JP4289528B2 - Friction-resistant cosmetic material and method for producing the same - Google Patents

Description

【００６５】
【表２】

【００６６】
表１の如く、比較例（比較例１及び３）に比べて、実施例（実施例１及び２）の耐摩耗性が向上し、表面が削られた際にも、実施例では導管柄が簡単に消失せず意匠性が保持されることが確認された。
また、表２の如く、実施例（実施例１及び実施例２）では、比較例２に比べて、実使用上問題の無い耐摩耗性を有しながら、表面滑り性として滑らかな表面を持つ事が確認された。なお、比較例４も実施例２同様に耐摩耗性及び表面滑り性は良好だが、表面に導管による凹凸が無く平滑で、表面質感に乏しかった。
【００６７】
【発明の効果】
▲１▼本発明の耐摩耗性を有する化粧材によれば、耐摩耗性を向上させる為のフィラーは内部の層の電離放射線硬化性樹脂層に含有させて、且つ該樹脂層をリコート性のリコート性電離放射線硬化性樹脂層として、この上に透明樹脂層を塗布形成してあるので、特に耐摩耗性に優れる上、フィラー添加による表面のざらつき感も発生しない。したがって、内装用途（水平面）等で表面に接触したものを損傷・摩耗させたりする問題を起こさずに、優れた耐摩耗性が得られる。しかも、最表面層としての透明樹脂層は、内部絵柄層に同調させた撥液性インキ層の撥液作用によって（内部絵柄層に同調した）、表面が凹凸状になっているので、意匠感・表面質感も豊かなものとなる。
▲２▼また、透明樹脂層に熱硬化性樹脂を使用する事により、安価且つ平易に優れた耐摩耗性が得られる。
▲３▼また、透明樹脂層に電離放射線硬化性樹脂を使用する事により、極めて優れた耐摩耗性が得られる。
【００６８】
▲４▼また、撥液性インキとして、メラミンアルキド樹脂とニトロセルロース系樹脂との混合樹脂をバインダーの樹脂として撥液剤を含有するインキを使用する事で、製造時に撥液性インキの硬化の為の加熱に例えば１８０℃等の高温を必要とせず、比較的低温（例えば１５０℃程度）での加熱硬化でも可能となり、従来は熱に弱くて使用できなかった薄紙や樹脂フィルム等で高熱で変形し易い様な基体でも使用できる様になる。
【図面の簡単な説明】
【図１】本発明の耐摩耗性を有する化粧材の一形態を例示する断面図。
【図２】本発明以外の化粧材の一例を示す断面図。
【図３】本発明以外の化粧材の一例を示す断面図。
【図４】本発明以外の化粧材の一例を示す断面図。
【図５】本発明以外の化粧材の一例を示す断面図。
【符号の説明】
１ 基体
２ 内部絵柄層
２Ａ 全ベタ層
２Ｂ 柄パターン層
２Ｂａ 柄パターン層
３ リコート性電離放射線硬化性樹脂層
３１ （フィラー未含有の）電離放射線硬化性樹脂層
４ 撥液性インキ層
５ 透明樹脂層
５１ （平坦な）透明樹脂層
Ｄ 化粧材
Ｆ フィラー[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative material used as a decorative paper for surface decoration of a home interior or furniture. In particular, the present invention relates to a decorative material having durable physical properties such as wear resistance that can be used on a horizontal surface of furniture.
[0002]
[Prior art]
Conventionally, among cosmetic materials used for applications such as building interiors and joinery, the outermost transparent resin layer as the top coat layer is a thermosetting two-component curable resin made of urethane resin or the like, or Curable resins such as ionizing radiation curable resins that are cured with ionizing radiation such as ultraviolet rays and electron beams are used from the viewpoint of wear resistance and durability of the stain resistant surface. In addition, ionizing radiation curable resins can impart better surface properties to transparent resin layers than thermosetting resins such as two-component curable urethane resins, but even in such cases, wear resistance and surface hardness are particularly important. In order to improve further, a filler is often added to the transparent resin layer.
For example, in Japanese Patent No. 2740943 (JP-A-8-183147), after a pattern layer is formed on a substrate, a crosslinkable resin (ionizing radiation curable resin, thermosetting resin, etc.) is used as the outermost surface layer thereon. ) Is provided with a wear-resistant resin layer containing a filler.
In JP-A-10-119226, a pattern layer is formed on a substrate, a heat-drying ionizing radiation curable resin layer for an intermediate layer is formed on the pattern layer, and a top coat is formed as the outermost surface layer. An ionizing radiation curable resin layer for a layer is formed, and the filler discloses a cosmetic material having a constitution in which the filler is contained in the above-mentioned heat drying ionizing radiation curable resin layer for an intermediate layer.
[0003]
[Problems to be solved by the invention]
However, as in the above-mentioned Japanese Patent No. 2740943, when a filler is contained in the outermost layer, sufficient physical properties such as wear resistance that can be used on a horizontal surface can be imparted. As the gloss decreases, the surface of the filler clogs and a rough surface is produced. When this is actually used, for example, for interior use (horizontal surface), there is a problem that the contacted material is damaged or worn. .
On the other hand, as described in JP-A-10-119226, the filler is not contained in the outermost surface layer, but is contained in an inner layer (thermal drying ionizing radiation curable resin layer for an intermediate layer) When the topcoat layer was provided on the surface, only the surface with a smooth surface and poor design feeling and surface texture was obtained.
[0004]
Accordingly, an object of the present invention is to provide a cosmetic material that is excellent in wear resistance, has no surface roughness, and has excellent design properties. Further, the present invention is to provide a cosmetic material that can be heated at the time of manufacture at a relatively low temperature (for example, about 150 ° C.), and can be a base that is easily deformed by high heat such as thin paper or a resin sheet.
[0005]
[Means for Solving the Problems]
  In order to solve the above-mentioned problems, in the cosmetic material having abrasion resistance according to the present invention, an internal pattern layer is formed on a substrate, a filler is contained on the internal pattern layer, and recoatable ionizing radiation curable having recoatability. A resin layer is formed, and a liquid repellent ink layer is partially formed on the recoatable ionizing radiation curable resin layer with the liquid repellent ink so as to synchronize with the pattern of the internal pattern layer. A curable resin coating liquid was applied to the entire surface of the layer and was repelled by the liquid repellent ink layer portion to form a transparent resin layer in an uneven shape on the surface.
[0006]
Thus, first, the filler is contained in the ionizing radiation curable resin layer of the inner layer, and the resin layer is used as a recoatable recoatable ionizing radiation curable resin layer, and a transparent resin layer is formed thereon by coating. Therefore, it is particularly excellent in wear resistance, and the surface roughness due to filler addition does not occur. Therefore, excellent wear resistance can be obtained without causing a problem of damaging or wearing an object in contact with the surface for interior use (horizontal plane) or the like. Moreover, the transparent resin layer as the outermost surface layer has an irregular surface due to the liquid repellent action of the liquid repellent ink layer that is synchronized with the internal pattern layer (synchronized with the internal pattern layer). -The surface texture will be rich.
[0007]
  In addition, the cosmetic material having wear resistance of the present invention,The liquid repellent ink is configured to contain a liquid repellent using a mixed resin of a melamine alkyd resin and a nitrocellulose resin as a binder resin. By using the liquid-repellent ink having such contents, a high temperature such as 180 ° C. is not required for heating for curing the liquid-repellent ink at the time of manufacture, and a relatively low temperature (for example, about 150 ° C.) is required. Heat curing is also possible, and it is possible to use even a base that is easily deformed by high heat, such as a thin paper or a resin film, which has been weak in heat and could not be used.
[0008]
  Further, the decorative material having abrasion resistance according to the present invention is a decorative material having the above structure, wherein the curable resin coating liquid for forming the transparent resin layer is used.It was set as the structure which consists of a thermosetting resin. Thus, by using a thermosetting resin for the transparent resin layer, excellent wear resistance can be obtained inexpensively and easily.
[0009]
  In the decorative material having wear resistance according to the present invention, the curable resin coating liquid for forming the transparent resin layer is made of an ionizing radiation curable resin in the decorative material having the above-described configuration. Thus, by using an ionizing radiation curable resin for the transparent resin layer, extremely excellent wear resistance can be obtained.
  Further, the method for producing a wear-resistant cosmetic material according to the present invention comprises forming a recoatable ionizing radiation curable resin layer having a recoatability by forming an internal pattern layer on a substrate and containing a filler on the internal pattern layer. After forming and crosslinking and curing the recoatable ionizing radiation curable resin layer, a mixed resin of melamine alkyd resin and nitrocellulose resin is a binder resin on the recoatable ionizing radiation curable resin layer and contains a liquid repellent. A liquid-repellent ink layer is partially formed with the liquid-repellent ink so as to synchronize with the pattern of the internal pattern layer, and a curable resin coating liquid is applied to the entire surface of the liquid-repellent ink layer to make the liquid-repellent A transparent resin layer is formed on the surface in an irregular shape by repelling the ink layer..
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the decorative material having wear resistance according to the present invention will be described with reference to the drawings.
[0011]
First, FIG. 1 is a cross-sectional view showing an embodiment of a decorative material D having wear resistance according to the present invention. The decorative material D is an all-solid layer 2A and an all-solid layer as an internal pattern layer 2 on a substrate 1. The recoatable ionizing radiation curable resin layer 3 containing the filler F is formed on the pattern pattern layer 2B on 2A, and the liquid repellent property is further formed on the recoatable ionizing radiation curable resin layer 3. A liquid-repellent ink layer 4 is partially formed so as to synchronize with the pattern of the internal pattern layer 3 with ink, and a curable resin coating liquid is applied to the entire surface of the liquid-repellent ink layer 4 to form a liquid-repellent ink. It is the structure which formed the transparent resin layer 5 in the uneven | corrugated shape on the surface by repelling in a layer part.
[0012]
The curable resin used for the transparent resin layer 4 may be a thermoplastic resin, but preferably a curable resin, such as a thermosetting resin, more preferably an ionizing radiation curable resin, is used for wear resistance. In addition, contamination resistance may be used.
In addition, when the liquid repellent ink is a liquid repellent ink containing a mixed resin of a melamine alkyd resin and a nitrocellulose resin as a binder resin and containing a liquid repellent, the heat curing of the liquid repellent ink is reduced at a low temperature (for example, It is preferable in that a substrate that is weak against high heat, such as thin paper or a resin film, can be used.
[0013]
Hereinafter, each layer will be described in detail.
[0014]
[Substrate]
There is no restriction | limiting in particular as a base | substrate 1, a shape, a material, another characteristic, etc. For example, the shape may be a sheet, a plate, a three-dimensional object, or the like. The material is paper, wood, metal, inorganic non-metal (ceramic, non-ceramic ceramics, etc.), resin, or the like. Moreover, any of those having ink permeability (paper, nonwoven fabric, etc.) and those having no ink permeability (resin sheet etc.) may be used.
Of these, paper-based or resin-based sheets (films) are typical, and if these are used as a substrate, the decorative material of the present invention can be a decorative sheet. In particular, in the embodiment using a specific ink composed of the amino alkyd resin or the like as the liquid repellent ink in the present invention, high temperature heating such as 180 ° C. is not necessary for heat curing of the liquid repellent ink at the time of manufacture. The substrate may be a low temperature (for example, about 150 ° C.), and may be used for paper-based substrates such as thin paper and resin-based (sheet) substrates, which were not easily used due to heat, and these substrates are suitable substrates.
[0015]
In the paper system, for example, paper such as thin paper, craft paper, high quality paper, linter paper, baryta paper, sulfuric acid paper, Japanese paper, and the like. In addition, paper is made of paper, resin such as acrylic resin, styrene butadiene rubber, melamine resin, urethane resin, etc. to strengthen the interlaminar strength between paper fibers or between other layers and to prevent scraping. May be added (impregnated with resin after papermaking or embedded during papermaking).
[0016]
Further, as the fibrous base material other than paper, non-woven fabric made of fibers such as polyester resin, acrylic resin, nylon, vinylon, and glass is also used. The non-woven fabric may be added with a resin such as an acrylic resin, a styrene butadiene rubber, a melamine resin, or a urethane resin (impregnated with a resin after paper making, or embedded during paper making), as in the case of the paper type.
[0017]
In the resin system, for example, polyolefin resins such as polyethylene, polypropylene, and olefin thermoplastic elastomer, vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer, polyethylene terephthalate, and polybutylene. Polyester resin such as terephthalate, acrylic resin such as polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), resin such as cellulose triacetate, cellophane, polycarbonate There are resin materials such as. These resins are used as sheets, plates, and three-dimensional objects.
In the resin system, a thermosetting resin plate made of a thermosetting resin such as phenol resin, urea resin, unsaturated polyester resin, urethane resin, epoxy resin, melamine resin, phenol resin, urea resin, unsaturated polyester resin, Resins such as so-called FRP (fiber reinforced plastic) plates made by impregnating and curing resin such as urethane resin, epoxy resin, melamine resin and diallyl phthalate resin on glass fiber nonwoven fabric, fabric, paper and other various fibrous substrates There is also a board.
[0018]
In the wood system, for example, there are wood materials such as veneer, plywood, particle board, fiberboard, and laminated wood made of cedar, straw, firewood, lawan, teak and the like. Woody systems are used as sheets, plates, and three-dimensional objects.
Moreover, in a metal system, there exist metal materials, such as iron, aluminum, stainless steel, copper, for example. Metal systems are used as sheets (foil), plates, and three-dimensional objects.
In inorganic non-metallic systems, for example, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium silicate, gypsum, gypsum slag, etc. There are non-ceramic ceramic materials, ceramic materials such as earthenware, ceramics, porcelain, setware, glass and glazing. Inorganic nonmetallic systems are mainly used as plates and three-dimensional objects.
[0019]
Alternatively, a substrate obtained by laminating two or more of the above-described various materials by a known means such as an adhesive or heat-sealing, and the like may be used. For example, resin-impregnated paper, FRP, etc. are examples thereof.
[0020]
Other characteristics include, for example, the presence or absence of ikin permeability. For example, the substrate having no ink permeability is a resin sheet made of vinyl chloride resin, polyethylene terephthalate (PET), polyolefin resin or the like, and the substrate having ink permeability is, for example, pure white paper for printing, inter-paper reinforced paper, Papers such as impregnated paper impregnated with a curable resin, and other fibrous substrates such as woven fabric and nonwoven fabric.
[0021]
The thickness of the substrate depends on the shape, material, use, etc., but when using a fibrous substrate such as paper, for example, the basis weight is 50 to 150 g / m.²The thickness is desirably about 50 to 300 μm.
[0022]
[Internal pattern layer]
The internal pattern layer 2 may be formed by a conventionally known forming method / material in a cosmetic material according to the desired design expression or required physical properties, and there is no particular limitation. The “inside” of the internal pattern layer is an expression for explicitly indicating that it is inside the liquid repellent ink layer formed as a conduit groove pattern or the like on the surface side with respect to the substrate.
[0023]
The internal pattern layer 2 may be formed by a conventionally known printing method or material such as gravure printing, silk screen printing, offset printing, electrophotographic copying, hand drawing (for example, handwriting). The pattern represented by the internal pattern layer is arbitrary, and for example, wood grain pattern, stone pattern, cloth pattern, tile tone pattern, brick tone pattern, leather pattern, letters, geometric pattern, full solid, etc. . Note that the entire solid layer of the entire surface can also be formed with a paint by a known coating method such as gravure coating or roll coating.
The internal pattern layer includes an all-solid layer 2A formed on the entire surface and a pattern pattern layer 2B partially formed to express a desired pattern shape. Although the whole solid layer 2A and the pattern pattern layer 2B may be used alone, there are usually many combinations of the whole solid layer 2A as a base and the pattern pattern layer 2B formed thereon (FIG. 1). reference).
[0024]
The ink (or paint) for the internal pattern layer is composed of a vehicle comprising a binder, a colorant such as a pigment or a dye, and various additives appropriately added thereto, as in the case of general ink (or paint). As the binder resin, for example, a general-purpose resin such as a chlorinated polyolefin resin, a polyester resin, an acrylic resin, a cellulose resin, a vinyl chloride-vinyl acetate copolymer, and a polyurethane resin can be selected. use. However, from the viewpoint of adhesion to the recoatable ionizing radiation curable resin layer, a nitrocellulose-based resin or an acrylic resin-based resin is desirable as the binder resin.
[0025]
Examples of the colorant include inorganic pigments such as titanium white, zinc white, dial, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, and carbon black, isoindolinone, Hansa Yellow A, quinacridone, and permanent red. Pearl luster made of organic pigments (including dyes) such as 4R, phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments such as aluminum and brass, titanium dioxide-coated mica, and foil powder such as basic lead carbonate ( Pearl) pigments may be used.
[0026]
[Recoat ionizing radiation curable resin layer]
The recoatable ionizing radiation curable resin layer 3 is a layer made of an ionizing radiation curable resin containing a filler in the layer and having recoatability (post-coating suitability). In the present invention, the recoatable ionizing radiation curable resin layer can be laminated with good adhesion even after it is completely cured before forming another layer on the layer. Therefore, the recoatable ionizing radiation curable resin layer is maintained in a state before complete curing such as uncured or semi-cured, and a liquid repellent ink layer or a transparent resin layer is formed on the layer by printing or coating. Even if not, it can be laminated with good adhesion.
On the other hand, a liquid repellent ink layer, a transparent resin layer, etc. are formed on the recoatable ionizing radiation curable resin in a state before complete curing, and thereafter, the recoatable ionizing radiation curable resin layer is formed. In the case of complete curing, when forming the liquid repellent ink layer or transparent resin layer, if the recoatable ionizing radiation curable resin layer is not in a non-adhesive state, the liquid repellent ink layer or transparent resin can be used with a printing machine or coating machine. A layer cannot be formed.
However, if the recoatable ionizing radiation curable resin layer can form a liquid repellent ink layer or a transparent resin layer with good adhesion even after complete curing, the recoatable ionizing radiation curable resin layer is in an adhesive state in the state before complete curing. However, it may be in a liquid state, and there is an advantage that an ionizing radiation curable resin can be freely selected according to the required physical properties.
[0027]
The “recoat property” as used in the present invention is composed of a urethane resin, ionizing radiation curable resin, melamine alkyd resin, other resin, etc. as a coating film on this (recoat property) ionizing radiation curable resin layer. It means that, when a liquid repellent ink layer or a transparent resin layer is laminated with an ink or a coating liquid, sufficient adhesion is maintained in actual use. Specifically, for example, an adhesion test specified in JIS K 5400 (after removing silicone and dirt on the surface of the coated film after recoating with an eraser, a cutting knife reaching at least the recoating ionizing radiation curable resin layer with a cutter knife) And recoatable ionizing radiation curable resin layer, and liquid repellent ink layer and transparent resin formed on it by peeling the cellophane adhesive tape attached to the surface and evaluating the peeled state of the coating film) The adhesion strength between the layers is such that these layers do not peel from each other.
The liquid repellent ink layer formed in a pattern in synchronization with the internal pattern layer is laminated by printing using ink, and the transparent resin layer once applied to the entire surface is usually formed by coating. Therefore, “recoating”, that is, recoating (or recoating) includes not only the coating method but also the meaning of lamination by other methods such as printing.
[0028]
As the ionizing radiation curable resin used for such a recoatable ionizing radiation curable resin layer, a prepolymer having a radical polymerizable unsaturated bond such as an acryloyl group or a cationic polymerizable functional group such as an epoxy group in the molecule. A composition comprising a monomer (including so-called oligomers) and / or a monomer that can be cured by ionizing radiation such as ultraviolet rays or electron beams is used. The prepolymer and monomer are used alone or in combination. Here, the ionizing radiation means electromagnetic waves or charged particles having energy capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used.
[0029]
Usually, unsaturated polyesters, polyacrylates, cationic polymerization type epoxies, etc. are used for the prepolymer, and styrene, acrylate ester, unsaturated carboxylic acid amide, etc. are used for the monomer.
[0030]
For example, examples of the prepolymer having a radically polymerizable unsaturated group in the molecule include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, Silicone (meth) acrylate or the like can be used. In addition, (meth) acrylate means a methacrylate or an acrylate.
Examples of prepolymers having a cationically polymerizable functional group in the molecule include epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and prepolymers of vinyl ether type resins such as fatty acid vinyl ethers and aromatic vinyl ethers. There is.
[0031]
Examples of the monomer having a radical polymerizable unsaturated group in the molecule include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like as monofunctional monomers. In addition, among polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate.
[0032]
In addition, in order to give recoat property to the layer which consists of ionizing radiation curable resin, and it becomes a recoatable ionizing radiation curable resin layer, the average molecular weight between bridge | crosslinking of ionizing radiation curable resin hardened | cured material will be about 200-1000. It is preferable to design in this way. As means for controlling the average molecular weight between cross-links, there are means such as reducing the concentration of added monomers and reducing the number of functional groups of the prepolymer or acrylate monomer when increasing the average molecular weight between cross-links. On the other hand, when lowering the average molecular weight between crosslinks, the monomer concentration may be increased or a trifunctional or higher acrylate monomer may be added. The average molecular weight between crosslinks is the average molecular weight between crosslinks = total molecular weight / number of crosslink points, and the total molecular weight is Σ (number of moles of each component × molecular weight of each component), and the number of crosslink points. Is Σ [{(number of functional groups of each component −1) × 2} × number of moles of each component].
[0033]
In addition, when making it harden | cure with an ultraviolet-ray or visible light, a photoinitiator is further added to the said ionizing radiation curable resin. In the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, and benzoin methyl ethers can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. be able to. The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
[0034]
As an ionizing radiation source, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light type fluorescent lamp, or a metal halide lamp is used as an ultraviolet ray source. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm is mainly used.
As the electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Preferably, those that irradiate electrons having an energy of 100 to 300 keV are used. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.
[0035]
By including the filler F in the recoatable ionizing radiation curable resin layer, the wear resistance is improved. As such a filler, for example, inorganic particles such as α-alumina, silica and silicon carbide, organic particles such as crosslinked acrylic resin beads, and the like are added to the composition made of the ionizing radiation curable resin. Although the particle shape and particle size of the filler are arbitrary, the spherical shape is desirable because of the problem of wear of the coating liquid coating apparatus for forming the recoatable ionizing radiation curable resin layer. The particle size of the filler is preferably an average particle size and is usually about 0.3 to 2 times the thickness of the recoatable ionizing radiation curable resin layer. If it is less than 0.3, it is difficult to obtain sufficient wear resistance, and if it exceeds 2, the filler may protrude from the surface of the recoatable ionizing radiation curable resin layer and fall off. In addition, due to surface irregularities, the printability and coating suitability of the liquid repellent ink layer and the transparent resin layer are deteriorated.
The filler content may be appropriately determined depending on the required physical properties and the like within a range that does not impair the transparency beyond the extent that the lower internal pattern layer can be seen through the recoatable ionizing radiation curable resin layer. .
[0036]
The ionizing radiation curable resin composed of the composition as described above is generally known in the art as a liquid coating liquid at room temperature (room temperature or appropriately heated coating temperature) such as roll coating and flow coating. Apply by coating method.
The thickness of the recoatable ionizing radiation curable resin layer is not particularly limited as long as it is appropriately selected according to the required physical properties such as the required degree of wear resistance, but is about 10 to 50 μm, for example.
[0037]
[Liquid repellent ink layer]
The liquid repellent ink layer 4 may be formed on the recoatable ionizing radiation curable resin layer partially in a pattern with the liquid repellent ink by a known method such as printing or coating. At this time, it is preferable that a liquid-repellent ink layer is partially formed so as to synchronize with the pattern of the internal pattern layer by a printing method or the like because a higher-design cosmetic material can be obtained. For example, the inner pattern layer is formed as a wood grain pattern, and the liquid repellent ink layer forms a wood grain conduit groove pattern as a pattern synchronized with the wood grain pattern.
FIG. 1 is a conceptual diagram, and all the liquid repellent ink layers 4 (partially formed) are drawn so as to be positioned roughly on the pattern pattern layer 2B which is a component of the internal pattern layer 2. . However, for example, the liquid repellent ink layer 4 is not necessarily provided on all the pattern pattern layers 2B so that the liquid repellent ink layer 4 is not drawn on the pattern pattern layer 2Bb. This is the same as in the case of known picture tuning.
[0038]
That is, the liquid repellent ink layer 4 may be formed by a conventionally known printing method such as gravure printing, silk screen printing, offset printing, electrophotographic copying, and hand drawing (for example, handwriting). The pattern represented by the liquid repellent ink layer is arbitrary, and may be, for example, a wood grain pattern, a stone pattern, a cloth pattern, a tile tone pattern, a brick tone pattern, a leather pattern, a character, a geometric pattern, and the like. Since it can be partially formed by a coating method such as spray coating, it may be formed by a coating method. In the case of coating, a coating liquid is used, but in the present invention, including this case, the liquid-repellent “ink” layer and the liquid-repellent “ink” are also referred to.
[0039]
The liquid repellent ink for forming the liquid repellent ink layer includes a vehicle composed of a binder, a liquid repellent, a colorant such as a pigment and a dye, and other additives as appropriate. The binder resin is basically not particularly limited, and may be a urethane resin, an ionizing radiation curable resin, or the like. In particular, a (binary) mixed resin of a melamine alkyd resin and a nitrocellulose resin is a preferred resin. is there. This is because the ternary mixed resin of urea, melamine alkyd resin, and nitrocellulose resin, which is a conventionally known resin system, requires heat treatment at 170 ° C. or higher for curing, whereas the above-described binary mixing is performed. This is because the resin can be cured by heating at a lower temperature of about 150 ° C. For this reason, it is possible to make a decorative material using a substrate such as a thin paper or a resin film, which has been difficult to use due to heat.
[0040]
A general-purpose liquid repellent may be used as the liquid repellent for imparting liquid repellency to the liquid repellent ink layer. For example, one type or two or more types such as non-reactive silicone and polyethylene wax are used as the liquid repellent. In addition, a liquid repellent agent is normally added about 1-10 weight part with respect to ink. If the amount added is less than this, the liquid repellent effect is insufficient, and the transparent resin layer cannot be completely repelled by, for example, a fine part of the conduit in the grain conduit groove pattern. Moreover, when there are more addition amounts than this, adhesion | attachment with a recoat ionizing radiation-curable resin layer will worsen.
[0041]
The liquid repellent ink layer may contain a colorant as in the case of the internal picture layer. For this purpose, the ink may be formed of a liquid repellent ink colored with a colorant. As the colorant, known colorants listed in the internal picture layer can be used. For example, when a wood grain conduit groove pattern is expressed by a liquid repellent ink layer, a dark liquid repellent ink layer such as black may be used.
[0042]
[Transparent resin layer]
The transparent resin layer 5 is a layer that determines the surface properties of the cosmetic material by being positioned as the outermost surface layer of the cosmetic material on the recoatable ionizing radiation curable resin layer after the liquid repellent ink layer 4 is formed. Due to the presence of the transparent resin layer as the outermost surface layer, even if the surface of the recoatable ionizing radiation curable resin layer is roughened due to the presence of the filler in the layer, the surface of the cosmetic material is not rough. Things will be possible. In addition, the filler to be included for the purpose of improving wear resistance is contained in the lower recoatable ionizing radiation curable resin layer, and it is not necessary to contain in this transparent resin layer. This can prevent problems such as surface roughness that may occur, and damage and abrasion of contact objects when the decorative surface is used in a horizontal plane. In addition, the transparent resin layer as the outermost surface layer can make the surface rough or in addition to a simple smooth surface, and can be arbitrarily adjusted in luster, so that a cosmetic material rich in design and surface texture can be obtained.
[0043]
As such a transparent resin layer 5, a general-purpose overcoat agent can be used. In particular, in order to improve surface performance in terms of wear resistance, the overcoat agent is preferably one using a curable resin. The curable resin may be a thermosetting resin, an ionizing radiation curable resin, or the like.
The transparent resin layer (generally also referred to as a top coat layer) may be formed by a known coating method such as roll coating or a known printing method such as gravure printing. The overcoat agent applied by coating or printing on the recoatable ionizing radiation curable resin layer on which the liquid repellent ink layer has been formed is in a liquid state before the solidification. The transparent resin layer is formed in an uneven shape by being repelled by the layer part and the liquid repellent ink layer part becomes a concave part, and then solidified by drying, curing or the like.
[0044]
As the thermosetting resin, a two-component curable resin can be used. For example, it is a two-component curable urethane resin. As a two-component curable urethane resin, a polyol such as acrylic polyol, polyester polyol, or polyether polyol is used as a main agent, and 2,4-tolylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone is used as a crosslinking agent (curing agent). What is necessary is just to select suitably from well-known urethane resins using polyisocyanate, such as diisocyanate.
Further, as the ionizing radiation curable resin, ionizing radiation curable resins as described in the above-mentioned recoatable ionizing radiation curable resin layer can be used. However, since the recoating property is unnecessary in the transparent resin layer, it is not necessary to add a filler and select a resin in consideration of the recoating property.
[0045]
In addition, although the filler for the purpose of improving abrasion resistance is not essential in the transparent resin layer, a filler may be contained as long as the surface roughness is not exhibited. The filler to be contained is the filler as described in the recoatable ionizing radiation curable resin layer.
[0046]
The transparent resin layer may contain a filler for adjusting the gloss, for example, to adjust the gloss. For example, a known matting agent such as silica, calcium carbonate or barium sulfate may be used. By adjusting the gloss, the transparent resin layer can express any glossiness from glossy to matte, and a cosmetic material rich in design and surface texture can be obtained.
[0047]
【Example】
Hereinafter, the decorative material having wear resistance of the present invention will be further described with reference to Examples and Comparative Examples. In the following, “parts” are all based on mass (weight).
[0048]
[Example 1]
A decorative material D having a layer structure as shown in FIG. 1 was produced as follows. As a decorative base paper to be used as a sheet-like substrate 1, on one side of a resin-impregnated paper impregnated with an acrylic resin latex, as an internal pattern layer 2, an all solid layer (colored solid layer) 2A having a thickness of 2 μm by a gravure printing method and a grain pattern The pattern pattern layer 2B was formed in this order. For all the solid layers, an ink in which a binder resin is a mixture of an acrylic resin and a nitrocellulose resin and a colorant is added is used. For the pattern pattern layer, an ink in which a binder resin is a mixture of a nitrocellulose resin and an alkyd resin and a colorant is added is used. Next, a coating film having a thickness of 25 μm was coated and formed using the following (electron beam curing type) recoatable ionizing radiation curable resin coating material, and then the electron beam irradiation was performed using an electron beam irradiation apparatus to crosslink the coating film. By curing, a recoatable ionizing radiation curable resin layer 3 containing alumina as the filler F was formed.
[0049]
Recoatable ionizing radiation curable resin paint
30 parts of urethane acrylate
20 parts bifunctional acrylate oligomer
10 parts of trifunctional acrylate oligomer
Silicone acrylate 3 parts
Spherical α-alumina (average particle size 25 μm) 20 parts
[0050]
Next, on the recoatable ionizing radiation curable resin layer, a two-component curable liquid repellent ink (the binder resin is a melamine alkyd resin and a nitrocellulose resin so as to synchronize with the pattern of the internal pattern layer. A mixed resin, containing silicone oil as a liquid repellent and cured with an organic acid catalyst), gravure-printed the wood grain conduit groove pattern, heat-dried and cured at 150 ° C. for 15 seconds, and the liquid repellent ink layer 4 Formed.
[0051]
Next, a transparent resin layer having a thickness of 3 μm was formed by applying a urethane-based topcoat agent on the entire surface by the gravure coating method as described below. Subsequently, it heat-dried at 60 degreeC for 3 days, and the transparent resin layer was fully hardened, and the decorative material D as shown in FIG. 1 used as a decorative sheet was obtained.
[0052]
Two-component curable urethane topcoat
100 parts of polyester polyol
Modified polyisocyanate 15 parts
5 parts of slip agent (silicone oil)
Diluent solvent (ethyl acetate + toluene) Appropriate amount
[0053]
[Example 2]
A decorative material D having the structure shown in FIG. 1 was produced as follows. In Example 1, after forming the internal pattern layer, the coating material used for forming the recoatable ionizing radiation curable resin layer was the following low-gloss coating material (containing spherical α-alumina as a filler and low gloss gloss adjustment) For this reason, it was changed to an amorphous silica and fine powdered silica) and cured in the same manner as in Example 1.
[0054]
Low gloss recoating ionizing radiation curable resin paint
30 parts of urethane acrylate
20 parts bifunctional acrylate oligomer
10 parts of trifunctional acrylate oligomer
Silicone acrylate 3 parts
Amorphous silica (average particle size 1.8μm) 15 parts
Fine powdered silica (average particle size 0.1 μm) 2 parts
Spherical α-alumina (average particle size 25 μm) 20 parts
[0055]
Next, after forming a liquid repellent ink layer in the same manner as in Example 1, the following top coat agent was applied, electron beam irradiation was performed using an electron beam irradiation device, the coating film was crosslinked and cured, and a low gloss transparent resin A layer was formed to obtain a cosmetic material.
[0056]
Top coat agent
Acrylic oligomer 50 parts
40 parts of 1,6-hexanediol acrylate
Amorphous silica (average particle size 1.8μm) 8 parts
Fine powder silica (average particle size 0.1 μm) 1 part
1-part methacrylate modified silicone
[0057]
[Comparative Example 1]
As a decorative material D as shown in FIG. 2, in Example 1, after forming the internal pattern layer 2 on the substrate 1, the formation of the recoatable ionizing radiation curable resin layer 3 and the liquid repellent ink layer 4 is omitted. A decorative material D was obtained by forming only the transparent resin layer 51 having a thickness of 3 μm in the same manner as in Example 1 (the surface is not uneven and flat because there is no liquid repellent ink layer).
[0058]
[Comparative Example 2]
As a decorative material D as shown in FIG. 3, in Example 1, the formation of the liquid repellent ink layer 4 and the transparent resin layer 5 is omitted, and the recoatable ionizing radiation curable resin layer 3 is used as the outermost surface layer. Was made into a cosmetic material D in the same manner as in Example 1.
[0059]
Ionizing radiation curable resin paint
50 parts of bisphenol A ethylene oxide-modified diacrylate
20 parts of trimethylolpropane ethylene oxide modified triacrylate
Spherical α-alumina (average particle size 25 μm) 20 parts
Amorphous silica (average particle size 1.8μm) 8 parts
Fine powder silica (average particle size 0.1 μm) 1 part
Both ends methacrylate modified silicone 1 part
[0060]
[Comparative Example 3]
As a decorative material D as shown in FIG. 4, the top coat used in Example 1 as an alternative to the recoatable ionizing radiation curable resin layer 3 after forming the internal pattern layer 2 on the substrate 1 in Example 1. A liquid repellent ink layer 4 was prepared in the same manner as in Example 1 except that an ionizing radiation curable resin layer 31 having a thickness of 3 μm and containing no filler was formed on the entire surface by gravure printing using an agent (containing no filler). And the transparent resin layer 5 was formed and the decorative material D was obtained.
[0061]
[Comparative Example 4]
As the decorative material D as shown in FIG. 5, in Example 1, the formation of the liquid-repellent ink layer 4 was omitted, and the transparent resin layer was formed as a flat transparent resin layer 51 with the surface not irregular. A cosmetic material D was obtained in the same manner as in Example 1.
[0062]
[Performance evaluation]
The results shown in Tables 1 and 2 were obtained by evaluating the wear resistance and the surface slipperiness as a feeling of surface roughness as follows.
[0063]
(1) Abrasion resistance: The test was evaluated by a method according to JIS K6902 (Testing method for thermosetting resin decorative plate).
{Circle around (2)} Surface slipperiness: With a cotton cloth pressed against a load of 30 kPa, a 10 cm distance was rubbed back and forth 10 times, and the damage of the cotton cloth was visually observed and evaluated.
[0064]
[Table 1]

[0065]
[Table 2]

[0066]
As shown in Table 1, compared to the comparative examples (Comparative Examples 1 and 3), the wear resistance of the Examples (Examples 1 and 2) is improved, and even when the surface is scraped, the pipe handle in the Examples is It was confirmed that the design was maintained without easily disappearing.
In addition, as shown in Table 2, in Examples (Example 1 and Example 2), the surface has a smooth surface as a surface slipperiness while having wear resistance with no problem in actual use as compared with Comparative Example 2. Things were confirmed. In Comparative Example 4, the abrasion resistance and the surface slipperiness were good as in Example 2, but the surface was smooth with no irregularities due to the conduit, and the surface texture was poor.
[0067]
【The invention's effect】
(1) According to the cosmetic material having wear resistance of the present invention, the filler for improving the wear resistance is contained in the ionizing radiation curable resin layer of the inner layer, and the resin layer is recoatable. As a recoatable ionizing radiation curable resin layer, a transparent resin layer is applied and formed thereon, so that it is particularly excellent in wear resistance and the surface roughness due to the addition of filler does not occur. Therefore, excellent wear resistance can be obtained without causing a problem of damaging or wearing an object in contact with the surface for interior use (horizontal plane) or the like. Moreover, the transparent resin layer as the outermost surface layer has an irregular surface due to the liquid repellent action of the liquid repellent ink layer that is synchronized with the internal pattern layer (synchronized with the internal pattern layer). -The surface texture will be rich.
(2) Further, by using a thermosetting resin in the transparent resin layer, excellent wear resistance can be obtained inexpensively and easily.
(3) Further, by using an ionizing radiation curable resin for the transparent resin layer, extremely excellent wear resistance can be obtained.
[0068]
(4) In addition, as a liquid repellent ink, by using an ink containing a liquid repellent with a mixed resin of a melamine alkyd resin and a nitrocellulose resin as a binder resin, the liquid repellent ink is cured during production. It does not require a high temperature such as 180 ° C for heating, and it can be cured by heating at a relatively low temperature (eg, about 150 ° C). This makes it possible to use even a substrate that is easy to handle.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating one embodiment of a wear-resistant decorative material of the present invention.
FIG. 2 is a cross-sectional view showing an example of a decorative material other than the present invention.
FIG. 3 is a cross-sectional view showing an example of a decorative material other than the present invention.
FIG. 4 is a cross-sectional view showing an example of a decorative material other than the present invention.
FIG. 5 is a cross-sectional view showing an example of a decorative material other than the present invention.
[Explanation of symbols]
1 Base
2 Internal pattern layer
2A All solid layers
2B Pattern pattern layer
2Ba handle pattern layer
3 Recoatable ionizing radiation curable resin layer
31 Ionizing radiation curable resin layer (without filler)
4 Liquid repellent ink layer
5 Transparent resin layer
51 (Flat) transparent resin layer
D Cosmetic material
F filler

Claims (4)

  An internal pattern layer is formed on a substrate, a recoatable ionizing radiation curable resin layer containing a filler and having a recoat property is formed on the internal pattern layer, and a melamine alkyd resin is formed on the recoatable ionizing radiation curable resin layer A liquid-repellent ink layer is partially formed by a liquid-repellent ink containing a liquid repellent and a mixed resin of nitrocellulose-based resin and a liquid-repellent agent so as to synchronize with the pattern of the internal pattern layer. A wear-resistant cosmetic material in which a transparent resin layer is formed in a concavo-convex shape on the surface by applying a curable resin coating liquid on the entire surface of the repellent ink layer and repelling the liquid repellent ink layer portion.   The wear-resistant cosmetic material according to claim 1, wherein the curable resin coating liquid forming the transparent resin layer is made of a thermosetting resin.   The wear-resistant cosmetic material according to claim 1, wherein the curable resin coating liquid forming the transparent resin layer is made of an ionizing radiation curable resin.   An internal pattern layer is formed on the substrate, a recoatable ionizing radiation curable resin layer containing a filler and having a recoat property is formed on the internal pattern layer, and the recoatable ionizing radiation curable resin layer is crosslinked and cured. A mixed resin of melamine alkyd resin and nitrocellulose-based resin is a binder resin and a liquid repellent ink containing a liquid repellent agent on the recoatable ionizing radiation curable resin layer so as to synchronize with the pattern of the internal pattern layer. A liquid-repellent ink layer is formed on the surface, and a curable resin coating liquid is applied to the entire surface of the liquid-repellent ink layer, and the liquid-repellent ink layer is repelled to form a transparent resin layer on the surface. A method for producing a formed decorative material having wear resistance.

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