JP6102989B2 - Floor decorative material - Google Patents

Description

  The present invention relates to a floor decorative material.

  Floor cosmetics (resin floors) with a resin base material used in non-residentials such as stores are used for outer wear and are likely to cause whitening scratches due to sand debris. A further improvement in the scratch resistance of the surface has been desired for flooring decorative materials (Patent Document 1).

  Here, the decorative material for flooring is a structure in which a decorative sheet is laminated on a resin base material. The scratch resistance on the surface of the decorative sheet is not only the physical properties of the decorative sheet itself, but is bonded to the back surface. It has been known that the physical properties of the resin substrate are greatly affected. For example, if the base material is too soft, dent scratches due to the deformation of the base material occur in the surface coating film, and if the base material is too hard, the load concentrates on the surface coating film, resulting in whitening scratches. There was a problem.

Japanese Examined Patent Publication No. 62-52111

  An object of the present invention is to provide a floor decorative material having excellent scratch resistance under high load conditions without deteriorating impact resistance.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have found that a resin base material having a specific tensile elastic modulus and a surface protection having a specific thickness and Martens hardness in a flooring decorative material. It discovered that the said subject could be solved by combining a decorative sheet provided with a layer. The present invention has been completed based on such findings.

That is, this invention relates to the following decorative sheets for floors.
1. It is a decorative material for floors in which a decorative sheet is laminated on a resin base material (a),
(1) The decorative sheet is formed by sequentially laminating at least a base sheet (A), a transparent resin layer, and a surface protective layer, and the base sheet (A) side of the decorative sheet is the resin base (A). It is laminated on the resin base material (a) so as to be located on the side,
(2) The surface protective layer has a layer thickness of 5 to 30 μm and a Martens hardness of 50 to 210 N / mm ² .
(3) the resin base material (A) is Ri tensile modulus 100~1600MPa der measured according to the provisions of JIS K7161,
(4) The base sheet (A) is made of polyvinyl chloride (PVC), polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene (PP), polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer (EVA). ), Ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ionomer, polyacrylic acid ester and polymethacrylic acid ester. And
The transparent resin layer is made of polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer. Formed of at least one thermoplastic resin selected from polymethylpentene, polyacrylic acid ester, polymethacrylic acid ester, polycarbonate and cellulose triacetate,
(5) The resin base material (a) is a single layer,
A decorative material for floors.
2. Item 2. The floor decorative material according to Item 1, wherein the surface protective layer contains an ionizing radiation curable resin.

  The floor decorative material of the present invention deteriorates impact resistance by combining a resin base material having a specific tensile elastic modulus and a decorative sheet having a surface protective layer having a specific layer thickness and Martens hardness. Excellent scratch resistance under high load conditions.

It is a figure which shows the diamond indenter (a) used for the measurement of the Martens hardness in this specification, the schematic diagram (b) of pushing operation, and an example (c) of pushing load and displacement. It is a schematic diagram (top view) which shows the shape of a sample when measuring the tensile elasticity modulus of a sample according to prescription | regulation of JISK7161. In the figure, R60 indicates the degree of curvature. It is a schematic diagram which shows the cross section of the one aspect | mode of the decorative material for floors of this invention.

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

The decorative material for flooring of the present invention is a decorative material for flooring in which a decorative sheet is laminated on the resin base material (a),
(1) The decorative sheet is formed by sequentially laminating at least a base sheet (A), a transparent resin layer, and a surface protective layer, and the base sheet (A) side of the decorative sheet is the resin base (A). It is laminated on the resin base material (a) so as to be located on the side,
(2) The surface protective layer has a layer thickness of 5 to 30 μm and a Martens hardness of 50 to 210 N / mm ² .
(3) The resin base material (a) has a tensile elastic modulus of 100 to 1600 MPa measured according to JIS K7161.
It is characterized by that.

  Hereinafter, each structure of the decorative material for floors of this invention is demonstrated.

Martens hardness The Martens hardness in this specification is a value measured using a surface film physical property tester (PICODENTOR HM-500, manufactured by Fisher Instruments Co., Ltd.). The specific measurement method is as follows. It is.

In this measurement method, using the diamond indenter (Vickers indenter) shown in FIG. 1 (a), the diamond indenter is pushed into the measurement sample as shown in FIG. 1 (b), and the diagonal line of the pyramidal depression formed on the surface is obtained. The surface area A (mm ² ) is calculated from the length of and the hardness is obtained by dividing the test load F (N). As shown in FIG. 1 (c), the indentation condition was that a load of 0 to 5 mN was first applied for 10 seconds, then held at a load of 5 mN for 5 seconds, and finally 5 Unloading to ~ 0mN is performed in 10 seconds. And the hardness calculated | required by F / A based on the surface area A and the test load F is the said Martens hardness (N / mm < ² >).

  In addition, in this specification, in order to avoid the influence of the hardness of layers other than a surface protective layer, the Martens hardness of the cross section of the surface protective layer was measured. In this case, the floor decorative sheet is embedded with a resin (cold-curing type epoxy two-component curable resin), allowed to stand at room temperature for 24 hours or more and then cured, and then the cured embedded sample is mechanically polished to surface. The cross section of the protective layer was exposed, and the Martens hardness of the cross section was measured by pushing a diamond indenter into the cross section (at a position avoiding the fine particles such as filler when the fine particles such as fillers were included in the layer).

Tensile elastic modulus The tensile elastic modulus in this specification is a value measured according to JIS K7161. Specifically, both ends (A and B in FIG. 2) of a test sample (resin base material (A)) punched into the shape shown in FIG. 2 using a tensile tester (Tensilon universal tester RTC-1250A). 50 mm / min. It is the value calculated | required by measuring the tensile elasticity modulus (MPa) at the time of pulling at the speed | rate.

Flooring decorative material In the flooring decorative material of the present invention, a decorative sheet is laminated on a resin base material (a).

Resin base material (A)
If the tensile modulus of the resin base material (a) is too high when a high load is applied, the decorative sheet will be dented together with the resin base material (a) and a dent will be generated. If it is too high, the load is difficult to disperse and whitening scratches are likely to occur, and it is 100 to 1600 MPa, and preferably 400 to 1500 MPa.

  The synthetic resin forming the resin base material (a) is not limited as long as the above-described tensile elastic modulus can be obtained, but a thermoplastic resin is preferable. For example, polypropylene (PP), polyethylene (PE), ethylene-propylene copolymer, polyacrylate ester, polymethacrylate ester, polyurethane, polyvinyl chloride (PVC), polymethylene, polymethylpentene, polyethylene terephthalate (PET), Examples include polybutylene terephthalate, polycarbonate, polyarylate, polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, and ABS. Among these resins, the resin base material (a) can be appropriately selected or used in combination of two or more resins so that the tensile elastic modulus of the resin base material (a) is in the above range.

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

  Various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, light stabilizers, etc., may be added to the resin base material (a). An agent may be included.

  The thickness of the resin base material (a) can be appropriately set depending on the use of the final product, the method of use, etc., but it is preferably 1 mm or more for the expression of scratch resistance and impact resistance, and the resin floor is directly pasted. In order not to pick up unevenness of the base, 2 mm or more is more preferable. The upper limit of the thickness of the resin base material (a) is not particularly limited, but is preferably 6 mm or less in consideration of cost and dimensional stability (gap and push-up).

  The shape of the resin base material (a) is not particularly limited, and may be a flat plate in consideration of installation on a flooring or the like.

  A decorative sheet for flooring described below is manufactured by laminating (stacking) a decorative sheet described below on such a resin base material (a) using, for example, an adhesive. Examples of the adhesive include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, and natural rubber as active ingredients. A known adhesive can be used.

  The laminated flooring material may be subjected to, for example, cutting, use of a tenoner, applying a V-shaped groove, chamfering on all sides, etc., depending on the properties of the final product.

In the decorative material for a decorative sheet floor, the decorative sheet is laminated on the above-mentioned resin base material (a), and at least the base material sheet (a), the transparent resin layer and the surface protective layer are laminated in order. It becomes. And it laminates | stacks on the said resin base material (a) so that the base material sheet (A) side of a decorative sheet may be located in the above-mentioned resin base material (A) side, and comprises the decorative material for floors.

Base sheet (I)
As the base sheet (A), for example, a sheet formed of a thermoplastic resin is suitable. Specifically, polyvinyl chloride (PVC), polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene (PP), polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) Acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ionomers, polyacrylic acid esters, polymethacrylic acid esters and the like can be mentioned.

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

  Various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, etc., may be added to the base sheet (A). An agent may be included.

  Although the thickness of a base material sheet (A) can be suitably set with the use of a final product, a usage method, etc., 50-150 micrometers is preferable normally and about 60-80 micrometers is more preferable.

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

If desired, the pattern / pattern layer decorative sheet may be provided with a pattern / pattern layer on the surface (front surface) of the base sheet (A).

  The design pattern layer imparts a desired design (design) to the floor decorative sheet, and the type of design is not 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, printing using ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form in the base-material sheet | seat surface by a method.

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

  As binder resin, polyester urethane resin, polyester urethane resin with hydrophilic treatment, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate A polymer, a rosin derivative, an alcohol adduct of a styrene-maleic anhydride copolymer, a cellulose resin, or the like can be used in combination.

  More specifically, for example, polyurethane-polyacrylic resin, polyacrylamide resin, poly (meth) acrylic acid resin, polyethylene oxide resin, poly N-vinylpyrrolidone resin, water-soluble polyester resin, water-soluble Polyamide resins, water-soluble amino resins, water-soluble phenol resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, etc. can be used. Further, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin modified or mixed resin, and other resins can also be used. The binder resin can be used alone or in combination 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. When forming a solid pattern pattern layer (also referred to as a colored concealment layer), for example, a gravure coating method, a gravure reverse coating method, a roll coating method, a knife coating method, an air knife coating method, a die coating Various coating methods such as a method, a lip coat method, a comma coat method, a kiss coat method, a flow coat method, and a dip coat method are also included.

  In addition to the above, for example, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. are used or combined with other forming methods. It may be used.

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

The adhesive layer decorative sheet may be provided with an adhesive layer between the above-described pattern layer and the transparent resin layer described below, if desired.

  The adhesive used in the adhesive layer can be appropriately selected depending on the components constituting the pattern layer or the transparent resin layer. For example, various adhesives including polyurethane resin, polyacrylic resin, polycarbonate resin, epoxy resin and the like can be used. In addition to the reactive curing type, an adhesive such as a hot melt type, an ionizing radiation curing type, and an ultraviolet curing type may be used.

  The adhesive layer may be transparent or translucent as long as the pattern layer can be recognized.

  In the present invention, a known easy adhesion treatment such as a corona discharge treatment, a plasma treatment, a degreasing treatment, a surface roughening treatment or the like can be applied to the adhesion surface as necessary.

  The adhesive layer can be formed, for example, by applying the adhesive on the pattern layer, drying it once, and then laminating a transparent resin. 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.

  The thickness of the adhesive layer varies depending on the transparent protective layer, the type of adhesive used, and the like, but generally may be about 0.1 to 30 μm.

Transparent resin layer The resin constituting the transparent resin layer is not limited as long as it is transparent or translucent within a range where the lower pattern layer can be visually recognized.

  Examples of such resins include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid ester copolymer. , Ionomer, polymethylpentene, polyacrylate, polymethacrylate, polycarbonate, cellulose triacetate and the like.

  For the transparent resin layer, if necessary, a filler, matting agent, foaming agent, flame retardant, lubricant, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, radical scavenger, soft component Various additives such as rubber (for example, rubber) may be included.

  Although the thickness of a transparent resin layer is not specifically limited, Preferably it is about 40-250 micrometers, More preferably, it is about 40-140 micrometers, More preferably, it is about 60-100 micrometers.

  If necessary, the transparent resin layer may be subjected to corona discharge treatment on the surface (front surface) in order to enhance the adhesion with the upper primer layer.

In the primer layer decorative sheet, a primer layer may be provided between the above-described transparent resin layer and the surface protective layer described below, if desired. The primer layer has a function of leveling the surface of the transparent resin layer and enhancing the adhesion between the transparent resin layer and the surface protective layer. Moreover, it has the effect of making it hard to produce a fine crack and whitening in the extending | stretching part of a surface protective layer.

  The primer composition constituting the primer layer is (meth) acrylic resin, urethane resin, (meth) acrylic / urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorine Polyethylene or the like is used.

  Moreover, it is preferable that the thickness of a primer layer is about 0.1-10 micrometers. When it is 0.1 μm or more, the effect of preventing the surface protective layer from cracking, breaking, whitening, etc. can be sufficiently exerted. On the other hand, if the thickness of the primer layer is 10 μm or less, when the primer layer is applied, the coating film is stable in drying and curing, so that the moldability does not fluctuate. From the above points, the thickness of the primer layer is preferably 0.1 to 10 μm.

  The primer layer can be formed by a direct coating method, for example, gravure coating, gravure reverse coating, gravure offset coating, spin coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, solid coating by silk screen, wire A bar coat, a flow coat, a comma coat, a pouring coat, a brush coat, a spray coat, etc. can be used.

Surface protective layer The surface protective layer is the outermost layer of the decorative sheet and is also the outermost layer of the decorative material for flooring. When a heavy load is applied, if the surface protective layer is too thin, whitening scratches are likely to occur. The layer thickness is 5 to 30 μm because the surface protective layer tends to break if it is too large. The layer thickness of the surface protective layer is preferably 10 to 25 μm.

When the surface protective layer is too soft, whitening damage is likely to occur, and when it is too hard, the Martens hardness is 50 to 210 N / mm ² . Further, the Martens hardness of the surface protective layer is preferably 80 to 180 N / mm ² , more preferably 100 to 160 N / mm ² .

  The Martens hardness of the surface protective layer can be appropriately set by 1) mixing two or more resins having different hardnesses, 2) mixing an elastomer with the resin, or the like. When using an ionizing radiation curable resin, which will be described later, for the surface protective layer, it is possible to change the number of polymerizable functional groups in one molecule or to use a mixture of resins having different numbers of functional groups. The hardness can also be adjusted to a desired value. Further, when a two-component curable urethane-based resin described later is used for the surface protective layer, the Martens hardness can be adjusted to a desired value by changing the mixing ratio of the polyol-based main agent and the isocyanate-based curing agent. .

  The resin component constituting the surface protective layer is not particularly limited as long as the thickness and Martens hardness of the surface protective layer are within the above ranges, but an ionizing radiation curable resin is preferable, and an electron radiation curable resin is more preferable. Thus, the ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) containing functional groups capable of undergoing a polymerization crosslinking reaction (curing reaction) by irradiation with ionizing radiation such as ultraviolet rays and electron beams. In addition, a transparent resin mainly composed of a monomer can be used. These prepolymers or monomers can be used alone or in combination.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000. As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  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 can be used. As a wavelength of ultraviolet rays, 190 to 380 nm is usually preferable.

  As the electron beam source, for example, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Among them, those capable of irradiating electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.

  The two-component curable urethane resin is not particularly limited. Among them, a polyol component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) having an OH group as a main component and an isocyanate component (tolylene diene) which is a curing agent component. Isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate and the like) can be used.

  Among these resins, the surface protective layer can be appropriately selected or used in combination of two or more resins so that the Martens hardness of the surface protective layer falls within the above range.

  The surface protective layer may contain a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye or a pigment, a solvent, or the like, if necessary.

  The surface protective layer is formed by, for example, applying an ionizing radiation curable resin or a two-component curable urethane resin on a transparent resin layer by a known coating method such as gravure coating or roll coating, and then curing the resin. Can be formed. In the case of an ionizing radiation curable resin, the resin is cured by irradiation with ionizing radiation.

Manufacturing method of decorative sheet Lamination of each layer constituting the decorative sheet includes, for example, (i) providing a back primer layer on the back surface of the base sheet, and (ii) printing a pattern layer on the front surface of the base sheet (Iii) forming an adhesive layer on the pattern printed pattern layer, (iv) laminating a transparent resin layer on the adhesive layer by extrusion lamination, and (v) the transparent resin layer After the corona discharge treatment is applied to the surface of the substrate, a primer layer is formed, and (vi) the surface protective layer of the present invention having a specific layer thickness and Martens hardness is applied to the surface by a roll coating method. If it exists, it can carry out by irradiating an electron beam.

The embossed decorative sheet may be embossed from the surface protective layer side.

  The embossing is performed to give a desired texture such as a wood grain pattern to the decorative sheet. For example, after heat-softening the transparent protective layer, a texture is imparted by pressing and shaping with an embossed plate having a concavo-convex pattern of a desired shape, and cooling and fixing. Embossing can be performed with a known single wafer or rotary embossing machine. Examples of the embossed concavo-convex pattern include a wood grain conduit groove, a float pattern (a concavo-convex pattern of a raised annual ring), a hairline, a grain, and a satin texture.

  When embossing is performed, the embossed recess may be filled with ink by wiping as necessary. For example, the embossed recess is filled with ink while scratching the surface with a doctor blade. As the ink to be filled (wiping ink), usually, an ink having a two-component curable urethane resin as a binder can be used. In particular, by performing a wiping process on the grain conduit groove irregularities, the product value can be increased by expressing a design closer to the actual grain.

Manufacturing method of flooring decorative material The flooring decorative material of the present invention can be manufactured by laminating a decorative sheet on the resin base material (a). For example, it can be made into a flooring decorative material by bonding the resin dressing (a) to the back of the decorative sheet (base sheet (I)) via a back primer layer and bonding them together.

  After joining with the resin dressing (a), for example, according to the characteristics of the final product, cutting, use of a tenoner, sane processing, provision of V-shaped grooves, chamfering on four sides, etc. may be performed.

  Next, the present invention will be specifically described with reference to experimental examples. However, the present invention is not limited to the examples.

Examples and Comparative Examples (Example 1)
A primer layer was provided on the back surface of a base sheet made of a colored polypropylene film (colored PP film) having a thickness of 60 μm. Next, a pattern layer was formed on the front surface of the base sheet by printing, and an adhesive layer was further formed on the pattern layer. On the adhesive layer, a transparent resin layer (polypropylene resin blend, thickness: 80 μm) was laminated by extrusion lamination. After the surface of this transparent resin layer was subjected to corona discharge treatment, a primer layer was formed by applying a two-component curable urethane resin.

The surface is coated with 15 μm of ionizing radiation curable resin having the following composition as a main component by a roll coating method, and then in an environment with an oxygen concentration of 200 ppm or less, using an electron beam irradiation device under conditions of an acceleration voltage of 175 keV and 5 Mrad A surface protective layer was formed by irradiating and curing with an electron beam, and a decorative sheet for floor was prepared. The Martens hardness in the cross-sectional direction of the surface protective layer was 110 N / mm ² (average value of 10 measured values).

-Bifunctional urethane acrylate oligomer 80 parts by mass (polyol component is polyester diol, glass transition point 25 ° C, molecular weight 1500)-Hexafunctional aliphatic urethane acrylate oligomer 20 parts by mass (glass transition point 200 ° C or higher, molecular weight 1500, Kyoeisha Chemical Co., Ltd.) Company made UA306H)
-14 parts by mass of matting agent (11 μm silica)

  The bifunctional urethane acrylate oligomer used means a urethane acrylate oligomer having two radical polymerizable acryloyl groups in one molecule. The hexafunctional urethane acrylate oligomer means a urethane acrylate oligomer having six radical polymerizable acryloyl groups in one molecule.

  The decorative sheet prepared above was bonded to a 3 mm thick polyvinyl chloride (PVC) resin base material (tensile modulus of 800 MPa) using an adhesive to prepare a floor decorative material.

  In the following, the tensile modulus of the resin substrate, the type of the resin substrate, the thickness of the resin substrate, the thickness of the transparent resin layer, the thickness of the surface protective layer and the Martens hardness (resin component ratio) are varied. And Examples 2 to 13 and Comparative Examples 3 to 8.

(Comparative Example 1)
A primer layer was provided on the back surface of a base sheet made of a colored polypropylene film having a thickness of 60 μm. Next, a pattern layer was formed on the front surface of the base sheet by printing, and an adhesive layer was further formed on the pattern print pattern layer. On the adhesive layer, a transparent resin layer (polypropylene resin blend, thickness: 80 μm) was laminated by extrusion lamination. After the corona discharge treatment was performed on the surface of the transparent resin layer, a primer layer was formed by applying a two-component curable urethane resin.

A two-component curable urethane resin was applied to the surface by a gravure coating method so that the thickness after drying was 15 μm, and a floor decorative sheet was produced. The Martens hardness in the cross-sectional direction of the cured coating film was 40 N / mm ² (average value of 10 measured values).

  The decorative sheet prepared above was bonded to a 3 mm-thick PVC resin base material (tensile elastic modulus: 800 MPa) using an adhesive to prepare a floor decorative material.

  Hereinafter, the thickness of the surface protective layer was varied to obtain Comparative Example 2.

  As a scratch resistance test of the floor decorative material obtained above, a coin scratch test and a steel ball drop test were performed.

<Evaluation method>
(1) Scratch resistance test (coin scratch test)
The scratch resistance of the floor decorative materials produced in Examples and Comparative Examples was evaluated by a coin scratch test. Specifically, a 100-yen coin inclined at 45 ° was brought into contact with the surface of the test piece, and the scratched state was evaluated when dragged in the horizontal direction while applying loads (3 kg load, 5 kg load and 7 kg load). The evaluation criteria are as follows.
<Judgment criteria>...
(Double-circle): A whitening crack and a remarkable dent crack do not generate | occur | produce even with a 7 kg load.
○: No whitening or significant dents are generated even at a load of 5 kg.
(Triangle | delta): A whitening crack and a remarkable dent crack do not generate | occur | produce even with a 3 kg load.
X: Whitening scratches or marked dents were generated at a load of 3 kg.

(2) Impact resistance test (steel ball drop test)
The impact resistance of the decorative materials for floors produced in Examples and Comparative Examples was evaluated by a steel ball drop test. Specifically, a 300 g steel ball was dropped onto a test piece from a height of 50 cm, and the appearance and the amount of dents were evaluated. The evaluation criteria are as follows.
<Criteria>
◯: There is no surface cracking and the dent amount is 300 μm or less.
X: Surface crack or dent amount is 300 μm or more.

  The evaluation results are shown in Tables 1 to 5 below.

  Table 1 shows a comparison of the elastic modulus of the resin base material. In the table, EB means curing by irradiation with ionizing radiation. PVC, PE and PP mean polyvinyl chloride, polyethylene and polypropylene, respectively. The same applies to Tables 2-5.

  Table 2 shows a comparison of the thickness of the resin base material.

  Table 3 shows a comparison of the thickness of the transparent resin layer.

  Table 4 shows a comparison of the Martens hardness of the surface protective layer.

  Table 5 shows a comparison of the layer thicknesses of the surface protective layer.

From the result of Tables 1-5, in the decorative material for flooring by which the decorative sheet was laminated | stacked on the resin base material, the layer thickness of the surface protection layer of the said decorative sheet is 5-30 micrometers, and Martens hardness is 50- It is 210 N / mm ² , and the tensile elastic modulus measured according to JIS K7161 of the resin base material is 100 to 1600 MPa, so that even under excessive use conditions (scratch resistance under high load), whitening scratches and dents It was confirmed that scratches were hardly generated.

(1) Surface protective layer (2) Transparent resin layer (3) Adhesive layer (4) Picture pattern layer (5) Base sheet (I)
(6) Resin base material (A)

Claims (2)

It is a decorative material for floors in which a decorative sheet is laminated on a resin base material (a),
(1) The decorative sheet is formed by sequentially laminating at least a base sheet (A), a transparent resin layer, and a surface protective layer, and the base sheet (A) side of the decorative sheet is the resin base (A). It is laminated on the resin base material (a) so as to be located on the side,
(2) The surface protective layer has a layer thickness of 5 to 30 μm and a Martens hardness of 50 to 210 N / mm ² .
(3) The resin base material (a) has a tensile elastic modulus of 100 to 1600 MPa measured according to JIS K7161.
(4) The base sheet (A) is made of polyvinyl chloride (PVC), polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene (PP), polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer (EVA). ), Ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ionomer, polyacrylic acid ester and polymethacrylic acid ester. And
The transparent resin layer is made of polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer. Formed of at least one thermoplastic resin selected from polymethylpentene, polyacrylic acid ester, polymethacrylic acid ester, polycarbonate and cellulose triacetate ,
(5) The resin base material (a) is a single layer,
A decorative material for floors.   The flooring decorative material according to claim 1, wherein the surface protective layer contains an ionizing radiation curable resin.

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