filed first.

[0003]

However, when a thin paper or a paper having good permeability is used as a base material, there is a problem that abrasion resistance is not obtained due to penetration of a resin of a coating composition. Further, there is a problem that the surface is poor in roughness design due to the penetration. In particular, when high wear resistance is required as in the case of a decorative material used for a floor surface, further excellent wear resistance is desired.

The present invention has been made in order to solve the above-mentioned drawbacks of the prior art, and has a superior abrasion resistance, a good design, and a good surface resin even if the base material has good permeability. When forming the layer, it does not wear the rolls and doctor knives of the coating device, and it is also possible to form a cosmetic material with improved abrasion resistance of the surface resin layer having a flexible base material. An object of the present invention is to provide a cosmetic material which has but is hard to be worn by others.

[0005]

The abrasion-resistant decorative material of the present invention comprises: (1) a coating material containing a binder composed of a crosslinkable resin and spherical particles having a higher hardness than the crosslinkable resin. An abrasion-resistant resin layer formed from the composition was provided on the surface of the substrate, and the average thickness of the abrasion-resistant resin layer was defined as t (mm), and the average particle size of the spherical particles was defined as d (mm). In the case, in a wear-resistant decorative material characterized by satisfying the following formula (1), the penetration of the wear-resistant resin composition between the base material and the wear-resistant resin layer is suppressed. A cosmetic material having a permeation-suppressing coating film having the property of causing 0.3t ≦ d ≦ 2.0t (1) (2) The permeation suppression coating film is made of a composition mainly composed of an oil-resistant resin. (1) The cosmetic material according to (1). (3) the oil-resistant resin is selected from the group consisting of a thermosetting resin such as a urethane resin, a polyvinyl alcohol resin, or an acrylic resin; or
The decorative material according to (2), which is a mixture of a material selected from the above group and a thermosetting resin. (4) The decorative material according to (2), wherein the oil-resistant resin comprises a thermosetting resin and an ionizing radiation-curable prepolymer, oligomer, or monomer. (5) The wear-resistant decorative material according to (1), wherein the spherical particles are spherical α-alumina. , Is the gist.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below in detail. The abrasion-resistant cosmetic material of the present invention (hereinafter, may be simply abbreviated as a cosmetic material) has a property of suppressing penetration of an abrasion-resistant resin composition or printing ink on the surface of a substrate. The suppression coating film and the wear-resistant resin layer are sequentially provided. The abrasion-resistant resin layer is formed from a coating composition containing a binder made of a crosslinkable resin and spherical particles having a higher hardness than the crosslinkable resin. The wear-resistant resin layer is located on the outermost surface of the decorative material to protect the surface,
It is a layer that gives abrasion resistance to the decorative material. In the present invention, it is also important that the wear-resistant resin layer is configured to contain spherical particles having a higher hardness than the crosslinkable resin.

[0007] The substrate may have no or low permeability of the abrasion-resistant resin composition (such as an ionizing radiation-curable resin composition). Mainly those having permeability of the radiation-curable resin composition. Broadly speaking, various papers, nonwoven fabrics, or woven fabrics, as well as plastic films or plastic sheets, even those that are porous or contain a large amount of filler have impregnating properties. Can be used. A fiber-reinforced plastic plate or the like can also be used because it has impregnating properties with the liquid resin composition. Wood-based substrates can be used because they have impregnation properties, and can be used for wood boards, plywood,
Examples include a particle board or a medium-density fiberboard called MDF. In addition, composites of the same group, such as paper, and composites of the different groups described above can also be used. Further, a material such as steel wool obtained by processing a metal into a fibrous shape can also be used.

The following are typical examples of various papers. That is, tissue paper, kraft paper,
It is titanium paper or the like. A resin-impregnated paper which has been impregnated with a resin in advance for the purpose of reinforcing between papers can also be used because it has impregnating properties.
In addition to these, it can also be used for linter paper, paperboard, and gypsum board base paper. A group of raw materials often used in the field of building materials, such as a raw material of vinyl wallpaper having a vinyl chloride resin layer containing a large amount of filler on the surface of paper, is also applicable. Furthermore, the present invention can be applied to the following papers used in the office field and ordinary printing and packaging. That is, it is coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper, or the like. Although different from these papers, the following woven or nonwoven fabrics of various fibers having the appearance and properties similar to paper can also be used as the base material for the decorative material. The various fibers are inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, or carbon fibers, or synthetic fibers such as polyester fibers or vinylon fibers.

[0009] Examples of the plastics constituting the plastic film or the plastic film which is porous or contains a large amount of filler include the following various materials. That is, polyethylene resin, polypropylene resin, polymethylene resin, polymethylpentene resin,
Polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene na Phthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, polyamide resin represented by nylon 6 or nylon 66, cellulose triacetate resin,
Cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, or the like.

[0010] Since the permeation suppression coating having the property of suppressing permeation of the ionizing radiation-curable resin composition may be formed at various positions, it is adhered to any of the base material, the colored layer, the wood pattern, and the like. And, of course, also need to have an adhesive property with the ionizing radiation-curable resin composition. However,
It is not always necessary to form a porous coating film such that the ionizing radiation-curable resin composition penetrates. In addition, when the ionizing radiation-curable resin composition is applied, it is difficult to dissolve apart from dissolution of only a part.

As the binder of the coating composition for forming a permeation-suppressing coating film selected from these viewpoints, a binder having a relatively high polarity which is soluble in alcohol and water is desirable. Alternatively, various acrylic resins and the like are suitable. As the acrylic resin, methyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate are commonly used and can be used. And other acrylic resins may be used. The polyvinyl alcohol resin, or various acrylic resins, etc.,
A thermosetting resin such as a polyurethane resin may be added for use.

Further, as a binder for the coating composition for forming a permeation suppression coating film, a thermosetting resin such as a polyurethane resin may be used. Further, a thermosetting resin such as a polyurethane resin, an ionizing radiation-curable prepolymer or oligomer,
Alternatively, a material to which a monomer is added may be used. For example, a preferable example is a mixture of a thermosetting component composed of an acrylic polyol or a polyester polyol and an isocyanate such as hexamethylene diisocyanate, and an ionizing radiation-curable prepolymer or oligomer such as an unsaturated polyester. The ionizing radiation-curable prepolymer, oligomer, or monomer is the same as that used for the later-described coating film composed of the ionizing radiation-curable resin composition.

The coating composition for forming a permeation-suppressed coating film using these resins is applied by gravure printing or roll coating, but if the thickness of the coating film is too large, the permeation-suppressing effect is exhibited. Since the layer of the permeation suppression coating itself is not very tough, the ionizing radiation-curable resin of the base material should be minimized so as not to impair the performance of the coating of the ionizing radiation-curable resin composition. Although it depends on the permeability of the composition, the thickness of the coating film after drying is preferably about 1 to 5 μm.

The spherical particles may have a smooth surface such as a true sphere, an ellipsoidal sphere obtained by flattening a sphere, and a shape close to the true sphere or the ellipsoidal sphere. The spherical particles preferably have no protrusions or corners on the particle surface, and have no so-called cutting edge. Spherical particles greatly improve the abrasion resistance of the surface resin layer itself compared to amorphous particles of the same material, and do not wear the coating device, and other objects that come into contact with the coating film after curing. And the transparency of the coating film is also increased, and the effect is particularly large when there is no cutting edge.

The amount of the spherical particles contained in the abrasion-resistant resin layer depends on the amount of the binder component 100 composed of the cured cross-linkable resin.
It is preferable to adjust the coating composition so as to be 5 to 20 parts by weight with respect to parts by weight. When the addition amount of the spherical particles 5 is small, the effect of the addition of the spherical particles such as improvement of abrasion resistance may not be sufficiently exerted. On the other hand, when the addition amount of the spherical particles 5 is too large, the binder of the crosslinkable resin may be insufficient. As a result, adverse effects such as the possibility that the flexibility of the coating film is reduced and the workability of the coating composition is reduced may occur.

The particle diameter of the spherical particles 5 is usually 5 to 100 μm.
m (average particle diameter) can be preferably used. If the average particle size of the spherical particles 5 is less than 5 μm, the coating may be opaque, while if the average particle size exceeds 100 μm, the surface smoothness of the coating may be reduced. As the particle diameter of the spherical particles 5 decreases, the wear resistance decreases. On the other hand, when the particle diameter of the spherical particles 5 is large, the abrasion resistance is improved. However, when the particle diameter is too large, uniform coating at the time of coating becomes difficult. For example, when the thickness of the wear-resistant resin layer is 10 to 30 μm, the spherical particles 5
Is preferably in the range of 10 to 50 μm.

More preferably, the average particle size of the spherical particles 5 is selected according to the thickness of the wear-resistant resin layer 3. In particular, when the average thickness of the wear-resistant resin layer 3 is t (mm) and the average particle diameter of the spherical particles 5 is d (mm), 0.3 t
It is desirable to select the spherical particles so as to satisfy ≦ d ≦ 2.0t. The average particle diameter d (mm) of the spherical particles 5 is 2.0
If the value exceeds t, the spherical particles 5 protrude from the surface of the wear-resistant resin layer 3 and the appearance of the layer may be deteriorated. On the other hand, when the average particle diameter d (mm) of the spherical particles 5 is less than 0.3 t, there is a possibility that sufficient wear resistance may not be obtained.

The material of the spherical particles 5 has only to be higher in hardness than the crosslinkable resin, and either inorganic particles or organic resin particles can be used. The difference in hardness between the spherical particles 5 and the crosslinkable resin is measured by a method such as Mohs hardness or Vickers hardness, and is preferably 1 or more when expressed in Mohs hardness, for example. The spherical particles 5 have a Knoop hardness of 1
It is preferably at least 300 kg / mm 2, more preferably
Knoop hardness is 1800 kg / mm2 or more.

The Knoop hardness referred to here is a minute indentation hardness measured using a Knoop indenter. The load when a diamond-shaped indentation is formed before the test is defined as the length of the longer diagonal line of the permanent dent. It is a value represented by a quotient divided by the projected area of the dent determined from the above. This test method is based on ASTM C-849.
It is described in.

The material of the spherical particles 5 is, specifically, α-alumina, silica, chromium oxide, iron oxide, diamond,
Examples include inorganic particles such as graphite, and organic resin particles such as synthetic resin beads such as cross-linked acryl. Examples of the α-alumina include fused alumina, Bayer method alumina, and the like, and examples of the inorganic particles other than the above include zirconia, titania, and a eutectic mixture of these with molten alumina, Bayer method alumina, and the like. As a method of making the shape of these inorganic particles spherical, the above-mentioned inorganic compound of a pulverized amorphous shape is charged into a high-temperature furnace having a melting point or higher and melted,
Examples of the method include a method of forming a sphere using surface tension, and a method of blowing the above-mentioned inorganic substance at a temperature higher than its melting point into a mist to form a sphere.

Particularly preferred spherical particles 5 include spherical α-alumina because they have very high hardness and a large effect on abrasion resistance, and spherical particles are relatively easily obtained. . As described in JP-A-2-55269, spherical α-alumina is obtained by adding a mineralizing agent or a crystallizing agent such as alumina hydrate, a halogen compound or a boron compound to a fused alumina or a sintered alumina. By adding a small amount to the pulverized product and subjecting it to a heat treatment at a temperature of 1400 ° C. or more for 2 hours or more, a cutting edge in alumina is reduced and, at the same time, a spherical shape can be obtained. Such a spherical alumina is available from Showa Denko KK as "Spherical Alumina A".
S-10, AS-20, AS-30, AS-40, AS
Various types of particles having an average particle size of "-50" are commercially available.

The spherical particles 5 can be treated on the surface of the particles. For example, treatment with a fatty acid such as stearic acid improves dispersibility. In addition, by treating the surface with a silane coupling agent, the adhesiveness with a crosslinkable resin used as a binder and the dispersibility of particles in a coating composition are improved. Examples of the silane coupling agent include an alkoxysilane having a radically polymerizable unsaturated bond such as vinyl and methacryl in the molecule and an alkoxysilane having a functional group such as epoxy, amino and mercapto in the molecule. Depending on the type of the crosslinkable resin used together with the spherical particles, the silane coupling agent may be, for example, an ionizing radiation-curable resin such as (meth) acrylate or the like, using an alkoxysilane having a radical polymerizable unsaturated bond, In the case of a two-part curable urethane resin, it is preferable to select the type of radically polymerizable unsaturated bond or functional group, such as using an alkoxysilane having an epoxy group or an amino group. Specific examples of the alkoxysilane having a radical polymerizable unsaturated bond include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, and γ-methacryloxypropyldimethylethoxy. Silane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ
-Acryloxypropylmethyldiethoxysilane, γ-
Examples include alkoxysilane having a radical polymerizable unsaturated bond in a molecule such as acryloxypropyldimethylethoxysilane and vinyltriethoxysilane, and alkoxysilane having a functional group such as epoxy, amino, and mercapto in a molecule.

The method of treating the surface of the spherical particles 5 with a 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 treatment amount (required amount) of the silane coupling agent with respect to the spherical particles may be set to a specific surface area of the spherical particles of 100.
On the other hand, a treatment amount at which the minimum coating area of the silane coupling agent is 10 or more is preferable. 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.

In the present invention, the crosslinkable resin used as a binder for forming the wear-resistant resin layer on the surface of the permeation-suppressed coating film is an ionizing radiation-curable resin or a thermosetting resin (room temperature-curable resin, Resin used as a crosslinkable resin of a conventionally known cosmetic material (including a reaction curable resin) can be used. As a crosslinkable resin, an ionizing radiation curable resin has a high curing speed and good workability, and it is easy to adjust physical properties of the resin such as flexibility and hardness. This is preferable because a sheet-like decorative material can be efficiently and continuously produced. Further, the selection of the above-mentioned crosslinkable resin can be appropriately selected according to the use of the decorative material.
The crosslinkable resin is applied by dispersing spherical particles in an uncrosslinked state, then crosslinked and cured to complete the coating film.

The higher the crosslink density of the crosslinkable resin, the higher the abrasion resistance but the lower the flexibility. Therefore, the cross-linking density of the cross-linkable resin, depending on the wear resistance and flexibility depending on the application of the cosmetic material, etc.
It is preferable to select one. The crosslink density can be represented by the average molecular weight between crosslinks.

The ionizing radiation curable resin used as the crosslinkable resin is, specifically, an ionizing radiation curable resin obtained by appropriately mixing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule. The composition which can be cured by the above 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 methacrylate, polyether methacrylate, polyol methacrylate and melamine methacrylate, polyester acrylates, and the like. Examples include acrylates such as epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

Examples of the urethane acrylate include a polyether urethane (meth) acrylate obtained by reacting a polyether diol with a diisocyanate.

Examples of the diisocyanate used for the above polyether-based urethane (meth) acrylate include isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and tolylene diisocyanate. Examples of the polyether diol include polyoxypropylene glycol, polyoxyethylene glycol, and polyoxytetramethylene glycol having a molecular weight of 500 to 3,000.

Hereinafter, a production example of urethane acrylate will be described. In a glass reaction vessel equipped with a dropping funnel, a thermometer, a reflux condenser, and a stirring rod, 1000 parts of polytetrameralene glycol having a molecular weight of 1,000 and 444 parts of isophorone diisocyanate were charged and reacted at 120 ° C. for 3 hours. Thereafter, the mixture was cooled to 80 ° C. or lower, 232 parts by weight of 2-hydroxyethyl acrylate was added, and the reaction was carried out at 80 ° C. until the isocyanate group disappeared to obtain a urethane acrylate.

Examples of monomers used for the ionizing radiation-curable resin include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, and acrylic acid. Acrylates such as butyl, methoxybutyl acrylate and phenyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate Esters, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl memethacrylate, 2- (N, N-dibenzylamino) methyl acrylate, acrylic Acid-2- (N Substituted amino alcohol esters of unsaturated acids such as N-diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate ,
Compounds such as 1,6 hexanediol diacrylate and triethylene glycol diacrylate; polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate; and / or Polythiol compounds having two or more thiol groups, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, and pentaerythritol tetrathioglycol.

Usually, one or more of the above compounds are used, if necessary, in a mixture. In order to impart ordinary coating suitability to the ionizing radiation-curable resin, the prepolymer or polythiol is used in combination with 5 or more. It is preferable that the content of the monomer and / or polythiol be not more than 95% by weight.

In selecting the monomer, when flexibility of the cured product is required, the amount of the monomer may be reduced as long as the coatability is not impaired, or a monofunctional or bifunctional acrylate monomer may be used. The structure has a relatively low crosslink density. In the case where the abrasion resistance, heat resistance, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not hinder coating suitability, or use a trifunctional or higher acrylate monomer. And a structure having a high crosslinking density can be obtained. In addition, a monofunctional monomer and a trifunctional or higher functional monomer may be mixed to adjust coating aptitude and physical properties of a cured product.

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

Further, a non-ionizing radiation curable resin for adjusting physical properties such as flexibility and surface hardness of the cured product can be added to the ionizing radiation curable resin. As the ionizing radiation non-curable resin, thermoplastic resins such as urethane-based, cellulose-based, polyester-based, acrylic-based, butyral-based, polyvinyl chloride, and polyvinyl acetate are used. Particularly, cellulose-based and urethane-based resins are used. Butyral is preferred from the viewpoint of flexibility.

When irradiating an ultraviolet ray to cure the ionizing radiation-curable resin having the above composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-aminoxime ester may be used as a photopolymerization initiator. , Tetramethylthiuram monosulfide,
Thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes, and photopolymerization accelerators (sensitizers)
N-butylamine, triethylamine, tri-n
-Butylphosphine and the like can be further mixed and used.

Specific examples of the thermosetting resin used as the crosslinkable resin include a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, and a polyurethane resin (two-pack polyurethane resin). ), An epoxy resin, an amino alkyd resin, a melamine-urea co-condensation resin, a silicon resin, a polysiloxane resin, 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, divalent or higher aliphatic or aromatic isocyanate can be used, but aliphatic isocyanate is preferable from the viewpoint of prevention of thermal discoloration and weather resistance. Specific isocyanates include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like.

The two-pack type polyurethane comprises a first solution comprising a polyol compound having an average of two or more hydroxyl groups in its molecular structure and a second solution comprising a polyisocyanate compound. What was blended so that equivalent ratio might be set to 0.7-1.5 is mentioned.

The epoxy resin includes an epoxy resin having an average of two or more epoxy groups in its molecular structure and a mono- or poly-amine having three or more active hydrogens in one molecule which react with the epoxy group. Examples include those blended such that the ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the mono or polyamine is 0.7 to 1.5.

In the coating composition comprising the crosslinkable resin as the binder and the spherical particles, in addition to the above components,
Colorants such as dyes and pigments, other CaCO3, BaSO
4. Additives usually added to paints and inks such as known matting regulators such as nylon resin beads and fillers such as extenders, defoamers, leveling agents, and thixotropic agents can be added.

In order to adjust the viscosity, a component of a crosslinkable resin can be dissolved in the coating composition for the abrasion-resistant resin layer, and a solvent having a boiling point at normal pressure of 70 to 150 ° C. Can be used in the composition in an amount of 30% by weight or less. If the amount of the solvent is in the range of 30% by weight or less,
Drying is smooth and there is no significant decrease in production speed.

As the above-mentioned solvent, those which are usually used for paints, inks and the like can be used. Specific examples thereof include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone methyl isobutyl ketone and cyclohexanone. Acetic acid esters such as ethyl acetate, isopropyl acetate and amyl acetate; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ethers such as dioxane, tetrahydrofuran and diisopropyl ether; and mixtures of two or more of these.

Next, a method for forming a wear-resistant resin layer on the surface of a permeation-suppressed coating film using the above-mentioned coating composition will be described. For the wear-resistant resin layer, a direct coating method of directly applying the coating composition to the surface of the permeation suppression coating film is used.

The above direct coating methods include gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat, flow coat , A comma coat, a pouring coat, a brush coat, a spray coat and the like can be used, and a gravure coat is preferable.

When an ionizing radiation-curable resin is used as the crosslinkable resin, the ionizing radiation irradiator used for curing the resin may be an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon A light source such as an arc, a black light lamp, or a metal halide lamp is used. When irradiating an electron beam, a Cockloft-Walton type, a bandeograph type, a resonance transformer type, an insulating core transformer type, or a linear type or a dynamic type is used. Various electron beam accelerators such as a tron type and a high frequency type are used.

The irradiation amount of the electron beam is usually 100 to 1000
Electrons having an energy of keV, preferably 100 to 300 keV, are irradiated at a dose of about 0.1 to 30 Mrad. When the irradiation amount is less than 0.1 Mrad, curing may be insufficient, and when the irradiation amount exceeds 30 Mrad, the cured coating film or the base material may be damaged.

A decorative layer may be formed between the substrate and the permeation-suppressing coating or between the permeation-suppressing coating and the abrasion-resistant resin layer. As an example of the decorative layer, a uniform and uniform colored layer, a grain pattern, a repelling pattern, or the like is usually formed by printing. The method of printing is arbitrary, but since the selection range of the binder resin in the ink is wide and the substrate having permeability is generally porous, it is better that the transfer amount of the ink is large, and in that sense, The gravure printing method is suitable. However, other printing methods are also applicable.

The ink for printing the uniform and uniform colored layer and the wood grain pattern preferably has some permeability to the base material in the sense of reinforcing the base material. When the resin composition is formed or when the ionizing radiation-curable resin composition is applied, the resin composition does not dissolve and flow or bleed, but it is desired that the resin composition has an affinity having a degree of adhesiveness. For example, cellulose resins such as ethyl cellulose, nitrocellulose, cellulose acetate, and cellulose acetate butyrate are suitable as the binder. Further, a thermosetting polyurethane resin-based ink may be used.

The ink forming the repelling pattern needs to have not only an adhesive force to the lower layer but also a tough film since the repelling pattern is located at the uppermost layer in that portion. For example, an amino alkyd resin or a thermosetting urethane resin is suitable as a binder for an ink composition for forming a repelled pattern. Alternatively, the repelling pattern 6 may be formed by using a repelling pattern forming ink containing the ionizing radiation-curable resin composition. Further, a substance for repelling the ionizing radiation-curable resin composition applied to the upper layer, such as silicone, fluororesin or wax, is added and kneaded to prepare and use the ink composition.

Since the permeation suppression coating having the property of suppressing permeation of the ionizing radiation-curable resin composition may be formed at various positions, the base material, the uniform and uniform colored layer , Wood grain pattern, and repellent pattern, it is necessary to have adhesiveness to the ionizing radiation curable resin composition. However, it is not always necessary to form a porous coating film such that the ionizing radiation-curable resin composition penetrates. In addition, when the ionizing radiation-curable resin composition is applied, it is difficult to dissolve apart from dissolution of only a part.

[0053]

Example 1 (Example 1) Construction material base paper (G
F506, 50 g / m2 of acrylic resin impregnated paper)
Transparent ink using a liquid-curable polyurethane resin as a binder (FE Sealer 2 liquid, manufactured by Dainichi Seika Kogyo Co., Ltd.)
Was printed twice with a 40-line gravure plate (5 g / m2).
2). Next, a pattern layer of the following colored solid layer was formed by a gravure multicolor printing press. Further, using a roll coater, the following paint was coated on the pattern layer at 25 g / m2.
2 after application, using an electron beam irradiation device, 175 KV,
By irradiation with 5 Mrad, the coating film was crosslinked and cured to form a surface protective film having a thickness of 25 micrometers, thereby producing a decorative material. The decorative material was laminated on a particle board having a thickness of 25 mm using a urea adhesive to produce a decorative plate having a good surface feel. The surface of this decorative board is weighed 1
Methyl ethyl ketone was soaked in a cotton wound around a Kg weight and wiped, and the number of times of wiping until the ink was removed by the cotton was 1,000 times. (Solvent Resistance Test) The abrasion resistance of this decorative board was evaluated by a JIS K6902 abrasion resistance test and found to be 600 times.

Colored solid layer Resin binder: Acrylic nitrified cotton mixed system Additive: Pigment (titanium oxide, etc.) Coating amount: 5 g / m2 DRY Picture layer Resin binder: Acrylic nitrated cotton mixed system Additive: Pigment (disazo type, etc.) : 4g / m2DRY

EB resin layer Resin blend Bisphenol A ethylene oxide diacrylate monomer 50% by weight Trimethylolpropane ethylene oxide triacrylate monomer 20% by weight Dispersant 2% by weight Matting silica 5% by weight Spherical alumina (average particle diameter 25 micrometers) 25% by weight Reactive silicone 0.5-2% by weight Coating amount after drying: 25 g / m 2

(Example 2) A decorative material and a good surface texture were obtained in the same manner as in Example 1 except that a paper-reinforced paper called FIX45 manufactured by Sanko Paper Co., Ltd. was used as a base paper for building materials. A decorative board was manufactured. The surface of this decorative board was wiped by soaking methyl ethyl ketone in a cotton wrapped around a weight of 1 kg, and the number of times of wiping until the ink was removed by the cotton was 800 times. (Solvent Resistance Test) The abrasion resistance of this decorative board was evaluated by a JIS K6902 abrasion resistance test and was 500 times.

(Comparative Example 1) In Example 1, a transparent ink (FE sealer, two components, manufactured by Dainichi Seika Kogyo Co., Ltd.) using a two-component curable polyurethane resin as a binder was produced without printing at all. The feel of the surface of the decorative material and veneer was rough. The surface of this decorative board is weighed 1
Kg weight was wrapped with cotton and soaked with methyl ethyl ketone and wiped, and the number of times of wiping until the ink was removed by cotton was 500 times. (Solvent Resistance Test) The abrasion resistance of this decorative board was evaluated by a JIS K6902 abrasion resistance test, and it was 200 times.

(Comparative Example 2) In Example 2, a transparent ink (FE sealer, two components, manufactured by Dainichi Seika Kogyo Co., Ltd.) using a two-component curable polyurethane resin as a binder was produced without any printing. The feel of the surface of the decorative material and veneer was rough. The surface of this decorative board is weighed 1
Kg weight was wrapped with cotton, soaked with methyl ethyl ketone and wiped, and the number of wipes until the ink was removed by cotton was 300 times. (Solvent resistance test) The abrasion resistance of this decorative board was evaluated by a JIS K6902 abrasion resistance test, and it was 100 times.

[0059]

According to the first to fifth aspects of the present invention, even when the base material is a thin paper or a paper having good permeability, the base material always has better abrasion resistance, has better design, and has a surface resin layer. While forming, it does not wear the rolls and doctor knives of the coating device, and it is also possible to form a cosmetic material with improved abrasion resistance of the surface resin layer having a flexible base material. Others can provide a cosmetic material that is hard to wear.

Continued on the front page F-term (reference) 4D075 CA02 DC02 DC31 DC38 EA19 EA21 EB19 EB22 EB38 EC02 4F100 AA19A AA21H AH03H AK01A AK21C AK25C AK51C AK51G AK54 AL05C AP03 AT00B BA03 BA07 BA10A BA10A EB13 CC08 CB54 GB81 HB00 HB31 JA20A JB07 JB07C JB13C JB14C JD01C JK07A JK09 JK12A YY00A

Claims (5)

[Claims] An abrasion-resistant resin layer formed from a coating composition containing a binder made of a crosslinkable resin and spherical particles having a higher hardness than the crosslinkable resin is provided on a surface of a substrate, When the average film thickness of the wear-resistant resin layer is t (mm) and the average particle diameter of the spherical particles is d (mm), the following (1)
In a cosmetic material having abrasion resistance characterized by satisfying the formula, between a substrate and a wear-resistant resin layer, a penetration-suppressing coating having a property of suppressing penetration of the abrasion-resistant resin composition. A cosmetic material having a film. 0.3t ≦ d ≦ 2.0t (1) 2. The cosmetic material according to claim 1, wherein the permeation suppression coating film is made of a composition containing an oil-resistant resin as a main component of the resin. 3. The oil-resistant resin is selected from the group consisting of a thermosetting resin such as a urethane resin, a polyvinyl alcohol resin, or an acrylic resin, or is selected from the group described above. 3. A cosmetic material according to claim 2, wherein the cosmetic material is a mixture of a thermosetting resin and a thermosetting resin. 4. The decorative material according to claim 2, wherein the oil-resistant resin comprises a thermosetting resin and an ionizing radiation-curable prepolymer, oligomer, or monomer. 5. The wear-resistant decorative material according to claim 1, wherein the spherical particles are spherical α-alumina.