WO2005100679A1

WO2005100679A1 - Decorative sheet for floor material and decorative material for floor using the same

Info

Publication number: WO2005100679A1
Application number: PCT/JP2005/006401
Authority: WO
Inventors: Hiroaki Nakayama; Ken Kimura; Kayo Ishihara; Hiroshi Masuda
Original assignee: Dai Nippon Printing Co., Ltd.
Priority date: 2004-03-31
Filing date: 2005-03-31
Publication date: 2005-10-27
Also published as: KR20080098452A; CN1938477A; KR100876787B1; KR20070009656A; JP2005290734A; JP4587692B2; JP2005290568A; CN100537226C; HK1103770A1

Abstract

A decorative sheet for a floor material, characterized in that it comprises a base material sheet comprising a polyolefin-based resin and, laminated thereon in the following order, a decorative layer, a transparent polyolefin-based resin layer having a thickness of 150 to 500 μm and a transparent surface-protecting layer; and a decorative material for a floor using the above decorative sheet. The decorative sheet for a floor material exhibits good resistance to scuffing, to marring by a caster or to impact, without the formation of a backer layer.

Description

Specification

Decorative sheet for floor material and decorative material for floor using the same

Technical field

The present invention relates to a decorative sheet for flooring and a decorative material for flooring using the same.

The floor decorative material of the present invention is useful, for example, as a floor material in buildings such as detached houses, apartments, condominiums, recreational facilities, and shops. Background art

[0003] Conventionally, as a floor decorative material, a wooden decorative veneer is applied by sticking a wooden decorative veneer to a wooden plywood, and after attaching the wooden plywood and a medium density fiberboard (MDF), the wooden decorative material is further applied to the MDF side. Those with a decorative veneer attached and painted are widely known.

[0004] While making efforts, wood veneer is a thin slice of natural wood, and it is desirable to refrain from using it in view of the issue of timber resource depletion and the growing global resource conservation movement. No. In recent years, instead of using a wooden veneer veneer made of natural wood, a shampoo sheet, in which a grain pattern or the like is artificially expressed by printing, has been used.

[0005] A decorative floor material using a decorative sheet has a high degree of freedom in design expression. Moreover, since the decorative sheet is a synthetic material, it has excellent weather resistance and water resistance.

[0006] While applying force, the floor decorative material using the decorative sheet has a much smoother and more uniform surface than the conventional floor decorative material using the wood veneer veneer. It has the disadvantage of being relatively noticeable.

[0007] In recent years, the use of furniture on casters, wheelchairs, and the like in the room has been increasing due to the westernization of the room furniture and the barrier-free environment. Shortage problem is pointed out. This is a problem that when a wheel is rolled by applying a large load to a small area, a dent is left along the locus on the surface of the floor covering material. In addition, it has been pointed out that there is a problem of insufficient impact resistance, in which a dent remains when a hard object falls onto the surface of a floor covering material.

[0008] A technique for improving the above-described problems such as scratch resistance and caster resistance has been proposed in Patent Document 1, for example. Patent Document 1 comprises a decorative sheet on the surface of a wooden substrate In the decorative material, a configuration is proposed in which a hard sheet layer made of a material having high hardness is provided between the wooden base material and the decorative sheet. Here, the hard sheet layer is a so-called backer layer, and is a reinforcing layer that imparts hardness, strength, and the like to the decorative sheet for flooring.

[0009] The floor decorative material using the floor decorative sheet having the packer layer is superior to conventional products in terms of strength, hardness and the like. However, the production of a decorative sheet for flooring having a knocker layer requires a step of attaching the knocker portion to another portion (for example, a printed sheet), and in this process, product loss tends to occur. There is.

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-11277

Disclosure of the invention

Problems to be solved by the invention

[0010] Accordingly, an object of the present invention is to provide a decorative sheet for flooring, which exhibits good scratch resistance, caster resistance, impact resistance, and the like without forming a knocker layer. .

[0011] Another object of the present invention is to provide a decorative floor material having good scratch resistance, caster resistance, impact resistance, and the like, using the decorative sheet for floor material.

Means for solving the problem

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a decorative sheet for flooring having at least a specific polyolefin-based resin layer achieves the above object, and completed the present invention. I came to.

[0013] That is, the present invention relates to the following decorative sheet for floor material and a decorative material for floor using the same.

[0014] 1. A decorative layer, a transparent polyolefin-based resin layer having a thickness of 150 to 500 μm, and a transparent surface protective layer are laminated at least in order on a base sheet made of a polyolefin-based resin. Decorative sheet for flooring.

[0015] 2. A pattern layer, a transparent adhesive layer, a transparent polypropylene resin layer having a thickness of 150 to 500 m, and an ionizing radiation-curable resin are also provided on a base sheet made of polyolefin resin. Item 2. The decorative sheet for flooring according to Item 1, wherein the transparent surface protective layer is laminated at least in order.

[0016] 3. Transparent polypropylene-based resin layer strength Item 3. The decorative sheet for flooring according to Item 2, having a tensile modulus of at least 100 MPa.

[0017] 4. The above item, wherein a colored concealing layer is further laminated between the base sheet and the picture pattern layer.

3. The decorative sheet for flooring according to 2.

[0018] 5. The decorative sheet for flooring according to the above item 2, wherein irregularities are formed on the front surface of the transparent surface protective layer.

[0019] 6. On a base sheet made of polyolefin resin, a decorative layer, a transparent polyolefin resin layer having a thickness of 300 to 500 µm, and a transparent surface protective layer having a thickness of 3 to 30 m are provided. 2. The decorative sheet for flooring according to the above item 1, which is laminated at least in order.

[0020] 7. The decorative sheet for flooring according to item 6, wherein the polyolefin resin in the transparent polyolefin resin layer is a homopolypropylene.

[0021] 8. The decorative sheet for flooring according to item 6, wherein the polyolefin resin in the transparent polyolefin resin layer has a homopolypropylene strength of 70% by weight or more.

[0022] 9. The decorative sheet for flooring according to item 6, wherein the homopolypropylene has a melting point of 150 to 170 ° C.

[0023] 10. The decorative sheet for flooring according to the above item 6, wherein the base sheet also comprising the polyolefin resin is a polypropylene resin film or a polyethylene resin film.

[0024] 11. A decorative floor material, comprising the base sheet side of the decorative sheet for floor material according to item 2 or 6 attached to an adherend.

Hereinafter, the decorative sheet for flooring of the present invention and the decorative material for flooring using the same will be described.

The decorative sheet for flooring of the present invention comprises a decorative layer, a transparent polyolefin-based resin layer having a thickness of 150 to 500; The layers are laminated at least in order.

Specific examples of the decorative sheet for flooring of the present invention and the decorative material for flooring using the same include those shown in the following embodiments 1 and 2. Hereinafter, Embodiments 1 and 2 will be described.

1. Flooring decorative sheet and flooring decorative material of Example # 1

The decorative sheet for flooring according to Embodiment 1 is formed on a base sheet made of polyolefin resin, A pattern layer, a transparent adhesive layer, a transparent polypropylene resin layer having a thickness of 150 to 500 m, and a transparent surface protective layer made of ionizing radiation-curable resin are laminated at least in order.

[0028] Certain material sheet

A sheet made of polyolefin resin is used as the base sheet. Normally, a film made of polyolefin resin should be used.

[0029] The polyolefin resin is not particularly limited, and those commonly used in the field of decorative sheets can be used. Examples include polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-butyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, and polyolefin-based thermoplastic elastomer. Can be Among these, polypropylene and polyolefin-based thermoplastic elastomers are particularly preferred.

[0030] A homopolymer or a copolymer containing polypropylene as a main component is also preferable. For example, homopolypropylene resin, random polypropylene resin, block polypropylene resin, and polypropylene having a polypropylene crystal part, and other than propylene. A-olefins having 2 to 20 carbon atoms; Other, ethylene, butene 1, 4-methylpentene 1, hexene 1 or Okute emissions - 1 propylene containing 15 mole ^_0/0 or more comonomers - alpha-Orefuin copolymer are also preferable.

[0031] Polyolefin-based thermoplastic elastomer is a block polymer using a highly crystalline and high melting point aromatic polyester for the hard segment and an amorphous polyether having a glass transition temperature of 70 ° C or less for the soft segment. is there. In particular, a mixture of a hard segment having high isotactic polypropylene strength and a soft segment having high atactic polypropylene strength in a weight ratio of 80:20 is preferred!

The polyolefin resin may be formed into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

[0033] The thickness of the substrate sheet is not particularly limited and can be set according to product characteristics.

150 m, preferably 50 to: LOO μm.

[0034] Additives may be added to the base sheet as necessary. As an additive, for example Examples thereof include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, and coloring agents (see below). The compounding amount of the additive can be appropriately set according to the product characteristics.

[0035] The colorant is not particularly limited, and a known colorant such as a pigment or a dye can be used. For example, inorganic pigments such as titanium white, zinc white, red petals, vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, etc .; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, Organic pigments (including dyes) such as Indaslen Blue RS and A-Rin Black; metal pigments such as aluminum and brass; pearlescent (pearl) pigments composed of foil powder such as titanium dioxide-coated mica and basic lead carbonate No. The coloring mode of the base sheet includes transparent coloring and opaque coloring (concealment coloring), and these can be arbitrarily selected. For example, when the ground color of the adherend (the base material to which the decorative sheet is adhered) is colored and concealed, opaque coloring may be selected. On the other hand, when the ground pattern of the adherend is made visible, transparent coloring may be selected.

[0036] One or both surfaces of the base sheet may be subjected to a surface treatment such as a corona discharge treatment, an ozone treatment, a plasma treatment, an ionizing radiation treatment, and a dichromic acid treatment, if necessary. For example, when performing a corona discharge treatment, the surface tension of the surface of the substrate sheet may be set to 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed in accordance with the usual method of each treatment.

[0037] A primer layer (for example, a primer for facilitating adhesion of an adherend, a primer for facilitating the formation of a pattern layer, and a primer Layer). By providing the primer layer, the interlayer adhesion with an adjacent layer (for example, an adherend) can be increased.

[0038] The primer layer can be formed by applying a known primer to one or both surfaces of the base sheet. Examples of the primer include a urethane-based primer which has strength such as acrylic-modified urethane-based resin, and a urethane-cellulose-based resin (for example, hexamethylene diisocyanate is added to a mixture of urethane and nitrified cotton). Primer agents that also have strong properties.

[0039] The coating amount of the primer is not particularly limited, but is usually 0.1 to: LOOgZm ² , preferably It is 0. l~50gZm ² about.

The thickness of the primer layer is not particularly limited, but is usually 0.01 to 10 μm, preferably 0.1 to 10 μm.

~: About m.

[0041] Picture barrel-like layer (decoration layer)

A pattern layer is formed on the base sheet (opposite to the surface on which the adherend is to be adhered, hereinafter referred to as the same side in each layer). The pattern layer is a layer for decorating the decorative sheet for flooring, and is one of the decorative layers.

[0042] The design pattern layer is for imparting a design property with a desired design to the decorative sheet for flooring, and the type of the design is not particularly limited. For example, wood pattern, stone pattern, sand pattern

, Tiled patterns, brickwork patterns, cloth patterns, leather patterns, geometric figures, characters, symbols, abstract patterns, and the like.

[0043] The method for forming the pattern layer is not particularly limited, and is obtained, for example, by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin and a resin. It may be formed by a printing method using a coloring ink, a coating agent or the like.

Examples of the coloring agent include inorganic pigments such as carbon black, titanium white, zinc white, red iron oxide, navy blue, cadmium red, and the like; Organic pigments such as linone pigments and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in combination of two or more. Fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like may be further added to these colorants.

[0045] The binder resin (vehicle) includes, for example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, and salted vinyl acetate. -Copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, cellulose Derivatives, rubber-based resins, and the like. These resins can be used alone or in combination of two or more.

As the solvent (or dispersion medium), for example, hexane, heptane, octane, toluene, xy Petroleum organic solvents such as len, ethylbenzene, cyclohexane, and methylcyclohexane; ester organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; methyl alcohol, ethyl alcohol, and normal propyl alcohol Alcohol-based organic solvents such as isopropyl alcohol, isopropyl alcohol, isopropyl alcohol, ethylene glycol, alcohol, and the like; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether organic solvents such as tyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in combination of two or more.

[0047] Examples of the printing method used for forming the picture pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When a solid pattern pattern layer is formed over the entire surface, for example, roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, etc. And various coating methods such as a dip coating method. In addition, a hand-drawing method, an ink-washing method, a photographic method, a transfer method, a laser beam drawing method, an electron beam drawing method, a partial vapor deposition method of metal or the like, an etching method, or a combination with other forming methods may be used. Yeah.

[0048] The thickness of the pattern layer is not particularly limited and can be appropriately set according to the product characteristics. The layer thickness at the time of coating is about 1 to 15 / ζπι, and the layer thickness after drying is 0.1 to: LO / zm.

[0049] Layering

Between the base sheet and the pattern layer, a colored concealing layer may be further laminated as necessary. The colored concealing layer is provided, for example, when it is desired to conceal the ground color of the front surface of the decorative sheet. In addition to the case where the base sheet is transparent and the case where the base sheet is concealed and colored, the base sheet may be formed to stabilize the concealing property. The coloring concealing layer is a layer that applies coloring to the decorative sheet for flooring, and is one of the decorative layers, like the picture pattern layer.

[0050] As the ink for forming the colored concealing layer, an ink for forming a picture pattern layer that can be concealed and colored can be used. [0051] The method for forming the colored concealing layer is preferably a method that can be formed so as to cover the entire base sheet (to be entirely solid). For example, the above-mentioned roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like are preferable.

[0052] The thickness of the colored concealing layer is not particularly limited and can be appropriately set according to the product characteristics. The layer thickness at the time of coating is 0.2 to: LO / zm, and the layer thickness after drying is 0.1. About 5 / ζπι.

[0053] Adhesive layer

A transparent adhesive layer is formed on the pattern layer. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. The adhesive layer is formed for bonding the pattern layer and the transparent polyester resin layer.

[0054] The adhesive is not particularly limited, and an adhesive known in the field of decorative sheets can be used.

[0055] Examples of adhesives known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin, and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Are listed. Further, a two-part curable polyurethane resin or a polyester resin using isocyanate as a curing agent can also be applied.

[0056] The adhesive layer is formed, for example, by applying an adhesive onto the pattern layer, applying a transparent polypropylene resin constituting the transparent polypropylene resin layer, and then drying and curing. it can. Conditions such as a drying temperature and a drying time are not particularly limited, and may be appropriately set according to the type of the adhesive. The method for applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, lino coat, gravure coat, gravureino coat, air knife coat, kiss coat, blade coat, smooth coat, and comma coat. One method or the like can be adopted.

[0057] The thickness of the adhesive layer is not particularly limited, but the thickness after drying is 0.1 to 30 m, preferably about 1 to 20 / ζπι.

[0058] Description Polyolefin resin layer

In the first embodiment, a transparent polypropylene resin layer having a thickness of 150 to 500 m is used as the transparent polyolefin resin layer. [0059] On the transparent adhesive layer, a transparent polypropylene resin layer having a thickness of 150 to 500 µm, preferably 300 to 500 µm is formed.

[0060] The transparent polypropylene resin layer is not particularly limited as long as it has the above-mentioned thickness, but a layer containing homopolypropylene is preferable. Although the content ratio of the homopolypropylene is not particularly limited, it is more preferable that the resin layer constituting the resin layer has a weight of 75% by weight or more, and that the resin layer substantially has a homopolypropylene alone.

[0061] The transparent polypropylene resin layer is preferably such that the resin layer alone has a tensile modulus of at least 100 MPa, particularly at least 1500 MPa. The upper limit of the tensile modulus is not particularly limited, but may be about 2000 MPa.

[0062] The tensile elastic modulus can be measured by preparing a transparent polypropylene resin sheet having the same thickness and material as the resin layer. Incidentally, the tensile elastic modulus in the present specification,

It is a value measured according to the provisions of JIS K6734 "Plastic Rigid Poly Shiridani Bullet Sheet Dimensions and Properties Part 2: Sheets with a thickness of less than lmm".

[0063] The transparent polypropylene resin layer may be formed by laminating the above transparent polypropylene resin on the transparent adhesive layer by, for example, a force rendering method, an inflation method, a T-die extrusion method, or the like. You can also use an existing film!

[0064] The surface of the transparent polypropylene-based resin layer, on which a transparent surface protective layer described later is formed, may be subjected to corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment as necessary. Surface treatment such as dichromic acid treatment. The surface treatment may be performed according to the usual method of each treatment.

[0065] If necessary, a primer layer (a primer layer for facilitating formation of a surface protective layer) may be provided on the surface.

[0066] The primer layer can be formed by applying a known primer agent to one or both sides of the base sheet. Examples of the primer include urethane-based primers that also have an acrylic-modified urethane resin and the like, and resin-based primers that also have a block copolymer of acrylic and urethane.

The amount of the primer applied is not particularly limited, but is usually 0.1 to: LOOgZm ² , preferably

It is 0. l~50gZm ² about. The thickness of the primer layer is not particularly limited, but is usually 0.01 to 10 μm, preferably 0.1 to 10 μm.

~: About m.

[0069] Description table

On the transparent polypropylene resin layer, a transparent surface protective layer made of ionizing radiation curable resin is formed. By forming a surface protective layer made of an ionizing radiation-curable resin, it is possible to enhance the abrasion resistance, impact resistance, stain resistance, scratch resistance, weather resistance, and the like of the decorative sheet.

[0070] The ionizing radiation-curable resin is not particularly limited, and may be a prepolymer (including oligomers) containing in its molecule a radical polymerizable double bond capable of undergoing a polymerization cross-linking reaction by irradiation with ionizing radiation such as ultraviolet light or an electron beam. ) And a transparent resin containing Z or a monomer as a main component can be used. These prepolymers or monomers can be used alone or as a mixture of two or more. The curing reaction is usually a cross-linking curing reaction.

[0071] Specifically, the prepolymer or monomer includes a radically polymerizable unsaturated group such as a (meth) atalyloyl group or a (meth) atalyloyloxy group in a molecule, or a cationically polymerizable functional group such as an epoxy group. And a compound having a group. Also preferred is a polyene Z thiol-based prepolymer, which is a combination of polyene and polythiol. Here, the (meth) atalyloyl group means an atalyloyl group or a methacryloyl group.

Examples of the prepolymer having a radical polymerizable unsaturated group include, for example, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. Rate, silicone (meth) acrylate and the like. The molecular weight is preferably about 250 to 100000.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxethyl (meth) acrylate. . Examples of the polyfunctional monomer include, for example, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethyl propane tri (meth) acrylate, trimethylol propane ethylene oxide tri (meth) acrylate, dipenta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. The

Examples of prepolymers having a cationically polymerizable functional group include epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy conjugates, and fatty acids-based ethers and aromatic-based ethers. An ether-based resin prepolymer may be used. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include polyurethane obtained by adding allylic alcohol to both ends of a polyurethane made of diol and diisocyanate.

[0075] As the ionizing radiation used to cure the ionizing radiation-curable resin, an electromagnetic wave or a charged particle having energy capable of causing a curing reaction of the molecules in the ionizing radiation-curable resin (composition) is used. . Usually, ultraviolet light or electron beam may be used, but visible light,

X-rays, ion beams or the like may be used.

As the ultraviolet light source, for example, 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, a metal halide lamp, etc. can be used. The wavelength of ultraviolet light is usually 190-380 nm.

As the electron beam source, for example, various electron beam accelerators such as a Cockcroft-Walton type, a Van degraft type, a resonance transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type are used. it can. Among them, those capable of irradiating electrons having an energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

[0078] The surface protective layer is formed, for example, by applying an ionizing radiation curable resin onto a transparent polypropylene resin layer by a known coating method such as gravure coating or roll coating, and then irradiating with ionizing radiation.できる Can be formed by curing resin.

[0079] The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the characteristics of the final product, but is usually about 0.1 to 50 / zm, preferably about 1 to 20 Pm.

[0080] Irregularities may be formed on the front surface (the surface exposed to the air) of the surface protective layer. Usually, an uneven pattern is formed by embossing. The embossing method is not particularly limited. For example, a method in which the front surface of the transparent acrylic resin layer is heated and softened, pressurized and shaped by an embossing plate, and then cooled is mentioned as a preferable method. . For embossing A known single-wafer or rotary embossing machine is used. Examples of the concavo-convex shape include a wood grain board conduit groove, a stone board surface unevenness (granite cleavage plane, etc.), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like.

Weathering agent

If necessary, a weathering agent may be added to at least one of the layers constituting the decorative sheet for flooring of the present invention. As the weathering agent, an ultraviolet absorber, a hindered amine light stabilizer and the like are preferable. These weathering agents can be used alone or in combination of two or more.

(UV absorber)

As the ultraviolet absorber, those having a basic component (particularly, a hydroxyl group) are particularly preferable. For example, 2- (2,1-hydroxy-1,3,5,1-di-tert-butylphenyl) 5chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'methylphenyl) 5 Benzotriazole, 2- (2,1-hydroxy-1,3-tert-amyl-5, -isobutylphenol) 5 Benzotriazole, 2- (2,1-hydroxy-1,3-isobutyl 5,1-methylphenyl) 2) -Hydroxyphenyl-5-chlorobenzene, such as 5-cyclobenzobenzotriazole, 2- (2,1-hydroxy-3,1-isobutyl-5,1-propylphenyl) -5-cyclobenzotriazole Triazole UV absorbers, 2- (2, -hydroxy-3,5, -di-tert-butylphenyl) benzotriazole, 2- (2, -hydroxy-1'-methylphenyl) 2,1-hydrazines such as benzotriazole Benzotriazole-based UV absorbers such as xyphenyl-benzotriazole-based UV absorbers, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 2,2'-dihydroxybenzophenone-based UV absorbers such as', 4,4'-tetrahydroxybenzophenone, and 2 such as 2hydroxy-4-methoxybenzophenone and 2,4dihydroxybenzophenone. Benzophenone ultraviolet absorbers such as hydroxybenzophenone ultraviolet absorbers, and salicylic ester ultraviolet absorbers such as salicylic acid phenol and 4tert-butyl-fe-rutharicylate are used. In addition, a reactive ultraviolet absorber in which an atatriloyl group or a methacryloyl group is introduced into a benzotriazole skeleton is also used. Among these, benzotriazole-based ultraviolet absorbers are particularly preferred. The amount of these UV absorbers added is usually 0.1 to 5 %.

[0082] The content of the ultraviolet absorber is not particularly limited, but is about 100 to 10,000 ppm by weight, preferably about 500 to 7500 ppm by weight in each layer. The layer to be added is not particularly limited, and can be appropriately set according to the product characteristics.

(Hindered amine light stabilizer)

In order to further prevent deterioration of each layer due to ultraviolet rays and improve weather resistance, it is preferable to add a hindered amine light stabilizer as another weathering agent. For example, bis (2,2,6,6-tetramethyl-4-piberidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4piberidyl) sebacate, etc. No. 4,826,625, and the like. The addition amount of these light stabilizers is not particularly limited, but is usually about 0.1 to 5% by weight based on the resin content.

[0083] When a hindered amine light stabilizer is added, it is preferable not to use a resin containing a chlorine atom in the layers constituting the decorative sheet, including the base sheet, from the viewpoint of improving weather resistance. . For example, when a resin containing a chlorine atom in a molecule such as a salted vinyl alcohol acetate copolymer or a chlorinated polyolefin is used as the binder resin, the chlorine-containing resin is acted upon by ultraviolet light or heat. If hydrogen chloride is generated from the dechlorination reaction from the hydrogen chloride, it reacts with the hindered amine-based light stabilizer to deactivate and inhibit its action, and the effect of the scavenger to improve the weather resistance may not be sufficiently exhibited. Because there is.

[0084] The content of the hindered amine light stabilizer is not particularly limited, but is about 100 to 10,000 ppm by weight, preferably about 500 to 7,500 ppm by weight in each layer. The layer to be added is not particularly limited, and can be appropriately set according to the product characteristics.

[0085] Ma)

The decorative sheet for flooring can be made into a decorative material for flooring by joining with various adherends. The material of the adherend is not particularly limited, and examples thereof include inorganic nonmetal-based, metal-based, wood-based, and plastic-based materials.

[0086] Specifically, for inorganic non-metals, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, silica Non-porcelain kiln for calcium acid, gypsum, gypsum slag, etc. Examples include industrial materials, earthenware, pottery, porcelain, setware, glass, and ceramic materials such as enamel.

[0087] Examples of the metal system include a metal material (metallic steel plate) such as iron, aluminum, and copper.

[0088] Examples of the wood-based material include veneer, plywood, partake board, fiberboard, laminated wood, and the like which also have strength such as cedar, cypress, oak, lauan, and teak.

[0089] Examples of the plastic type include resin materials such as polypropylene, ABS resin, and phenol resin.

[0090] The shape of the adherend is not particularly limited, and may be a flat plate in consideration of installation on a flooring or the like.

[0091] After bonding with the adherend, for example, cutting, processing using a tenoner, provision of V-shaped grooves, chamfering of four sides, and the like may be performed according to the characteristics of the final product.

[0092] 2. Application 2 ffl i ^ t sea! Ffl i t used

The decorative sheet for a flooring material according to Embodiment 2 has a decorative layer, a transparent polyolefin-based resin layer having a thickness of 300 to 500 / zm, and a thickness of 3 to 30 m on a base sheet made of a polyolefin-based resin. It is formed by laminating a transparent surface protective layer at least in order.

FIG. 4 shows a schematic cross-sectional view (an example) of the decorative sheet for flooring according to the second embodiment.

The decorative sheet for flooring 100 is provided with a primer layer 15 on one side of a base sheet 10 (polyolefin-based thermoplastic resin film) made of polyolefin-based resin, and a colored concealment layer 17 on the primer layer 15. The decorative layer 12 (printing layer) composed of the (solid printing layer) and the pattern layer 16 is formed by printing in order, and the transparent polyolefin resin layer 11 is formed on the decorative layer 12 via the transparent adhesive layer 18. Are laminated, and a transparent surface protective layer 14 is formed on the surface of the transparent polyolefin resin layer 11.

[0094] Certain material sheet 10

The base sheet 10 is an olefin-based thermoplastic resin film. Examples of the olefin-based thermoplastic resin include polypropylene resin, polyethylene resin, ethylene propylene copolymer, polyolefin-based resin such as polyolefin-based thermoplastic elastomer resin, polyethylene terephthalate resin, and polyethylene naphthalate resin. , Copolymerized polyester Fats (eg, PET-G resin, which is 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin), polyester resins such as amorphous polyester resin, polyatary resin-tolyl resin, polymethyl Acrylic resin such as metatarylate resin, polychlorinated butyl resin and the like can be used.

[0095] Polyolefin resin film has a good track record in building material applications because of its adhesiveness to the transparent polyolefin resin layer 11, prevention of sheet curl after lamination (because of the tendency to curl when dissimilar materials are laminated). (Durability such as weather resistance, workability such as embossing) are preferable.

[0096] The film 10 may or may not be colored with a known colorant. The thickness of the finolem 10 is 50 μm or more, preferably about 50 to 150 μm, and more preferably 50 to 80 μm. If the thickness of the film is too thin, concealment will be insufficient when concealment is required. The upper limit of the thickness is not particularly limited, but as long as it is 50 m or more, it is preferable that the thickness be as thin as possible. On the other hand, the use of thicker ones leads to higher costs, and those that are easily available are up to 150 m.

[0097] Primer layer

The primer layer 15 is provided for the purpose of improving the adhesiveness between the polyolefin resin layer 11 and the decorative layers such as the picture pattern layer 16 and the colored concealing layer 17 .In the present invention, the primer layer is provided arbitrarily. Do it!

[0098] Examples of the resin forming the primer layer include ester resin, urethane resin, acrylic resin, polycarbonate resin, salted vinyl-vinyl acetate copolymer, polybutyral resin, and nitrocellulose. And the like. These resins may be used alone or in combination to form a coating composition or an ink composition. At the time of formation, it may be formed to a thickness of about 1 to 6 m using a known coating means such as a roll coating method or a gravure printing method.

[0099] Decorative layer 12

FIG. 4 shows a picture pattern layer 16 and a coloring hiding layer 17 as the decorative layer 12. The pattern pattern layer 16 and the color concealment layer 17 can be generally formed on the film 10 using ink by a known printing method such as gravure printing, offset printing, or silk screen printing. In FIG. 4, both the picture pattern layer 16 and the colored concealing layer 17 are shown. Or just one of them.

[0100] Examples of the picture pattern layer 16 include a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric pattern, a character, a symbol, a line drawing, and various abstract patterns. The thickness of the pattern is usually about 1 to 15 / ζπι. The color concealing layer 17 is formed by solid printing with a color ink having concealing properties, and its thickness is usually about 1 to about LO / zm.

[0101] As the ink composition used for the picture pattern layer 16 and the color hiding layer 17, as a vehicle, chlorinated polyolefin such as chlorinated polyethylene or chlorinated polypropylene, polyester, polyurethane, polyacrylic acid, and polyacetic acid, which have an isocyanate and a polyol power One or two or more types of butyl, polychlorinated butyl, chloridized butyl-butyl acetate copolymer, cellulose resin, polyamide resin, etc. are used as a mixture, and pigments, solvents, and various auxiliaries are used. It is possible to use a product obtained by adding the above. In consideration of environmental issues and adhesiveness to the surface to be printed, it is preferable to use one or a mixture of two or more of polyurethane, polyacryl, polyamide resin and the like, which also have polyester and isocyanate and polyol properties.

[0102] Description Polyolefin resin layer 11

For the transparent polyolefin-based resin layer 11, the same polyolefin-based resin used for the above-mentioned polyolefin-based resin film 10 can be used. Above all, from the viewpoint of imparting caster resistance, such as surface physical properties, workability, economy, waste (including incineration), etc. Is desirably a resin having a strength of 70% by weight or more of homopolypropylene. In the present invention, a homopolypropylene having a melting point of 150 to 170 ° C is preferably used. More preferably, a homopolypropylene having a flexural modulus of at least 100 MPa, a tensile yield strength of at least 30 MPa, and a Rockwell hardness of at least 75 is used.

[0103] The homopolypropylene means a homopolymer of a propylene monomer. In addition, the resin may be contained in addition to the homopolypropylene, and the resin is not particularly limited as long as there is no production problem in the process up to the production of the flooring material.

[0104] The melting point is represented by a value measured by JIS K7121, flexural modulus is JIS K7171, tensile yield strength is JIS K 7161, Rockwell hardness is IS K7202.

[0105] The polypropylene used in the present invention can be produced by a known polymerization method, and is commercially available. The trade name is F-704NP: available from Idemitsu Petrochemical Co., Ltd.

In the present invention, the transparent polyolefin resin layer 11 has a thickness of 300 m or more. If the thickness is less than 300 μm, sufficient caster resistance may not be obtained. The upper limit of the thickness is not particularly limited, but is set to be 500 m or less from the viewpoint of productivity and cost. In the present invention, since a transparent resin is used as the polyolefin resin, the presence of the thick polyolefin resin layer 11 in the present invention enhances the transparency, thereby giving the flooring a high-grade appearance. The effect is accompanied.

[0107] Adhesive layer 18

The transparent adhesive layer 18 bonds the film 10 on which the decorative layer 12 is formed and the transparent polyolefin resin layer 11 to each other. Examples of the lamination method with the transparent polyolefin resin layer 11 include a dry lamination method or a wet lamination method with the adhesive layer 18 interposed therebetween, a heat lamination method with or without the interposition of the adhesive layer 18, and a high-frequency lamination method. For example, an extrusion lamination method in which a transparent thermoplastic resin is extruded in a molten state and laminated at the same time can be applied. In the extrusion laminating method, an adhesive resin layer such as an acid-modified olefin resin or olefin- (meth) acrylate copolymer resin as the adhesive layer agent 18 is combined with the resin layer 11. The layers may be formed simultaneously by coextrusion. Prior to the lamination, the surface to be bonded to the resin layer 11 is provided with a surface for facilitating adhesion such as corona discharge, ozone treatment, plasma treatment, ionizing radiation treatment, acid treatment, alkali treatment, and anchor treatment. I'll do it.

[0108] Proof of Commerce

The transparent surface protective layer 14 provided on the surface of the decorative sheet 100 for flooring will be described. The transparent surface protective layer 14 is provided in order to impart surface properties such as scratch resistance, abrasion resistance, water resistance, and stain resistance required for floor decorative materials. The resin forming the surface protective layer 14 may be a curable resin such as a known thermosetting resin or ionizing radiation-curable resin. The thickness of the transparent surface protective layer is 1 to: LOO / zm, preferably 3 to 30 / ζπι. More specifically, the technical matters relating to the surface protective layer described in paragraphs [0031] to [0044] of the specification of Patent Document 1 can be applied as they are to the present invention. Quoted here as part of the book. Preferred in the present invention is an ionizing radiation-curable resin having a high surface hardness and excellent productivity. The

[0109] Recoat resin layer

In providing the surface protective layer 14 made of ionizing radiation-curable resin on the surface of the decorative sheet 100 for flooring, the surface on which the surface protective layer 14 is formed, that is, the surface of the resin layer 11 in the example shown in FIG. It is necessary to ensure sufficient adhesion between the surface protective layer 14 made of ionizing radiation curable resin. For this purpose, the surface of the resin layer 11 is subjected to a surface activation treatment such as a corona discharge treatment or an ozone treatment, or the thermoplastic resin constituting the resin layer 11 and the surface protective layer 14 are formed. It is desirable to provide a recoatable resin layer on the surface of the resin layer 11 in which the resin composition has excellent adhesiveness to both the ionizing radiation-curable resin and the resin composition.

[0110] As the recoatable resin layer, for example, thermosetting resins such as urethane resin, epoxy resin, phenol resin, urea resin, alkyd resin, and polyester resin are preferable. Among them, it is most preferable to use a two-part curable urethane resin prepared by mixing a polyol and an isocyanate. As the polyol conjugate, for example, an acrylic polyol compound, a polyether polyol compound, a polyester polyol compound, etc. can be used. Among them, adhesion and internal aggregation with thermoplastic resin and ionizing radiation-curable resin are particularly preferable. From the viewpoint of balance with force, it is most desirable to use a polyester polyol.

[0111] The coating amount of the recoatable resin layer is preferably about 0.1 to 2.0 m after drying. Examples of the method for forming the recoatable resin layer include various conventionally known coating methods such as a gravure coating method, a microgravure coating method, a roll coating method, a knife coating method, an air knife coating method, a lip coating method, and a die coating method. Any construction method can be adopted.

No.

[0112] Adherend material (Taisho certain material 2)

The wood substrate 2 (see FIG. 3) is not particularly limited, and includes, for example, veneer, wood veneer, wood plywood, parttake made of various materials such as cedar, cypress, Ritsu, pine, lauan, teak, and melapy. And medium-density fiberboard (MDF). In addition, from the viewpoint of providing a moisture-proof effect, for example, a moisture-proof layer may be formed on one surface of the wood substrate. [0113] The wooden base material 2 and the decorative sheet for floor material 1 are bonded together to form a decorative material for floor. The method of attaching or laminating the decorative sheet for flooring to the wooden substrate is not limited, and for example, a method of attaching the decorative sheet to the substrate with an adhesive can be employed.

[0114] The adhesive may be appropriately selected from known adhesives according to the type of the base material and the like. Examples include polyacetate, polyvinyl chloride, vinyl chloride'butyl acetate copolymer, ethylene'acrylic acid copolymer, ionomers, butadiene'acryl-tolyl rubber, neoprene rubber, natural rubber and the like.

[0115] From the viewpoint of improving the adhesion between the wooden base material 2 and the decorative sheet 1 for flooring, a primer layer is provided on the other surface (rear surface) opposite to the surface protective layer side of the decorative sheet of the present invention. May be provided. The above description regarding the primer layer (15) can be similarly applied to the back primer layer. In this case, a filler such as silica or barium sulfate may be added for the purpose of preventing blocking.

[0116] The decorative sheet for flooring of the present invention is a flooring that has excellent scratch resistance on the surface and excellent caster resistance without forming a conventionally provided knocker on the back surface of the resin film 10. And

The invention's effect

[0117] The decorative sheet for flooring of the present invention exhibits good scratch resistance, caster resistance, impact resistance and the like even without a knocker layer. Such a decorative sheet for flooring can be a highly useful flooring decorative material by being attached to an adherend.

[0118] The decorative sheet for flooring of the present invention does not require the formation of a packer layer, so that the production process can be simplified and the production loss caused by the conventional packer layer formation process can be eliminated. .

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view of a decorative sheet for flooring produced in Example 1.

FIG. 2 is a schematic cross-sectional view of the decorative floor material manufactured in Example 1.

FIG. 3 is a schematic sectional view of a floor decorative material according to the present invention.

FIG. 4 is a schematic sectional view of a decorative sheet for flooring of the present invention (particularly, Embodiment 2).

FIG. 5 is a schematic configuration diagram of a caster resistance tester. Explanation of reference numerals

A Embossed uneven pattern

B Transparent surface protective layer

C Transparent polyolefin resin layer

D Transparent adhesive layer

E Pattern layer

F Polyolefin resin base material

G Backside primer layer

H V-shaped groove

I Decorative sheet for flooring

J adhesive layer

κ wood substrate

1 Decorative sheets for flooring

2 Wood substrate

10 Polyolefin resin film

11 Transparent polyolefin resin layer

12 Decoration layer (print layer)

14 Transparent surface protective layer

15 Primer layer

16 Picture layer

17 Color hiding layer

18 Transparent adhesive layer

100 Decorative sheet for flooring

1000 Caster resistance test equipment

1001 weight

1002 Load section

1003 Adjustment handle

1010 Caster fixing base 1011 casters

1012 samples

1013 Sample holder

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

[0122] Details

(Production of decorative sheet for flooring)

A 60 μm-thick colored polypropylene film having both surfaces subjected to corona discharge treatment was prepared as a base sheet F. Gravure printing of a solution of urethane-cellulose resin (resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of a mixture of urethane and nitrified cotton) on one side of base sheet F Coating was performed by a method so that the solid content was ² gZm ² to form a backside primer layer G.

[0123] An acrylic urethane resin (a resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of acrylic polyol) on the opposite side to the surface on which the backside primer layer G is formed. The solution was applied by gravure printing so as to have a solid content of ² gZm ² to form a printing primer layer (not shown).

[0124] An acrylic urethane resin (resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of acrylic polyol) on a printing primer layer (not shown). A 2 m-thick colored concealing layer (not shown) and a 4 μm grain pattern layer E were formed by a gravure printing method using the solution as a printing ink.

On the [0125] design pattern layer E, a urethane榭脂adhesive solid content was applied E such that 10 g / m ^2, further polypropylene榭脂heated melt extrusion by a T-die extruder, lO A transparent adhesive layer D having a thickness of ^ m and a transparent polypropylene resin layer C having a thickness of 200 µm were formed. The tensile modulus of the resin layer C alone was 1500 MPa, and the resin layer C was substantially formed of only homopolypropylene.

[0126] After applying a corona discharge treatment to the surface of the transparent polypropylene-based resin layer C, an acrylic urethane-based resin (100 parts by weight of hexyl methylene) was applied to the corona discharge-treated surface. A resin (resin) solution containing 5 parts by weight of diisocyanate was applied by gravure printing so that the solid content was 1 gZm ² to form a primer layer (not shown) for forming a transparent surface protective layer.

On the [0127] transparent surface protective layer forming a primer layer (not shown), a urethane Atari rate based electron beam curing榭脂solids and the coating 'dry so that 15GZm ² by a roll coating method Thus, an uncured electron beam-curable resin layer was formed. Then, in an environment with an oxygen concentration of 200 ppm, the uncured resin layer is irradiated with an electron beam under the conditions of an accelerating voltage of 125 KeV and 5 Mrad to cure the resin. A protective surface protective layer B) was formed.

[0128] Next, a 50 m-deep woodgrain-like irregular pattern A was formed on the transparent surface protective layer B by embossing.

[0129] Through the above process, a decorative sheet for flooring was produced.

(Preparation of floor cosmetics)

The primer layer on the back side of the decorative sheet I for flooring material obtained above is coated with a water-soluble urethane-modified ethylene 'vinyl acetate-based emulsion adhesive layer J of about 4 m thick J

It was stuck to K to produce a laminated plywood.

[0130] After cutting the laminated plywood to a predetermined size (1 x 6), the four sides were cut using a tenoner, and the V-shape of the depth reaching the transparent surface protection layer Karaura plywood was obtained. The groove H was formed in the long direction and the short direction. In addition, the long side surfaces of the laminated plywood were chamfered.

[0131] After applying a water-based two-component curable urethane-based coloring paint to the V-shaped groove and chamfered portion

And a wiping treatment.

[0132] Through the above process, a floor decorative material was produced.

Examples 2 to 3 and Comparative Example 1

A floor decorative material was produced in the same manner as in Example 1, except that the thickness of the transparent polypropylene resin layer was changed as shown in Table 1 below.

[Table 1] Thickness of transparent polypropylene resin layer (m)

Example 2 3 0 0

Example 3 4 0 0

Comparative Example 1 8 0

[0135] Test example 1

An impact resistance test was performed on the decorative floor materials produced in Examples 1 to 4 and Comparative Example 1. Specifically, two types of impact resistance tests, a Dupont type and a falling ball type (based on JIS K5600-5-3), were performed. The impact resistance test was performed on portions other than the grooves, avoiding the V-shaped grooves formed on the floor covering material. The results are shown in Table 2 below.

[Table 2]

[0137] In the case of floor decorative materials, the strength depends on the specific use of the decorative material. In general, in the DuPont type and ball drop type impact resistance tests, if the dent amount is 400 m or less, the impact resistance Can be fully exhibited.

[0138] Participant test example 1

In the same manner as in Test Example 1, two types of impact resistance tests of a Dubon type and a falling ball type were performed on a conventional floor covering decorative material having a knocker layer.

[0139] The conventional floor covering material is a 400-μm-thick amorphous polyethylene terephthalate (A-PET) packer on the back side of the decorative sheet of Comparative Example 1 with a polyester urethane adhesive. The laminate was produced by laminating the A-PET surface of the laminate and a 12 mm thick Rawan plywood via a water-soluble urethane-modified ethylene'butyl acetate-based emulsion adhesive layer.

[0140] The test results are shown in Table 3 below.

[0141] [Table 3] Depression amount of floor cosmetics (m)

Avon type Falling ball type

Conventional product 2 7 0 2 6 0

[0142] Ornament IA

One side of a 60 μm-thick colored polypropylene film treated with corona discharge on both sides is provided with a 2 m-thick two-component curable urethane-based primer layer and the other surface is a two-component curable urethane-based primer layer and acrylic urethane A wood-grained printing layer was formed with a system printing ink.

Next, a transparent homopolypropylene resin (melting point: 170 ° C.) having a flexural modulus of 1500 MPa, a tensile yield strength of 38 MPa, and a Rockwell hardness of 80 was melted on a urethane-based adhesive using a T-die extruder. A laminate was prepared by extruding the thermoplastic polypropylene resin layer to a thickness of 300 / zm.

[0144] A urethane-based primer layer having a thickness of 2 µm was formed on the transparent homopolypropylene resin surface of the laminate. On the urethane-based primer layer, an ionizing radiation-curable resin was dried by a gravure reverse coating method, applied to a thickness of 15 πι, and dried to form an uncured ionizing radiation-curable resin layer. The uncured radiation-curable resin layer is cured by irradiating it with an electron beam (acceleration voltage: 175 keV, irradiation amount: 5 Mrad) in an environment with an oxygen concentration of 200 PPM or less. A protective layer was formed, and embossing was performed from the surface protective layer side with a wood-pipe-shaped embossing plate having a depth of 50 μm to form a wood-pipe-shaped irregular pattern. A decorative sheet was prepared as described above.

[0145] Example B

A transparent homopolypropylene resin (melting point: 170 ° C) with a flexural modulus of 1500 MPa, a tensile yield strength of 38 MPa, and a Rockwell hardness of 80 (melting point: 170 ° C) is applied to the wood-grained printed layer with a urethane-based adhesive to a thickness of 400 using a T-die extruder. A decorative sheet of the present invention was produced in the same manner as in Example A, except that a laminate was produced by extruding to / zm.

[0146] Comparative example A

A transparent random polypropylene resin with a flexural modulus of 600 MPa, a tensile yield strength of 26 MPa, and a Rockwell hardness of 72 (melting point: 145 ° C) on a wood-grained printed layer via a urethane adhesive ) Was extruded with a die extruder to a thickness of 300 m to produce a laminate, in the same manner as in Example A, except that a laminate was produced.

[0147] The random polypropylene resin used in this comparative example is a random copolymer of ethylene and propylene.

[0148] Comparative example B

A transparent homopolypropylene resin (melting point: 170 ° C) with a flexural modulus of 1500 MPa, tensile yield strength of 38 MPa, and Rockwell hardness of 80 (melting point: 170 ° C) is applied on a wood-grained printed layer with a urethane adhesive to a thickness of 200 using a T-die extruder. A decorative sheet as a comparative example was produced in the same manner as in Example A, except that a laminate was produced by extruding to / zm.

[0149] Comparative Example C

Flexural modulus 1500MPa, Tensile yield strength 38MPa, Rockwell hardness 80, transparent homopolypropylene resin (melting point 170 ° C) 50% by weight, flexural modulus 600MPa, tension on urethane-based adhesive on wood-grained printed layer A laminated layer is formed by extruding a resin layer containing 50% by weight of transparent random polypropylene resin with a yield strength of 26 MPa and a Rockwell hardness of 72 (melting point: 145 ° C) to a thickness of 400 / zm using a T-die extruder. A decorative sheet as a comparative example was produced in the same manner as in Example A except that the decorative sheet was produced.

[0150] Reporting Law

Using a 12 mm thick rawan plywood as a wood substrate, the decorative sheets for flooring obtained in Examples A and B and Comparative Examples A to C were laminated via a water-soluble urethane-based emulsion adhesive. Affixed to a wood substrate to produce a floor decorative material.

[0151] Evaluation (caster resistance)

For the flooring material obtained using the decorative sheets obtained in Examples A and B and Comparative Examples A to C, the caster resistance was measured using a caster resistance tester L6-04 (manufactured by Asano Machine Co., Ltd.). Was evaluated using

[0152] Fig. 5 shows a schematic configuration diagram of the caster resistance test apparatus L6-04. The caster-resistant tester 1000 has a weight part 1002 that can change the load with a weight 1001, an adjustment handle 1003, a rotatable caster fixing base 1010 (fixing base: diameter 320 mm, caster mounting part diameter: 260 mm), and Equal intervals on caster fixing base (Equivalent triangle inside circular fixing base It is equipped with three casters 1011 attached to the apex position at the time of drawing, and a sample holder 1013 (80 cm in diameter and 80 mm in thickness) (made of acrylic). The caster used was 420SA-N (wheel: nylon) (average diameter 75 mm, thickness 25 mm) obtained from HANMMER CASTER.

[0153] A floor material (sample) (30cm x 30cm) to be tested is fixed to a sample fixing base 1013, a 30kg weight 1001 is put on the weighted portion 1002, and an adjustment nozzle 1003 is used to adjust the floor material on the decorative layer side of the floor material. Three casters 1011 were brought into contact with the surface (total load 70 kgZm ² ), and the caster fixing base 1010 was operated, and was rotated counterclockwise every 20 minutes at a speed of 20 rpm to make 1000 rotations.

[0154] The caster resistance was evaluated based on the presence or absence of cracks generated on the floor material surface, and ranked as follows.

[0155] 〇: Depression depth is less than 70 m

△: Depression depth is 70 μm or more and less than 100 μm

： Dent depth 100 111 or more

[0156] [Table 4]

[0157] It should be noted that caster resistance can be evaluated with other test machines as long as the evaluation can be made equivalent to L6-04 (manufactured by Asano Machine Co., Ltd.).

Claims

The scope of the claims

[I] A decorative material for flooring, in which a decorative layer, a transparent polyolefin resin layer having a thickness of 150 to 500 m, and a transparent surface protective layer are laminated at least in order on a base sheet made of polyolefin resin. Sheet.

[2] On a base sheet made of polyolefin resin, a pattern layer, a transparent adhesive layer, a transparent polypropylene resin layer 150 to 500 m thick, and a transparent resin made of ionizing radiation-curable resin The decorative sheet for flooring according to claim 1, wherein the functional surface protective layer is laminated at least in order.

[3] The decorative sheet for flooring according to claim 2, wherein the transparent polypropylene-based resin layer contains homopolypropylene, and the resin layer alone has a tensile modulus of at least 100 MPa.

[4] The decorative sheet for flooring according to claim 2, wherein a colored concealing layer is further laminated between the base sheet and the pattern layer.

[5] The decorative sheet for flooring according to claim 2, wherein irregularities are formed on the front surface of the transparent surface protective layer.

[6] At least a decorative layer, a transparent polyolefin resin layer having a thickness of 300 to 500 m, and a transparent surface protective layer having a thickness of 3 to 30 m are provided on a base sheet made of polyolefin resin at least in order. The decorative sheet for flooring according to claim 1, wherein the decorative sheet is laminated.

[7] The polyolefin resin of the transparent polyolefin resin layer is homopolypropylene

The decorative sheet for flooring according to claim 6,

[8] The decorative sheet for flooring according to claim 6, wherein the polyolefin resin in the transparent polyolefin resin layer has a homopolypropylene strength of 70% by weight or more.

[9] The decorative sheet for flooring according to claim 6, wherein the homopolypropylene has a melting point of 150 to 170 ° C.

[10] The decorative sheet for flooring according to claim 6, wherein the base sheet made of polyolefin resin is a polypropylene resin film or a polyethylene resin film.

[II] A floor decorative material, wherein the decorative sheet for floor material according to claim 2 or 6 is adhered to an adherend on a base sheet side.