JP2014062452A - Decorative material for floor material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material for a floor material which is excellent in smoothness and dent resistance.SOLUTION: In a decorative material for a floor material which is formed by laminating a decorative layer, formed by laminating a synthetic resin layer, a substrate sheet, a picture pattern layer, a transparent resin layer, and a transparent surface protective layer in this order, on a wood substrate so that the synthetic resin layer comes into contact with the wood substrate, (1) at least one selected from the group consisting of the substrate sheet and the transparent resin layer has a tensile elastic modulus, measured according to JIS K6734, of 1,000 MPa or less, and (2) the synthetic resin layer has a thickness of 50-210 μm and has a tensile elastic modulus, measured according to JIS K6734, of 1,000-2,500 MPa.

Description

  The present invention relates to a decorative material for flooring.

  Conventionally, a polyvinyl chloride resin sheet is frequently used as a constituent material of a decorative sheet for resin flooring. As a manufacturing method of a polyvinyl chloride resin sheet, there is a method of adding a plasticizer to a polyvinyl chloride resin (Patent Document 1). In the case of using a sheet, there is an advantage that the polyvinyl chloride resin sheet hardness (hard to soft) can be easily adjusted and the embossing can be easily performed by adjusting the addition amount of the plasticizer.

  However, polyvinyl chloride resin may release harmful graphite and chlorine-based gas during incineration. In recent years, instead of polyvinyl chloride resin, polyolefin resin that does not release chlorine gas during incineration has come to be used.

  By the way, the decorative material for flooring is mainly required to have smoothness and dent resistance.

  In order to improve the smoothness of the decorative material for flooring, a decorative layer having high hardness has been conventionally used. However, a decorative layer with high hardness has a problem that cracks and dents are likely to occur due to impact, for example, that is, the dent scratch resistance is insufficient.

JP 2004-019343 A

  The main object of the present invention is to provide a decorative material for flooring that is excellent in smoothness and dent resistance.

  As a result of intensive studies, the present inventor has found that the above object can be achieved by using a specific decorative layer, and has completed the present invention.

  That is, the present invention relates to the following decorative material for flooring.

JIS described in this specification refers to Japanese Industrial Standards.
1. Synthetic resin layer, base material sheet, pattern layer, transparent adhesive layer, transparent resin layer and transparent surface protective layer are laminated in order. A flooring decorative material laminated on a base material,
(1) At least one selected from the group consisting of a base sheet and a transparent resin layer has a tensile elastic modulus of 1000 MPa or less in accordance with JIS K6734,
(2) The synthetic resin layer has a tensile elastic modulus of 1000 MPa or more in accordance with JIS K6734.
Cosmetics for flooring.
2. The decorative material for flooring according to claim 1, wherein at least one layer selected from the group consisting of a synthetic resin layer, a base sheet and a transparent resin layer contains a polyolefin-based resin as a resin component.
3. The decorative material for flooring according to claim 1, wherein the synthetic resin layer contains a crystallization nucleating agent.
4). Item 2. The flooring decorative material according to Item 1, wherein the decorative layer has a thickness of 200 to 300 µm.

  The decorative material for flooring of the present invention is excellent in smoothness and dent resistance.

  Moreover, the decorative material for flooring of the present invention has excellent smoothness and dent resistance even when the thickness of the decorative layer is 300 μm or less. Since a decorative layer having a thickness of 300 μm or less can be easily cut, the decorative material for flooring of the present invention can be mass-produced by continuous lamination. Furthermore, in the decorative material for flooring of the present invention, by setting the thickness of the decorative layer to 200 μm or more, water resistance can be imparted in addition to smoothness and dent resistance.

  The decorative material for flooring of the present invention comprises a synthetic resin layer, a base sheet, a pattern layer, a transparent adhesive layer, a transparent resin layer, and a transparent surface protective layer, which are laminated in order. A flooring decorative material laminated on a wooden substrate so that the layer is in contact with the wooden substrate, wherein (1) at least one selected from the group consisting of a substrate sheet and a transparent resin layer is JIS It has a tensile elastic modulus of 1000 MPa or less in accordance with K6734, and (2) the synthetic resin layer has a tensile elastic modulus of 1500 MPa or more in conformity with JIS K6734.

  According to the present invention, when at least one selected from the group consisting of a base sheet and a transparent resin layer in a decorative layer has a tensile elastic modulus of 1000 MPa or less in accordance with JIS K6734, Cracks can be effectively prevented. That is, excellent dent resistance can be imparted to the decorative material for flooring. In particular, the tensile elastic modulus according to JIS K6734 of at least one of the base sheet and the transparent resin layer is preferably 600 to 1000 MPa.

  Moreover, according to this invention, smoothness can be improved by providing a synthetic resin layer between a wooden base material and a base material sheet. And according to the said synthetic resin layer, the dent of the decorative material for flooring by the impact from the outside can be prevented effectively. That is, the synthetic resin layer can further improve the dent resistance. In particular, in the present invention, by setting the tensile elastic modulus of the synthetic resin layer to 1000 MPa or more, excellent smoothness and dent resistance can be imparted to the flooring decorative material. The tensile elastic modulus according to JIS K6734 of the synthetic resin layer is desirably 1500 MPa or more, and more desirably 1500 to 2500 MPa.

  In addition, the tensile elasticity modulus in this specification is a value measured in accordance with the provisions of JIS K6734 “Plastics—Hard Polyvinyl Chloride Sheet—Dimensions and Properties—Part 2: Sheet with a Thickness of Less than 1 mm”.

  Specifically, using a tensile tester (Tensilon universal tester RTC-1250A), a test sample punched into the shape of FIG. 2 (synthetic resin layer, and selected from the group consisting of a base sheet and a transparent resin layer) When the both ends (A and B in FIG. 2) are pulled at a speed of 50 mm / min., The tensile elastic modulus (MPa) is measured when the test sample is cut at the central portion. It is the value obtained by doing.

  As described above, the decorative material for flooring of the present invention is one in which the tensile modulus of elasticity of at least one layer selected from the group consisting of a base sheet and a transparent resin layer and the synthetic resin layer is set within a specific range. It is. In order to suitably set the tensile elastic modulus of these layers within the above range, the decorative material for flooring of the present invention is at least one layer selected from the group consisting of a synthetic resin layer, a base sheet and a transparent resin layer. However, it is preferable that polyolefin resin is included as a resin component. In particular, the synthetic resin layer can easily have a tensile elastic modulus of 1000 MPa or more by further including a crystallization nucleating agent.

  Here, the crystallization nucleating agent is a resin component for forming a synthetic resin layer. The crystallization nucleating agent is uniformly finely dispersed in the resin composition to form crystal nuclei that serve as a starting point for crystallization. An additive that promotes crystallization. When the synthetic resin layer contains a crystallization nucleating agent, uniform and fine crystals are generated in the synthetic resin layer, so that the crystallinity of the synthetic resin layer is increased and the tensile modulus, thermal deformation temperature, etc. Optical properties such as mechanical properties and transparency are improved.

  Moreover, it is preferable that the thickness of the decorative layer in the decorative material for flooring of this invention is 200-300 micrometers.

  By making the thickness of the decorative layer 300 μm or less, the decorative layer can be easily cut, which facilitates mass production. That is, the decorative material for flooring of the present invention can be produced by a method of continuously laminating a decorative layer on a wooden base material and then cutting the decorative layer according to the size of the wooden base material.

  Moreover, by making the thickness of the decorative layer 200 μm or more, in addition to smoothness and dent scratch resistance, excellent water resistance can be imparted to the decorative material for flooring.

  Hereinafter, the flooring decorative material will be described as an example.

Synthetic resin layer The smoothness of the decorative material for flooring can be improved by interposing the synthetic resin layer between the woody base material and the base material sheet.

  The synthetic resin layer preferably contains a polyolefin resin as a resin component.

  Examples of the polyolefin-based resin include polyethylene (high density polyethylene, medium density polyethylene, low density polyethylene), polypropylene, and the like. These can be used alone or in combination of two or more. Among these, polypropylene is particularly preferable. Examples of polypropylene include homopolypropylene, random polypropylene, and block polypropylene. Of these, homopolypropylene is particularly desirable.

  In addition, a resin component other than the polyolefin resin may be used as the resin component of the synthetic resin layer. For example, vinyl chloride resin, polystyrene, polyamide resin, polyimide resin, polyamideimide resin, fluorine resin, urethane resin, polysulfone, polycarbonate, polyacetal, polyphenylene ether, methacrylic resin, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, polyethylene naphthalate (PEN) , Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate, amorphous polyethylene terephthalate (so-called A-PET) [Mitsubishi Chemical Corporation: Novaclear (trade name)], polyethylene terephthalate copolymer (PETG) Etc. Among these, A-PET is particularly preferable. A-PET is desirably used together with PEN for the purpose of imparting heat resistance.

  The content of the polyolefin-based resin in the synthetic resin layer is preferably 90 to 100% by weight, and more preferably 95 to 100% by weight.

  The synthetic resin layer preferably contains a crystallization nucleating agent. By including a crystallization nucleating agent, the tensile elastic modulus of the synthetic resin layer can be further improved. Examples of the crystallization nucleating agent include bis (p-methylbenzylidene) sorbitol, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, rosin metal salt, and rosin derivative metal salt. A metal salt of benzoic acid or the like can be used. Examples of the metal salt of rosin, metal salt of rosin derivative and metal salt of benzoic acid include sodium salt, copper salt, zinc salt and the like. These crystallization nucleating agents can be used singly or in combination. In particular, in the present invention, the crystallization nucleating agent is at least one selected from the group consisting of bis (p-methylbenzylidene) sorbitol and 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate. It is preferable to use seeds. The content of the crystallization nucleating agent may be appropriately set so that the tensile elastic modulus based on JIS K6734 of the synthetic resin layer is 1000 MPa or more, but with respect to 100 parts by weight of the resin component of the synthetic resin layer, Usually 0.05 to 0.4 parts by weight, preferably 0.1 to 0.3 parts by weight.

  The synthetic resin layer may be formed by laminating a resin composition containing the resin component and the like on a base sheet by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like. Moreover, you may use a preformed film as the said synthetic resin layer.

  The thickness of the synthetic resin layer is not particularly limited, and is usually about 50 to 210 μm, preferably about 100 to 200 μm.

Although it does not specifically limit as a base material sheet Base film, The film containing polyolefin resin as a resin component is preferable from the point which can set the tensile elasticity modulus based on JISK6734 to 1000 Mpa or less easily. 90-100 weight% is preferable and, as for content of polyolefin resin in a base material sheet, 95-100 weight% is more preferable.

  The polyolefin resin is not particularly limited, and those usually used in the field of decorative sheets can be used. For example, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Is mentioned. These can be used alone or in combination of two or more. Among these, polypropylene, polyolefin-based thermoplastic elastomers and the like are particularly preferable.

  The polyolefin resin is preferably a homopolymer or a copolymer mainly composed of polypropylene. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a copolymer of a crystalline part of polypropylene and an α-olefin having 2 to 20 carbon atoms other than propylene can be given. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferable.

  The polyolefin-based thermoplastic elastomer is a block polymer having a highly crystalline and high melting point aromatic polyester as a hard segment and an amorphous polyether having a glass transition temperature of −70 ° C. or less as a soft segment. In particular, an elastomer obtained by mixing a hard segment made of isotactic polypropylene and a soft segment made of atactic polypropylene at a weight ratio of 80:20 is preferable.

  A well-known additive may be mix | blended with a base material sheet as needed. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, and a colorant (see below). These can be used alone or in combination of two or more. About the compounding quantity of the said additive, it can set suitably according to a product characteristic.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Organic pigments (including dyes) such as blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. These can be used alone or in combination of two or more. The coloring mode of the base sheet includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of the adherend (base material to which the decorative sheet is bonded) is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend visible, transparent coloring may be selected.

  The base sheet is obtained by forming a resin composition containing the resin component or the like into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

  The thickness of the said base material sheet is not specifically limited, Usually, 50-150 micrometers, Preferably it is about 60-80 micrometers.

  One or both surfaces of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface may be 35 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  On one side or both sides of the base sheet, a primer layer (for example, a back surface primer layer for facilitating adhesion of the adherend, a primer layer for facilitating the formation of the pattern layer) is provided as necessary. It may be provided. By providing the primer layer, interlayer adhesion with an adjacent layer (for example, an adherend) can be increased.

  A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. Examples of the primer agent include a urethane resin primer agent made of acrylic modified urethane resin, a primer agent made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), and the like. Is mentioned. These can be used alone or in combination of two or more.

Although the application amount of the primer agent is not particularly limited, it is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

You may form an adhesive bond layer in the base material sheet sticking surface of an adhesive bond synthetic resin layer as needed.

  It does not specifically limit as an adhesive agent, For example, a polyamide resin, an acrylic resin, a vinyl acetate resin, a urethane resin etc. are mentioned. These can be used alone or in combination of two or more. The adhesive layer can be formed, for example, by applying an adhesive on the synthetic resin layer, applying a resin constituting the adhesive layer, and drying and curing. Conditions such as drying temperature and drying time are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

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

A primer layer may be formed on the wood base material sticking surface of the primer layer synthetic resin layer as necessary. The primer layer can be formed by applying a known primer agent.

  Examples of the primer agent include a urethane resin primer agent made of acrylic modified urethane resin, a primer agent made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), and the like. Is mentioned. These can be used alone or in combination of two or more.

Although the application amount of the primer agent is not particularly limited, it is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

A design pattern layer is formed on the design pattern layer base sheet (opposite to the wood base material attachment surface, hereinafter the same side in each layer).

  The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The method for forming the pattern layer is not particularly limited. For example, a colored ink or coating 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 by the printing method etc. which used the agent etc.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and 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 further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These resins can be used alone or in admixture of two or more.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Inorganic solvents and the like, such as water; chlorinated organic solvents. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  Examples of the printing method used for forming the 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.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate 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.

A colored concealment layer may be further formed between the colored concealment layer base sheet and the pattern layer, if necessary. The colored masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. Of course, when the base sheet is transparent, even when the base sheet is concealed, it may be formed to stabilize the concealment.

  As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used.

  The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). For example, the 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 described above are preferable.

  The thickness of the colored concealing layer is not particularly limited and can be set as appropriate according to the product characteristics. The layer thickness during coating is about 0.2 to 10 μm, and the layer thickness after drying is about 0.1 to 5 μm.

Transparent 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 transparent and colorless, colored and translucent. This adhesive layer is formed in order to bond the pattern layer and the transparent resin layer.

  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 the adhesive 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. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied. These can be used alone or in combination of two or more. As the two-component curable polyurethane resin, the same ones as the two-component curable polyurethane resin described in the item of the transparent surface protective layer below can be used.

  The transparent adhesive layer can be formed, for example, by applying an adhesive on the pattern layer, applying a resin constituting the transparent resin layer, and drying and curing. Conditions such as drying temperature and drying time are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

  Although the thickness of a transparent adhesive bond layer is not specifically limited, The thickness after drying is 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.

  Although it does not specifically limit as a transparent resin layer, The resin layer which contains polyolefin resin as a resin component from the point which can set the tensile elasticity modulus based on JISK6734 to 1000 Mpa or less is preferable.

  As the polyolefin resin, the same resins as the polyolefin resin can be used.

  90-100 weight% is preferable and, as for content of the said polyolefin resin in the said transparent resin layer, 95-100 weight% is more preferable.

  The thickness of the transparent resin layer is usually about 40 to 250 μm, preferably about 60 to 100 μm.

  The transparent resin layer may be obtained by laminating a resin composition containing the above resin component or the like on the transparent adhesive layer by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like. It may be used.

  On the surface of the transparent resin layer, on which the transparent surface protective layer described later is formed, the surface of corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, etc., as necessary Processing may be performed. The surface treatment may be performed according to a conventional method for each treatment.

  Moreover, you may provide a primer layer (primer layer for making formation of a surface protective layer easy) on the surface as needed.

  The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. Examples of the primer agent include a urethane resin-based primer agent composed of an acrylic-modified urethane resin and the like, and a resin-based primer agent composed of a block copolymer of acrylic and urethane.

Although the application amount of the primer agent is not particularly limited, it is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

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

  Although it does not specifically limit as a material used for a transparent surface protective layer, In this invention, it is desirable to use a two-component curable polyurethane resin. The two-component curable polyurethane resin is not particularly limited as long as it has a polyol as a main component and an isocyanate as a curing agent.

  The polyol and isocyanate used in the two-part curable polyurethane resin are not limited, but the polyol includes polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate having two or more hydroxyl groups in the molecule. A polyol etc. are mentioned. Isocyanates include aliphatic or alicyclic isocyanates. Examples of the alicyclic isocyanate include IPDI (isophorone diisocyanate), hydrogenated MDI (hydrogenated diphenylmethane diisocyanate), and the like. Examples of the aliphatic isocyanate include 1,6-hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate.

  The transparent surface protective layer is desirably formed of an aqueous composition in that the effect of reducing VOC and the like is further enhanced. As the aqueous composition, a composition containing an aqueous binder can be used. The aqueous binder may be in any form such as an aqueous resin solution or an aqueous resin emulsion. The resin used for these can use the thing similar to the aqueous | water-based binder of the aqueous composition used for formation of the said pattern layer.

  In the present invention, an ionizing radiation curable resin can also be used as the transparent surface protective layer. When an ionizing radiation curable resin is used, more excellent scratch resistance, weather resistance and the like can be obtained.

  A well-known thing or a commercial item can be used for ionizing radiation curable resin. 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, for example, methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, urethane acrylates, polyester acrylate, polyether acrylate, urethane acrylate, polyol acrylate, There are acrylates such as melamine acrylate.

  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, methacrylic acid esters such as 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- Dibenzylamino) methyl, acrylic acid-2- (N, N-diethylamino) propyl, and the like.

  Other unsaturated 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, triethylene Compounds such as glycol diacrylate, polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, and / or polythiol compounds having two or more thiol groups in the molecule For example, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropiolate, dipen There is pentaerythritol tetra thio glycol, and the like. Examples of the acrylate monomer having three or more functional groups include trimethylolpropane triacrylate, pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

  Although the formation method of the transparent surface protection layer by ionizing radiation curable resin is not limited, For example, it can form by irradiating ionizing radiation to the coating film of the composition (paint) containing ionizing radiation curable resin. The ionizing radiation may be any ionizing radiation curable resin contained in the paint and any energy that can act on the radical photopolymerization initiator / sensitizer as an additive to initiate a radical polymerization reaction. And electromagnetic waves such as γ rays. Among these, the electron beam is most practical from the viewpoint of the curing ability of the coating film and the simplicity of the irradiation device. In the case of electron beam irradiation, for example, the film may be crosslinked and cured by electron beam irradiation under conditions of 175 keV and 5 Mrad (50 kGy). In the case where the transparent surface protective layer is formed of an ionizing radiation curable resin, it is desirable to previously provide a primer layer (particularly a primer layer of urethane resin) on the transparent resin layer as a base.

  Although the thickness of a transparent protective layer is not limited, Usually, it is desirable to set it as 0.1-50 micrometers, especially 1-20 micrometers.

Weathering agent At least one of the layers constituting the decorative layer of the present invention may contain a weathering agent, if necessary. 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 admixture of two or more. For example, when the synthetic resin layer contains polypropylene as a resin component, it is preferable to contain the weathering agent in the synthetic resin layer for the purpose of imparting weather resistance.

  Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a triazine ultraviolet absorber. Although it does not limit as said light stabilizer, For example, a hindered amine light stabilizer can be used suitably.

  The content of the light proofing agent in the layer constituting the decorative layer is not particularly limited. For example, when the ultraviolet absorbent is contained in the synthetic resin layer, the concentration of the ultraviolet absorbent in the resin composition for forming the synthetic resin layer may be set to about 1000 to 10,000 ppm. What is necessary is just to set the density | concentration of the light stabilizer in the resin composition for forming the said synthetic resin layer to about 1000-10000 ppm when making the said synthetic resin layer contain a light stabilizer.

The decorative material for flooring The decorative material for flooring of the present invention can be produced, for example, by continuously laminating the roll-shaped decorative layer on a wooden substrate.

  As a method of laminating a decorative layer on a wooden substrate, for example, by applying an adhesive on the wooden substrate, placing the decorative layer on the coated surface side, and applying pressure from the decorative layer side with a roll, A method of laminating both is preferred. In addition, in the decorative material for flooring of this invention, when an adhesive bond layer is formed on a wooden base material by the application of an adhesive agent, this adhesive bond layer is not included in the concept of the said decorative layer.

  Examples of the wood substrate used in the present invention include veneer, plywood, particle board, fiber board, laminated wood made of cedar, straw, firewood, lauan, teak and the like.

  After lamination, the decorative layer may be cut according to the size of the wooden substrate.

  In addition, the floor covering decorative material of the present invention may be subjected to actual processing of four sides, provision of V-shaped grooves, and the like using a tenoner as necessary. Further, a wiping process may be performed after applying the paint. The paint is not particularly limited, but an aqueous two-component curable urethane-based colored paint is preferable.

  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 layer having the structure shown in FIG. 1 was produced by the following method.

An acrylic-urethane resin (5 parts by weight of hexamethylene diisocyanate is added to 100 parts by weight of an acrylic polyol) on a base sheet 5 made of a colored polypropylene film having a thickness of 60 μm (the tensile elastic modulus of the sheet alone is 600 MPa). The resin) solution was applied by gravure printing so that the solid content was 2 g / m ² to form a printing primer layer (not shown).

  By a gravure printing method using a printing ink with an acrylic-urethane resin (a resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of an acrylic polyol) on a printing primer layer (not shown). A woodgrain pattern layer 4 was formed.

A primer layer (not shown) is formed by applying a urethane-cellulose resin solution on the surface of the base sheet 5 opposite to the pattern layer 4 by a gravure printing method so that the solid content is 2 g / m ^2. did.

  The urethane-cellulose-based resin solution is prepared by adding urethane and nitrified cotton to a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone, and further adding hexamethylene diisocyanate to 5 parts by weight with respect to 100 parts by weight of the mixture of urethane and nitrified cotton. It was prepared by adding a part.

A urethane resin adhesive is applied onto the pattern layer 4 so that the solid content is 8 g / m ² , and a polypropylene resin is heated and melt-extruded by a T-die extruder to obtain a transparent adhesive having a thickness of 8 μm. An agent layer 3 and a transparent resin layer 2 having a thickness of 80 μm were formed. The tensile modulus of the resin layer 2 alone was 600 MPa.

After the corona discharge treatment is applied to the surface of the transparent resin layer 2, an acrylic-urethane resin (resin formed by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of acrylic polyol) is gravure-printed on the corona discharge treatment surface. A primer layer (not shown) for forming a transparent surface protective layer was formed by coating so that the solid content was 1 g / m ² by the method.

On a primer layer (not shown) for forming a transparent surface protective layer, a urethane acrylate electron beam curable resin is applied and dried so as to have a solid content of 15 g / m ² by a roll coating method, and is uncured. The electron beam curable resin layer was formed. Thereafter, 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 acceleration voltage of 125 KeV and 5 Mrad to cure the resin, and a 15 μm thick electron beam curable resin layer (transparent surface protective layer 1 ) Was formed.

  Next, an uneven pattern having a grain conduit shape of 50 μm in depth was formed on the transparent surface protective layer 1 by embossing.

Further, an adhesive layer 6 was formed by applying a urethane resin adhesive to the primer layer (not shown) side of the base sheet 5 so that the solid content was 8 g / m ² . The thickness of the adhesive layer 6 was 8 μm. Subsequently, a synthetic resin layer 7 having a thickness of 120 μm was laminated on the adhesive layer 6 by a dry lamination method. The synthetic resin layer 7 is obtained by heat-melt-extruding a composition containing homopolypropylene, bis (p-methylbenzylidene) sorbitol (crystallization nucleating agent), a triazine ultraviolet absorber and a hindered amine light stabilizer with a T-die extruder. This was produced. The amount of bis (p-methylbenzylidene) sorbitol used was 0.1 parts by weight with respect to 100 parts by weight of homopolypropylene. The amount of the triazine-based ultraviolet absorber used was such that the concentration of the triazine-based ultraviolet absorber in the resin composition was 2000 ppm. Further, the amount of the hindered amine light stabilizer used was such that the concentration of the hindered amine light stabilizer in the resin composition was 1000 ppm.

  The tensile elastic modulus of the synthetic resin layer 7 alone was 1500 MPa.

  The decorative layer was produced by the above process.

  The thickness of the produced decorative layer was 300 μm.

  The decorative layer obtained above was wound up in a roll shape so that the synthetic resin layer 7 side was the lower surface (winding inner side).

  Next, a modified ethylene / vinyl acetate emulsion adhesive was applied onto a 12 mm thick lauan plywood to form an adhesive layer having a thickness of 10 μm.

  Next, a plurality of the lauan plywoods were placed side by side with the adhesive layer side up, and then the decorative layer was continuously laminated on the adhesive layer to prepare a decorative plywood.

  After cutting the decorative layer of the decorative plywood to the size of the lauan plywood, the tenor is used to perform the actual processing of the four sides, and the V-shaped groove with a depth from the transparent surface protective layer to the lauan plywood is elongated. It was formed in the scale direction and the short direction. Moreover, the longitudinal direction side part of the laminated plywood was chamfered.

  A wiping treatment was performed after applying a water-based two-component curable urethane-based colored paint to the V-shaped groove and chamfer.

  Through the above process, a decorative material for flooring was manufactured.

  Table 1 shows the smoothness, dent resistance and water resistance of the resulting decorative material for flooring.

Comparative Example 1
A decorative layer was produced in the same manner as in Example 1 except that the synthetic resin layer 7 was not laminated. The thickness of the decorative layer was 180 μm.

  Using the obtained decorative layer, a flooring decorative material was produced in the same manner as in Example 1.

  Table 1 shows the smoothness, dent resistance and water resistance of the resulting decorative material for flooring.

Comparative Example 2
In the production of the synthetic resin layer 7, a decorative material for flooring is produced in the same manner as in Example 1 except that the composition to be heated and extruded does not contain bis (p-methylbenzylidene) sorbitol (crystallization nucleating agent). did.

  The tensile elastic modulus of the synthetic resin layer 7 alone was 900 MPa.

  Table 1 shows the smoothness, dent resistance and water resistance of the resulting decorative material for flooring.

Test Example 1 (Smoothness)
The smoothness of the decorative layer surface of the decorative material for flooring obtained in Examples and Comparative Examples was confirmed. Specifically, the flooring decorative material is installed so that the light incident on the surface of the flooring decorative material becomes oblique light, and whether or not the unevenness due to the wooden base material and / or the transparent adhesive layer is concealed is visually checked. Was observed.

  The case where the unevenness | corrugation by a wooden base material and / or a transparent adhesive layer was concealed was evaluated as (circle), and the thing where the unevenness | corrugation was not concealed was evaluated as x.

Test example 2 (dentation resistance)
Visual confirmation of the depression of the decorative layer portion when pressing an iron cylinder jig with a diameter of 20 mm inclined at 45 ° with a load of 50 N on the decorative layer portion of the decorative material for flooring obtained in Examples and Comparative Examples did.

  The case where the dent was not conspicuous was evaluated as ◯, and the case where the dent was conspicuous was evaluated as ×.

Test example 3 (water resistance)
A polyethylene ring was fixed to the groove portion of the decorative material for flooring obtained in Examples and Comparative Examples using a sealing material. Tap water was put into the polyethylene ring and left for 144 hours, and then the appearance of the flooring decorative material was visually confirmed.

  The case where there was no change in appearance was evaluated as ◯, and the case where there was no change was evaluated as ×.

1 is a conceptual diagram (cross-sectional view) of a decorative material for flooring produced in Example 1. FIG. FIG. 2 is a top view of a test sample to be measured when measuring the tensile elastic modulus in accordance with the provisions of JIS K6734 “Plastics—Rigid polyvinyl chloride sheet—Dimensions and characteristics—Part 2: Sheet having a thickness of less than 1 mm”. It is.

DESCRIPTION OF SYMBOLS 1 ... Transparent surface protective layer 2 ... Transparent resin layer 3 ... Transparent adhesive layer 4 ... Picture pattern layer 5 ... Base material sheet 6 ... Adhesive layer 7 ...・ Synthetic resin layer 8 ... Primer layer

Claims (4)

A decorative layer formed by laminating a synthetic resin layer, a substrate sheet, a pattern layer, a transparent resin layer, and a transparent surface protective layer in this order is laminated on the wooden substrate so that the synthetic resin layer is in contact with the wooden substrate. It is a decorative material for flooring,
(1) At least one selected from the group consisting of a base sheet and a transparent resin layer has a tensile elastic modulus of 1000 MPa or less in accordance with JIS K6734,
(2) The synthetic resin layer has a thickness of 50 to 210 μm and a tensile elastic modulus of 1000 to 2500 MPa in accordance with JIS K6734.
Cosmetics for flooring.   The decorative material for flooring according to claim 1, wherein at least one layer selected from the group consisting of a synthetic resin layer, a base sheet and a transparent resin layer contains a polyolefin-based resin as a resin component.   The decorative material for flooring according to claim 1, wherein the synthetic resin layer contains a crystallization nucleating agent.   The decorative material for flooring according to claim 1, wherein a transparent adhesive layer is further laminated between the design pattern layer and the transparent resin layer.

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