JP4003990B2 - Cosmetic material - Google Patents

Description

【００４２】
比較例２
実施例１と同じ基材とインクを用い、実施例１と同様に絵柄層を形成し、次いで該絵柄層の上に下記のように球状粒子を含む塗工用樹脂組成物をロールコートにてコーティングし、実施例１と同様の条件にて電子線を照射し、樹脂を完全に硬化させ膜厚２５μｍの表面保護層を形成した。

【００４３】
〔耐摩耗性の評価〕
上記実施例及び比較例で得られた化粧材について、耐摩耗性をＪＩＳＫ−６９０２に準ずる方法により、Ｓ−４２、５００ｇ荷重の下で測定した。その結果を表１に示す。
【００４４】
【表１】

【００４５】
【発明の効果】
本発明の化粧材は、上述したように表面保護層が、特定の膜厚になるような粒径の有機粒子を含み、かつ電離放射線硬化性樹脂により構成されているために、鮮明な凹凸が得られ、極めて優れた意匠性が得られるという効果を有する。
【００４６】
また、本発明の化粧材は、表面保護層に特定の架橋間平均分子量を有する電離放射線硬化性樹脂を用い、かつ上記の有機粒子に特定の硬度を有する球状粒子を併用することにより、さらに耐摩耗性に優れ、同時に意匠的に優位性の高い表面を持った化粧材が得られるという効果を有する。
【図面の簡単な説明】
【図１】本発明の化粧材の一例を示す縦断面図である。
【図２】本発明の化粧材の別の例を示す縦断面図である。
【符号の説明】
１ 基材
２ ベタ層
３ 絵柄層
４ 表面保護層
５ 有機粒子
６ 電離放射線硬化性樹脂層
７ 球状粒子[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cosmetic material. In particular, the present invention relates to an improvement in design of a decorative material having wear resistance.
[0002]
[Prior art]
A conventional decorative paper having a surface protective layer is known which contains only spherical particles having a Knoop hardness of 1300 kg / cm ² or more in the surface protective layer.
[0003]
[Problems to be solved by the invention]
However, the above conventional decorative paper has poor design because the surface of the surface protective layer is flat and has no irregularities.
[0004]
In view of the above problems, the present invention has been made in order to eliminate the above-described conventional defects, and an object of the present invention is to provide a wear material having excellent design properties and wear resistance.
[0005]
[Means for Solving the Problems]
The present invention, at least one surface in a solid layer, picture layer of the base material, the surface protective layer is provided from the substrate side in this order, the surface protective layer, the film thickness of the surface protective layer 1.2 to 2 Inorganic containing organic particles composed of urethane particles having a particle size of 0.0 times, and having a particle size of 1/2 to 2/3 times the particle size of the organic particles and a Knoop hardness of 1300 kg / cm ² or more decorative material characterized by comprising the ionizing radiation curable resin containing the spherical particles consisting of particles, and the gist.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a longitudinal sectional view showing an example of the decorative material of the present invention. In the present invention, the decorative material is configured such that a solid layer 2, a pattern layer 3, and a surface protective layer 4 are provided on the surface of the substrate 1 in this order from the substrate 1 side.
[0007]
Base material 1 is thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, so-called vinyl wallpaper original fabric in which polyvinyl chloride is sol-coated or dry-laminated, or high-quality paper, coated paper, art Paper such as paper, sulfate paper, glassine paper, parchment paper, paraffin paper, sheets or films made of inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber, polyester, vinylon, etc. Woven or non-woven fabrics using organic resins, polyolefin resins such as polyethylene and polypropylene, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer , Polyethylene terephthalate, polybutylene terephthalate, etc. Sheet made of polyester resin, acrylic resin such as polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), cellulose triacetate, cellophane, polycarbonate, or the like Films, metal foils such as aluminum, iron, stainless steel, and copper can be used. The thickness of the base material 1 is arbitrary.
[0008]
As the solid layer 2, an ink composition or the like obtained by appropriately mixing a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent as needed for the vehicle is used. Can do.
[0009]
The vehicle is appropriately selected from thermoplastic resins, thermosetting resins, ionizing radiation curable resins and the like according to the application, required physical properties, printability, and the like. Examples of the thermoplastic resin include cellulose derivatives such as ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxyethyl cellulose, cellulose acetate propionate, styrene resins such as polystyrene and poly α-methylstyrene, styrene copolymers, and polymethyl methacrylate. , Acrylic resins such as polyethyl methacrylate, polyethyl acrylate and polybutyl acrylate, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, vinyl copolymers such as polyvinyl butyral, rosin, rosin modified Examples thereof include rosin ester resins such as maleic acid resin, rosin-modified phenol resin, and polymerized rosin, natural or synthetic resins such as coumarone resin, vinyl toluene resin, and polyamide resin.
[0010]
Thermosetting resins include phenolic resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon Resins, polysiloxane resins, and the like, and a curing agent such as a cross-linking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, and an extender are added to these as necessary. As the curing agent, isocyanate is usually unsaturated polyester resin, polyurethane resin, amine is epoxy resin, peroxide such as methyl ethyl ketone peroxide, radical initiator such as azobisisobutyronitrile is unsaturated polyester Often used for resins. As the isocyanate, a divalent or higher aliphatic or aromatic isocyanate can be used, but an aliphatic isocyanate is desirable from the viewpoint of prevention of thermal discoloration and weather resistance. Specific examples include tolylene diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like. Moreover, in order to accelerate | stimulate hardening reaction, you may heat after coating as needed. For example, in the case of isocyanate-cured urethane-curable unsaturated polyester resin or polyurethane resin, it is usually about 1 to 5 days at 40 to 60 ° C., and in the case of polysiloxane resin, it is usually about 1 to 300 minutes at 80 to 150 ° C. .
[0011]
Moreover, as ionizing radiation resin, the thing similar to what is used for the surface protective layer 4 mentioned later can be used.
[0012]
Examples of the pigment that can be contained in the ink composition include commonly used organic or inorganic pigments. As the yellow pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as isoindolinone, and inorganic pigments such as yellow lead, yellow iron oxide, cadmium yellow, titanium yellow and antimony yellow can be used. As the red pigment, azo pigments such as monoazo, disazo and polyazo, organic pigments such as quinacridone, inorganic pigments such as petals, vermilion, cadmium red and chrome vermilion can be used. As the blue pigment, organic pigments such as phthalocyanine blue and indanthrene blue, and inorganic pigments such as bitumen, ultramarine blue and cobalt blue can be used. As the black pigment, organic pigments such as aniline black and inorganic pigments such as carbon black can be used. Examples of white pigments include inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide.
[0013]
In order to form the solid layer 2, screen solid printing is used, or various known coating methods such as roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating. Using a method such as blade coating, smooth coating, comma coating, spray coating, pouring coating, or brush coating, the film thickness is usually about 1.0 to 10.0 μm when dried.
[0014]
The pattern layer 3 is a layer in which a pattern composed of a line, a surface, or a combination thereof, or a pattern composed of a pattern, a figure, a character, or a combination thereof is formed with an ink. It is not necessarily a continuous layer. As the pattern layer 3, the same ink composition as that used for the solid layer 2 can be used. The pattern layer 3 is formed by applying the ink constituting the layer 3 by coating or printing, followed by drying and curing. As a method of providing the pattern layer 3, various known methods such as relief printing such as gravure, letterpress and flexo, planographic printing such as planographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing and ink jet printing are used. Can be used.
[0015]
The surface protective layer 4 is obtained by curing an ionizing radiation curable resin composition described later. The film thickness of the surface protective layer 4 is usually about 15 to 35 g / m ² . The surface protective layer 4 is composed of an ionizing radiation curable resin 6 containing organic particles 5 having a particle size that is 1.2 to 2.0 times the film thickness T of the layer 4. That is, the ionizing radiation curable composition containing the organic particles 5 in the ionizing radiation curable resin 6 is applied to the pattern layer 3 side of the pattern layer 3 and cured to form the surface protective layer 4. When the ionizing radiation curable resin 6 contains organic particles 5 that are 1.2 to 2.0 times the thickness of the surface protective layer 4 and can partially protrude on the surface of the surface protective layer 4. The surface protective layer 4 is configured.
[0016]
Although the film thickness T of the surface protective layer 4 is arbitrary, it is usually 15 to 35 μm, and generally about 25 μm.
[0017]
Examples of the organic particles 5 include plastic beads made of a synthetic polymer compound. Examples of the type include resins such as acrylic, polycarbonate, urethane, melamine, styrene, and fluorine resin. Of these, organic particles made of acrylic and urethane resins are preferred because of their good coating suitability and ink stability. The particle diameter of the organic particles is preferably 5 to 100 μm, and more preferably 10 to 50 μm. If the particle size of the organic particles is less than 5 μm, a sufficient effect cannot be obtained, and if it exceeds 100 μm, the coating suitability may be reduced.
[0018]
The organic particles 5 have a particle size such that the thickness of the surface protective layer 4 is 1.2 to 2.0 times, and the thickness of the surface protective layer 4 is less than 1.2. There is a drawback that surface irregularities become poor. Moreover, when it exceeds 2.0 times, there exists a fault that surface scratch property will become weak. By containing organic particles, there is an effect that a smooth surface property can be obtained as compared with the case where inorganic particles are contained. The organic particles 5 preferably have transparency, and the higher the transparency, the more preferable.
[0019]
The content of the organic particles 5 is preferably 5 to 20% by weight. Within this range, a decorative sheet having an uneven feeling can be produced. In addition, there exists a possibility that surface unevenness may become scarce when it remove | deviates from the said range.
[0020]
In the present invention, the ionizing radiation curable resin 6 constituting the surface protective layer 4 is an ionizing radiation curable resin having an average molecular weight between crosslinks of 150 to 1000, and the ionizing radiation curable constituting the surface protective layer 4. It is preferable that the resin 6 further contains spherical particles 7 having a Knoop hardness of 1300 kg / cm ² or more. With such a configuration, the wear resistance is further improved.
[0021]
The Knoop hardness referred to here is the micro indentation hardness measured using a Knoop indenter, and the load when the diamond-shaped indentation was made before the test was obtained from the length of the diagonal line of the longer permanent recess. It is a value represented by the quotient divided by the projected area. This test method is described in ASTM C-849.
[0022]
Specific examples of the material of the spherical particles 7 include inorganic particles such as α-alumina, silica, chromium oxide, iron oxide, diamond, and graphite. The α-alumina includes fused alumina, Bayer method alumina, and the other inorganic particles include zirconia, titania, and eutectic mixtures with these, fused alumina, Bayer method alumina, and the like. . The method of making the shape of these inorganic particles spherical is a method in which the pulverized amorphous inorganic compound is charged into a high-temperature furnace having a melting point or higher and melted, and is made spherical by using surface tension. And a method in which a material melted at a high temperature equal to or higher than the melting point is blown into a mist to make it spherical.
[0023]
Particularly preferable spherical particles 7 include spherical α-alumina because they are very hard and have a great effect on wear resistance, and a spherical shape is relatively easy to obtain. As described in JP-A-2-55269, a small amount of a spherical α-alumina is added to a pulverized product such as fused alumina, sintered alumina, etc. Then, by performing 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 is obtained. Such spherical alumina is commercially available from Showa Denko KK as “Spherical Alumina AS-10, AS-20, AS-30, AS-40, AS-50”.
[0024]
Moreover, the spherical particle 7 can process the particle | grain surface. For example, treatment with a fatty acid such as stearic acid improves dispersibility. Further, by treating the surface with a silane coupling agent, the adhesion with the crosslinkable resin used as the binder and the dispersibility of the particles in the coating composition are improved. Examples of the silane coupling agent include alkoxylane having a radical polymerizable unsaturated bond in the molecule.
[0025]
When the ionizing radiation curable resin 6 has an average molecular weight between crosslinks within the above range, an effect of being excellent in scratch resistance, contamination resistance, solvent resistance, and water resistance can be obtained. Further, when spherical particles 7 having Knoop hardness of 1300 kg / cm ² or more are contained, there is an effect that wear resistance can be imparted. The spherical particles 7 may be organic particles, but inorganic particles are preferred because of the good ink settling stability. The spherical particles 7 preferably have transparency, and the higher the transparency, the more preferable.
[0026]
The spherical particles 7 may have a surface surrounded by a smooth curved surface, such as a true sphere, or an elliptic sphere obtained by flattening a sphere, a true sphere, or a shape close to an elliptic sphere. In particular, a spherical shape with no projections or corners on the particle surface and no so-called cutting edge is preferable. Spherical particles 7 significantly improve the wear resistance of the surface resin layer itself as compared to irregularly shaped particles of the same material, and do not wear the coating apparatus, and are in contact with the coating film after curing. There is a feature that the film is not worn, and the transparency of the coating film is also increased, and the effect is particularly great when there is no cutting edge.
[0027]
In the above, the particle diameter of the spherical particle 7 is preferably 1/2 to 2/3 times the particle diameter of the organic particle 5 for the reason of expressing a uniform uneven feeling. It is preferably 0.5 to 1.0 times. The content of the spherical particles 7 is preferably 15 to 25% by weight.
[0028]
The ionizing radiation curable resin used for the surface protective layer 4 is a transparent resin having an energy quantum capable of polymerizing and crosslinking molecules of electromagnetic waves or charged particle beams and curable by ionizing radiation such as ultraviolet rays and electron beams. Thus, a composition in which prepolymers, oligomers and / or monomers having a polymerizable unsaturated bond or an epoxy group in the molecule are appropriately mixed is used. Examples of these compositions include acrylates such as urethane acrylate, polyester acrylate, and epoxy acrylate, silicon resins such as siloxane, polyester, and epoxy.
[0029]
Examples of the prepolymer and oligomer include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates, polyester methacrylate, polyether methacrylate, polyol methacrylate, methacrylates such as melamine methacrylate, polyester acrylate, epoxy acrylate, Examples include acrylates such as urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate.
[0030]
Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, Acrylic esters such as methoxybutyl acrylate and phenyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzylamino) ethyl acrylate, methacrylic acid-2 -(N, N-dimethylamino) methyl, a Substituted aminoalcohol esters of unsaturated acids such as 2-hydroxy (N, N-diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl Polyfunctional compounds such as glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, etc., dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. And / or a polythiol compound having two or more thiol groups in the molecule, for example, trimethylolpropane trithioglycolate , Trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like.
[0031]
The above compounds are used alone or in combination of two or more as required. In order to impart ordinary coating suitability to the resin composition, 5% by weight or more of the prepolymer or oligomer, the monomer and It is preferable that the polythiol is 95% by weight or less.
[0032]
When selecting a monomer, if the flexibility of the cured product is required, the amount of the monomer is reduced within a range that does not hinder the suitability of coating, or a monofunctional or bifunctional acrylate monomer. To give a structure with a relatively low crosslink density. In addition, when the heat resistance, hardness, solvent resistance, etc. of the cured product are required, the amount of monomer is increased within a range that does not hinder coating suitability, or an acrylate monomer having three or more functions is added. It is preferable to use a high crosslink density structure. It is also possible to adjust coating suitability and physical properties of the cured product by mixing a 1,2-functional monomer and a tri- or higher functional monomer. Examples of the monofunctional acrylate monomer as described above include 2-hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate, and the like. Examples of the bifunctional acrylate monomer include ethylene glycol diacrylate and 1,6-hexanediol acrylate, and examples of the trifunctional or higher acrylate monomer include trimethylolpropane triacrylate, pentaerythritol hexaacrylate, diester. Examples include pentaerythritol hexaacrylate.
[0033]
Further, in order to adjust the physical properties such as flexibility and surface hardness of the cured product, the following ionizing radiation non-curable resin is added to 1 to 70 with respect to at least one of the prepolymer, oligomer and monomer. The mixture can be used by weight%, preferably 5 to 50% by weight. As the ionizing radiation non-curable resin, a thermoplastic resin such as urethane, fiber base, polyester, acrylic, butyral, polyvinyl chloride, and polyvinyl acetate can be used. Elementary, urethane and butyral are preferred.
[0034]
When the ionizing radiation curable resin composition as described above is cured with ultraviolet rays in particular, acetophenones, benzophenones, Michler benzoylbenzoate, α-amylo is used as a photopolymerization initiator for the ionizing radiation curable resin composition. Mixtures of n-butylamine, triethylamine, tri-n-butylphosphine, and the like can be used as oxime esters, tetramethylthiuram monosulfide, thioxanthones, and / or photosensitizers.
[0035]
In the present invention, since the surface protective layer 4 contains organic particles 5 and spherical particles 7, the particles 5 and 7 are mixed and dispersed in the ionizing radiation curable resin composition described above.
[0036]
The surface protective layer 4 is formed by applying the ionizing radiation curable resin composition as described above by coating or the like and then irradiating and curing the ionizing radiation. The ionizing radiation curable composition can use the same method as the method of applying the ink composition for forming the solid layer 2 described above, and usually has a thickness of about 0.1 to 100 μm at the time of drying. Apply.
[0037]
Among the ionizing radiations, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp, or the like can be used. Also, as the electron beam source, various electron beam accelerators such as a Cockroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency, etc. are used, preferably 100 to 1000 keV, preferably Irradiates electrons with energy of 100 to 300 keV. The irradiation dose of the electron beam is usually about 0.5 to 30 Mrad.
[0038]
The decorative material of the present invention can be suitably used for members that require surface protection performance such as bedding and wall surfaces and that require a high design.
[0039]
【Example】
Next, the present invention will be described in more detail with specific examples.
Example 1
Using impregnated paper (GF-601 manufactured by Kojin Co., Ltd., basis weight 60 g / m ² ) as the base material, solid printing and wood grain pattern by gravure printing on the product name “HAT” manufactured by The Inktech Co., Ltd. Is printed on the pattern layer, and a coating resin composition having the following composition is coated on the pattern layer by roll coating, and an accelerating voltage of 175 KeV and an irradiation dose using an electron beam irradiation apparatus. The surface protective layer having a film thickness of 15 μm (referring to the film thickness of the portion not including particles; hereinafter the same) was formed by irradiating the electron beam so as to be 5 Mrad and completely curing the resin. The obtained cosmetic material was a cosmetic material having a highly superior surface design.
Composition of coating resin composition Electron beam curable resin (mainly epoxy acrylate) 100 parts by weight Spherical urethane particles (average particle size 25 μm) 10 parts by weight Silicone acrylate 2 parts by weight
Comparative Example 1
Using the same substrate and ink as in Example 1, a pattern layer was formed in the same manner as in Example 1, and then a coating resin composition having the following composition was coated on the pattern layer by roll coating. 1 was irradiated with an electron beam to completely cure the resin to form a surface protective layer having a thickness of 15 μm.
Composition of Resin Composition for Coating 100 parts by weight of electron beam curable resin (based on epoxy acrylate) Spherical urethane particles (average particle size 5 μm) 10 parts by weight of silicone acrylate 2 parts by weight
Example 2
Using the same base material and ink as in Example 1, a picture layer is formed in the same manner as in Example 1, and then a coating resin composition containing organic particles and spherical particles is rolled onto the picture layer as described below. The film was coated with a coat and irradiated with an electron beam under the same conditions as in Example 1 to completely cure the resin to form a surface protective layer having a thickness of 25 μm. The obtained decorative material was excellent in wear resistance and the surface of the decorative material was highly superior in design.

[0042]
Comparative Example 2
Using the same base material and ink as in Example 1, a pattern layer was formed in the same manner as in Example 1, and then a coating resin composition containing spherical particles was applied on the pattern layer as described below by roll coating. Coating was performed, and an electron beam was irradiated under the same conditions as in Example 1 to completely cure the resin to form a surface protective layer having a thickness of 25 μm.

[0043]
[Evaluation of wear resistance]
About the decorative material obtained by the said Example and comparative example, abrasion resistance was measured on S-42 and a 500-g load by the method according to JISK-6902. The results are shown in Table 1.
[0044]
[Table 1]

[0045]
【The invention's effect】
As described above, the decorative material of the present invention includes organic particles having a particle size such that the surface protective layer has a specific thickness and is made of an ionizing radiation curable resin. Obtained, and has the effect that an extremely excellent design property is obtained.
[0046]
In addition, the decorative material of the present invention is further improved by using an ionizing radiation curable resin having a specific average molecular weight between crosslinks for the surface protective layer, and using spherical particles having a specific hardness in combination with the organic particles. It has an effect that a cosmetic material having a surface having excellent wear characteristics and a high design superiority can be obtained at the same time.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view showing an example of a decorative material of the present invention.
FIG. 2 is a longitudinal sectional view showing another example of the decorative material of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Base material 2 Solid layer 3 Picture layer 4 Surface protective layer 5 Organic particle 6 Ionizing radiation curable resin layer 7 Spherical particle

Claims (1)

A solid layer, a pattern layer, and a surface protective layer are provided in this order from the substrate side on at least one side of the base material, and the surface protective layer is 1.2 to 2.0 times the film thickness of the surface protective layer. Spherical particles made of inorganic particles containing organic particles made of urethane particles having a particle size such that the particle size is 1/2 to 2/3 times the particle size of the organic particles and the Knoop hardness is 1300 kg / cm ² or more. A cosmetic material comprising an ionizing radiation curable resin containing particles.

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