JP5326453B2 - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet having excellent flaw resistance in addition to slip preventability and contamination resistance. <P>SOLUTION: This invention relates to the decorative sheet having a surface protective layer 5 comprising polymer beads 6 on the outermost surface, wherein: (1) each polymer bead 6 requires force of &gt;10 MPa for compressing the volume of the bead by 10%; (2) the average particle diameter of the polymer beads 6 is 1 to 200 &mu;m; and (3) the relation between the average particle diameter (&phiv;) of the polymer beads 6 and the thickness (D) of the surface protective layer 5 satisfies D&le;&phiv;&le;3D. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a decorative sheet.

  The decorative sheet is used by sticking it on the surface of a wooden board, a plastic board or the like for the purpose of surface protection, decoration, and the like. And the decorative board obtained by this is used for various building materials, furniture, etc.

  Accordingly, the decorative sheet is required to have, for example, scratch resistance and contamination resistance.

  However, the conventional decorative sheet having scratch resistance and stain resistance generally has a smooth surface. Therefore, when it is used for flooring, flooring, etc., it is slippery when a person walks and there is a risk of falling.

  Therefore, for the purpose of imparting anti-slip properties to the decorative sheet, thermoplastic resin beads having a glass transition point of 0 ° C. or higher and lower than 25 ° C. and thermoplastic resin beads having −25 ° C. or higher and lower than 0 ° C. were added to the surface of the decorative sheet. A flooring has been proposed (Patent Document 1). The floor material of patent document 1 forms a surface protective layer by applying the coating liquid containing the thermoplastic resin bead of -25 degreeC or more and less than 0 degreeC.

  However, since the beads tend to aggregate, there is a problem that it is difficult to produce the intended flooring.

  Patent Documents 2 and 3 disclose floor materials that are imparted with stain resistance while maintaining anti-slip properties on the surface by adding a thermoplastic polymer or hard particles to the surface layer.

  In addition, as cosmetic materials using resin beads, cosmetic materials imparted with designability and wear resistance by adding organic particles or the like to the surface protective layer have been reported (Patent Documents 4 and 5).

  However, although the flooring materials (decorative materials) of Patent Documents 2 to 5 have slip resistance and stain resistance, there is a problem in that scratch resistance is poor.

  Therefore, it is desired to develop a cosmetic material having excellent scratch resistance in addition to slip resistance and stain resistance.

In addition, Patent Document 6 discloses that scratch resistance can be improved by blending silica particles in the outermost surface layer as a prior document related to the present invention.
JP 2006-2518 A JP 2004-225456 A JP 2001-254504 A JP 2001-129937 A JP-A-11-227116 JP 2007-118596 A

  The main object of the present invention is to provide a decorative sheet having excellent scratch resistance in addition to slip resistance and stain resistance.

  As a result of earnest research, the inventor is a decorative sheet having a surface protective layer containing polymer beads on the outermost surface, using specific polymer beads, and the average particle diameter of the polymer beads and the surface protective layer. It has been found that the above-mentioned object can be achieved when the thickness of the film is in a specific relationship, and the present invention has been completed.

That is, the present invention relates to the following decorative sheet and decorative plate.
1. A decorative sheet having a surface protective layer containing polymer beads on the outermost surface,
(1) The polymer beads are polymer beads that require a force exceeding 10 MPa to compress the volume of the beads by 10%,
(2) The average particle diameter of the polymer beads is 1 to 200 μm,
(3) the relationship between the thickness (D) of the average particle diameter (phi) and the surface protective layer of the polymeric beads Ri D ≦ φ ≦ 3D der,
(4) The surface protective layer has a dynamic friction coefficient of 0.4 to 1.0 and a static friction coefficient of 0.4 to 1.0.
Makeup sheet.
2. Item 2. The decorative sheet according to Item 1, wherein the polymer beads are acrylic polymer beads.
3. Item 3. The decorative sheet according to Item 1 or 2, wherein the polymer beads are polymer beads that require a force of 20 MPa or more to compress the volume of the beads by 10%.
4). Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the polymer beads have an average particle size of 1 to 100 µm.
5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the surface protective layer has a thickness of 1 to 200 µm.
6). The decorative sheet according to any one of Items 1 to 5, wherein the surface protective layer is an ionizing radiation curable resin layer formed by resin crosslinking of an ionizing radiation curable resin.
7. Item 7. The decorative sheet according to any one of Items 1 to 6, further comprising a pattern layer, a transparent resin layer, a primer layer, and the surface protective layer in this order on the substrate sheet.
8). A decorative board in which the decorative sheet is laminated on an adherend so that the surface protective layer of the decorative sheet according to any one of Items 1 to 7 becomes an outermost surface layer.

The decorative sheet of the present invention is a decorative sheet having a surface protective layer containing polymer beads on the outermost surface,
(1) The polymer beads are polymer beads that require a force exceeding 10 MPa to compress the volume of the beads by 10%,
(2) The average particle diameter of the polymer beads is 1 to 200 μm,
(3) The relationship between the average particle diameter (φ) of the polymer beads and the thickness (D) of the surface protective layer is D ≦ φ ≦ 3D.

(Surface protective layer)
The decorative sheet of the present invention has a surface protective layer containing polymer beads on the outermost surface.

  By forming the surface protective layer, the surface of the decorative sheet can be easily scratched and the scratch resistance can be improved.

  The surface protective layer contains polymer beads. By containing the polymer beads, slip resistance can be suitably imparted to the decorative sheet.

  The polymer bead is a polymer that requires a force exceeding 10 MPa, preferably a force of 20 MPa or more, more preferably a force of 20 to 50 MPa, and even more preferably a force of 20 to 30 MPa to compress the volume of the beads by 10%. It is a bead. By using polymer beads with the force exceeding 10 MPa, it is possible to impart scratch resistance to the decorative sheet. In particular, when polymer beads having a force of 20 MPa or more are used, the scratch resistance is dramatically improved.

  The compressive strength can be measured in accordance with JIS K7208.

  The average particle diameter (φ) of the polymer beads is 1 to 200 μm, preferably 1 to 100 μm, more preferably 5 to 50 μm. In the present invention, as long as the average particle diameter (φ) of the polymer beads satisfies the range of 1 to 200 μm, two or more kinds of polymer beads having different average particle diameters can be contained in the surface protective layer.

  The thickness of the surface protective layer is not particularly limited as long as it does not interfere with the effects of the present invention, but is preferably 1 to 200 μm, more preferably 1 to 100 μm, and even more preferably 5 to 50 μm.

  In the present specification, “the thickness of the surface protective layer” refers to the thickness of the portion of the surface protective layer that does not include the beads, and does not refer to the thickness of the convex portion formed by the beads.

  The relationship between the average particle diameter (φ) of the polymer beads and the thickness (D) of the surface protective layer is D ≦ φ ≦ 3D, preferably D ≦ φ ≦ 2D. When the relationship between φ and D is D ≦ φ ≦ 3D, the decorative sheet can exhibit excellent scratch resistance and slip resistance.

  In addition, when the relationship between φ and D is D> φ, the decorative sheet cannot exhibit sufficient slip resistance. Further, when the relationship between φ and D is φ> 3D, there is a problem that the beads are likely to be lost from the surface protective layer in use.

  It is preferable that the surface protective layer contains polymer beads so that the surface has irregularities. In the decorative sheet of the present invention, the polymer beads are usually present inside the surface protective layer, but a part of the polymer beads protrudes from the surface of the surface protective layer as long as the effect of the present invention is not hindered (surface protective layer). You may break through).

  The average particle size of the polymer beads can be measured by a known method such as a laser diffraction method, a Coulter counter method, or a precipitation method. The average particle diameter means a particle diameter (D50) corresponding to a cumulative frequency of 50%.

  Examples of the polymer beads include known or commercially available polymer beads such as acrylic polymer beads, urethane polymer beads, styrene polymer beads, and polyester polymer beads. These polymer beads may be used alone or in combination of two or more. In particular, in the present invention, it is preferable to use acrylic polymer beads as the polymer beads. By using acrylic polymer beads, the scratch resistance and stain resistance of the decorative sheet can be improved.

  The shape of the polymer beads is usually spherical, but is not particularly limited to a spherical shape as long as the effect of the present invention is not hindered. The polymer beads may be colored. By appropriately coloring, depending on the type of the pattern, there may be a case where a stereoscopic effect close to the real thing (for example, natural wood, natural leather, etc.) can be suitably imparted.

  The dynamic friction coefficient of the surface protective layer containing polymer beads is preferably 0.4 to 1.0, and more preferably 0.5 to 0.8. When the dynamic friction coefficient of the surface protective layer is 0.4 to 1.0, excellent slip resistance can be exhibited.

  The static friction coefficient of the surface protective layer is preferably 0.4 to 1.0, more preferably 0.5 to 0.8. When the static friction coefficient of the surface protective layer is 0.4 to 1.0, excellent slip resistance can be exhibited.

  About the said dynamic friction coefficient and a static friction coefficient, it can measure according to the prescription | regulation of JISK7125.

  The surface protective layer is preferably transparent when a pattern layer is formed in the lower layer.

The surface protective layer is preferably an ionizing radiation curable resin layer formed by resin crosslinking of an ionizing radiation curable resin from the viewpoint of scratch resistance and the like.
The ionizing radiation curable resin refers to a resin that crosslinks and cures when irradiated with ultraviolet rays, electron beams, or the like.

  As the ionizing radiation curable resin, a known or commercially available product can be used. Specifically, a composition containing at least one of a prepolymer, an oligomer and a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is used.

  Examples of the prepolymer or oligomer include methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, polyester acrylate, polyether acrylate, urethane acrylate, polyol acrylate, and melamine acrylate. Examples include acrylates.

  Monomers include styrene monomers such as styrene and α-methylstyrene, acrylic acid such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, and phenyl acrylate. Examples include esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, and lauryl methacrylate.

  As substituted amino alcohol esters of unsaturated acids, acrylic acid-2- (N, N-diethylamino) ethyl, methacrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N -Substituted amino alcohol esters of unsaturated acids such as -dibenzylamino) methyl and acrylic acid-2- (N, N-diethylamino) propyl.

  In addition, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neobenzyl glycol diacrylate, 1,6-hexanediol diacrylate, ethyl carbitol acrylate, diethylene glycol diacrylate, Multifunctional materials such as triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate; Trimethylolpropane trithioglycolate, Trime Trimethylolpropane tri thio propiolate, there is a polythiol compound having two or more thiol groups in the molecule, such as dipentaerythritol tetra thioglycolic.

  About the resin of the said illustration, 1 type (s) or 2 or more types can be used together.

  The content of the polymer beads in the surface protective layer is preferably 1 to 50 parts by weight and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the matrix resin. When the content of the resin beads is 1 to 50 parts by weight with respect to 100 parts by weight of the matrix resin, slip resistance can be suitably imparted to the decorative sheet.

  About the formation method of the surface protection layer by ionizing radiation curable resin, what is necessary is just to follow a well-known method. For example, a composition (coating material) containing an ionizing radiation curable resin may be prepared and applied by a known coating method such as a gravure coating method or a roll coating method. The coating amount of the composition in this case is not particularly limited, and may be set as appropriate so that the thickness of the surface protective layer falls within the above range.

  After application, the formed coating film is irradiated with ionizing radiation. Ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion beam, etc. There is. In particular, ultraviolet rays, electron beams, and the like can be used as ionizing radiation. In particular, the surface protective layer is preferably a layer formed by irradiating the coating film containing the ionizing radiation curable resin with an electron beam. By irradiating the electron beam, a surface protective layer uniformly crosslinked with resin can be obtained with certainty. Moreover, when the resin is crosslinked by electron beam irradiation, the resin can be stably crosslinked and cured without using a photopolymerization initiator, and unlike the resin crosslinking by UV irradiation, the curing reaction rate is influenced by temperature. This is advantageous in that it does not receive much.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of about 190 to 380 nm can be used.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The acceleration voltage of the electron beam is generally about 100 to 1000 keV, preferably about 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  The decorative sheet of the present invention only needs to have the surface protective layer on the outermost surface, and the specific configuration may be appropriately set according to the use of the decorative sheet. For example, the decorative sheet which has a pattern layer, a transparent resin layer, a primer layer, and the said surface protective layer in order on a base material sheet is mentioned.

  Hereinafter, the decorative sheet of the present invention will be specifically described with a decorative sheet having a pattern layer, a transparent resin layer, a primer layer, and the surface protective layer in order on a base sheet as a representative example.

(Base material sheet)
A pattern layer etc. are laminated | stacked one by one on the surface (front surface) of a base material sheet.

  As the base sheet, for example, a sheet (film) formed of a thermoplastic resin is suitable. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer Examples include polymers, ionomers, acrylic esters, and methacrylic esters. The said base material sheet is formed by using these resin individually or in combination of 2 or more types.

  The base material sheet may be colored. In this case, a coloring material (pigment or dye) can be added to the above thermoplastic resin for coloring. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. These can be selected from one or more known or commercially available ones. Further, the addition amount of the colorant may be appropriately set according to the desired color tone.

  The base sheet contains various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers as necessary. It may be.

  Although the thickness of a base material sheet can be suitably set with the use of a final product, a usage method, etc., generally 20-300 micrometers is preferable.

  If necessary, the base sheet may be subjected to corona discharge treatment on the surface (front surface) in order to enhance the adhesion of the ink forming the pattern layer. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method. Moreover, you may give a corona discharge process to the back surface of a base material sheet, and may form a back surface primer layer as needed.

(Picture layer)
The pattern layer provides a desired pattern (design) to the decorative sheet, and the type of the pattern is not limited. For example, a wood grain pattern, a leather pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a geometric figure, a character, a symbol, an abstract pattern, and the like can be given.

  The method for forming the pattern layer is not particularly limited. For example, printing using ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form in the base-material sheet | seat surface by a method. As the ink, an aqueous composition can be used from the viewpoint of reducing the VOC of the decorative sheet.

  Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  As binder resin, in addition to polyester urethane resin treated with hydrophilicity, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative Alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, and the like can also be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above natural rubber, etc. Resin can also be used. The binder resin can be used alone or in combination of two or more.

  The pattern layer may be formed by a known printing method such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, or an ink jet printing method.

  The thickness of the pattern layer is not particularly limited and can be appropriately set according to product characteristics. The layer thickness at the time of coating is about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.

(Colored hiding layer)
In the decorative sheet of the present invention, a colored concealing layer may be further formed between the base sheet and the pattern layer.

  The colored concealment layer only needs to conceal the ground color of the adherend when the decorative sheet and the adherend are joined, and is usually formed so as to cover the base sheet.

  The known printing method can be used for forming the colored concealing layer. Moreover, the ink used for formation of the said picture layer can be used as it is.

  The known printing method can be used for forming the colored concealing layer.

The coating amount is desirably in the range of ^{2 to} 30 g / m2.

  The thickness of the colored masking layer is usually about 0.1 to 20 μm, preferably about 1 to 10 μm.

(Transparent adhesive layer)
In order to improve the adhesion between the transparent resin layer and the pattern layer described later, a transparent adhesive layer may be formed. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

  Examples of known adhesives in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins, and thermosetting resins such as urethane resins. These colorants are used alone or in combination of two or more. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  The known printing method can be used for forming the transparent adhesive layer.

  Although the thickness of a transparent adhesive bond layer is not specifically limited, The thickness after drying is about 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

(Transparent resin layer)
A transparent resin layer is formed on the transparent adhesive layer.

  The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. Examples of the resin constituting the transparent resin layer include polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, and ethylene / acrylic acid ester copolymer. Examples thereof include coalescence, ionomer, polymethylpentene, acrylic acid ester, methacrylic acid ester, polycarbonate, and cellulose triacetate. These resins are used alone or in combination of two or more.

  Preferably, a polyolefin resin typified by polypropylene resin is used. Therefore, when using polyolefin-type resin as a transparent resin layer, the various polyolefin-type resin quoted as what comprises a base material sheet can be used.

  The transparent resin layer may be colored as long as it has transparency, but it is particularly desirable not to add a colorant.

  The method for forming the transparent resin layer is not limited, for example, a method of laminating a preformed sheet or film on an adjacent layer, an adjacent layer by melt-extruding a resin composition capable of forming a transparent resin layer Any of a method of coating on top and a method of laminating together with an adjacent layer can be employed. Examples of the laminating method include a laminating method by a dry laminating method.

  The thickness of the transparent resin layer is usually about 20 to 200 μm, but may exceed the above range depending on the use of the decorative sheet.

(Primer layer)
By providing the primer layer, the formation of the surface protective layer can be facilitated. The primer layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and translucent.

  The primer layer can be formed by applying a known or commercially available primer agent on the transparent resin layer. In particular, the primer layer is preferably a layer formed by crosslinking a resin. Examples of the primer agent for forming such a layer include a urethane resin primer agent made of an acrylic-modified urethane resin and the like, a resin primer agent made of a block copolymer of acrylic and urethane, and the like. These primer agents are used alone or in combination of two or more.

The primer layer may contain silica as a matting agent. The content of silica in the primer agent is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin component,
10-40 weight part is more preferable.

  Furthermore, you may make a primer agent contain a well-known additive as needed. For example, the adhesiveness of the said transparent resin layer and the said surface protective layer can be improved more by making a primer agent contain a hexamethylene diisocyanate type hardening | curing agent.

  For the formation of the primer layer, the above known methods can be used. For example, a method similar to the method of forming the surface protective layer using the ionizing radiation curable resin can be employed.

  The thickness of the primer layer is not particularly limited, but is usually about 0.1 to 100 μm, preferably about 0.5 to 15 μm.

Decorative plate The decorative plate of the present invention is formed by laminating the decorative sheet on an adherend such that the surface protective layer of the decorative sheet is the outermost surface layer.

  The adherend is not limited, and the same materials as known decorative sheets can be used. For example, a wood material, a metal, ceramics, plastics, glass, etc. are mentioned. In particular, the decorative sheet of the present invention can be suitably used for a wood material. Specifically, wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. ) And the like.

  The lamination method is not limited. For example, a method of sticking a decorative sheet to an adherend with an adhesive or the like can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like. These adhesives are used alone or in combination of two or more.

  The decorative board manufactured in this way is, for example, interior decoration materials for buildings such as walls, ceilings and floors, surface decorative boards for furniture such as window frames, doors and handrails, furniture or light electrical appliances, cabinets such as OA equipment. It can be used for a surface decorative board. In particular, the decorative board of the present invention can be suitably used as a floor decorative material.

  The decorative sheet of the present invention is excellent in scratch resistance. Moreover, the decorative sheet of the present invention is also excellent in slip resistance and stain resistance. Therefore, the decorative board laminated with the decorative sheet of the present invention can be used for various building materials, furniture and the like. In particular, the decorative board of the present invention can be suitably used as a decorative material for floors because of its excellent scratch resistance, anti-slip property and stain resistance.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
A decorative sheet having the structure shown in FIG. 1 was produced by the following method.

  On the base material sheet 1 made of a colored polypropylene film having a thickness of 60 μm, a 4 μm-thick grain pattern pattern layer 2 was formed by a gravure printing method using a colored ink using an acrylic resin as a binder resin.

  Next, a polypropylene resin sheet was laminated on the pattern layer 2 by a dry lamination method to form a transparent resin layer 3 having a thickness of 80 μm.

  On the surface of the transparent resin layer 3, acrylic urethane resin, silica (30 parts by weight with respect to 100 parts by weight of acrylic urethane resin), and hexamethylene diisocyanate curing agent (20 parts with respect to 100 parts by weight of acrylic urethane resin). A primer layer 4 having a thickness of 1 μm was formed by a gravure printing method using a resin composition comprising (parts by weight).

Furthermore, on the primer layer 4, a resin composition containing urethane acrylate oligomer (ionizing radiation curable resin) and acrylic polymer beads having an average particle size of 36 μm as polymer beads (10 parts by weight with respect to 100 parts by weight of urethane acrylate oligomer). The product was coated and dried by gravure printing so that the solid content was 15 g / m ² to form an uncured coating film.

  The polymer beads have a force (10% compressive strength) required to compress the volume of the beads by 10% to 20 to 30 MPa.

  Thereafter, in an environment with an oxygen concentration of 200 ppm, the uncured resin layer is irradiated with an electron beam under conditions of an acceleration voltage of 125 KeV and 5 Mrad to cure the resin, and the surface protective layer 5 containing the polymer beads 6 (layer thickness: 15 μm) was formed.

Example 2
A decorative sheet was produced in the same manner as in Example 1 except that acrylic polymer beads having a 10% compressive strength of 20 to 30 MPa and an average particle size of 30 μm were used as the polymer beads.

Example 3
As the polymer beads, acrylic polymer beads having a 10% compressive strength of 20 to 30 MPa and an average particle diameter of 20 μm and acrylic polymer beads having an 10% compressive strength of 20 to 30 MPa and an average particle diameter of 30 μm are urethane. A decorative sheet was prepared in the same manner as in Example 1 except that 5 parts by weight were used per 100 parts by weight of the acrylate oligomer.

Example 4
As polymer beads, acrylic polymer beads having a 10% compressive strength of 20 to 30 MPa and an average particle size of 30 μm and acrylic polymer beads having an 10% compressive strength of 20 to 30 MPa and an average particle size of 36 μm are urethane. A decorative sheet was prepared in the same manner as in Example 1 except that 5 parts by weight were used per 100 parts by weight of the acrylate oligomer.

Example 5
As polymer beads, acrylic polymer beads having a 10% compressive strength of 20 to 30 MPa and an average particle diameter of 20 μm and acrylic polymer beads having an average particle diameter of 20 to 30 MPa and an average particle diameter of 36 μm are urethane. A decorative sheet was prepared in the same manner as in Example 1 except that 5 parts by weight were used per 100 parts by weight of the acrylate oligomer.

Example 6
As polymer beads, acrylic polymer beads having a 10% compressive strength of 20 to 30 MPa and an average particle diameter of 20 μm, acrylic polymer beads having an average particle diameter of 20 to 30 MPa and an average particle diameter of 30 μm, and 10% A decorative sheet was prepared in the same manner as in Example 1 except that 3 parts by weight of acrylic polymer beads having a compressive strength of 20 to 30 MPa and an average particle size of 36 μm were used for 100 parts by weight of the urethane acrylate oligomer. Produced.

Comparative Example 1
A decorative sheet was prepared in the same manner as in Example 1 except that polymer beads were not used.

Comparative Example 2
A decorative sheet was produced in the same manner as in Example 1 except that styrene polymer beads having a 10% compressive strength of 10 MPa or less and an average particle diameter of 50 μm were used as the polymer beads.

Comparative Example 3
A decorative sheet was produced in the same manner as in Example 1 except that styrene polymer beads having a 10% compressive strength of 10 MPa or less and an average particle diameter of 30 μm were used as the polymer beads.

Test Example 1 (Scratch resistance)
The flaw resistance of the decorative sheets prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was confirmed using a Hoffman scratch tester (BYK-Gardnar).

  Specifically, a scratch blade (a cylindrical edge portion having a diameter of 7 mm) is set so as to contact the surface protective layer of the decorative sheet at an angle of 45 degrees, and the surface is moved by pulling the scratch blade. Rubbed. At that time, it was confirmed whether or not the surface protective layer was damaged by changing the load applied to the scratch blade by 100 g in the range of 300 to 700 g.

  The case where the surface hardly changed was evaluated as ◯, the case where a slight change was observed on the surface was evaluated as Δ, and the case where the surface was greatly conspicuous was evaluated as ×.

  The results are shown in Tables 1 and 2.

  Note that a decorative sheet having scratch resistances of ◯ and Δ is acceptable as a product.

Test example 2 (contamination resistance)
The stain resistance of the decorative sheets prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was confirmed.
Specifically, 1 cm square absorbent cotton is placed on the surface protective layer, and after impregnating the absorbent with a contaminant, the absorbent cotton is covered with a watch glass so that the contaminant does not dry, and allowed to stand for 24 hours. It was.

  After 24 hours, the contamination state of the decorative sheet was confirmed by visual observation. A decorative sheet having a stain resistance superior to that of the decorative sheet of Comparative Example 1 (conventional product) is ◎, a decorative sheet having a stain resistance equivalent to that of the conventional product is ○, and the stain resistance is slightly less than that of the conventional product. The inferior decorative sheet was evaluated as Δ, and the decorative sheet that was considerably inferior in stain resistance as compared with the conventional product was evaluated as ×.

  In this test example, red ink, blue ink, and blue black ink were separately tested as contaminants.

  The results are shown in Tables 1 and 2.

Test example 3 (friction coefficient measurement)
The static friction coefficient and the dynamic friction coefficient of the decorative sheets prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were measured.

  The measurement was performed according to JIS K 7125.

  The results are shown in Tables 1 and 2.

FIG. 1 is a conceptual diagram (cross-sectional view) of a decorative sheet produced in Examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material sheet 2 ... Picture layer 3 ... Transparent resin layer 4 ... Primer layer 5 ... Surface protective layer 6 ... Polymer bead

Claims (8)

A decorative sheet having a surface protective layer containing polymer beads on the outermost surface,
(1) The polymer beads are polymer beads that require a force exceeding 10 MPa to compress the volume of the beads by 10%,
(2) The average particle diameter of the polymer beads is 1 to 200 μm,
(3) the relationship between the thickness (D) of the average particle diameter (phi) and the surface protective layer of the polymeric beads Ri D ≦ φ ≦ 3D der,
(4) The surface protective layer has a dynamic friction coefficient of 0.4 to 1.0 and a static friction coefficient of 0.4 to 1.0.
Makeup sheet. The decorative sheet according to claim 1, wherein the polymer beads are acrylic polymer beads. The decorative sheet according to claim 1 or 2, wherein the polymer beads are polymer beads that require a force of 20 MPa or more to compress the volume of the beads by 10%. The decorative sheet according to any one of claims 1 to 3, wherein an average particle diameter of the polymer beads is 1 to 100 µm. The decorative sheet according to claim 1, wherein the surface protective layer has a thickness of 1 to 200 μm. The decorative sheet according to claim 1, wherein the surface protective layer is an ionizing radiation curable resin layer formed by resin crosslinking of an ionizing radiation curable resin. The decorative sheet according to any one of claims 1 to 6, comprising a pattern layer, a transparent resin layer, a primer layer, and the surface protective layer in this order on the base sheet. A decorative board in which the decorative sheet is laminated on an adherend so that the surface protective layer of the decorative sheet according to any one of claims 1 to 7 becomes an outermost surface layer.

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