JP5962385B2 - Decorative sheet for flooring - Google Patents

Description

  The present invention relates to a decorative sheet for flooring having a surface protective layer that has scratch resistance, anti-slip properties, and water-based wax adhesion, and curling is suppressed.

  Conventionally, as a decorative sheet for flooring, a sheet provided with a surface protective layer for imparting scratch resistance is known. Such a surface protective layer uses a method of increasing the thickness in order to impart scratch resistance required for a decorative sheet for flooring. However, if the thickness of the surface protective layer is increased, the decorative sheet for flooring is used. There is a problem that the curl when forming a roll becomes strong, making it difficult to roll laminate.

  In order to solve the above problem, the surface protective layer contains 10 to 20% by weight of glass beads having a particle size of 1/3 to 2/3 of the thickness of the ultraviolet curable surface protective layer, and a wax component. A floor decorative sheet containing 3 to 5% by weight has been proposed (see Patent Document 1). Such a decorative sheet for floors exhibits scratch resistance by containing glass beads having a specific particle diameter and a wax component in the surface protective layer.

  However, in such a decorative sheet for flooring, the wax component used for the surface protective layer has not been sufficiently studied, and in order to show the scratch resistance required for the decorative sheet for flooring, the content of the wax component It is necessary to increase. If the content of the wax component is increased to show sufficient scratch resistance, when the floor decorative sheet for flooring is applied to the floor surface, when the aqueous wax is applied to the surface as maintenance of the flooring material, There is a problem of poor adhesion. Further, when the content of the wax component is increased, there is a problem that the floor surface becomes slippery.

  Therefore, development of a decorative sheet for flooring having a surface protective layer that has scratch resistance, anti-slip property, and water-based wax adhesion required for the decorative sheet for flooring and that suppresses the occurrence of curling is desired. ing.

JP 2010-236204 A

  An object of the present invention is to provide a decorative sheet for flooring having a surface protective layer that has scratch resistance, anti-slip property, and water-based wax adhesion, and curling is suppressed.

  As a result of intensive studies, the present inventors have found that in a decorative sheet for flooring having a surface protective layer, the surface protective layer is made of polyethylene wax having a melting point of 110 ° C. or less, and the resin component 100 that forms the surface protective layer. In order to complete the present invention, it is found that 0.2 to 0.6 parts by weight with respect to parts by weight and the thickness of the surface protective layer is set to 20 to 40 μm to achieve the above object. It came.

That is, the present invention relates to the following decorative sheet.
1. A flooring decorative sheet having a surface protective layer,
(1) The surface protective layer contains 0.2 to 0.6 parts by weight of polyethylene wax having a melting point of 110 ° C. or less with respect to 100 parts by weight of the resin component forming the surface protective layer,
(2) The surface protective layer has a thickness of 20 to 40 μm.
A decorative sheet for flooring.
2. Item 2. The decorative sheet for flooring according to Item 1, wherein the polyethylene wax includes at least one selected from oxidation-modified polyethylene wax, acid-modified polyethylene wax, and monomer-modified polyethylene wax.
3. Item 3. The decorative sheet for flooring according to Item 1 or 2, wherein the surface protective layer contains a hard filler.
4). Item 4. The decorative sheet for flooring according to any one of Items 1 to 3, wherein a pattern layer, a transparent resin layer, and the surface protective layer are sequentially laminated on the base material sheet.
5. Item 5. The decorative sheet for flooring according to Item 4, further comprising a primer layer for forming a surface protective layer between the transparent resin layer and the surface protective layer.

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

  The decorative sheet for flooring of the present invention has a surface protective layer. (1) The surface protective layer contains polyethylene wax having a melting point of 110 ° C. or less with respect to 100 parts by weight of the resin component forming the surface protective layer. 0.2 to 0.6 parts by weight, and (2) the thickness of the surface protective layer is 20 to 40 μm.

  The decorative sheet for flooring of the present invention having the above characteristics has a surface protective layer having a specific thickness, and contains a specific polyethylene wax in a specific content in the surface protective layer, so that it has scratch resistance and slip resistance. It is excellent, and when the aqueous wax is applied to the surface as a maintenance of the flooring material, the adhesiveness of the aqueous wax is excellent.

  In addition, since the thickness of the surface protective layer is in a specific range, the amount of the polyethylene wax in the resin component forming the surface protective layer is sufficient, and the wax is present on the surface of the coating film of the surface protective layer before curing. By surfacing, a sufficient amount of wax appears on the surface of the surface protective layer, and excellent scratch resistance can be exhibited.

  Furthermore, the occurrence of curling is suppressed because the thickness of the surface protection increase is in a specific range.

(Surface protective layer)
The surface protective layer is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, water resistance, and stain resistance required for the decorative sheet. As the resin for forming the surface protective layer, a curable resin such as a thermosetting resin or an ionizing radiation curable resin is preferable. In particular, ionizing radiation curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

  Examples of the method for forming the surface protective layer with a thermosetting resin include a method in which a solution of a thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method and then dried and cured. The coating amount of the solution is about 20 to 40 μm, preferably about 20 to 35 μm, in terms of solid content after the solution is dried.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more prepolymers, oligomers and monomers having a polymerizable unsaturated bond or epoxy group that can be crosslinked by irradiation with ionizing radiation in the molecule can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.

  Examples of the ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and electron beams are preferable.

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

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

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it is about 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable resins.

  As a method for forming a protective layer with an ionizing radiation curable resin, for example, a solution of an ionizing radiation curable resin may be applied by a coating method such as a gravure coating method or a roll coating method. The coating amount of the solution is about 20 to 40 μm, preferably about 20 to 35 μm, in terms of solid content after the solution is dried.

  The increase in surface protection of the decorative sheet for flooring of the present invention contains polyethylene wax having a melting point of 110 ° C. or lower. As the polyethylene wax having a melting point of 110 ° C. or lower, one prepared using a modified polyethylene wax can be used. For example, the polyethylene wax can be appropriately selected from an oxidized modified polyethylene wax, an acid modified polyethylene wax, and a monomer modified polyethylene wax. A polyethylene wax having a melting point adjusted to 110 ° C. by mixing is exemplified. Further, a polyethylene wax having a melting point adjusted to 110 ° C. or less by mixing the modified wax and a known unmodified polyethylene wax other than the modified wax may be used. The polyethylene wax having a melting point of 110 ° C. or lower includes at least one selected from oxidation-modified polyethylene wax, acid-modified polyethylene wax, and monomer-modified polyethylene wax, so that the melting point is adjusted to 110 ° C. or lower. preferable.

  When the surface protective layer contains the polyethylene wax having the melting point of 110 ° C. or less, the surface protective layer and the aqueous wax are excellent in adhesion. The melting point is preferably 105 ° C. or lower. The melting point is preferably 103 ° C. or higher, and more preferably 100 ° C. or higher. In the present specification, the melting point of the polyethylene wax is a value measured by using a differential scanning calorimeter (DSC) under the condition of increasing the temperature from 0 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. .

  The oxidation-modified polyethylene wax refers to a wax obtained by oxidizing polyethylene and introducing a polar group such as a hydroxyl group. Since the oxidatively modified polyethylene wax has a polar group such as a hydroxyl group, it can exhibit excellent properties in adhesion to an aqueous wax.

  The acid-modified polyethylene wax refers to a wax obtained by polymerizing an acid by random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization or the like on polyethylene, or a wax obtained by neutralizing these with metal ions. Since the acid-modified polyethylene wax has a functional group such as a carboxyl group, the acid-modified polyethylene wax can exhibit characteristics excellent in adhesion with an aqueous wax.

  The monomer-modified polyethylene wax refers to a wax in which a part of ethylene monomer is substituted with a monomer having a functional group such as a carboxyl group or a hydroxyl group when the polyethylene wax is polymerized. Since the monomer-modified polyethylene wax has a functional group such as a carboxyl group and a hydroxyl group, the monomer-modified polyethylene wax can exhibit characteristics excellent in adhesion to an aqueous wax.

  Content of the said polyethylene wax is 0.2-0.6 weight with respect to 100 weight part of resin components which are curable resins, such as the said thermosetting resin or ionizing radiation curable resin, and which forms a surface protective layer. Part. It is preferable that it is 0.2-0.5 weight part. By setting the content of the polyethylene wax in the above range, the decorative sheet for flooring is excellent in scratch resistance, anti-slip property, and adhesion of the aqueous wax.

  The surface protective layer preferably contains a hard filler for the purpose of further improving scratch resistance. The hard filler is not particularly limited as long as the scratch resistance of the surface protective layer can be further improved, but it is preferable to use spherical inorganic fine particles. Examples of the inorganic fine particles include powdered aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, Diamond, gold sand, glass fiber, fused silica and the like can be mentioned.

  Specific examples of the hard filler include spherical silica particles described in Japanese Patent No. 4834999.

The pore volume of the hard filler is preferably less than 1.0 ml / g, more preferably 0 ml / g or more and less than 1.0 ml / g. The apparent specific gravity when the hard filler is silica is preferably more than 0.4 g / cm ² and not more than 2.2 g / cm ² .

  The content of the hard filler is 1 to 10 parts by weight with respect to 100 parts by weight of the resin component forming the surface protective layer, which is a curable resin such as the thermosetting resin or ionizing radiation curable resin. Is preferred.

  The average particle size of the hard filler is preferably 1 to 5 μm.

  The surface protective layer may contain a matting agent as necessary. Although it does not specifically limit as said matting agent, For example, a silica is mentioned. The silica is preferably an amorphous, non-spherical particle in that the matte effect can be sufficiently exhibited.

  As the matting agent, one having a pore volume of 1.8 to 3.0 ml / g, an apparent specific gravity of 0.05 to 0.22 g / ml, and an oil absorption of 300 ml / 100 g or more is used. It is preferable. It is more preferable to use one having a pore volume of 1.9 to 2.5 ml / g, an apparent specific gravity of 0.10 to 0.20 g / ml, and an oil absorption of 300 to 400 ml / 100 g. By using a matting agent having a pore volume of 1.8 to 3.0 ml / g, an effect of irregular reflection of light can be efficiently obtained, so that a good matting effect can be obtained.

  It is preferable that content of the said matting agent is 8-20 weight part with respect to 100 weight part of resin components which form a surface protective layer. Moreover, it is preferable that the average particle diameter of the said matting agent is 9-15 micrometers.

  The surface protective layer has a thickness of 20 to 40 μm. When the thickness of the surface protective layer is less than 20 μm, the scratch resistance is poor. If it is thicker than 40 μm, curling of the decorative sheet for flooring tends to occur. The thickness of the surface protective layer is preferably 20 to 35 μm.

  The surface protective layer may contain an ultraviolet absorber, a light stabilizer, a plasticizer, a stabilizer, a filler, a dispersant, a colorant such as a dye and a pigment, a solvent, an antibacterial agent, and the like, if necessary. .

  The layer structure of the decorative sheet for flooring of the present invention is not particularly limited as long as it has the surface protective layer. For example, a pattern layer, a transparent resin layer, and the above-mentioned on the base sheet. What laminated | stacked a surface protective layer in order is preferable. Moreover, the layer structure which laminates | stacks a pattern pattern layer, an adhesive bond layer, a transparent resin layer, a primer layer, and the said surface protective layer in order on a base material sheet | seat is also suitable.

  Hereinafter, as a specific description of the layer configuration, the above-described layer configuration will be exemplified, and layers other than the surface protective layer will be described. The backer layer will also be described.

(Substrate sheet)
Although it does not limit as a base material sheet, the base material sheet which contains polyolefin resin as a resin component is preferable. Essentially, a sheet made of polyolefin resin is used.

  It does not specifically limit as polyolefin resin, What is normally used in the field | area of a decorative sheet 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. Among these, polypropylene, polyolefin-based thermoplastic elastomers and the like are particularly preferable.

  A homopolymer or copolymer having polypropylene as a main component is also preferable, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part and having 2 to 20 carbon atoms other than propylene. -Olefins. 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 preferably a mixture of isotactic polypropylene in the hard segment and atactic polypropylene in the soft segment in a weight ratio of 80:20.

  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.

  The thickness of the base sheet is not particularly limited and can be set according to the product characteristics, but is usually 40 to 150 μm, preferably about 50 to 100 μm.

  An 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). The blending amount of the additive can be appropriately set according to the product characteristics.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments; 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.

  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 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  A primer layer may be provided on one side or both sides of the base sheet as necessary.

  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.

The application amount of the primer agent is not particularly limited, but is usually 0.1 to 20 g / m ² , preferably about 0.5 to 10 g / m ² .

(Pattern pattern layer)
A pattern layer can be formed on the base sheet. 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 resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, 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. When forming a solid pattern pattern layer, for example, 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 Various coating methods such as a coating method may be mentioned. In addition, 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. may be used or combined with other forming methods. Good.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate according to the product characteristics, but the layer thickness after drying is about 0.1 to 20 μm.

(Transparent adhesive layer)
A transparent adhesive layer may be 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. The transparent 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.

  For example, the adhesive layer is applied on the pattern layer (strictly, on the base sheet so as to cover the pattern layer), dried, laminated with a transparent resin layer, and then cured. Can be formed. 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.

(Transparent resin layer)
The transparent resin layer may be colored as long as it is transparent, and may be translucent as long as the pattern layer is visible.

  Examples of the resin include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, and ionomer. , Polymethylpentene, acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate and the like. Among the above, polyolefin resins such as polypropylene are preferable. More preferably, it is a polyolefin resin having stereoregularity. When using a polyolefin resin, it is desirable to form a transparent resin layer by extruding a molten polyolefin resin.

  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.

  The thickness of the transparent resin layer is not particularly limited, but is generally about 10 to 150 μm.

  The surface of the transparent resin layer on which the surface protective layer is formed is subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment as necessary. Also good. The surface treatment may be performed according to a conventional method for each treatment.

(Primer layer)
A primer layer for facilitating formation of the surface protective layer can be provided on the transparent resin layer.

  The primer layer can be formed by applying a known primer agent to 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.

The application amount of the primer agent is not particularly limited, but is usually 0.1 to 20 g / m ² , preferably about 0.5 to 10 g / m ² .

(Embossing)
After laminating the surface protective layer on the transparent resin layer, the front surface of the surface protective layer may be embossed.

  The embossing method is not particularly limited, and for example, a preferable method is to heat soften the front surface of the surface protective layer, pressurize and shape with an emboss plate, and then cool. For embossing, a known single-wafer or rotary embossing machine is used. Examples of the concavo-convex shape include a wood grain plate conduit groove, a stone plate surface unevenness (such as granite cleaved surface), a cloth surface texture, a satin texture, a grain, a hairline, a ridge line, and the like.

(Backer layer)
Backer layer on the back side of the base sheet (if the back side of the base sheet has a pattern layer), a backer layer (synthesizing to increase the scratch resistance and reduce the influence of the substrate) (Resin layer) may be provided. In addition, the above scratch resistance refers to a dent scratch when a load is applied partially, and the decorative sheet of the present invention has sufficient scratch resistance without providing a backer layer, but a backer layer is provided. Thus, various performances such as scratch resistance can be further enhanced.

  As a method for forming the backer layer, extrusion molding of a molten resin is suitable, for example, extrusion molding using a T die is suitable.

  As a method of adhering the back surface of the base material sheet and the backer layer, a method of adhering the base material sheet and the backer layer obtained by extruding the molten resin by heat fusion, the base material sheet and the backer layer For example, a method of bonding by providing an adhesive layer (further, if necessary, a primer layer) between them may be used.

  The resin constituting the backer layer is not limited, but a thermoplastic resin such as polyethylene, polypropylene (PP), polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate. (A-PET), highly heat-resistant polyalkylene terephthalate [for example, polyethylene terephthalate in which a part of ethylene glycol is substituted with 1,4-cyclohexanedimethanol, diethylene glycol or the like, so-called trade name PET-G (Eastman Chemical) Company)), polybutylene terephthalate (PBT), polycarbonate, polyarylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate Coalescence, polyimide, polystyrene, polyamide, ABS (acrylonitrile - butadiene - styrene copolymer) and the like. These resins can be used alone or in combination of two or more.

  The thickness of the backer layer can be set as appropriate depending on the use of the final product, the method of use, etc., but is generally preferably 100 to 800 μm. Among these, 400-600 micrometers is more preferable.

  If necessary, the backer layer may be subjected to known easy adhesion treatment such as corona discharge treatment, plasma treatment, degreasing treatment, surface roughening treatment, and the like on the adhesion surface. Further, a primer layer may be further provided on the back surface in consideration of adhesiveness with the adherend.

  In the decorative sheet for flooring of the present invention, the surface protective layer contains 0.2 to 0.6 parts by weight of polyethylene wax having a melting point of 110 ° C. or less with respect to 100 parts by weight of the resin component forming the surface protective layer. In addition, since the thickness of the surface protective layer is 20 to 40 μm, it has scratch resistance, anti-slip property, and water-based wax adhesion, and curling is suppressed.

It is sectional drawing showing an example of the decorative sheet for flooring of this invention.

  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 colored polypropylene sheet (thickness 60 μm) was prepared as a base sheet.

  After performing the corona discharge treatment on the front surface and the back surface of the base sheet, a primer agent was applied to each of the front surface and the back surface to form a primer layer (each thickness: 2 μm). The primer agent is a mixture of 100 parts by weight of a resin composition and 5 parts by weight of hexamethylene diisocyanate (curing agent). The resin composition contains an acrylic urethane copolymer, an acrylic polyol, and a triazine ultraviolet absorber (5 mass). %).

  Next, a pattern layer (thickness 2 μm) was formed on the primer layer on the surface, and a transparent adhesive layer (thickness 3 μm) was formed thereon. A transparent thermoplastic polypropylene resin was heated and melt-extruded by a T-die extruder on the transparent adhesive layer to form a transparent resin layer (thickness 80 μm).

  Next, a corona discharge treatment was applied to the surface of the transparent resin layer, and a two-component curable urethane resin was applied to form a primer layer (thickness 2 μm) on the transparent resin layer.

  Next, the surface protective layer-forming composition was applied on the primer layer with a thickness of 25 μm by a gravure coating method. The composition for forming a surface protective layer comprises 80 parts by weight of a bifunctional urethane acrylate oligomer as a resin component (weight average molecular weight 1500 glass transition temperature -55 ° C.) and a hexafunctional aliphatic urethane acrylate oligomer (weight average molecular weight 1500 glass transition temperature). 20 parts by weight of UA306H manufactured by Kyoeisha Chemical Co., Ltd. at 200 ° C. or higher, and 0.5 parts by weight of polyethylene wax having a melting point of 110 ° C. or lower as a lubricant with respect to 100 parts by weight of the resin component. Furthermore, 14 parts by weight of amorphous silica having an average particle diameter of 11 μm was included as a matting agent, and 5 parts by weight of spherical silica having an average particle diameter of 3 μm was included as a hard filler. The polyethylene wax having a melting point of 110 ° C. or lower is prepared by mixing 50 parts by weight of an unmodified polyethylene wax having a melting point of 116 ° C. and 50 parts by weight of an oxidized modified polyethylene wax having a melting point of 104 ° C. ° C.

  Next, in an atmosphere having an oxygen concentration of 200 ppm, the coating film of the composition for forming a surface protective layer is irradiated with an electron beam under the conditions of an acceleration voltage of 175 keV and 5 Mrad (50 kGy) to crosslink and cure the coating film. Thus, a surface protective layer was formed.

Finally, a decorative sheet for flooring was produced by embossing the front surface of the surface protective layer under the conditions of a sheet temperature of 140 ° C. and a pressure of 10 to 40 kg / cm ² .

Examples 2-7, Comparative Examples 1-11
Examples 2 to 7 and the comparison were made in the same manner as in Example 1 except that the type of wax used, the wax mixing ratio, the wax melting point, the amount of added wax, and the thickness of the surface protective layer were changed as shown in Tables 1 to 3. The decorative sheets for flooring of Examples 1 to 11 were produced.

(Evaluation method)
Scratch resistance (Hoffman scratch test)
The test was conducted using a Hoffman scratch tester manufactured by BYK-GARDNER, USA. Specifically, the scratch blade (φ7 cylindrical blade) was set so as to contact the surface of the decorative sheet for flooring at an angle of 45 °, and the tester was moved on the decorative material. The load (weight) was gradually increased, and the test was repeated until scratches, indentations and the like were generated on the surface of the decorative sheet for flooring.

The evaluation criteria are as follows.
No scratches observed at a load of 1: 1500 g or more 2: No scratches observed at a load of 1400 g or more and less than 1500 g 3: No scratches observed at a load of 1300 g or more and less than 1400 g 4: 1300 g Scratches occurred under load
Acrylic resin-based aqueous wax (trade name: manufactured by Linley Co., Ltd.) is evenly applied to the surface of the decorative sheet for water-based wax adhesive flooring. After curing for 24 hours, 1 mL of water is dropped on the surface to which the wax is applied. After leaving for 5 minutes, water was wiped off and the cellophane tape was immediately peeled off for evaluation. The evaluation criteria are as follows.
1: No peeling 2: No peeling less than 50% 3: No more than 50% peeling 4: Complete peeling
Slip properties Shinto Scientific friction coefficient measuring instrument Co., Ltd. (trade name: HEIDON Tribo gear Muse TYPE: 94i) was used to measure the coefficient of friction of the floor material for a decorative sheet surface. The measurement was carried out by rubbing the surface of the decorative sheet for flooring with a metal contact without attaching a sliding piece such as a cloth to the metal contact of the measuring instrument. In this measurement, if the friction coefficient is 0.17 or more, it is difficult to slip and is suitable as a decorative sheet for flooring.

A decorative sheet for curl-strength flooring was prepared in 400 m, wound up in a roll and stored for one month. After storage for one month, roll laminate processing is performed using the decorative sheet for flooring, and when the curling is strong enough to lift the decorative sheet for flooring from the base material, roll laminate processing is considered impossible and the following evaluation criteria Evaluated according to.
1: No curling 2: Curling is possible but roll laminating is possible 3: Curling is occurring and roll laminating is not possible The wax contained in the surface protective layer In order to measure the effect of the type on the scratch resistance, the scratch resistance was evaluated for Examples 1 to 3 and Comparative Examples 1 to 5. The results are shown in Table 1.

  As is clear from the results in Table 1, the decorative sheets for flooring of Examples 1 to 3 in which the surface protective layer contains polyethylene wax having melting points of 110 ° C. and 105 ° C. are excellent in scratch resistance. I understood.

  Moreover, although the surface protective layer also had excellent scratch resistance in the decorative sheets for flooring of Comparative Examples 4 and 5 containing polyethylene wax having melting points of 116 ° C. and 115 ° C., the test for Table 2 described later was performed. In, water-based wax adhesiveness was inferior.

  On the other hand, the decorative sheet for flooring of Comparative Example 1 in which the surface protective layer did not contain wax, Comparative Example 2 containing natural wax, and Comparative Example 3 containing modified polypropylene wax had poor scratch resistance. .

  Evaluation about the said flaw resistance, water-based wax adhesiveness, and slipperiness was performed about Examples 1-5 and Comparative Examples 1 and 4-9. The results are shown in Table 2.

  As is clear from the results in Table 2, the surface protective layer is a polyethylene wax having a melting point of 110 ° C. or less in the range of 0.2 to 0.6 parts by weight with respect to 100 parts by weight of the resin component forming the surface protective layer. The decorative sheet for flooring of Examples 1 to 5 having a surface protective layer thickness in the range of 20 to 40 μm was excellent in scratch resistance, slip resistance, and aqueous wax adhesion. .

  On the other hand, the decorative sheet for flooring of Comparative Example 1 containing no wax in the surface protective layer is inferior in scratch resistance, and the decorative sheet for flooring of Comparative Example 6 having a low polyethylene wax content is also scratch resistant. It was inferior.

  Further, the decorative sheets for flooring of Comparative Examples 7 to 9 having a large content of polyethylene wax are inferior in aqueous wax adhesion, and the decorative sheet for flooring of Comparative Example 9 having a large content of polyethylene wax is particularly The slipperiness was also poor.

  Moreover, the decorative sheet for flooring of Comparative Examples 4 and 5 having a high melting point of polyethylene wax was inferior in aqueous wax adhesion.

  Evaluations on the scratch resistance, aqueous wax adhesion, and curl strength were performed on Examples 1, 6 and 7, and Comparative Examples 1, 10 and 11. The results are shown in Table 3.

  As is clear from the results in Table 3, the surface protective layer is a polyethylene wax having a melting point of 110 ° C. or less, in the range of 0.2 to 0.6 parts by weight with respect to 100 parts by weight of the resin component forming the surface protective layer. The decorative sheet for flooring of Examples 1, 6 and 7 in which the thickness of the surface protective layer is in the range of 20 to 40 μm is excellent in scratch resistance, water-based wax adhesion, and curl generation Was suppressed.

  On the other hand, the decorative sheet for flooring of Comparative Example 10 having a thin surface protective layer was inferior in scratch resistance.

  Moreover, although the thickness of the surface protective layer is in the range of 20 to 40 μm, the decorative sheet for flooring of Comparative Example 1 which does not contain wax in the surface protective layer was also inferior in scratch resistance.

  Furthermore, the decorative sheet for flooring of Comparative Example 11 in which the surface protective layer does not contain wax and the thickness of the surface protective layer is 50 μm was excellent in scratch resistance, but the curl was strongly generated and the roll laminating process was performed. It was impossible.

1. 1. Primer layer 2. base material sheet Wood grain pattern layer 4. 4. Transparent adhesive layer 5. Transparent resin layer Primer layer 7. Surface protective layer

Claims (5)

A flooring decorative sheet having a surface protective layer,
(1) The surface protective layer contains 0.2 to 0.6 parts by weight of polyethylene wax having a melting point of 110 ° C. or less with respect to 100 parts by weight of the resin component forming the surface protective layer,
(2) The surface protective layer has a thickness of 20 to 40 μm.
A decorative sheet for flooring.   The decorative sheet for flooring according to claim 1, wherein the polyethylene wax includes at least one selected from oxidation-modified polyethylene wax, acid-modified polyethylene wax, and monomer-modified polyethylene wax.   The decorative sheet for flooring according to claim 1 or 2, wherein the surface protective layer contains a hard filler.   The decorative sheet for flooring according to any one of claims 1 to 3, wherein a pattern layer, a transparent resin layer, and the surface protective layer are sequentially laminated on a base material sheet.   The decorative sheet for flooring according to claim 4, further comprising a primer layer between the transparent resin layer and the surface protective layer.

Images