WO2021066035A1 - Decorative material for floor - Google Patents

Decorative material for floor Download PDF

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Publication number
WO2021066035A1
WO2021066035A1 PCT/JP2020/037222 JP2020037222W WO2021066035A1 WO 2021066035 A1 WO2021066035 A1 WO 2021066035A1 JP 2020037222 W JP2020037222 W JP 2020037222W WO 2021066035 A1 WO2021066035 A1 WO 2021066035A1
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WO
WIPO (PCT)
Prior art keywords
layer
decorative
olefin resin
surface protective
protective coat
Prior art date
Application number
PCT/JP2020/037222
Other languages
French (fr)
Japanese (ja)
Inventor
小川　哲
孝志 土井
宏樹 河西
啓介 鶴田
洋平 清水
Original Assignee
大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Publication of WO2021066035A1 publication Critical patent/WO2021066035A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/04—Flooring or floor layers composed of a number of similar elements only of wood or with a top layer of wood, e.g. with wooden or metal connecting members

Definitions

  • the present invention relates to a decorative material for floors.
  • a decorative material having a design is generally used.
  • surface performance such as scratch resistance, stain resistance, and weather resistance is insufficient if the pattern layer is provided directly on the base material. Therefore, the surface performance such as scratch resistance, stain resistance, and weather resistance is usually insufficient.
  • Surface performance is imparted by laminating a decorative sheet on which a transparent resin film is laminated.
  • Patent Document 1 describes a decorative sheet for being laminated on a base material, which has at least a first transparent resin layer, a pattern layer, a second transparent resin layer, and a transparent protective layer.
  • a decorative sheet is disclosed, which is provided in order and the transparent protective layer is composed of an ionizing radiation curable resin.
  • Patent Document 2 in a decorative sheet having a first olefin resin layer, a second olefin resin layer, and a surface protective layer in this order, the indentation hardness HIT ⁇ 2> of the second olefin resin layer is described.
  • a decorative sheet is disclosed in which the indentation hardness HIT ⁇ 1> of the surface protective layer satisfies a specific relationship.
  • An object of the present invention is to solve the above-mentioned problems, and to provide a floor decorative material having extremely excellent scratch resistance that can prevent not only scratches and dents but also gloss change. To do.
  • the present inventors have conducted a diligent study and found that a decorative sheet having one or more base film layers including a decorative layer and a surface protective coat layer and a wooden base material are laminated for a floor.
  • the decorative material by controlling the indentation hardness of the surface protective coat layer and the total thickness of the decorative sheet within a specific range, in addition to preventing scuffing and denting scratches, it is also possible to prevent gloss change. We have found that we can do this, and have completed the present invention.
  • the present invention is a floor decorative material in which a decorative sheet including one or more base film layers including a decorative layer and a surface protective coat layer and a wood base material are laminated, and the surface protective coat layer is the same.
  • a floor decorative material having an indentation hardness of 160 MPa or more and a total thickness of the decorative sheet of 200 ⁇ m or more.
  • the surface protective coat layer preferably has a thickness of 10 ⁇ m or more and 30 ⁇ m or less. Further, in the floor decorative material of the present invention, the surface protective coat layer preferably has an indentation hardness of 300 MPa or less.
  • the base film layer has a first olefin resin layer, and the indentation hardness of the first olefin resin layer is preferably 80 MPa or more.
  • the thickness of the first olefin resin layer is preferably 120 ⁇ m or more and 300 ⁇ m or less.
  • the base film layer has a backer layer on the side opposite to the side on which the surface protective coat layer is laminated.
  • the backer layer preferably has a thickness of 100 ⁇ m or more.
  • the wood base material is preferably plywood.
  • the present invention can provide a floor decorative material having extremely excellent scratch resistance that can prevent not only scratches and dents but also gloss change.
  • FIG. 1 It is sectional drawing which shows typically an example of the decorative material for a floor of this invention.
  • FIG. 1 is a schematic cross-sectional view of a decorative sheet
  • (b) is a schematic cross-sectional view of a decorative sheet having an uneven shape.
  • (A) and (b) are cross-sectional views schematically showing a preferable example of the floor decorative material of the present invention.
  • (A) to (c) are diagrams for explaining the method for measuring the indentation hardness of the present specification.
  • the lower and upper limits of the numerical range represented by "-" mean "greater than or equal to or less than” (for example, if ⁇ to ⁇ , it is greater than or equal to ⁇ or less than ⁇ ).
  • the floor decorative material of the present invention has a structure in which a decorative sheet including one or more base film layers including a decorative layer and a surface protective coat layer and a wood base material are laminated.
  • FIG. 1 is a cross-sectional view schematically showing an example of a decorative material for a floor. As shown in FIG. 1, in the floor decorative material 100, a decorative sheet 10 having a surface protective coat layer 1 and a base film layer 2 and a wood base material 20 are laminated.
  • the decorative sheet 10 includes a surface protective coat layer 1 and one or more base film layers 2 including the decorative layer.
  • the surface protective coat layer 1 has an indentation hardness of 160 MPa or more
  • the decorative sheet 10 has an indentation hardness of 160 MPa or more.
  • the total thickness is 200 ⁇ m or more.
  • the decorative sheet 10 has a total thickness of 200 ⁇ m or more. If the total thickness of the decorative sheet 10 is less than 200 ⁇ m, dents and scratches cannot be prevented.
  • the total thickness of the decorative sheet 10 is preferably 220 ⁇ m or more, more preferably 240 ⁇ m or more, and even more preferably 250 ⁇ m or more.
  • the upper limit of the total thickness of the decorative sheet 10 is not particularly limited, but is preferably 500 ⁇ m or less, and more preferably 400 ⁇ m or less.
  • FIG. 2A is a schematic cross-sectional view of the decorative sheet
  • FIG. 2B is a schematic cross-sectional view of the decorative sheet having an uneven shape.
  • the length from the surface A to the surface B is the "total thickness" of the decorative sheet 10, as shown in FIG. 2 (a).
  • the length from the surface A to the surface B is the "total thickness” of the decorative sheet 10, as shown in FIG. 2 (b).
  • the decorative sheet 10 has a surface protective coat layer 1.
  • the surface protective coat layer 1 has an indentation hardness of 160 MPa or more. When the indentation hardness of the surface protective coat layer 1 is less than 160 MPa, it is not possible to prevent the gloss change.
  • the surface protective coat layer 1 preferably has an indentation hardness of 200 MPa or more, more preferably 240 MPa or more.
  • the surface protective coat layer 1 preferably has an indentation hardness of 300 MPa or less, and more preferably 290 MPa or less. If the indentation hardness of the surface protective coat layer 1 exceeds 300 MPa, it becomes brittle and the gloss change can be prevented. For embossing, cracks may easily occur during shaping.
  • the "indentation hardness" of each layer is indicated by the nanoindentation hardness measured using a surface film physical property tester Tribo Indenter (registered trademark) "TI-950” (manufactured by HYSITRON). ..
  • the method for measuring the indentation hardness (HIT) of each layer using the tribo indenter (registered trademark) "TI-950” is as follows.
  • a load of 0 to 100 ⁇ N is applied to the surface protective coat layer 1 in 10 seconds ( That is, it is held for 5 seconds with a load of 10 ⁇ N / s) and then 100 ⁇ N (Fmax), and finally unloading from 100 to 0 ⁇ N is performed in 10 seconds. Further, for the first olefin resin layer 3 described later, a load of 0 to 50 ⁇ N is first applied for 5 seconds (that is, 10 ⁇ N / s), then a load of 50 ⁇ N (Fmax) is held for 5 seconds, and finally 50 to 50 ⁇ N. Unloading up to 0 ⁇ N is performed in 10 seconds.
  • the thickness of the layer to be the measurement sample in the pushing direction may be 1.0 ⁇ m or more (preferably 1.5 ⁇ m or more).
  • Ap is calculated by 24.50 [hmax- ⁇ (hmax-hr)] 2 (where ⁇ is a correction factor due to the geometric shape of the indenter and hr remains on the surface after unloading. The depth of the triangular pyramidal geometry.).
  • the decorative sheet is embedded with a resin (cold-curing type epoxy two-component curing resin), left at room temperature for 24 hours or more to cure, and then the cured embedded sample is mechanically polished to form a layer to be measured.
  • the hardness of the cross section of each layer is increased by exposing the cross section of the above layer and pushing the Berkovich indenter 31 into the cross section of the layer to be measured (when the layer contains fine particles such as a filler, the position where the fine particles are avoided).
  • the indentation hardness at 10 points was measured so as not to cause bias, and the average value at 10 points was the "indentation hardness of the surface protective coat layer 1" and the "first olefin resin layer", respectively.
  • the surface protective coat layer 1 improves the surface characteristics such as stain resistance, scratch resistance, and chemical resistance of the decorative sheet 10, and further cures the curable resin composition from the viewpoint of satisfying the above-mentioned indentation hardness. It is preferably composed of things.
  • the curable resin composition include a resin composition containing a curable resin such as a thermosetting resin, a two-component curable resin, and an ionizing radiation curable resin, from the viewpoint of obtaining more excellent surface characteristics.
  • a resin composition containing a two-component curable resin and an ionizing radiation curable resin is preferable.
  • thermosetting resin examples include unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, and guanamine resin.
  • examples thereof include melamine-urea cocondensate resin, silicon resin, and polysiloxane resin.
  • a curing agent such as a cross-linking agent and a polymerization initiator, and a polymerization accelerator can be added to the thermosetting resin.
  • a curing agent isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resin, polyurethane resin, etc., organic amine, etc. can be added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutylnitrile, etc.
  • a radical initiator can be added to the unsaturated polyester resin.
  • Examples of the method for forming the surface protective coat layer 1 with the thermosetting resin include a method in which a solution of the thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, and dried and cured.
  • the two-component curable resin is not particularly limited as long as it is a resin that can be cured by a main agent and a curing agent, and is preferably a two-component curable resin in which the main agent is a polyol (polyhydric alcohol) and the curing agent is an isocyanate curing agent.
  • Urethane resin can be mentioned.
  • the main agent examples include polyols such as polyethylene glycol, polypropylene glycol, butylene glycol, neopentyl glycol, and 1,6-hexanediol; polyols having a hydroxyl group as a functional group such as acrylic polyol, polyester polyol, and polyether polyol; and the like. Is preferably mentioned. These can be used alone or in combination of two or more.
  • isocyanate curing agent a conventionally known compound may be appropriately used, and for example, aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), and naphthalene diisocyanate; 1,6-hexa.
  • aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), and naphthalene diisocyanate; 1,6-hexa.
  • Polyisocyanates such as methylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), and aliphatic (or alicyclic) isocyanates such as hydrogenated tolylene diisocyanate are used.
  • adducts or multimers of these various isocyanates for example, adducts of tolylene diisocyanate, trimers of to
  • the ionizing radiation curable resin includes ionizing radiation, that is, electromagnetic waves or charged particle beams having energy quanta capable of polymerizing or cross-linking molecules, for example, ultraviolet rays (UV) or electron beams (EB), as well as X-rays.
  • ionizing radiation that is, electromagnetic waves or charged particle beams having energy quanta capable of polymerizing or cross-linking molecules, for example, ultraviolet rays (UV) or electron beams (EB), as well as X-rays.
  • the ionizing radiation curable resin can be appropriately selected from the commonly used polymerizable monomers, polymerizable oligomers and prepolymers.
  • the polymerizable monomer for example, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable.
  • the polyfunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule. For example, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, etc.
  • Preferred examples include trimerol propantri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These (meth) acrylate monomers can be used alone or in combination of two or more.
  • polymerizable oligomer examples include oligomers having a radically polymerizable unsaturated group in the molecule, such as urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, and polyether (meth) acrylate.
  • Preferred examples include (meth) acrylate oligomers such as oligomers and acrylic (meth) acrylate oligomers. These polymerizable oligomers can be used alone or in combination of two or more.
  • the curable resin composition may contain a dispersant or the like, which will be described later, in addition to the curable resin.
  • the curable resin composition is an ultraviolet absorber, an ultraviolet shielding agent, a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a cross-linking agent, and an infrared absorber as long as the object of the present invention is not impaired.
  • Antistatic agent, adhesive improver, leveling agent, tincture imparting agent, coupling agent, plasticizer, defoaming agent, filler, blocking inhibitor, lubricant, solvent and the like can be added.
  • a weather resistant agent such as an ultraviolet absorber and a light stabilizer.
  • Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, acrylonitrile-based, and examples of the light stabilizer include hindered amine-based, acrylate-based, oxamide-based, and cyanoacrylate-based. Be done.
  • the surface protective coat layer 1 can contain a dispersant.
  • the dispersant include polymer surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicone oils, waxes, modified resins and the like.
  • the nanoshells described in International Publication No. 2018/159660 and the like can also be preferably used. These dispersants can be used alone or in combination of two or more.
  • the content of the dispersant is preferably 0.01 part by mass or more and 30 parts by mass or less, and more preferably 0.05 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin component forming the surface protective coat layer 1. It is preferably 0.1 part by mass or more and 10 parts by mass or less, and 0.3 parts by mass or more and 5 parts by mass or less is particularly preferable.
  • the surface protective coat layer 1 preferably contains inorganic fine particles from the viewpoint of further improving scratch resistance.
  • the inorganic fine particles include silica, alumina, aluminosilicate, kaolinite, calcium carbonate, barium sulfate, and glass. Further, the indent hardness of the surface protective coat layer 1 can be adjusted by controlling the type and content of the inorganic fine particles.
  • the average particle size of the inorganic fine particles is not limited, but is preferably 20 ⁇ m or less, more preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 2 ⁇ m or more and 15 ⁇ m or less.
  • the average particle size of the inorganic fine particles is 50% particle size (d50: median size) when the particles in the solution are measured by a dynamic light scattering method and the particle size distribution is expressed by a volume cumulative distribution.
  • the 50% particle size can be measured using, for example, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).
  • the content of the inorganic fine particles is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 25 parts by mass or less, and 5 parts by mass with respect to 100 parts by mass of the resin component forming the surface protective coat layer 1. More than 20 parts by mass is more preferable.
  • the thickness of the surface protective coat layer 1 is preferably 10 ⁇ m or more and 30 ⁇ m or less. When the thickness of the surface protective coat layer 1 is 10 ⁇ m or more and 30 ⁇ m or less, it is possible to suitably prevent scuffing and denting scratches and gloss change, and further preferably prevent cracking of the decorative sheet 10. It is possible to improve the handleability.
  • the thickness of the surface protective coat layer 1 is more preferably 12 ⁇ m or more and 25 ⁇ m or less, and further preferably 15 ⁇ m or more and 20 ⁇ m or less.
  • the decorative sheet 10 has one or more base film layers 2 including a decorative layer.
  • the base film layer 2 include a first olefin resin layer, a second olefin resin layer, a backer layer, and the like, in addition to the decorative layer.
  • FIG. 3 is a schematic cross-sectional view of a preferred example of the floor decorative material of the present invention. As shown in FIG. 3A, in the floor decorative material 100, a decorative sheet 10 having a surface protective coat layer 1 and a base film layer 2 and a wood base material 20 are laminated, and the base film layer 2 is , The first olefin resin layer 3, the decorative layer 4, the second olefin resin layer 5, and the backer layer 6 may be included.
  • a decorative sheet 10 having a surface protective coat layer 1 and a base film layer 2 and a wood base material 20 are laminated, and the base film layer is formed.
  • Reference numeral 2 denotes a layer including the first olefin resin layer 3, the decorative layer 4, and the second olefin resin layer 5. Each layer constituting the base film layer 2 will be described.
  • the first olefin resin layer 3 preferably has an indentation hardness of 80 MPa or more.
  • the indentation hardness of the first olefin resin layer 3 is 80 MPa or more, the floor decorative material of the present invention can be more preferably prevented from being scratched.
  • the indentation hardness of the first olefin resin layer 3 is more preferably 100 MPa or more, further preferably 115 MPa or more, and particularly preferably 130 MPa or more.
  • scratches can be prevented particularly preferably.
  • the indentation hardness of the first olefin resin layer 3 is more preferably 200 MPa or less, further preferably 180 MPa or less.
  • the method for measuring the indentation hardness of the first olefin resin layer 3 is as described above.
  • the first olefin resin layer 3 is a layer made of an olefin resin.
  • the olefin resin include homopolymers of olefins such as ethylene, propylene and butene; block copolymers of ethylene-propylene and random copolymers; at least one of ethylene and propylene, and butene, penten, hexene and the like. Polymers with at least one other olefin; a polymer with at least one of ethylene and propylene and at least one other monomer such as vinyl acetate and vinyl alcohol; and the like. Among them, polyethylene and polypropylene are preferable, and polyethylene is more preferable, from the viewpoint of obtaining excellent scratch resistance and good bending workability.
  • the polyethylene may be a homopolymer of ethylene, or an ⁇ -olefin such as ethylene and another comonomer copolymerizable with ethylene (for example, propylene, 1-butene, 1-hexene, 1-octene). It may be a copolymer with vinyl acetate, vinyl alcohol, etc.).
  • the polyethylene resin include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (VLDPE), and ultra-high-density polyethylene (Ultra-high-density polyethylene).
  • HDPE high-density polyethylene
  • MDPE medium-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • VLDPE ultra-low-density polyethylene
  • UHMWPE crosslinked polyethylene
  • the polypropylene may be a homopolymer of propylene, or ⁇ -olefin such as ethylene, 1-butene, 1-hexene, 1-octene, etc., which can be copolymerized with propylene. It may be a copolymer with vinyl acetate, vinyl alcohol, etc.). These polypropylenes may be used alone or in combination of two or more. In the present invention, a homopolymer of propylene (homopolypropylene) is particularly preferable from the viewpoint of excellent scratch resistance and bendability.
  • the indentation hardness of the base film layer 2 can be appropriately set by using the first olefin resin layer 3 as a microcrystallized olefin resin layer or the like.
  • the microcrystallized olefin resin layer can be obtained, for example, by adding a crystal nucleating agent to the olefin resin composition forming the first olefin resin layer 3, melting it, and then cooling it.
  • a cooling method for example, cooling by a chill roll method in which a material extruded from a die is brought into contact with a cooling roll (chill roll) through which cooling water has passed during extrusion molding is used for cooling.
  • crystal nucleating agent examples include metal salt-based crystal nucleating agents such as fatty acid metal salts, phosphonic acid metal salts, phosphoric acid ester metal salts, benzoic acid metal salts, piperinate metal salts, and rosin metal salts; fatty acid esters and fats.
  • metal salt-based crystal nucleating agents such as fatty acid metal salts, phosphonic acid metal salts, phosphoric acid ester metal salts, benzoic acid metal salts, piperinate metal salts, and rosin metal salts; fatty acid esters and fats.
  • organic crystal nucleating agents such as group amide, benzylidene sorbitol, quinacridone and cyanine blue
  • inorganic crystal nucleating agents such as talc.
  • the crystal nucleating agent one in which the above crystal nucleating agent is encapsulated in a nanoshell can also be used.
  • the crystal nucleating agent contained in the nanoshell By using the crystal nucleating agent contained in the nanoshell, the crystal nucleating agent is more uniformly dispersed in the first olefin resin layer 3, so that it is easy and stable regardless of various conditions such as melting conditions and cooling conditions.
  • the indentation hardness can be suitably adjusted, and excellent scratch resistance and good bending workability can be obtained.
  • the nanoshell those described in International Publication No. 2018/159660 and the like can be appropriately selected and used.
  • the content of the crystal nucleating agent in the first olefin resin layer 3 is preferably 0.01 to 5 parts by mass, preferably 0.02 to 3 parts by mass with respect to 100 parts by mass of the resin component forming the first olefin resin layer 3. Parts are more preferable, 0.03 to 1 part by mass is further preferable, and 0.05 to 0.5 part by mass is particularly preferable.
  • the content of the crystal nucleating agent is within the above range, it is easy to uniformly disperse in the resin forming the first olefin resin layer 3, the effect as a crystal nucleating agent is easily obtained, and the indene of the base film layer 2 is easily obtained.
  • the tension hardness can be suitably adjusted, and excellent scratch resistance and bending workability can be obtained.
  • the first olefin resin layer 3 has a thickness from the viewpoint of obtaining excellent scratch resistance and bending workability. Is preferably 30 ⁇ m or more and 120 ⁇ m or less, more preferably 40 ⁇ m or more and 110 ⁇ m or less, further preferably 50 ⁇ m or more and 100 ⁇ m or less, and particularly preferably 55 ⁇ m or more and 85 ⁇ m or less. If the thickness of the first olefin resin layer 3 is less than 30 ⁇ m, the scratch resistance and impact resistance (particularly dent resistance) are inferior, and the tension applied during printing when printing or coating with a printing machine is the first.
  • the olefin resin layer 3 may be stretched. Further, when the floor decorative material 100 has the backer layer 6 described later, if the thickness of the first olefin resin layer 3 exceeds 120 ⁇ m, the surface protective coat layer 1 may be cracked or broken in the bending process. Impact resistance (particularly crack resistance) may be inferior.
  • the thickness of the first olefin resin layer 3 is preferably 120 ⁇ m or more and 300 ⁇ m or less, and the thickness is preferably 120 ⁇ m or more and 300 ⁇ m or less. It is more preferably 145 ⁇ m or more and 250 ⁇ m or less, and further preferably 170 ⁇ m or more and 200 ⁇ m or less.
  • the decorative sheet 10 has a decorative layer 4 from the viewpoint of improving the design.
  • the decorative layer 4 is provided, for example, between the first olefin resin layer 3 and the second olefin resin layer 5, between the first olefin resin layer 3 and the surface protective coat layer 1, on the surface protective coat layer 1 or the like. be able to.
  • the decorative layer 4 may be, for example, a colored layer (so-called solid colored layer) that covers the entire surface, or a pattern layer formed by printing various patterns using ink and a printing machine. It may be a combination of these. Further, the decorative layer may be provided at a plurality of locations within the same layer, or may be provided not only in one layer but also in a plurality of layers.
  • the design can be improved while concealing the color by using a solid colored layer.
  • the solid coloring layer and the pattern layer may be combined.
  • the background pattern of the decorative board base material is utilized, only the pattern layer may be provided without the solid coloring layer. Good.
  • the ink used for the decorative layer 4 is a binder mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, or the like. used.
  • a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, or the like. used.
  • the binder is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (polymer).
  • the colorant includes, for example, white pigment, iron black, chrome yellow, titanium yellow, valve handle, cadmium red, ultramarine, and cobalt from the viewpoint of coloring and hiding the ground color of the wood base material 20 and improving the design.
  • Inorganic pigments such as blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments composed of scaly foil pieces such as aluminum and brass; scaly pigments such as titanium dioxide-coated mica and basic lead carbonate.
  • a colorant such as a pearl bright pigment made of foil pieces can also be used.
  • the pattern includes a stone pattern that imitates the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), or a cloth pattern that imitates a cloth grain or a cloth-like pattern.
  • a stone pattern that imitates the surface of a rock
  • a marble pattern for example, a travertin marble pattern
  • a cloth pattern that imitates a cloth grain or a cloth-like pattern.
  • tiled patterns, brickwork patterns, etc. and there are also patterns such as parquet, patchwork, etc. that combine these patterns.
  • These patterns are formed by multicolor printing with ordinary yellow, red, blue, and black process colors, and also by multicolor printing with special colors, which is performed by preparing plates of the individual colors that make up the pattern. Will be done.
  • the thickness of the decorative layer 4 may be appropriately selected according to a desired pattern, but is preferably 0.5 to 20 ⁇ m from the viewpoint of coloring and hiding the ground color of the decorative board base material and improving the design. 1 to 10 ⁇ m is more preferable, and 2 to 5 ⁇ m is even more preferable.
  • the second olefin resin layer 5 is a layer made of an olefin resin.
  • the olefin resin forming the second olefin resin layer 5 include the same olefin resin capable of forming the first olefin resin layer 3. Of these, polyethylene and polypropylene are preferable from the viewpoint of excellent scratch resistance and bendability.
  • the second olefin resin layer 5 may be colored if necessary.
  • a colorant may be added to the olefin resin.
  • the colorant the pigment or dye used in the above-mentioned decorative layer 4 can be used.
  • the second olefin resin layer 5 preferably has a thickness of 30 ⁇ m or more and 120 ⁇ m or less, more preferably 40 ⁇ m or more and 110 ⁇ m or less, and 50 ⁇ m or more and 100 ⁇ m or less. It is more preferably 55 ⁇ m or more and 95 ⁇ m or less.
  • the decorative sheet 10 may include a backer layer 6 on the lowermost layer of the decorative sheet 10, that is, on the side of the second olefin resin layer 5 of the decorative sheet 10.
  • a backer layer 6 By providing the backer layer 6, it is possible to suitably prevent scooping scratches, dent scratches and gloss change, and it is possible to preferably impart impact resistance.
  • the backer layer 6 examples include a synthetic resin backer layer and a foamed resin backer layer, and it is preferable that the backer layer 6 is provided on the lowermost layer of the decorative sheet 10 (the side opposite to the side on which the surface protective coat layer 1 is laminated).
  • Examples of the resin constituting the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, and highly heat-resistant polyalkylene terephthalate [for example, a part of ethylene glycol is 1 , 4-Cyclohexanedimethanol, polyethylene terephthalate substituted with diethylene glycol, etc., so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate-isophthalate copolymer, Examples thereof include amorphous polyester (A-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS and the like. These resins can be used alone or in combination of two or more.
  • the synthetic resin backer layer may contain hollow beads.
  • the type, particle size, content, etc. of the hollow beads those described in JP-A-2014-188941 can be applied.
  • Examples of the method for forming the synthetic resin backer layer include calendar molding, extrusion molding of molten resin, and the like. Of these, extrusion molding of molten resin is preferable, and for example, extrusion molding using a T-die is more preferable.
  • the foamed resin backer layer may be further lower than the synthetic resin backer layer (on the side opposite to the side having the uneven shape).
  • the foamed resin backer layer those described in JP-A-2014-188941 can be applied.
  • the backer layer preferably has a thickness of 100 ⁇ m or more. When the thickness of the backer layer is 100 ⁇ m or more, dents and scratches can be more preferably prevented, and impact resistance can be made excellent.
  • the backer layer preferably has a thickness of 120 ⁇ m or more, and more preferably 200 ⁇ m or more.
  • the upper limit of the thickness of the backer layer is preferably 1000 ⁇ m or less, more preferably 600 ⁇ m or less, and even more preferably 400 ⁇ m or less.
  • the decorative sheet 10 may have a primer layer.
  • the primer layer is a layer mainly provided for improving the adhesion of each layer.
  • the primer layer can be provided on, for example, one side or both sides of the first olefin resin layer 3, one side or both sides of the second olefin resin layer 5, and the like. Further, as in the case of the primer layer, in order to improve the adhesion of each layer, one or both sides of the first olefin resin layer 3 and the second olefin resin layer 5 are subjected to physical surface treatment such as an oxidation method or an unevenness method. Alternatively, surface treatment such as chemical surface treatment may be performed.
  • the primer layer is made of, for example, a resin composition obtained by appropriately mixing a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, and the like with a binder exemplified as a binder that can be used for the decorative layer. Can be formed.
  • the thickness of the primer layer is preferably 0.2 ⁇ m or more and 10 ⁇ m or less, more preferably 0.5 ⁇ m or more and 8 ⁇ m or less, and further preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • the decorative sheet 10 may have an uneven shape.
  • the uneven shape may be present at least in the surface protective coat layer 1 of the decorative sheet 10, and the depth of the uneven shape may remain in the surface protective coat layer 1 or the second olefin resin.
  • the uneven shape pattern examples include a wood grain board conduit groove, a stone board surface unevenness, a cloth surface texturer, a satin finish, a grain, a hairline, and a perforated groove.
  • the uneven pattern is preferably a pattern synchronized with the pattern of the decorative layer 4.
  • the decorative layer 4 has a wood grain pattern
  • the wood grain board conduit groove is selected as the concave pattern and the wood grain of the decorative layer 4 and the wood grain of the concave portion are synchronized, a more realistic and textured, luxurious feeling is obtained.
  • a decorative sheet with a texture can be obtained.
  • a resin composition for forming the second olefin resin layer 5 is prepared, a first olefin resin layer is formed by a method such as a melt extrusion method, and a decorative layer 4 is formed on the second olefin resin layer 5.
  • a resin composition for forming the first olefin resin layer 3 is prepared, the first olefin resin layer 3 is formed by a method such as a melt extrusion method, and the first olefin resin layer 3 is formed.
  • the uncured layer coated with the curable resin composition is cured by irradiating it with heating or ionizing radiation to form the surface protective coat layer 1.
  • an adhesive is applied to at least one surface of the decorative layer 4 and the first olefin resin layer 3, and the decorative layer 4 and the first olefin resin layer 3 are attached so as to face each other to protect the surface.
  • a decorative sheet 10 having a layer 1, a first olefin resin layer 3, a decorative layer 4, and a second olefin resin layer 5 in this order can be produced.
  • the backer layer 6 is formed by a known method, for example, the backer layer 6 produced by a T-die extrusion method or the like and the second olefin resin layer 5 are laminated by dry lamination via a thermal laminate or an adhesive. Can be formed.
  • a method such as extrusion lamination, dry lamination, wet lamination, thermal lamination, etc. is used to extrude the first olefin resin layer 3 by using the resin composition for forming the first olefin resin layer 3 after forming the decorative layer 4.
  • the curable resin composition was applied onto the first olefin resin layer 3 by adhering and pressure-bonding the resin through an adhesive and / or a thermoplastic resin such as an acid-modified polyolefin resin to form a laminate.
  • the surface protective coat layer 1 By irradiating the uncured layer with heating or ionizing radiation to cure it to form the surface protective coat layer 1, the second olefin resin layer 5, the decorative layer 4, the first olefin resin layer 3, and the surface protection are also formed.
  • a decorative sheet having the coat layer 1 in order can be produced.
  • the decorative layer 4 is formed by applying the ink used for forming the decorative layer 4 on the first olefin resin layer 3 or the second olefin resin layer 5 to provide a desired colored layer and pattern layer.
  • the ink can be applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method, preferably a gravure printing method.
  • the curable resin composition is preferably applied to a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat or the like so that the thickness after curing becomes a predetermined thickness. It is carried out by a known method, more preferably by a gravure coat.
  • the uncured resin layer formed by applying the resin composition is made into a cured product by irradiating it with ionizing radiation such as an electron beam or ultraviolet rays. ,
  • ionizing radiation such as an electron beam or ultraviolet rays.
  • the acceleration voltage thereof can be appropriately selected according to the resin to be used and the thickness of the layer, but usually the uncured resin layer can be cured at an acceleration voltage of about 70 to 300 kV. preferable.
  • the irradiation dose is preferably an amount at which the crosslink density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
  • the electron beam source is not particularly limited, and for example, a cockloft Walton type, a bandegraft type, a resonance transformer type, an insulated core transformer type, or various electron beam accelerators such as a linear type, a dynamitron type, and a high frequency type are used. be able to.
  • ultraviolet rays When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted.
  • the ultraviolet source is not particularly limited, and for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like is used.
  • the surface protective coat layer 1 may be formed by performing a heat treatment according to the resin composition to be used and curing the surface protective coat layer 1.
  • the resin composition forming the primer layer is applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. Can be formed.
  • embossing When forming the uneven shape, it is preferable to adopt embossing in consideration of easiness of work.
  • the embossing may be performed by a usual method using a known single-wafer or rotary embossing machine.
  • the wood base material 20 examples include at least one kind such as medium density wood fiberboard, high density wood fiberboard, particle board, coniferous plywood, hardwood plywood, early-maturing plywood, cork sheet, and cork-containing composite base material. ..
  • the wood base material 20 is preferably plywood. Since the wood base material 20 is made of plywood, it is possible to suitably prevent scooping scratches, dent scratches, and gloss change.
  • examples of the coniferous tree include Abies sachalinensis, Larch, Ezo spruce, cedar, cypress, pine, sequoia, spruce and the like.
  • Examples of hardwoods include lauan, cinnamon, hippopotamus, sen, beech, oak, and meranchi.
  • Examples of early-maturing trees include poplar, falcata, acacia, chamelele, eucalyptus, and terminaria.
  • the number of laminated wood single boards is not limited, but usually 3 to 7 is preferable, and 5 to 7 is more preferable.
  • the adhesive used for producing wood plywood is not limited, and known woodworking adhesives can be widely used.
  • the adhesive examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylic nitrile rubber, neoprene rubber, natural rubber and the like as active ingredients. And the adhesive to be mentioned. Further, examples of the thermosetting adhesive include melamine-based, phenol-based, and urea-based (vinyl acetate-urea-based, etc.) adhesives.
  • the thickness of the wood base material 20 is not limited, but is preferably about 2 mm or more and 15 mm or less, and more preferably 2 mm or more and 12 mm or less.
  • the laminating method for laminating the decorative sheet 10 and the wood base material 20 is not limited, and for example, a method of adhering each of them with an adhesive or the like can be adopted.
  • the adhesive may be appropriately selected from known adhesives.
  • reactive hot melt adhesives such as polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, urethane-based reactive hot melt, and butadiene-acrylic nitrile.
  • examples include rubber, neoprene rubber, and natural rubber.
  • Example 1 As the second olefin resin layer, a colored polypropylene film having a thickness of 60 ⁇ m was prepared, and a decorative layer (thickness of 5 ⁇ m) was laminated on one surface of the film with a gravure printing machine. Next, as the first olefin resin layer, a polypropylene film (clear) having a thickness of 60 ⁇ m and an indentation hardness of 50 MPa was prepared and bonded to the decorative layer via an adhesive.
  • the ionizing radiation curable resin composition for the surface protective coating layer with a gravure coat on the surface of the first olefin resin layer After applying the ionizing radiation curable resin composition for the surface protective coating layer with a gravure coat on the surface of the first olefin resin layer, it is cured by irradiating it with ionizing radiation to obtain a thickness of 15 ⁇ m and an indentation hardness.
  • a surface protective coat layer made of an ionizing radiation curable resin of 250 MPa was provided. Further, the uneven pattern of the wood grain conduit pattern was formed by embossing by heat pressure from the side where the surface protective coat layer was formed.
  • a 120 ⁇ m-thick polypropylene film was laminated on the back surface of the second olefin resin layer (the side surface opposite to the side having the decorative layer) to form a backer layer, and a decorative sheet was prepared.
  • the decorative sheet and the wood base material are bonded to each other via an adhesive (so that the side surface of the decorative sheet opposite to the side having the surface protective coat layer is in contact with the wood base material) to prepare the floor decorative material of Example 1. did.
  • Example 2 A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 15 ⁇ m and an indentation hardness of 160 MPa was provided on the surface of the first olefin resin layer. did.
  • Example 3 A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 15 ⁇ m and an indentation hardness of 300 MPa was provided on the surface of the first olefin resin layer. did.
  • Example 4 A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 30 ⁇ m and an indentation hardness of 250 MPa was provided on the surface of the first olefin resin layer. did.
  • Example 5 A floor decorative material was produced in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 10 ⁇ m and an indentation hardness of 250 MPa was provided on the surface of the first olefin resin layer. did.
  • Example 6 A floor decorative material was prepared in the same manner as in Example 5 except that a polypropylene film (clear) having a thickness of 60 ⁇ m and an indentation hardness of 130 MPa was prepared as the first olefin resin layer.
  • a polypropylene film (clear) having a thickness of 60 ⁇ m and an indentation hardness of 130 MPa was prepared as the first olefin resin layer.
  • Example 7 As the first olefin resin layer, a polypropylene film (clear) having a thickness of 180 ⁇ m and an indentation hardness of 130 MPa was prepared, and a floor cosmetic was prepared in the same manner as in Example 1 except that a backer layer was not formed on the decorative sheet. The material was prepared.
  • Example 8 A floor decorative material was prepared in the same manner as in Example 7 except that a polypropylene film (clear) having a thickness of 180 ⁇ m and an indentation hardness of 90 MPa was prepared as the first olefin resin layer.
  • Example 1 A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 15 ⁇ m and an indentation hardness of 150 MPa was provided on the surface of the first olefin resin layer. did.
  • Example 2 A floor decorative material was produced in the same manner as in Example 1 except that the backer layer was not formed on the decorative sheet.
  • Comparative Example 3 A floor decorative material was produced in the same manner as in Comparative Example 2 except that the decorative sheet and the MDF base material were bonded to each other via an adhesive.
  • Example 4 A floor decorative material was produced in the same manner as in Example 1 except that the backer layer was changed to a thickness of 50 ⁇ m.
  • Example 5 A floor decorative material was produced in the same manner as in Example 7 except that the first olefin resin layer was changed to a thickness of 110 ⁇ m.
  • Pencil hardness test The floor decorative materials produced in Examples and Comparative Examples were tested using pencils with a hardness of 2H according to JIS K5600-5-4: 1999, and the following items were evaluated. .. The results are shown in Table 1. As for the comprehensive judgment shown in Table 1, those with an evaluation of "+/-" or higher in all the evaluations were regarded as acceptable.
  • the floor decorative materials produced in Examples 1 to 8 were all "+/-" or higher in the evaluation of gloss change, scooping scratches, and dent scratches, and could be judged to be acceptable by comprehensive judgment.
  • the floor decorative material produced in Examples 1, 3, 4, 7 and 8 in which the indentation hardness of the surface protective coat layer is 250 MPa or more and the thickness of the surface protective coat layer is 15 to 30 ⁇ m is a pencil. It was excellent in all hardness tests.
  • the indentation hardness of the first olefin resin layer is 100 MPa or more, so that the scratches are more preferable. It was confirmed that it can be prevented.
  • the floor decorative material produced in Comparative Example 1 in which the indentation hardness of the surface protective coat layer was less than 160 MPa could not prevent the gloss change, and the total thickness of the decorative sheet was less than 200 ⁇ m.
  • the floor decorative materials produced in Comparative Examples 2 to 5 could not prevent dents and scratches.

Abstract

The present invention provides a decorative material for floor having extremely excellent scratch resistance that can prevent not only scratches and dents but also gloss change. The present invention relates to a decorative material for floor in which a decorative sheet that includes one or more base film layers including a decorative layer and a surface protective coat layer is laminated with a wood base material, and which is characterized in that the surface protective coat layer has an indentation hardness of 160 MPa or more, and the decorative sheet has a total thickness of 200 μm or more.

Description

床用化粧材Floor decorative material
本発明は、床用化粧材に関する。 The present invention relates to a decorative material for floors.
建材、家具、家電製品等において、使用する部材を加飾したい場合には、意匠を備える化粧材が一般的に用いられている。
通常、化粧材では、基材上に直接絵柄層を設けただけの構成では耐傷性、耐汚染性、耐候性等の表面性能が不十分となるため、基材上に設けた絵柄層上に透明性樹脂フィルムを積層した化粧シートをラミネートすることにより、表面性能を付与している。 In building materials, furniture, home appliances, etc., when it is desired to decorate the members to be used, a decorative material having a design is generally used.
Normally, in a decorative material, surface performance such as scratch resistance, stain resistance, and weather resistance is insufficient if the pattern layer is provided directly on the base material. Therefore, the surface performance such as scratch resistance, stain resistance, and weather resistance is usually insufficient. Surface performance is imparted by laminating a decorative sheet on which a transparent resin film is laminated.
例えば、特許文献１には、基材に積層して用いるための化粧シートであって、当該シートは、少なくとも第一透明性樹脂層、絵柄層、第二透明性樹脂層及び透明性保護層を順に有し、当該透明性保護層が、電離放射線硬化型樹脂から構成されることを特徴とする化粧シートが開示されている。 For example, Patent Document 1 describes a decorative sheet for being laminated on a base material, which has at least a first transparent resin layer, a pattern layer, a second transparent resin layer, and a transparent protective layer. A decorative sheet is disclosed, which is provided in order and the transparent protective layer is composed of an ionizing radiation curable resin.
また、例えば、特許文献２には、第一オレフィン樹脂層、第二オレフィン樹脂層、及び表面保護層をこの順に有する化粧シートにおいて、上記第二オレフィン樹脂層のインデンテーション硬さＨＩＴ＜２＞と前記表面保護層のインデンテーション硬さＨＩＴ＜１＞とが特定の関係を満たすことを特徴とする化粧シートが開示されている。 Further, for example, in Patent Document 2, in a decorative sheet having a first olefin resin layer, a second olefin resin layer, and a surface protective layer in this order, the indentation hardness HIT <2> of the second olefin resin layer is described. A decorative sheet is disclosed in which the indentation hardness HIT <1> of the surface protective layer satisfies a specific relationship.
近年、木質基材の表面に床用化粧シートを貼り合わせた床用化粧材が多く発売されているが、耐傷性能を更に向上してほしいとの要望が出始めている。
これまでは、市場クレーム及びコンプレイン指摘となる床用化粧材の傷の現象は、抉れ傷又は凹み傷が大半であり、代用試験として実施している引き掻き試験（鉛筆硬度試験等）においても傷の評価は、「抉れ傷又は凹み傷」の発生の有無で評価されてきた。 In recent years, many floor decorative materials in which a floor decorative sheet is attached to the surface of a wooden base material have been put on the market, but there are beginning to be requests for further improvement in scratch resistance.
Until now, the phenomenon of scratches on floor decorative materials, which has been pointed out by market complaints and complains, has been mostly scratches or dents, and in scratch tests (pencil hardness test, etc.) conducted as a substitute test. The evaluation of the scratches has been made based on the presence or absence of "scratches or dents".
ところが、市場の要求品質の上昇に伴い、従来なら問題視されていなかった「艶変化」と呼ばれる現象についても、傷としてコンプレイン指摘を受けるようになっており、「艶変化」が発生しにくい床用化粧材の開発が望まれている。
上述した「艶変化」は、表面に荷重が加わった状態で引き摺られた際、抉れ傷または凹み傷が発生しないまでも表面が平滑になり、そのことで表面を照らした光の反射状態が変化することで表面の艶の見え方が異なることにより発生する現象である。
特許文献１及び２では、「艶変化」については検討されておらず、更なる改善の余地があった。 However, with the rise in quality demands of the market, the phenomenon called "gloss change", which was not regarded as a problem in the past, is now being pointed out as a scratch, and "gloss change" is less likely to occur. The development of decorative materials for floors is desired.
In the above-mentioned "gloss change", when the surface is dragged with a load applied, the surface becomes smooth even if there are no scratches or dents, and as a result, the reflected state of the light that illuminates the surface is changed. This is a phenomenon that occurs when the surface gloss looks different due to changes.
In Patent Documents 1 and 2, "gloss change" is not examined, and there is room for further improvement.
特開２００５－７４６８３号公報Japanese Unexamined Patent Publication No. 2005-74683 国際公開第２０１８／１５９６６０号International Publication No. 2018/159660
本発明は、上述した課題を解決するものであり、抉れ傷及び凹み傷の防止に加えて、艶変化をも防止できる極めて優れた耐傷性能を有する床用化粧材を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems, and to provide a floor decorative material having extremely excellent scratch resistance that can prevent not only scratches and dents but also gloss change. To do.
本発明者らは、上述した課題を解決するため鋭意検討したところ、化粧層を含む１層以上のベースフィルム層及び表面保護コート層を備える化粧シートと、木質基材とが積層された床用化粧材において、表面保護コート層のインデンテーション硬さ、及び、化粧シートの総厚みを特定の範囲に制御することにより、抉れ傷及び凹み傷の防止に加えて、艶変化をも防止することができることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above-mentioned problems, the present inventors have conducted a diligent study and found that a decorative sheet having one or more base film layers including a decorative layer and a surface protective coat layer and a wooden base material are laminated for a floor. In the decorative material, by controlling the indentation hardness of the surface protective coat layer and the total thickness of the decorative sheet within a specific range, in addition to preventing scuffing and denting scratches, it is also possible to prevent gloss change. We have found that we can do this, and have completed the present invention.
すなわち、本発明は、化粧層を含む１層以上のベースフィルム層及び表面保護コート層を備える化粧シートと、木質基材とが積層された床用化粧材であって、上記表面保護コート層のインデンテーション硬さが１６０ＭＰａ以上であり、上記化粧シートの総厚みが、２００μｍ以上であることを特徴とする床用化粧材である。
本発明の床用化粧材において、上記表面保護コート層は、厚みが１０μｍ以上３０μｍ以下であることが好ましい。
また、本発明の床用化粧材において、上記表面保護コート層は、インデンテーション硬さが３００ＭＰａ以下であることが好ましい。
また、本発明の床用化粧材において、上記ベースフィルム層は、第一オレフィン樹脂層を有しており、上記第一のオレフィン樹脂層のインデンテーション硬さが８０ＭＰａ以上であることが好ましい。
また、上記第一オレフィン樹脂層は、厚みが１２０μｍ以上３００μｍ以下であることが好ましい。
また、本発明の床用化粧材において、上記ベースフィルム層は、上記表面保護コート層が積層される側と反対側に、バッカー層を有することが好ましい。
また、本発明の床用化粧材において、上記バッカー層は、厚みが１００μｍ以上であることが好ましい。
また、本発明の床用化粧材において、上記木質基材は、合板であることが好ましい。 That is, the present invention is a floor decorative material in which a decorative sheet including one or more base film layers including a decorative layer and a surface protective coat layer and a wood base material are laminated, and the surface protective coat layer is the same. A floor decorative material having an indentation hardness of 160 MPa or more and a total thickness of the decorative sheet of 200 μm or more.
In the floor decorative material of the present invention, the surface protective coat layer preferably has a thickness of 10 μm or more and 30 μm or less.
Further, in the floor decorative material of the present invention, the surface protective coat layer preferably has an indentation hardness of 300 MPa or less.
Further, in the floor decorative material of the present invention, the base film layer has a first olefin resin layer, and the indentation hardness of the first olefin resin layer is preferably 80 MPa or more.
The thickness of the first olefin resin layer is preferably 120 μm or more and 300 μm or less.
Further, in the floor decorative material of the present invention, it is preferable that the base film layer has a backer layer on the side opposite to the side on which the surface protective coat layer is laminated.
Further, in the floor decorative material of the present invention, the backer layer preferably has a thickness of 100 μm or more.
Further, in the floor decorative material of the present invention, the wood base material is preferably plywood.
本発明は、抉れ傷及び凹み傷の防止に加えて、艶変化をも防止できる極めて優れた耐傷性能を有する床用化粧材を提供することができる。 INDUSTRIAL APPLICABILITY The present invention can provide a floor decorative material having extremely excellent scratch resistance that can prevent not only scratches and dents but also gloss change.
本発明の床用化粧材の一例を模式的に示す断面図である。It is sectional drawing which shows typically an example of the decorative material for a floor of this invention. （ａ）は、化粧シートの模式的な断面図であり、（ｂ）は、凹凸形状を有する化粧シートの模式的な断面図である。(A) is a schematic cross-sectional view of a decorative sheet, and (b) is a schematic cross-sectional view of a decorative sheet having an uneven shape. （ａ）及び（ｂ）は、本発明の床用化粧材の好ましい一例を模式的に示す断面図である。(A) and (b) are cross-sectional views schematically showing a preferable example of the floor decorative material of the present invention. （ａ）～（ｃ）は、本明細書のインデンテーション硬さの測定方法を説明する図である。(A) to (c) are diagrams for explaining the method for measuring the indentation hardness of the present specification.
以下、本発明の床用化粧材について説明する。
なお、以下の記載において、「～」で表される数値範囲の下限上限は「以上以下」を意味する（例えば、α～βならば、α以上β以下である）。 Hereinafter, the floor decorative material of the present invention will be described.
In the following description, the lower and upper limits of the numerical range represented by "-" mean "greater than or equal to or less than" (for example, if α to β, it is greater than or equal to α or less than β).
本発明の床用化粧材は、化粧層を含む１層以上のベースフィルム層及び表面保護コート層を備える化粧シートと、木質基材とが積層された構成を有する。
図１は、床用化粧材の一例を模式的に示す断面図である。
図１に示すように、床用化粧材１００は、表面保護コート層１及びベースフィルム層２を備える化粧シート１０と、木質基材２０とが積層されている。 The floor decorative material of the present invention has a structure in which a decorative sheet including one or more base film layers including a decorative layer and a surface protective coat layer and a wood base material are laminated.
FIG. 1 is a cross-sectional view schematically showing an example of a decorative material for a floor.
As shown in FIG. 1, in the floor decorative material 100, a decorative sheet 10 having a surface protective coat layer 1 and a base film layer 2 and a wood base material 20 are laminated.
＜化粧シート＞
化粧シート１０は、表面保護コート層１及び化粧層を含む１層以上のベースフィルム層２を備えており、表面保護コート層１は、インデンテーション硬さが１６０ＭＰａ以上であり、化粧シート１０は、総厚みが２００μｍ以上である。 <Cosmetic sheet>
The decorative sheet 10 includes a surface protective coat layer 1 and one or more base film layers 2 including the decorative layer. The surface protective coat layer 1 has an indentation hardness of 160 MPa or more, and the decorative sheet 10 has an indentation hardness of 160 MPa or more. The total thickness is 200 μm or more.
（総厚み）
化粧シート１０は、総厚みが２００μｍ以上である。
化粧シート１０の総厚みが２００μｍ未満であると、凹み傷を防止することができない。
化粧シート１０は、総厚みが２２０μｍ以上であることが好ましく、２４０μｍ以上であることがより好ましく、２５０μｍ以上であることがさらに好ましい。
化粧シート１０は、総厚みの上限は特に限定されないが、５００μｍ以下であることが好ましく、４００μｍ以下であることがより好ましい。 (Total thickness)
The decorative sheet 10 has a total thickness of 200 μm or more.
If the total thickness of the decorative sheet 10 is less than 200 μm, dents and scratches cannot be prevented.
The total thickness of the decorative sheet 10 is preferably 220 μm or more, more preferably 240 μm or more, and even more preferably 250 μm or more.
The upper limit of the total thickness of the decorative sheet 10 is not particularly limited, but is preferably 500 μm or less, and more preferably 400 μm or less.
ここで、化粧シート１０の総厚みについて説明する。
図２（ａ）は、化粧シートの模式的な断面図であり、図２（ｂ）は、凹凸形状を有する化粧シートの模式的な断面図である。
化粧シート１０が凹凸形状を有さない場合には、図２（ａ）に示すように、表面Ａから表面Ｂまでの長さが化粧シート１０の「総厚み」である。
また、化粧シート１０が凹凸形状を有する場合においても、図２（ｂ）に示すように、表面Ａから表面Ｂまでの長さが化粧シート１０の「総厚み」である。
続いて、化粧シート１０を構成する各層について説明する。 Here, the total thickness of the decorative sheet 10 will be described.
FIG. 2A is a schematic cross-sectional view of the decorative sheet, and FIG. 2B is a schematic cross-sectional view of the decorative sheet having an uneven shape.
When the decorative sheet 10 does not have an uneven shape, the length from the surface A to the surface B is the "total thickness" of the decorative sheet 10, as shown in FIG. 2 (a).
Further, even when the decorative sheet 10 has an uneven shape, the length from the surface A to the surface B is the "total thickness" of the decorative sheet 10, as shown in FIG. 2 (b).
Subsequently, each layer constituting the decorative sheet 10 will be described.
（表面保護コート層）
化粧シート１０は、表面保護コート層１を有する。
表面保護コート層１は、インデンテーション硬さが１６０ＭＰａ以上である。
表面保護コート層１のインデンテーション硬さが１６０ＭＰａ未満の場合には、艶変化を防止することができない。
表面保護コート層１は、インデンテーション硬さが２００ＭＰａ以上であることが好ましく、２４０ＭＰａ以上であることがより好ましい。
一方、表面保護コート層１は、インデンテーション硬さが３００ＭＰａ以下であることが好ましく、２９０ＭＰａ以下であることがより好ましい。
表面保護コート層１のインデンテーション硬さが３００ＭＰａを超えると、脆くなってしまい、艶変化を防止できるが、抉れ傷が発生し易くなったり、化粧シート１０の取り扱い時や意匠性を付与するためのエンボス賦形時に割れが生じ易くなることがある。 (Surface protective coat layer)
The decorative sheet 10 has a surface protective coat layer 1.
The surface protective coat layer 1 has an indentation hardness of 160 MPa or more.
When the indentation hardness of the surface protective coat layer 1 is less than 160 MPa, it is not possible to prevent the gloss change.
The surface protective coat layer 1 preferably has an indentation hardness of 200 MPa or more, more preferably 240 MPa or more.
On the other hand, the surface protective coat layer 1 preferably has an indentation hardness of 300 MPa or less, and more preferably 290 MPa or less.
If the indentation hardness of the surface protective coat layer 1 exceeds 300 MPa, it becomes brittle and the gloss change can be prevented. For embossing, cracks may easily occur during shaping.
本明細書において、各層の「インデンテーション硬さ」は、表面皮膜物性試験機トライボインデンター（登録商標）「ＴＩ－９５０」（ＨＹＳＩＴＲＯＮ社製）を用いて測定されるナノインデンテーション硬さで示す。
なお、トライボインデンター（登録商標）「ＴＩ－９５０」を用いた各層のインデンテーション硬さ（ＨＩＴ）の測定方法は次の通りである。 In the present specification, the "indentation hardness" of each layer is indicated by the nanoindentation hardness measured using a surface film physical property tester Tribo Indenter (registered trademark) "TI-950" (manufactured by HYSITRON). ..
The method for measuring the indentation hardness (HIT) of each layer using the tribo indenter (registered trademark) "TI-950" is as follows.
（１）図４（ａ）に示されるバーコビッチ圧子を用いて、図４（ｂ）に示すように測定試料３０にバーコビッチ圧子３１を後述の押込み条件にて、荷重をかける方向３２の矢印方向に押込み、表面にできた三角錐型の幾何学的形状から、「装置標準の方法で補正した接触投影面積（Ａｐ）（ｍｍ２）」を計算し、最大試験荷重（Ｆｍａｘ）を前記Ａｐで除することにより硬さを求める。
すなわち、ＨＩＴ＝Ｆｍａｘ／Ａｐである。
（２）ここで、押込み条件は、室温（実験室環境温度）において、図４（ｃ）に示される通り、表面保護コート層１については、先ず０～１００μＮまでの負荷を１０秒間で加え（すなわち１０μＮ／ｓ）、次に１００μＮ（Ｆｍａｘ）の負荷で５秒間保持し、最後に１００～０μＮまでの除荷を１０秒間で行う。
また、後述する第一オレフィン樹脂層３については、先ず０～５０μＮまでの負荷を５秒間で加え（すなわち１０μＮ／ｓ）、次に５０μＮ（Ｆｍａｘ）の負荷で５秒間保持し、最後に５０～０μＮまでの除荷を１０秒間で行う。
通常、押し込み量（ｈ）は１００～１５０ｎｍ程度であるため、測定試料となる層の押し込み方向の厚さは１．０μｍ以上（好適には１．５μｍ以上）であればよい。Ａｐは、２４．５０〔ｈｍａｘ－ε（ｈｍａｘ－ｈｒ）〕２で算出される（ここで、εは圧子の幾何学的形状による補正係数であり、ｈｒは除荷後の表面に残存している三角錐型の幾何学的形状の深さである。）。
（３）なお、硬さの測定に際し、測定試料３０となる層以外の層の硬さの影響を回避するために測定対象の層の断面の硬さを測定する。すなわち、化粧シートを樹脂（冷間硬化タイプのエポキシ２液硬化樹脂）で包埋し、室温で２４時間以上放置して硬化させた後、硬化した埋包サンプルを機械研磨して測定対象の層の断面を露出させ、測定対象の層の断面（充填剤等の微粒子が層中に含まれる場合には当該微粒子を避けた位置）にバーコビッチ圧子３１を押込むことにより各層の断面の硬さを測定する。
（４）各層について、それぞれ偏りが生じないように１０箇所のインデンテーション硬さを測定し、１０箇所の平均値をそれぞれ「表面保護コート層１のインデンテーション硬さ」、「第一オレフィン樹脂層３のインデンテーション硬さ」とする。 (1) Using the Berkovich indenter shown in FIG. 4 (a), as shown in FIG. 4 (b), the Berkovich indenter 31 is applied to the measurement sample 30 in the direction of the arrow in the direction 32 in which the load is applied under the pressing conditions described later. The "contact projection area (Ap) (mm 2 ) corrected by the standard method of the device" is calculated from the triangular pyramidal geometric shape formed on the surface by pushing, and the maximum test load (Fmax) is divided by the above Ap. The hardness is obtained by doing.
That is, HIT = Fmax / Ap.
(2) Here, as the pressing condition, at room temperature (laboratory environmental temperature), as shown in FIG. 4 (c), first, a load of 0 to 100 μN is applied to the surface protective coat layer 1 in 10 seconds ( That is, it is held for 5 seconds with a load of 10 μN / s) and then 100 μN (Fmax), and finally unloading from 100 to 0 μN is performed in 10 seconds.
Further, for the first olefin resin layer 3 described later, a load of 0 to 50 μN is first applied for 5 seconds (that is, 10 μN / s), then a load of 50 μN (Fmax) is held for 5 seconds, and finally 50 to 50 μN. Unloading up to 0 μN is performed in 10 seconds.
Since the pushing amount (h) is usually about 100 to 150 nm, the thickness of the layer to be the measurement sample in the pushing direction may be 1.0 μm or more (preferably 1.5 μm or more). Ap is calculated by 24.50 [hmax-ε (hmax-hr)] 2 (where ε is a correction factor due to the geometric shape of the indenter and hr remains on the surface after unloading. The depth of the triangular pyramidal geometry.).
(3) When measuring the hardness, the hardness of the cross section of the layer to be measured is measured in order to avoid the influence of the hardness of the layers other than the layer to be the measurement sample 30. That is, the decorative sheet is embedded with a resin (cold-curing type epoxy two-component curing resin), left at room temperature for 24 hours or more to cure, and then the cured embedded sample is mechanically polished to form a layer to be measured. The hardness of the cross section of each layer is increased by exposing the cross section of the above layer and pushing the Berkovich indenter 31 into the cross section of the layer to be measured (when the layer contains fine particles such as a filler, the position where the fine particles are avoided). Measure.
(4) For each layer, the indentation hardness at 10 points was measured so as not to cause bias, and the average value at 10 points was the "indentation hardness of the surface protective coat layer 1" and the "first olefin resin layer", respectively. The indentation hardness of 3 ".
表面保護コート層１は、化粧シート１０の耐汚染性、耐擦傷性、耐薬品性等の表面特性を向上させ、更に上述したインデンテーション硬さを満足させる観点から、硬化性樹脂組成物の硬化物からなることが好ましい。
上記硬化性樹脂組成物としては、例えば、熱硬化性樹脂、２液硬化性樹脂、電離放射線硬化性樹脂等の硬化性樹脂を含む樹脂組成物が挙げられ、より優れた表面特性を得る観点から、硬化性樹脂として２液硬化性樹脂、電離放射線硬化性樹脂を含む樹脂組成物が好ましい。 The surface protective coat layer 1 improves the surface characteristics such as stain resistance, scratch resistance, and chemical resistance of the decorative sheet 10, and further cures the curable resin composition from the viewpoint of satisfying the above-mentioned indentation hardness. It is preferably composed of things.
Examples of the curable resin composition include a resin composition containing a curable resin such as a thermosetting resin, a two-component curable resin, and an ionizing radiation curable resin, from the viewpoint of obtaining more excellent surface characteristics. As the curable resin, a resin composition containing a two-component curable resin and an ionizing radiation curable resin is preferable.
上記熱硬化性樹脂としては、例えば、不飽和ポリエステル樹脂、ポリウレタン樹脂（２液硬化型ポリウレタンも含む）、エポキシ樹脂、アミノアルキッド樹脂、フェノール樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹脂、グアナミン樹脂、メラミン－尿素共縮合樹脂、珪素樹脂、ポリシロキサン樹脂等が挙げられる。 Examples of the thermosetting resin include unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, and guanamine resin. Examples thereof include melamine-urea cocondensate resin, silicon resin, and polysiloxane resin.
上記熱硬化性樹脂には、架橋剤、重合開始剤等の硬化剤、重合促進剤を添加することができる。例えば、硬化剤としてはイソシアネート、有機スルホン酸塩等が不飽和ポリエステル樹脂やポリウレタン樹脂等に添加でき、有機アミン等がエポキシ樹脂に添加でき、メチルエチルケトンパーオキサイド等の過酸化物、アゾイソブチルニトリル等のラジカル開始剤が不飽和ポリエステル樹脂に添加できる。 A curing agent such as a cross-linking agent and a polymerization initiator, and a polymerization accelerator can be added to the thermosetting resin. For example, as a curing agent, isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resin, polyurethane resin, etc., organic amine, etc. can be added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutylnitrile, etc. A radical initiator can be added to the unsaturated polyester resin.
上記熱硬化性樹脂で表面保護コート層１を形成する方法は、例えば、熱硬化性樹脂の溶液をロールコート法、グラビアコート法等の塗布法で塗布し、乾燥及び硬化させる方法が挙げられる。 Examples of the method for forming the surface protective coat layer 1 with the thermosetting resin include a method in which a solution of the thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, and dried and cured.
上記２液硬化性樹脂としては、主剤と硬化剤とにより硬化する樹脂であれば特に制限はなく、好ましくは主剤をポリオール（多価アルコール）とし、硬化剤をイソシアネート硬化剤とする２液硬化性ウレタン樹脂が挙げられる。 The two-component curable resin is not particularly limited as long as it is a resin that can be cured by a main agent and a curing agent, and is preferably a two-component curable resin in which the main agent is a polyol (polyhydric alcohol) and the curing agent is an isocyanate curing agent. Urethane resin can be mentioned.
上記主剤としては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ブチレングリコール、ネオペンチルグリコール、１，６－ヘキサンジオール等のポリオール；アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール等の官能基として水酸基を有するポリオール；等が好ましく挙げられる。これらは単独又は複数種を混合して使用できる。 Examples of the main agent include polyols such as polyethylene glycol, polypropylene glycol, butylene glycol, neopentyl glycol, and 1,6-hexanediol; polyols having a hydroxyl group as a functional group such as acrylic polyol, polyester polyol, and polyether polyol; and the like. Is preferably mentioned. These can be used alone or in combination of two or more.
上記イソシアネート硬化剤としては、従来公知の化合物を適宜使用すればよく、例えば、２，４－トリレンジイソシアネート（ＴＤＩ）、キシレンジイソシアネート（ＸＤＩ）、ナフタレンジイソシアネート等の芳香族イソシアネート；１，６－ヘキサメチレンジイソシアネート（ＨＭＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、メチレンジイソシアネート（ＭＤＩ）、水素添加トリレンジイソシアネート等の脂肪族（ないしは脂環式）イソシアネート；等のポリイソシアネートが用いられる。また、これら各種イソシアネートの付加体又は多量体、例えば、トリレンジイソシアネートの付加体、トリレンジイソシアネート３量体（ｔｒｉｍｅｒ）なども用いられる。 As the isocyanate curing agent, a conventionally known compound may be appropriately used, and for example, aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), and naphthalene diisocyanate; 1,6-hexa. Polyisocyanates such as methylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), and aliphatic (or alicyclic) isocyanates such as hydrogenated tolylene diisocyanate are used. Further, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like are also used.
上記電離放射線硬化性樹脂は、電離放射線、すなわち電磁波又は荷電粒子線のうち、分子を重合あるいは架橋し得るエネルギー量子を有するもの、例えば、紫外線（ＵＶ）又は電子線（ＥＢ）の他、Ｘ線、γ線などの電磁波、α線、イオン線等の荷電粒子線を照射することにより硬化する樹脂である。具体的には、電離放射線硬化性樹脂としては、慣用されている重合性モノマー、重合性オリゴマー及びプレポリマーの中から適宜選択して用いることができる。 The ionizing radiation curable resin includes ionizing radiation, that is, electromagnetic waves or charged particle beams having energy quanta capable of polymerizing or cross-linking molecules, for example, ultraviolet rays (UV) or electron beams (EB), as well as X-rays. , A resin that cures by irradiating electromagnetic waves such as γ-rays and charged particle beams such as α-rays and ion rays. Specifically, the ionizing radiation curable resin can be appropriately selected from the commonly used polymerizable monomers, polymerizable oligomers and prepolymers.
上記重合性モノマーとしては、例えば、分子中にラジカル重合性不飽和基を持つ（メタ）アクリレート系モノマーが好適であり、なかでも多官能（メタ）アクリレートモノマーが好ましい。多官能（メタ）アクリレートモノマーとしては、分子内にエチレン性不飽和結合を２個以上有する（メタ）アクリレートモノマーであればよく、例えば、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が好ましく挙げられる。これらの（メタ）アクリレートモノマーは、単独で、又は２種以上を組み合わせて用いることができる。 As the polymerizable monomer, for example, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule. For example, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, etc. Preferred examples include trimerol propantri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These (meth) acrylate monomers can be used alone or in combination of two or more.
上記重合性オリゴマーとしては、例えば、分子中にラジカル重合性不飽和基を持つオリゴマー、例えばウレタン（メタ）アクリレートオリゴマー、エポキシ（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、ポリエーテル（メタ）アクリレートオリゴマー、アクリル（メタ）アクリレートオリゴマー等の（メタ）アクリレートオリゴマーが好ましく挙げられる。
これらの重合性オリゴマーは、単独で、又は２種以上を組み合わせて用いることができる。 Examples of the polymerizable oligomer include oligomers having a radically polymerizable unsaturated group in the molecule, such as urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, and polyether (meth) acrylate. Preferred examples include (meth) acrylate oligomers such as oligomers and acrylic (meth) acrylate oligomers.
These polymerizable oligomers can be used alone or in combination of two or more.
上記硬化性樹脂組成物は、上記の硬化性樹脂の他、後述する分散剤等が含まれていてもよい。 The curable resin composition may contain a dispersant or the like, which will be described later, in addition to the curable resin.
上記硬化性樹脂組成物は、添加剤として、本発明の目的を損なわない範囲で、紫外線吸収剤、紫外線遮蔽剤、光安定剤、耐摩耗性向上剤、重合禁止剤、架橋剤、赤外線吸収剤、帯電防止剤、接着性向上剤、レベリング剤、チクソ性付与剤、カップリング剤、可塑剤、消泡剤、充填剤、ブロッキング防止剤、滑剤、溶剤等を添加することができる。中でも、耐候性向上のために、紫外線吸収剤、光安定剤等の耐候剤等を含有することが好ましい。 As an additive, the curable resin composition is an ultraviolet absorber, an ultraviolet shielding agent, a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a cross-linking agent, and an infrared absorber as long as the object of the present invention is not impaired. , Antistatic agent, adhesive improver, leveling agent, tincture imparting agent, coupling agent, plasticizer, defoaming agent, filler, blocking inhibitor, lubricant, solvent and the like can be added. Above all, in order to improve the weather resistance, it is preferable to contain a weather resistant agent such as an ultraviolet absorber and a light stabilizer.
上記紫外線吸収剤としては、例えば、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系、サリチレート系、アクリロニトリル系等が挙げられ、光安定剤としては、ヒンダードアミン系、アクリレート系、オキサミド系、シアノアクリレート系等が挙げられる。 Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, acrylonitrile-based, and examples of the light stabilizer include hindered amine-based, acrylate-based, oxamide-based, and cyanoacrylate-based. Be done.
上記表面保護コート層１は、分散剤を含有することができる。
上記分散剤としては、高分子界面活性剤、脂肪酸金属塩、シランカップリング剤、チタネートカップリング剤、シリコーンオイル、ワックス、変性樹脂等が挙げられる。
また、国際公開第２０１８／１５９６６０号等に記載のナノシェルを好適に用いることもできる。
これらの分散剤は、単独で、又は２種以上を組み合わせて用いることができる。 The surface protective coat layer 1 can contain a dispersant.
Examples of the dispersant include polymer surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicone oils, waxes, modified resins and the like.
Further, the nanoshells described in International Publication No. 2018/159660 and the like can also be preferably used.
These dispersants can be used alone or in combination of two or more.
上記分散剤の含有量は、表面保護コート層１を形成する樹脂成分１００質量部に対して、０．０１質量部以上３０質量部以下が好ましく、０．０５質量部以上１５質量部以下がより好ましく、０．１質量部以上１０質量部以下が更に好ましく、０．３質量部以上５質量部以下が特に好ましい。 The content of the dispersant is preferably 0.01 part by mass or more and 30 parts by mass or less, and more preferably 0.05 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin component forming the surface protective coat layer 1. It is preferably 0.1 part by mass or more and 10 parts by mass or less, and 0.3 parts by mass or more and 5 parts by mass or less is particularly preferable.
表面保護コート層１は、さらに、耐擦傷性を向上する観点から、無機微粒子を含有することが好ましい。
上記無機微粒子としては、シリカ、アルミナ、アルミノシリケート、カオリナイト、炭酸カルシウム、硫酸バリウム及びガラス等が挙げられる。
また、上記無機微粒子の種類や含有量を制御することにより、表面保護コート層１のインデンテーション硬さを調節することもできる。 The surface protective coat layer 1 preferably contains inorganic fine particles from the viewpoint of further improving scratch resistance.
Examples of the inorganic fine particles include silica, alumina, aluminosilicate, kaolinite, calcium carbonate, barium sulfate, and glass.
Further, the indent hardness of the surface protective coat layer 1 can be adjusted by controlling the type and content of the inorganic fine particles.
上記無機微粒子の平均粒子径は限定的ではないが、２０μｍ以下が好ましく、その中でも１μｍ以上２０μｍ以下が好ましく、２μｍ以上１５μｍ以下がより好ましい。
上記無機微粒子の平均粒子径は、溶液中の該粒子を動的光散乱方法で測定し、粒子径分布を体積累積分布で表したときの５０％粒子径（ｄ５０：メジアン径）である。５０％粒子径は、例えば、Ｍｉｃｒｏｔｒａｃ粒度分析計（日機装株式会社製）を用いて測定することができる。 The average particle size of the inorganic fine particles is not limited, but is preferably 20 μm or less, more preferably 1 μm or more and 20 μm or less, and more preferably 2 μm or more and 15 μm or less.
The average particle size of the inorganic fine particles is 50% particle size (d50: median size) when the particles in the solution are measured by a dynamic light scattering method and the particle size distribution is expressed by a volume cumulative distribution. The 50% particle size can be measured using, for example, a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).
上記無機微粒子の含有量は、表面保護コート層１を形成する樹脂成分１００質量部に対して、１質量部以上３０質量部以下が好ましく、２質量部以上２５質量部以下がより好ましく、５質量部以上２０質量部以下がさらに好ましい。 The content of the inorganic fine particles is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 25 parts by mass or less, and 5 parts by mass with respect to 100 parts by mass of the resin component forming the surface protective coat layer 1. More than 20 parts by mass is more preferable.
表面保護コート層１の厚さは、１０μｍ以上３０μｍ以下であることが好ましい。
表面保護コート層１の厚さが１０μｍ以上３０μｍ以下であることにより、抉れ傷及び凹み傷と、艶変化とを好適に防止することができ、更に、化粧シート１０の割れを好適に防止することができ、取り扱い性を向上することもできる。
表面保護コート層１の厚さは、１２μｍ以上２５μｍ以下であることがより好ましく、１５μｍ以上２０μｍ以下であることが更に好ましい。 The thickness of the surface protective coat layer 1 is preferably 10 μm or more and 30 μm or less.
When the thickness of the surface protective coat layer 1 is 10 μm or more and 30 μm or less, it is possible to suitably prevent scuffing and denting scratches and gloss change, and further preferably prevent cracking of the decorative sheet 10. It is possible to improve the handleability.
The thickness of the surface protective coat layer 1 is more preferably 12 μm or more and 25 μm or less, and further preferably 15 μm or more and 20 μm or less.
（ベースフィルム層）　
化粧シート１０は、化粧層を含む１層以上のベースフィルム層２を有する。
ベースフィルム層２としては、化粧層の他、第一オレフィン樹脂層、第二オレフィン樹脂層、及び、バッカー層等が挙げられる。
図３は、本発明の床用化粧材の好ましい一例を模式的な断面図である。
図３（ａ）に示すように、床用化粧材１００は、表面保護コート層１及びベースフィルム層２を備える化粧シート１０と、木質基材２０とが積層されており、ベースフィルム層２は、第一オレフィン樹脂層３、化粧層４、第二オレフィン樹脂層５及びバッカー層６を含む層であってもよい。
また、図３（ｂ）に示すように、床用化粧材１００は、表面保護コート層１及びベースフィルム層２を備える化粧シート１０と、木質基材２０とが積層されており、ベースフィルム層２は、第一オレフィン樹脂層３、化粧層４及び第二オレフィン樹脂層５を含む層であってもよい。
ベースフィルム層２を構成する各層について説明する。 (Base film layer)
The decorative sheet 10 has one or more base film layers 2 including a decorative layer.
Examples of the base film layer 2 include a first olefin resin layer, a second olefin resin layer, a backer layer, and the like, in addition to the decorative layer.
FIG. 3 is a schematic cross-sectional view of a preferred example of the floor decorative material of the present invention.
As shown in FIG. 3A, in the floor decorative material 100, a decorative sheet 10 having a surface protective coat layer 1 and a base film layer 2 and a wood base material 20 are laminated, and the base film layer 2 is , The first olefin resin layer 3, the decorative layer 4, the second olefin resin layer 5, and the backer layer 6 may be included.
Further, as shown in FIG. 3B, in the floor decorative material 100, a decorative sheet 10 having a surface protective coat layer 1 and a base film layer 2 and a wood base material 20 are laminated, and the base film layer is formed. Reference numeral 2 denotes a layer including the first olefin resin layer 3, the decorative layer 4, and the second olefin resin layer 5.
Each layer constituting the base film layer 2 will be described.
（第一オレフィン樹脂層）
第一オレフィン樹脂層３は、インデンテーション硬さが８０ＭＰａ以上であることが好ましい。
第一オレフィン樹脂層３のインデンテーション硬さが８０ＭＰａ以上であると、本発明の床用化粧材に、抉れ傷をより好適に防止することができる。
第一オレフィン樹脂層３は、インデンテーション硬さが１００ＭＰａ以上であることがより好ましく、１１５ＭＰａ以上であることが更に好ましく、１３０ＭＰａ以上であることが特に好ましい。床用化粧材１００が後述するバッカー層６を有する場合（すなわち、図３（ａ）の場合）に、抉れ傷を特に好適に防止することができる。
また、第一オレフィン樹脂層３は、インデンテーション硬さが２００ＭＰａ以下であることがより好ましく、１８０ＭＰａ以下であることがさらに好ましい。
なお、第一オレフィン樹脂層３のインデンテーション硬さの測定方法は、上述した通りである。 (First olefin resin layer)
The first olefin resin layer 3 preferably has an indentation hardness of 80 MPa or more.
When the indentation hardness of the first olefin resin layer 3 is 80 MPa or more, the floor decorative material of the present invention can be more preferably prevented from being scratched.
The indentation hardness of the first olefin resin layer 3 is more preferably 100 MPa or more, further preferably 115 MPa or more, and particularly preferably 130 MPa or more. When the floor decorative material 100 has the backer layer 6 described later (that is, in the case of FIG. 3A), scratches can be prevented particularly preferably.
Further, the indentation hardness of the first olefin resin layer 3 is more preferably 200 MPa or less, further preferably 180 MPa or less.
The method for measuring the indentation hardness of the first olefin resin layer 3 is as described above.
第一オレフィン樹脂層３は、オレフィン樹脂からなる層である。
上記オレフィン樹脂としては、例えば、エチレン、プロピレン、ブテン等のオレフィンの単独重合体；エチレン－プロピレンのブロック共重合体、ランダム共重合体；エチレン及びプロピレンの少なくとも一種と、ブテン、ペンテン、ヘキセン等の少なくとも一種の他のオレフィンとの共重合体；エチレン及びプロピレンの少なくとも一種と、酢酸ビニル、ビニルアルコール等の少なくとも一種の他の単量体との共重合体；等が挙げられる。
なかでも、優れた耐擦傷性と良好な曲げ加工性とを得る観点から、ポリエチレン、ポリプロピレンが好ましく、ポリエチレンがより好ましい。 The first olefin resin layer 3 is a layer made of an olefin resin.
Examples of the olefin resin include homopolymers of olefins such as ethylene, propylene and butene; block copolymers of ethylene-propylene and random copolymers; at least one of ethylene and propylene, and butene, penten, hexene and the like. Polymers with at least one other olefin; a polymer with at least one of ethylene and propylene and at least one other monomer such as vinyl acetate and vinyl alcohol; and the like.
Among them, polyethylene and polypropylene are preferable, and polyethylene is more preferable, from the viewpoint of obtaining excellent scratch resistance and good bending workability.
上記ポリエチレンは、エチレンの単独重合体であってもよいし、エチレンと、エチレンと共重合可能な他のコモノマー（例えば、プロピレン、１－ブテン、１－ヘキセン、１－オクテン等のα－オレフィン、酢酸ビニル、ビニルアルコール等）との共重合体であってもよい。
ポリエチレン樹脂としては、例えば、高密度ポリエチレン（ＨＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、直鎖低密度ポリエチレン（ＬＬＤＰＥ）、超低密度ポリエチレン（ＶＬＤＰＥ）、超高分子量ポリエチレン（ＵＨＭＷＰＥ）、架橋ポリエチレン（ＰＥＸ）等が挙げられる。
これらのポリエチレンは、１種単独で使用してもよいし、２種以上を併用してもよい。 The polyethylene may be a homopolymer of ethylene, or an α-olefin such as ethylene and another comonomer copolymerizable with ethylene (for example, propylene, 1-butene, 1-hexene, 1-octene). It may be a copolymer with vinyl acetate, vinyl alcohol, etc.).
Examples of the polyethylene resin include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (VLDPE), and ultra-high-density polyethylene (Ultra-high-density polyethylene). UHMWPE), crosslinked polyethylene (PEX) and the like.
These polyethylenes may be used alone or in combination of two or more.
上記ポリプロピレンは、プロピレンの単独重合体であってもよいし、プロピレンと、プロピレンと共重合可能な他のコモノマー（例えば、エチレン、１－ブテン、１－ヘキセン、１－オクテン等のα－オレフィン；酢酸ビニル、ビニルアルコール等）との共重合体であってもよい。
これらのポリプロピレンは１種単独で使用してもよいし、２種以上を併用してもよい。本発明においては、優れた耐擦傷性と曲げ加工性の観点から、プロピレンの単独重合体（ホモポリプロピレン）であることが特に好ましい。 The polypropylene may be a homopolymer of propylene, or α-olefin such as ethylene, 1-butene, 1-hexene, 1-octene, etc., which can be copolymerized with propylene. It may be a copolymer with vinyl acetate, vinyl alcohol, etc.).
These polypropylenes may be used alone or in combination of two or more. In the present invention, a homopolymer of propylene (homopolypropylene) is particularly preferable from the viewpoint of excellent scratch resistance and bendability.
ベースフィルム層２のインデンテーション硬さは、第一オレフィン樹脂層３を微結晶化オレフィン樹脂層とすること等によって適宜設定することができる。 The indentation hardness of the base film layer 2 can be appropriately set by using the first olefin resin layer 3 as a microcrystallized olefin resin layer or the like.
上記微結晶化オレフィン樹脂層を得るためには、例えば、第一オレフィン樹脂層３を形成するオレフィン樹脂組成物に結晶核剤を含有させて溶融し、次いで冷却することにより行うことができる。
この場合、冷却方法としては、例えば、押出し成型時において冷却水を通した冷却ロール（チルロール）にダイから押し出された材料を接触させて冷却を行なうチルロール法による冷却が挙げられる。 The microcrystallized olefin resin layer can be obtained, for example, by adding a crystal nucleating agent to the olefin resin composition forming the first olefin resin layer 3, melting it, and then cooling it.
In this case, as a cooling method, for example, cooling by a chill roll method in which a material extruded from a die is brought into contact with a cooling roll (chill roll) through which cooling water has passed during extrusion molding is used for cooling.
上記結晶核剤としては、例えば脂肪酸金属塩、ホスホン酸の金属塩、リン酸エステル金属塩、安息香酸金属塩、ピメリン酸金属塩、ロジン金属塩等の金属塩系結晶核剤；脂肪酸エステル、脂肪族アミド、ベンジリデンソルビトール、キナクリドン、シアニンブルー等の有機系結晶核剤；タルク等の無機系結晶核剤；等が挙げられる。
また、上記結晶核剤としては、上記の結晶核剤がナノシェルに内包されたものを用いることもできる。ナノシェルに内包された結晶核剤を用いることにより、第一オレフィン樹脂層３中において結晶核剤がより均一に分散するため、溶融条件、冷却条件等の諸条件によらず、容易にかつ安定的に、インデンテーション硬さを好適に調節することができ、また優れた耐擦傷性と良好な曲げ加工性とが得られる。
なお、上記ナノシェルとしては、国際公開第２０１８／１５９６６０号等に記載のものを適宜選択して用いることができる。 Examples of the crystal nucleating agent include metal salt-based crystal nucleating agents such as fatty acid metal salts, phosphonic acid metal salts, phosphoric acid ester metal salts, benzoic acid metal salts, piperinate metal salts, and rosin metal salts; fatty acid esters and fats. Examples thereof include organic crystal nucleating agents such as group amide, benzylidene sorbitol, quinacridone and cyanine blue; and inorganic crystal nucleating agents such as talc.
Further, as the crystal nucleating agent, one in which the above crystal nucleating agent is encapsulated in a nanoshell can also be used. By using the crystal nucleating agent contained in the nanoshell, the crystal nucleating agent is more uniformly dispersed in the first olefin resin layer 3, so that it is easy and stable regardless of various conditions such as melting conditions and cooling conditions. In addition, the indentation hardness can be suitably adjusted, and excellent scratch resistance and good bending workability can be obtained.
As the nanoshell, those described in International Publication No. 2018/159660 and the like can be appropriately selected and used.
第一オレフィン樹脂層３における上記結晶核剤の含有量は、第一オレフィン樹脂層３を形成する樹脂成分１００質量部に対して、０．０１～５質量部が好ましく、０．０２～３質量部がより好ましく、０．０３～１質量部が更に好ましく、０．０５～０．５質量部が特に好ましい。
上記結晶核剤の含有量が上記範囲内であると、第一オレフィン樹脂層３を形成する樹脂中に均一に分散しやすく、結晶核剤としての効果が得られやすく、ベースフィルム層２のインデンテーション硬さを好適に調節することができ、また優れた耐擦傷性と曲げ加工性とが得られる。 The content of the crystal nucleating agent in the first olefin resin layer 3 is preferably 0.01 to 5 parts by mass, preferably 0.02 to 3 parts by mass with respect to 100 parts by mass of the resin component forming the first olefin resin layer 3. Parts are more preferable, 0.03 to 1 part by mass is further preferable, and 0.05 to 0.5 part by mass is particularly preferable.
When the content of the crystal nucleating agent is within the above range, it is easy to uniformly disperse in the resin forming the first olefin resin layer 3, the effect as a crystal nucleating agent is easily obtained, and the indene of the base film layer 2 is easily obtained. The tension hardness can be suitably adjusted, and excellent scratch resistance and bending workability can be obtained.
床用化粧材１００が後述するバッカー層６を有する場合（すなわち、図３（ａ）の場合）、第一オレフィン樹脂層３は、優れた耐擦傷性と曲げ加工性とを得る観点から、厚みが３０μｍ以上１２０μｍ以下が好ましく、４０μｍ以上１１０μｍ以下がより好ましく、５０μｍ以上１００μｍ以下が更に好ましく、５５μｍ以上８５μｍ以下が特に好ましい。
第一オレフィン樹脂層３の厚さが３０μｍ未満であると、耐擦傷性や耐衝撃性（特に耐凹み性）が劣ったり、印刷機で印刷やコーティングを施す際に印刷時に加わる張力で第一オレフィン樹脂層３が伸びてしまうおそれがある。
また、床用化粧材１００が後述するバッカー層６を有する場合、第一オレフィン樹脂層３の厚さが１２０μｍを超えると、曲げ加工において表面保護コート層１に亀裂や破断を生じてしまうことや耐衝撃性（特に耐割れ性）が劣ってしまうおそれがある。 When the floor decorative material 100 has the backer layer 6 described later (that is, in the case of FIG. 3A), the first olefin resin layer 3 has a thickness from the viewpoint of obtaining excellent scratch resistance and bending workability. Is preferably 30 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less, further preferably 50 μm or more and 100 μm or less, and particularly preferably 55 μm or more and 85 μm or less.
If the thickness of the first olefin resin layer 3 is less than 30 μm, the scratch resistance and impact resistance (particularly dent resistance) are inferior, and the tension applied during printing when printing or coating with a printing machine is the first. The olefin resin layer 3 may be stretched.
Further, when the floor decorative material 100 has the backer layer 6 described later, if the thickness of the first olefin resin layer 3 exceeds 120 μm, the surface protective coat layer 1 may be cracked or broken in the bending process. Impact resistance (particularly crack resistance) may be inferior.
床用化粧材１００が後述するバッカー層６を有さない場合（すなわち、図３（ｂ）の場合）、第一オレフィン樹脂層３は、厚みが１２０μｍ以上３００μｍ以下であることが好ましく、厚みが１４５μｍ以上２５０μｍ以下であることがより好ましく、１７０μｍ以上２００μｍ以下であることが更に好ましい。
上記厚みを有することにより、後述するバッカー層６を有さなくても、抉れ傷及び凹み傷の防止に加えて、艶変化をも防止できる極めて優れた耐傷性能を好適に付与することができる。 When the floor decorative material 100 does not have the backer layer 6 described later (that is, in the case of FIG. 3B), the thickness of the first olefin resin layer 3 is preferably 120 μm or more and 300 μm or less, and the thickness is preferably 120 μm or more and 300 μm or less. It is more preferably 145 μm or more and 250 μm or less, and further preferably 170 μm or more and 200 μm or less.
By having the above thickness, it is possible to suitably impart extremely excellent scratch resistance that can prevent not only scratches and dents but also gloss change without having the backer layer 6 described later. ..
（化粧層）
化粧シート１０は、意匠性を向上させる観点から、化粧層４を有する。
化粧層４は、例えば、第一オレフィン樹脂層３と第二オレフィン樹脂層５との間、又は第一オレフィン樹脂層３と表面保護コート層１との間、表面保護コート層１上等に設けることができる。 (Cosmetic layer)
The decorative sheet 10 has a decorative layer 4 from the viewpoint of improving the design.
The decorative layer 4 is provided, for example, between the first olefin resin layer 3 and the second olefin resin layer 5, between the first olefin resin layer 3 and the surface protective coat layer 1, on the surface protective coat layer 1 or the like. be able to.
化粧層４は、例えば、全面を被覆する着色層（いわゆるベタ着色層）であってもよいし、種々の模様をインキと印刷機を使用して印刷することにより形成される絵柄層であってもよいし、またこれらを組み合わせたものであってもよい。
更に、化粧層は同一層内で複数箇所に設けてもよいし、一層だけでなく複数の層で設けてもよい。 The decorative layer 4 may be, for example, a colored layer (so-called solid colored layer) that covers the entire surface, or a pattern layer formed by printing various patterns using ink and a printing machine. It may be a combination of these.
Further, the decorative layer may be provided at a plurality of locations within the same layer, or may be provided not only in one layer but also in a plurality of layers.
例えば、木質基材２０の地色を着色隠蔽する場合には、ベタ着色層とすることで、着色隠蔽しつつ、意匠性を向上させることができる。更に意匠性を向上させる観点から、ベタ着色層と絵柄層とを組み合わせてもよいし、一方、化粧板基材の地模様を生かす場合は、ベタ着色層とせずに絵柄層のみを設ければよい。 For example, when the ground color of the wood base material 20 is colored and concealed, the design can be improved while concealing the color by using a solid colored layer. From the viewpoint of further improving the design, the solid coloring layer and the pattern layer may be combined. On the other hand, when the background pattern of the decorative board base material is utilized, only the pattern layer may be provided without the solid coloring layer. Good.
化粧層４に用いられるインキとしては、バインダーに顔料、染料等の着色剤、体質顔料、溶剤、安定剤、可塑剤、触媒、硬化剤、紫外線吸収剤、光安定剤等を適宜混合したものが使用される。 The ink used for the decorative layer 4 is a binder mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, or the like. used.
上記バインダーとしては特に制限はなく、例えば、ウレタン樹脂、アクリルポリオール樹脂、アクリル樹脂、エステル樹脂、アミド樹脂、ブチラール樹脂、スチレン樹脂、ウレタン－アクリル共重合体、ポリカーボネート系ウレタン－アクリル共重合体（ポリマー主鎖にカーボネート結合を有し、末端、側鎖に２個以上の水酸基を有する重合体（ポリカーボネートポリオール）由来のウレタン－アクリル共重合体）、塩化ビニル－酢酸ビニル共重合体樹脂、塩化ビニル－酢酸ビニル－アクリル共重合体樹脂、塩素化プロピレン樹脂、ニトロセルロース樹脂、酢酸セルロース樹脂等の樹脂が好ましく挙げられる。これらのバインダーは、単独で、又は複数種を組み合わせて用いることができる。 The binder is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (polymer). Urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the main chain and two or more hydroxyl groups in the terminal and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride- Resins such as vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin are preferable. These binders can be used alone or in combination of two or more.
上記着色剤としては、木質基材２０の地色を着色隠蔽し、かつ意匠性を向上させる観点から、例えば、白色顔料、鉄黒、黄鉛、チタン黄、弁柄、カドミウム赤、群青、コバルトブルー等の無機顔料；キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルー等の有機顔料又は染料；アルミニウム、真鍮等の鱗片状箔片からなる金属顔料；二酸化チタン被覆雲母、塩基性炭酸鉛等の鱗片状箔片からなる真珠光沢（パール）顔料等の着色剤を用いることもできる。 The colorant includes, for example, white pigment, iron black, chrome yellow, titanium yellow, valve handle, cadmium red, ultramarine, and cobalt from the viewpoint of coloring and hiding the ground color of the wood base material 20 and improving the design. Inorganic pigments such as blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments composed of scaly foil pieces such as aluminum and brass; scaly pigments such as titanium dioxide-coated mica and basic lead carbonate. A colorant such as a pearl bright pigment made of foil pieces can also be used.
化粧層４として絵柄層を有する場合、その模様としては、木目模様、大理石模様（例えばトラバーチン大理石模様）等の岩石の表面を模した石目模様、布目や布状の模様を模した布地模様、タイル貼模様、煉瓦積模様等があり、これらを複合した寄木、パッチワーク等の模様もある。これらの模様は通常の黄色、赤色、青色、および黒色のプロセスカラーによる多色印刷によって形成される他、模様を構成する個々の色の版を用意して行う特色による多色印刷等によっても形成される。 When the decorative layer 4 has a pattern layer, the pattern includes a stone pattern that imitates the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), or a cloth pattern that imitates a cloth grain or a cloth-like pattern. There are tiled patterns, brickwork patterns, etc., and there are also patterns such as parquet, patchwork, etc. that combine these patterns. These patterns are formed by multicolor printing with ordinary yellow, red, blue, and black process colors, and also by multicolor printing with special colors, which is performed by preparing plates of the individual colors that make up the pattern. Will be done.
化粧層４の厚さは、所望の絵柄に応じて適宜選択すればよいが、化粧板基材の地色を着色隠蔽し、かつ意匠性を向上させる観点から、０．５～２０μｍが好ましく、１～１０μｍがより好ましく、２～５μｍが更に好ましい。 The thickness of the decorative layer 4 may be appropriately selected according to a desired pattern, but is preferably 0.5 to 20 μm from the viewpoint of coloring and hiding the ground color of the decorative board base material and improving the design. 1 to 10 μm is more preferable, and 2 to 5 μm is even more preferable.
（第二オレフィン樹脂層）
第二オレフィン樹脂層５は、オレフィン樹脂からなる層である。
第二オレフィン樹脂層５を形成するオレフィン樹脂としては、第一オレフィン樹脂層３を形成し得るオレフィン樹脂と同じものが例示できる。
なかでも、優れた耐擦傷性と曲げ加工性の観点から、ポリエチレン、ポリプロピレンが好ましい。 (Second olefin resin layer)
The second olefin resin layer 5 is a layer made of an olefin resin.
Examples of the olefin resin forming the second olefin resin layer 5 include the same olefin resin capable of forming the first olefin resin layer 3.
Of these, polyethylene and polypropylene are preferable from the viewpoint of excellent scratch resistance and bendability.
第二オレフィン樹脂層５は、必要に応じて着色されていてもよい。
この場合は、上記オレフィン樹脂に着色剤を添加すればよい。上記着色剤としては、上述した化粧層４で用いる顔料又は染料が使用できる。 The second olefin resin layer 5 may be colored if necessary.
In this case, a colorant may be added to the olefin resin. As the colorant, the pigment or dye used in the above-mentioned decorative layer 4 can be used.
第二オレフィン樹脂層５は、優れた耐擦傷性と曲げ加工性の観点から、厚さが３０μｍ以上１２０μｍ以下であることが好ましく、４０μｍ以上１１０μｍ以下であることがより好ましく、５０μｍ以上１００μｍ以下であることが更に好ましく、５５μｍ以上９５μｍ以下であることが特に好ましい。 From the viewpoint of excellent scratch resistance and bending workability, the second olefin resin layer 5 preferably has a thickness of 30 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less, and 50 μm or more and 100 μm or less. It is more preferably 55 μm or more and 95 μm or less.
（バッカー層）　
化粧シート１０は、化粧シート１０の最下層、すなわち、化粧シート１０の第二オレフィン樹脂層５側にバッカー層６を備えていてもよい。
バッカー層６を備えることにより、抉れ傷及び凹み傷と艶変化とを好適に防止することができ、耐衝撃性を好適に付与することができる。 (Backer layer)
The decorative sheet 10 may include a backer layer 6 on the lowermost layer of the decorative sheet 10, that is, on the side of the second olefin resin layer 5 of the decorative sheet 10.
By providing the backer layer 6, it is possible to suitably prevent scooping scratches, dent scratches and gloss change, and it is possible to preferably impart impact resistance.
上記バッカー層６としては、合成樹脂バッカー層及び発泡樹脂バッカー層が挙げられ、化粧シート１０の最下層（表面保護コート層１が積層される側と反対側）に有することが好ましい。 Examples of the backer layer 6 include a synthetic resin backer layer and a foamed resin backer layer, and it is preferable that the backer layer 6 is provided on the lowermost layer of the decorative sheet 10 (the side opposite to the side on which the surface protective coat layer 1 is laminated).
上記合成樹脂バッカー層を構成する樹脂としては、例えば、ポリプロピレン、エチレン－ビニルアルコール共重合体、ポリエチレン、ポリメチルペンテン、ポリエチレンテレフタレート、耐熱性の高いポリアルキレンテレフタレート〔例えば、エチレングリコールの一部を１，４－シクロヘキサンジメタノールやジエチレングリコール等で置換したポリエチレンテレフタレートである、いわゆる商品名ＰＥＴ－Ｇ（イーストマンケミカルカンパニー製）〕、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレンナフタレート－イソフタレート共重合体、非晶性ポリエステル（Ａ－ＰＥＴ）、ポリカーボネート、ポリアリレート、ポリイミド、ポリスチレン、ポリアミド、ＡＢＳ等が挙げられる。これらの樹脂は単独又は２種以上で使用できる。 Examples of the resin constituting the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, and highly heat-resistant polyalkylene terephthalate [for example, a part of ethylene glycol is 1 , 4-Cyclohexanedimethanol, polyethylene terephthalate substituted with diethylene glycol, etc., so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate-isophthalate copolymer, Examples thereof include amorphous polyester (A-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS and the like. These resins can be used alone or in combination of two or more.
上記合成樹脂バッカー層は、中空ビーズを含有してもよい。
上記中空ビーズの種類、粒子径、及び、含有量等は、特開２０１４－１８８９４１号公報に記載のものを適用することができる。 The synthetic resin backer layer may contain hollow beads.
As the type, particle size, content, etc. of the hollow beads, those described in JP-A-2014-188941 can be applied.
上記合成樹脂バッカー層を形成する方法としては、カレンダー成形、溶融樹脂の押出し成形等が挙げられる。なかでも溶融樹脂の押出し成形が好適であり、例えば、Ｔダイを用いた押出し成形がより好適である。 Examples of the method for forming the synthetic resin backer layer include calendar molding, extrusion molding of molten resin, and the like. Of these, extrusion molding of molten resin is preferable, and for example, extrusion molding using a T-die is more preferable.
上記発泡樹脂バッカー層は、上記合成樹脂バッカー層よりも更に下層（凹凸形状を有する側と反対側）に有していてもよい。
上記発泡樹脂バッカー層は、特開２０１４－１８８９４１号公報に記載のものを適用することができる。 The foamed resin backer layer may be further lower than the synthetic resin backer layer (on the side opposite to the side having the uneven shape).
As the foamed resin backer layer, those described in JP-A-2014-188941 can be applied.
上記バッカー層は、厚みが１００μｍ以上であることが好ましい。
上記バッカー層の厚みが１００μｍ以上であることにより、凹み傷をより好適に防止することができ、耐衝撃性にも優れたものとすることができる。
上記バッカー層は、厚みが１２０μｍ以上であることがより好ましく、２００μｍ以上であることが更に好ましい。
上記バッカー層の厚みの上限としては、１０００μｍ以下が好ましく、６００μｍ以下がより好ましく、４００μｍ以下がさらに好ましい。 The backer layer preferably has a thickness of 100 μm or more.
When the thickness of the backer layer is 100 μm or more, dents and scratches can be more preferably prevented, and impact resistance can be made excellent.
The backer layer preferably has a thickness of 120 μm or more, and more preferably 200 μm or more.
The upper limit of the thickness of the backer layer is preferably 1000 μm or less, more preferably 600 μm or less, and even more preferably 400 μm or less.
（その他）
化粧シート１０は、プライマー層を有していてもよい。
上記プライマー層は、主に各層の密着性の向上を図るために設けられる層である。 (Other)
The decorative sheet 10 may have a primer layer.
The primer layer is a layer mainly provided for improving the adhesion of each layer.
化粧シート１０において、プライマー層は、例えば、第一オレフィン樹脂層３の片面又は両面、第二オレフィン樹脂層５の片面又は両面、等に設けることができる。
また、プライマー層と同様に、各層の密着性の向上を図るため、第一オレフィン樹脂層３、第二オレフィン樹脂層５の片面又は両面に、酸化法、凹凸化法等の物理的表面処理、又は化学的表面処理等の表面処理を施してもよい。 In the decorative sheet 10, the primer layer can be provided on, for example, one side or both sides of the first olefin resin layer 3, one side or both sides of the second olefin resin layer 5, and the like.
Further, as in the case of the primer layer, in order to improve the adhesion of each layer, one or both sides of the first olefin resin layer 3 and the second olefin resin layer 5 are subjected to physical surface treatment such as an oxidation method or an unevenness method. Alternatively, surface treatment such as chemical surface treatment may be performed.
上記プライマー層は、例えば、上記の装飾層に用い得るバインダーとして例示したバインダーに、溶剤、安定剤、可塑剤、触媒、硬化剤、紫外線吸収剤、光安定剤等を適宜混合した樹脂組成物により形成することができる。 The primer layer is made of, for example, a resin composition obtained by appropriately mixing a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, and the like with a binder exemplified as a binder that can be used for the decorative layer. Can be formed.
上記プライマー層の厚さは、密着性を向上させる観点から、０．２μｍ以上１０μｍ以下が好ましく、０．５μｍ以上８μｍ以下がより好ましく、１μｍ以上５μｍ以下が更に好ましい。 From the viewpoint of improving adhesion, the thickness of the primer layer is preferably 0.2 μm or more and 10 μm or less, more preferably 0.5 μm or more and 8 μm or less, and further preferably 1 μm or more and 5 μm or less.
（凹凸形状）
化粧シート１０は、凹凸形状を有していてもよい。
上記凹凸形状は、化粧シート１０の表面保護コート層１に少なくとも存在していればよく、凹凸形状の深さは表面保護コート層１内に留まるものであってもよいし、また第二オレフィン樹脂層５まで至るものがあってもよい。
優れた質感（触感）を得る観点から、表面保護コート層１内に留まるものだけでなく、第二オレフィン樹脂層５まで至るもの、第一オレフィン樹脂層３まで至るものが組み合わされていることが好ましい。 (Concave and convex shape)
The decorative sheet 10 may have an uneven shape.
The uneven shape may be present at least in the surface protective coat layer 1 of the decorative sheet 10, and the depth of the uneven shape may remain in the surface protective coat layer 1 or the second olefin resin. There may be up to layer 5.
From the viewpoint of obtaining an excellent texture (tactile sensation), not only those that stay in the surface protective coat layer 1 but also those that reach the second olefin resin layer 5 and those that reach the first olefin resin layer 3 are combined. preferable.
上記凹凸形状の模様としては、例えば木目板導管溝、石板表面凹凸、布表面テクスチャア、梨地、砂目、ヘアライン、万線条溝等がある。意匠性を向上させる観点から、上記凹凸形状の模様は、化粧層４の絵柄と同調させた模様であることが好ましい。
例えば、化粧層４が木目模様の場合は、凹部の模様として木目板導管溝を選択し、かつ化粧層４の木目と凹部の木目とを同調させると、よりリアルで質感に溢れた、高級感のある化粧シートが得られる。 Examples of the uneven shape pattern include a wood grain board conduit groove, a stone board surface unevenness, a cloth surface texturer, a satin finish, a grain, a hairline, and a perforated groove. From the viewpoint of improving the design, the uneven pattern is preferably a pattern synchronized with the pattern of the decorative layer 4.
For example, when the decorative layer 4 has a wood grain pattern, if the wood grain board conduit groove is selected as the concave pattern and the wood grain of the decorative layer 4 and the wood grain of the concave portion are synchronized, a more realistic and textured, luxurious feeling is obtained. A decorative sheet with a texture can be obtained.
（化粧シートの製造方法）
化粧シート１０の製造方法について、化粧シート１０の好ましい態様の一つである、厚さ方向において、表面保護コート層１、第一オレフィン樹脂層３、化粧層４、第二オレフィン樹脂層５、及びバッカー層６を順に有する化粧シート１０を例にとって、その製造方法の一例を説明する。 (Manufacturing method of decorative sheet)
Regarding the method for producing the decorative sheet 10, in the thickness direction, which is one of the preferred embodiments of the decorative sheet 10, the surface protective coat layer 1, the first olefin resin layer 3, the decorative layer 4, the second olefin resin layer 5, and An example of a manufacturing method thereof will be described by taking a decorative sheet 10 having the backer layer 6 in order as an example.
まず、第二オレフィン樹脂層５を形成する樹脂組成物を用意して、溶融押出法等の方法により第一オレフィン樹脂層を製膜し、該第二オレフィン樹脂層５の上に、化粧層４を形成する。
また、これとは別に、第一オレフィン樹脂層３を形成する樹脂組成物を用意して、溶融押出法等の方法により第一オレフィン樹脂層３を製膜し、該第一オレフィン樹脂層３の上に、硬化性樹脂組成物を塗布した未硬化層に、加熱又は電離放射線を照射して硬化させて、表面保護コート層１を形成する。 First, a resin composition for forming the second olefin resin layer 5 is prepared, a first olefin resin layer is formed by a method such as a melt extrusion method, and a decorative layer 4 is formed on the second olefin resin layer 5. To form.
Separately from this, a resin composition for forming the first olefin resin layer 3 is prepared, the first olefin resin layer 3 is formed by a method such as a melt extrusion method, and the first olefin resin layer 3 is formed. The uncured layer coated with the curable resin composition is cured by irradiating it with heating or ionizing radiation to form the surface protective coat layer 1.
次いで、化粧層４及び第一オレフィン樹脂層３の少なくとも一方の面に接着剤を塗布し、化粧層４と第一オレフィン樹脂層３とが対向するようにして貼着することにより、表面保護コート層１、第一オレフィン樹脂層３、化粧層４及び第二オレフィン樹脂層５を順に有する化粧シート１０を製造することができる。
また、バッカー層６は、例えば、Ｔダイ押出し法などで作製したバッカー層６と、第二オレフィン樹脂層５とを、熱ラミネートや接着剤を介してドライラミネートにより積層するなど、公知の方式で形成することができる。 Next, an adhesive is applied to at least one surface of the decorative layer 4 and the first olefin resin layer 3, and the decorative layer 4 and the first olefin resin layer 3 are attached so as to face each other to protect the surface. A decorative sheet 10 having a layer 1, a first olefin resin layer 3, a decorative layer 4, and a second olefin resin layer 5 in this order can be produced.
Further, the backer layer 6 is formed by a known method, for example, the backer layer 6 produced by a T-die extrusion method or the like and the second olefin resin layer 5 are laminated by dry lamination via a thermal laminate or an adhesive. Can be formed.
上記製造方法において、化粧層４を形成した後、第一オレフィン樹脂層３を形成する樹脂組成物を用いて、第一オレフィン樹脂層３を押出ラミネーション、ドライラミネーション、ウエットラミネーション、サーマルラミネーション等の方法により接着剤及び／又は酸変性ポリオレフィン樹脂等の熱可塑性樹脂を介して接着及び圧着させて積層して形成し、次いで、該第一オレフィン樹脂層３の上に、硬化性樹脂組成物を塗布した未硬化層に、加熱又は電離放射線を照射して硬化させて、表面保護コート層１を形成することによっても、第二オレフィン樹脂層５、化粧層４、第一オレフィン樹脂層３、及び表面保護コート層１を順に有する化粧シートを製造することができる。 In the above production method, a method such as extrusion lamination, dry lamination, wet lamination, thermal lamination, etc. is used to extrude the first olefin resin layer 3 by using the resin composition for forming the first olefin resin layer 3 after forming the decorative layer 4. Then, the curable resin composition was applied onto the first olefin resin layer 3 by adhering and pressure-bonding the resin through an adhesive and / or a thermoplastic resin such as an acid-modified polyolefin resin to form a laminate. By irradiating the uncured layer with heating or ionizing radiation to cure it to form the surface protective coat layer 1, the second olefin resin layer 5, the decorative layer 4, the first olefin resin layer 3, and the surface protection are also formed. A decorative sheet having the coat layer 1 in order can be produced.
化粧層４は、第一オレフィン樹脂層３又は第二オレフィン樹脂層５上に化粧層４の形成に用いられるインキを塗布して所望の着色層、絵柄層を設けることにより形成される。
該インキの塗布は、グラビア印刷法、バーコート法、ロールコート法、リバースロールコート法、コンマコート法等の公知の方式、好ましくはグラビア印刷法により行うことができる。 The decorative layer 4 is formed by applying the ink used for forming the decorative layer 4 on the first olefin resin layer 3 or the second olefin resin layer 5 to provide a desired colored layer and pattern layer.
The ink can be applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method, preferably a gravure printing method.
表面保護コート層１の形成において、硬化性樹脂組成物の塗布は、硬化後の厚さが所定の厚さとなるように、好ましくはグラビアコート、バーコート、ロールコート、リバースロールコート、コンマコート等の公知の方式により、より好ましくはグラビアコートにより行う。 In the formation of the surface protective coat layer 1, the curable resin composition is preferably applied to a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat or the like so that the thickness after curing becomes a predetermined thickness. It is carried out by a known method, more preferably by a gravure coat.
表面保護コート層１の形成に電離放射線樹脂組成物を用いる場合、該樹脂組成物の塗布により形成した未硬化樹脂層は、電子線、紫外線等の電離放射線を照射して硬化物とすることで、表面保護コート層１となる。ここで、電離放射線として電子線を用いる場合、その加速電圧については、用いる樹脂や層の厚みに応じて適宜選定し得るが、通常加速電圧７０～３００ｋＶ程度で未硬化樹脂層を硬化させることが好ましい。
照射線量は、電離放射線硬化性樹脂の架橋密度が飽和する量が好ましく、通常５～３００ｋＧｙ（０．５～３０Ｍｒａｄ）、好ましくは１０～５０ｋＧｙ（１～５Ｍｒａｄ）の範囲で選定される。
電子線源としては、特に制限はなく、例えばコックロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、あるいは直線型、ダイナミトロン型、高周波型等の各種電子線加速器を用いることができる。 When an ionizing radiation resin composition is used to form the surface protective coat layer 1, the uncured resin layer formed by applying the resin composition is made into a cured product by irradiating it with ionizing radiation such as an electron beam or ultraviolet rays. , The surface protective coat layer 1. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected according to the resin to be used and the thickness of the layer, but usually the uncured resin layer can be cured at an acceleration voltage of about 70 to 300 kV. preferable.
The irradiation dose is preferably an amount at which the crosslink density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and for example, a cockloft Walton type, a bandegraft type, a resonance transformer type, an insulated core transformer type, or various electron beam accelerators such as a linear type, a dynamitron type, and a high frequency type are used. be able to.
上記電離放射線として紫外線を用いる場合には、波長１９０～３８０ｎｍの紫外線を含むものを放射する。紫外線源としては特に制限はなく、例えば高圧水銀燈、低圧水銀燈、メタルハライドランプ、カーボンアーク燈等が用いられる。 When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. The ultraviolet source is not particularly limited, and for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like is used.
表面保護コート層１の形成に熱硬化性樹脂組成物を用いる場合は、使用する樹脂組成物に応じた熱処理を施して、硬化させて表面保護コート層１を形成すればよい。 When a thermosetting resin composition is used for forming the surface protective coat layer 1, the surface protective coat layer 1 may be formed by performing a heat treatment according to the resin composition to be used and curing the surface protective coat layer 1.
上記プライマー層を設ける場合は、上記プライマー層を形成する樹脂組成物を、例えば、グラビア印刷法、バーコート法、ロールコート法、リバースロールコート法、コンマコート法等の公知の方式で塗布して形成することができる。 When the primer layer is provided, the resin composition forming the primer layer is applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. Can be formed.
上記凹凸形状を形成する場合、作業の容易さを考慮すると、エンボス加工を採用することが好ましい。上記エンボス加工は、公知の枚葉又は輪転式のエンボス機を使用する通常の方法により行えばよい。 When forming the uneven shape, it is preferable to adopt embossing in consideration of easiness of work. The embossing may be performed by a usual method using a known single-wafer or rotary embossing machine.
＜木質基材＞
木質基材２０としては、例えば、中密度木質繊維板、高密度木質繊維板、パーティクルボード、針葉樹合板、広葉樹合板、早成樹合板、コルクシート、コルク含有複合基材等の少なくとも１種が挙げられる。
木質基材２０は、合板であることが好ましい。
木質基材２０が合板であることにより、抉れ傷及び凹み傷と艶変化とを好適に防止することができる。 <Wood base material>
Examples of the wood base material 20 include at least one kind such as medium density wood fiberboard, high density wood fiberboard, particle board, coniferous plywood, hardwood plywood, early-maturing plywood, cork sheet, and cork-containing composite base material. ..
The wood base material 20 is preferably plywood.
Since the wood base material 20 is made of plywood, it is possible to suitably prevent scooping scratches, dent scratches, and gloss change.
ここで、針葉樹としては、例えば、椴松、唐松、蝦夷松、杉、ヒノキ、パイン、セコイヤ、トウヒ等が挙げられる。広葉樹としては、例えば、ラワン、シナ、カバ、セン、ブナ、ナラ、メランチ等が挙げられる。また、早成樹としては、ポプラ、ファルカタ、アカシア、カメレレ、ユーカリ、ターミナリア等が挙げられる。 Here, examples of the coniferous tree include Abies sachalinensis, Larch, Ezo spruce, cedar, cypress, pine, sequoia, spruce and the like. Examples of hardwoods include lauan, cinnamon, hippopotamus, sen, beech, oak, and meranchi. Examples of early-maturing trees include poplar, falcata, acacia, chamelele, eucalyptus, and terminaria.
針葉樹合板、広葉樹合板、早成樹合板等の木質合板を用いる場合の木質単板の積層数（プライ数）は限定的ではないが、通常３～７枚が好ましく、５～７枚がより好ましい。また、木質合板作製時に用いる接着剤も限定されず、公知の木工用接着剤が広く使用できる。 When wood plywood such as softwood plywood, hardwood plywood, and early-maturing plywood is used, the number of laminated wood single boards (number of plies) is not limited, but usually 3 to 7 is preferable, and 5 to 7 is more preferable. Further, the adhesive used for producing wood plywood is not limited, and known woodworking adhesives can be widely used.
上記接着剤としては、例えば、ポリ酢酸ビニル、ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、エチレン－アクリル酸共重合体、アイオノマー、ブタジエン－アクリルニトリルゴム、ネオプレンゴム、天然ゴム等を有効成分とする接着剤が挙げられる。また、熱硬化型接着剤として、メラミン系、フェノール系、ユリア系（酢酸ビニル－尿素系など）等の接着剤も挙げられる。 Examples of the adhesive include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylic nitrile rubber, neoprene rubber, natural rubber and the like as active ingredients. And the adhesive to be mentioned. Further, examples of the thermosetting adhesive include melamine-based, phenol-based, and urea-based (vinyl acetate-urea-based, etc.) adhesives.
木質基材２０の厚さは限定的ではないが、２ｍｍ以上１５ｍｍ以下程度が好ましく、２ｍｍ以上１２ｍｍ以下がより好ましい。 The thickness of the wood base material 20 is not limited, but is preferably about 2 mm or more and 15 mm or less, and more preferably 2 mm or more and 12 mm or less.
化粧シート１０と、木質基材２０とを積層する積層方法は限定されず、例えば、接着剤によりそれぞれを貼着する方法等を採用することができる。
上記接着剤は、公知の接着剤から適宜選択すればよい。例えば、ポリ酢酸ビニル、ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、エチレン－アクリル酸共重合体、アイオノマー、ウレタン系反応型ホットメルトなどの反応型ホットメルト接着剤等や、ブタジエン－アクリルニトリルゴム、ネオプレンゴム、天然ゴム等が挙げられる。
これら接着剤は、単独で又は２種以上を組み合わせて用いることができる。 The laminating method for laminating the decorative sheet 10 and the wood base material 20 is not limited, and for example, a method of adhering each of them with an adhesive or the like can be adopted.
The adhesive may be appropriately selected from known adhesives. For example, reactive hot melt adhesives such as polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, urethane-based reactive hot melt, and butadiene-acrylic nitrile. Examples include rubber, neoprene rubber, and natural rubber.
These adhesives can be used alone or in combination of two or more.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、この例によって限定されるものではない。 Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.
（実施例１）　
第二オレフィン樹脂層として、６０μｍ厚の着色ポリプロピレンフィルムを準備し、その一方の面上にグラビア印刷機にて化粧層（５μｍ厚）を積層した。
次いで、第一オレフィン樹脂層として、６０μｍ厚、インデンテーション硬さが５０ＭＰａのポリプロピレンフィルム（クリヤー）を準備し、接着剤を介して、上記化粧層と貼り合わせた。
上記第一オレフィン樹脂層の面上に、グラビアコートにて表面保護コート層用の電離放射線硬化性樹脂組成物を塗布した後、電離放射線を照射して硬化させ、１５μｍ厚、インデンテーション硬さが２５０ＭＰａの電離放射線硬化性樹脂による表面保護コート層を設けた。
更に、表面保護コート層が形成された側から熱圧によるエンボス加工を施すことにより、木目導管柄の凹凸模様を形成した。
その後、上記第二オレフィン樹脂層の裏面（化粧層を有する側と反対側面）に、１２０μｍ厚のポリプロピレンフィルムを貼り合わせてバッカー層を形成し、化粧シートを作製した。
上記化粧シートと木質基材とを接着剤を介して（化粧シートの表面保護コート層を有する側と反対側面が木質基材と接するように）貼り合わせ、実施例１の床用化粧材を作製した。 (Example 1)
As the second olefin resin layer, a colored polypropylene film having a thickness of 60 μm was prepared, and a decorative layer (thickness of 5 μm) was laminated on one surface of the film with a gravure printing machine.
Next, as the first olefin resin layer, a polypropylene film (clear) having a thickness of 60 μm and an indentation hardness of 50 MPa was prepared and bonded to the decorative layer via an adhesive.
After applying the ionizing radiation curable resin composition for the surface protective coating layer with a gravure coat on the surface of the first olefin resin layer, it is cured by irradiating it with ionizing radiation to obtain a thickness of 15 μm and an indentation hardness. A surface protective coat layer made of an ionizing radiation curable resin of 250 MPa was provided.
Further, the uneven pattern of the wood grain conduit pattern was formed by embossing by heat pressure from the side where the surface protective coat layer was formed.
Then, a 120 μm-thick polypropylene film was laminated on the back surface of the second olefin resin layer (the side surface opposite to the side having the decorative layer) to form a backer layer, and a decorative sheet was prepared.
The decorative sheet and the wood base material are bonded to each other via an adhesive (so that the side surface of the decorative sheet opposite to the side having the surface protective coat layer is in contact with the wood base material) to prepare the floor decorative material of Example 1. did.
（実施例２）
第一オレフィン樹脂層の面上に、１５μｍ厚、インデンテーション硬さが１６０ＭＰａの電離放射線硬化性樹脂による表面保護コート層を設けたこと以外は、実施例１と同様にして床用化粧材を作製した。 (Example 2)
A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 15 μm and an indentation hardness of 160 MPa was provided on the surface of the first olefin resin layer. did.
（実施例３）
第一オレフィン樹脂層の面上に、１５μｍ厚、インデンテーション硬さが３００ＭＰａの電離放射線硬化性樹脂による表面保護コート層を設けたこと以外は、実施例１と同様にして床用化粧材を作製した。 (Example 3)
A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 15 μm and an indentation hardness of 300 MPa was provided on the surface of the first olefin resin layer. did.
（実施例４）
第一オレフィン樹脂層の面上に、３０μｍ厚、インデンテーション硬さが２５０ＭＰａの電離放射線硬化性樹脂による表面保護コート層を設けたこと以外は、実施例１と同様にして床用化粧材を作製した。 (Example 4)
A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 30 μm and an indentation hardness of 250 MPa was provided on the surface of the first olefin resin layer. did.
（実施例５）
第一オレフィン樹脂層の面上に、１０μｍ厚、インデンテーション硬さが２５０ＭＰａの電離放射線硬化性樹脂による表面保護コート層を設けたこと以外は、実施例１と同様にして床用化粧材を作製した。 (Example 5)
A floor decorative material was produced in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 10 μm and an indentation hardness of 250 MPa was provided on the surface of the first olefin resin layer. did.
（実施例６）
第一オレフィン樹脂層として、６０μｍ厚、インデンテーション硬さが１３０ＭＰａのポリプロピレンフィルム（クリヤー）を準備したこと以外は、実施例５と同様にして床用化粧材を作製した。 (Example 6)
A floor decorative material was prepared in the same manner as in Example 5 except that a polypropylene film (clear) having a thickness of 60 μm and an indentation hardness of 130 MPa was prepared as the first olefin resin layer.
（実施例７）
第一オレフィン樹脂層として、１８０μｍ厚、インデンテーション硬さが１３０ＭＰａのポリプロピレンフィルム（クリヤー）を準備し、化粧シートにバッカー層を形成しなかったこと以外は、実施例１と同様にして床用化粧材を作製した。 (Example 7)
As the first olefin resin layer, a polypropylene film (clear) having a thickness of 180 μm and an indentation hardness of 130 MPa was prepared, and a floor cosmetic was prepared in the same manner as in Example 1 except that a backer layer was not formed on the decorative sheet. The material was prepared.
（実施例８）
第一オレフィン樹脂層として、１８０μｍ厚、インデンテーション硬さが９０ＭＰａのポリプロピレンフィルム（クリヤー）を準備したこと以外は、実施例７と同様にして床用化粧材を作製した。 (Example 8)
A floor decorative material was prepared in the same manner as in Example 7 except that a polypropylene film (clear) having a thickness of 180 μm and an indentation hardness of 90 MPa was prepared as the first olefin resin layer.
（比較例１）
第一オレフィン樹脂層の面上に、１５μｍ厚、インデンテーション硬さが１５０ＭＰａの電離放射線硬化性樹脂による表面保護コート層を設けたこと以外は、実施例１と同様にして床用化粧材を作製した。 (Comparative Example 1)
A floor decorative material was prepared in the same manner as in Example 1 except that a surface protective coat layer made of an ionizing radiation curable resin having a thickness of 15 μm and an indentation hardness of 150 MPa was provided on the surface of the first olefin resin layer. did.
（比較例２）
化粧シートにバッカー層を形成しなかったこと以外は、実施例１と同様にして床用化粧材を作製した。 (Comparative Example 2)
A floor decorative material was produced in the same manner as in Example 1 except that the backer layer was not formed on the decorative sheet.
（比較例３）
化粧シートとＭＤＦ基材とを接着剤を介して貼り合わせたこと以外は、比較例２と同様にして床用化粧材を作製した。 (Comparative Example 3)
A floor decorative material was produced in the same manner as in Comparative Example 2 except that the decorative sheet and the MDF base material were bonded to each other via an adhesive.
（比較例４）
バッカー層を５０μｍ厚に変更した以外は、実施例１と同様にして床用化粧材を作製した。 (Comparative Example 4)
A floor decorative material was produced in the same manner as in Example 1 except that the backer layer was changed to a thickness of 50 μm.
（比較例５）
第一オレフィン樹脂層を１１０μｍ厚に変更した以外は、実施例７と同様にして床用化粧材を作製した。 (Comparative Example 5)
A floor decorative material was produced in the same manner as in Example 7 except that the first olefin resin layer was changed to a thickness of 110 μm.
＜評価方法＞
（インデンテーション硬さ）
表面保護コート層及び第一オレフィン樹脂層のインデンテーション硬さは、明細書本文に記載の方法により測定した。 <Evaluation method>
(Indentation hardness)
The indentation hardness of the surface protective coat layer and the first olefin resin layer was measured by the method described in the main text of the specification.
（１）鉛筆硬度試験
実施例及び比較例で作製した床用化粧材について、ＪＩＳ　Ｋ５６００－５－４：１９９９に準じて、２Ｈの硬度の鉛筆を用いて試験を実施し、下記項目について評価した。その結果を表１に示した。
なお、表１に記載の総合判断は、全ての評価で「＋／－」以上の評価であったものを合格とした。
（艶変化）
＋：目視で判別できない
＋／－：目視で僅かに分かるが目立たない
－：目視で容易に判別でき、目立つ
（抉れ傷）
＋：傷長さが２ｍｍ未満
＋／－：傷長さが２ｍｍ以上、３ｍｍ未満
－：傷長さが３ｍｍを超える
（凹み傷）
＋：目視で凹みが判別できない
＋／－：目視で凹みが僅かに分かるが目立たない
－：目視で容易に凹みを判別でき、目立つ (1) Pencil hardness test The floor decorative materials produced in Examples and Comparative Examples were tested using pencils with a hardness of 2H according to JIS K5600-5-4: 1999, and the following items were evaluated. .. The results are shown in Table 1.
As for the comprehensive judgment shown in Table 1, those with an evaluation of "+/-" or higher in all the evaluations were regarded as acceptable.
(Gloss change)
+: Cannot be visually identified +/-: Slightly visible but inconspicuous-: Easy to visually identify and conspicuous (scratch)
+: Scratch length less than 2 mm +/-: Scratch length 2 mm or more and less than 3 mm-: Scratch length more than 3 mm (dented scratch)
+: The dent cannot be visually identified +/-: The dent is slightly visible but inconspicuous-: The dent can be easily identified visually and is conspicuous
（２）鋼球落下試験
実施例及び比較例で作製した床用化粧材を砂上に置き、５００ｇの鋼球を高さ７５ｃｍから落下させ、凹み深さや、割れの有無について以下の基準で評価した。
＋：凹み深さが２００μｍ以下で割れがなし
＋／－：凹み深さが２００μｍ以下で割れがある
－：凹み深さが２００μｍを超える (2) Steel ball drop test The floor decorative materials prepared in Examples and Comparative Examples were placed on sand, 500 g of steel balls were dropped from a height of 75 cm, and the depth of dents and the presence or absence of cracks were evaluated according to the following criteria. ..
+: No crack when the dent depth is 200 μm or less +/-: There is a crack when the dent depth is 200 μm or less-: The dent depth exceeds 200 μm
（３）化粧シート取り扱い適性
実施例及び比較例で作製した床用化粧材の作製工程において、化粧シートの割れの有無を以下の基準で評価した。
＋＋：化粧シート割れが発生しない
＋：　化粧シートの割れの発生頻度が０％を超えており、５％以下である
＋／－：化粧シート割れの発生頻度が５％を越えており、１０％以下である
－：化粧シート割れの発生頻度が１０％を超える (3) Suitability for handling decorative sheets In the steps of producing the decorative materials for floors produced in Examples and Comparative Examples, the presence or absence of cracks in the decorative sheets was evaluated according to the following criteria.
++: Decorative sheet cracks do not occur ++: The frequency of decorative sheet cracks exceeds 0% and is 5% or less +/-: The frequency of decorative sheet cracks exceeds 5% and is 10% The following-: The frequency of cracking of the decorative sheet exceeds 10%.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
実施例１～８で作製した床用化粧材は、艶変化、抉れ傷及び凹み傷の評価において、全て「＋／－」以上であり、総合判断で合格と判定できるものであった。
特に、表面保護コート層のインデンテーション硬さが２５０ＭＰａ以上であり、表面保護コート層の厚みが１５～３０μｍである実施例１、３、４、７及び８で作製した床用化粧材では、鉛筆硬度試験の全てにおいて優れていた。
また、実施例５及び６で作製した床用化粧材の比較から、バッカー層を有する場合には、第一オレフィン樹脂層のインデンテーション硬さが１００ＭＰａ以上であることにより、抉れ傷をより好適に防止できることが確認された。
一方で、表面保護コート層のインデンテーション硬さが１６０ＭＰａ未満であった比較例１で作製した床用化粧材では、艶変化を防止することができず、化粧シートの総厚みが２００μｍ未満であった比較例２～５で作製した床用化粧材では、凹み傷を防止することができなかった。 The floor decorative materials produced in Examples 1 to 8 were all "+/-" or higher in the evaluation of gloss change, scooping scratches, and dent scratches, and could be judged to be acceptable by comprehensive judgment.
In particular, the floor decorative material produced in Examples 1, 3, 4, 7 and 8 in which the indentation hardness of the surface protective coat layer is 250 MPa or more and the thickness of the surface protective coat layer is 15 to 30 μm is a pencil. It was excellent in all hardness tests.
Further, from the comparison of the floor decorative materials produced in Examples 5 and 6, when the backer layer is provided, the indentation hardness of the first olefin resin layer is 100 MPa or more, so that the scratches are more preferable. It was confirmed that it can be prevented.
On the other hand, the floor decorative material produced in Comparative Example 1 in which the indentation hardness of the surface protective coat layer was less than 160 MPa could not prevent the gloss change, and the total thickness of the decorative sheet was less than 200 μm. The floor decorative materials produced in Comparative Examples 2 to 5 could not prevent dents and scratches.
本発明によれば、抉れ傷及び凹み傷の防止に加えて、艶変化をも防止できる極めて優れた耐傷性能を有する床用化粧材を得ることができる。 According to the present invention, it is possible to obtain a floor decorative material having extremely excellent scratch resistance that can prevent not only scratches and dents but also gloss change.
　１　　　表面保護コート層
　２　　　ベースフィルム層
　３　　　第一オレフィン樹脂層
　４　　　化粧層
　５　　　第二オレフィン樹脂層
　６　　　バッカー層
　１０　　化粧シート
　２０　　木質基材
　３０　　測定試料
　３１　　バーコビッチ圧子
　３２　　荷重をかける方向
　１００　床用化粧材 1 Surface protective coat layer 2 Base film layer 3 First olefin resin layer 4 Decorative layer 5 Second olefin resin layer 6 Backer layer 10 Decorative sheet 20 Wood base material 30 Measurement sample 31 Berkovich indenter 32 Direction to apply load 100 Floor decorative material

Claims (8)

  1. 化粧層を含む１層以上のベースフィルム層及び表面保護コート層を備える化粧シートと、木質基材とが積層された床用化粧材であって、
    前記表面保護コート層は、インデンテーション硬さが１６０ＭＰａ以上であり、
    前記化粧シートは、総厚みが２００μｍ以上である
    ことを特徴とする床用化粧材。     A floor decorative material in which a decorative sheet having one or more base film layers including a decorative layer and a surface protective coat layer and a wood base material are laminated.
    The surface protective coat layer has an indentation hardness of 160 MPa or more.
    The decorative sheet is a floor decorative material having a total thickness of 200 μm or more.
  2. 前記表面保護コート層は、厚みが１０μｍ以上３０μｍ以下である請求項１に記載の床用化粧材。 The floor decorative material according to claim 1, wherein the surface protective coat layer has a thickness of 10 μm or more and 30 μm or less.
  3. 前記表面保護コート層は、インデンテーション硬さが３００ＭＰａ以下である請求項１又は２に記載の床用化粧材。 The floor decorative material according to claim 1 or 2, wherein the surface protective coat layer has an indentation hardness of 300 MPa or less.
  4. 前記ベースフィルム層は、第一オレフィン樹脂層を有しており、前記第一のオレフィン樹脂層のインデンテーション硬さが８０ＭＰａ以上である請求項１～３のいずれか一項に記載の床用化粧材。 The floor cosmetic according to any one of claims 1 to 3, wherein the base film layer has a first olefin resin layer, and the indentation hardness of the first olefin resin layer is 80 MPa or more. Material.
  5. 前記第一オレフィン樹脂層は、厚みが１２０μｍ以上３００μｍ以下である請求項４に記載の床用化粧材。 The floor decorative material according to claim 4, wherein the first olefin resin layer has a thickness of 120 μm or more and 300 μm or less.
  6. 前記ベースフィルム層は、前記表面保護コート層が積層される側と反対側に、バッカー層を有する請求項１～４のいずれか一項に記載の床用化粧材。 The floor decorative material according to any one of claims 1 to 4, wherein the base film layer has a backer layer on the side opposite to the side on which the surface protective coat layer is laminated.
  7. 前記バッカー層は、厚みが１００μｍ以上である請求項６に記載の床用化粧材。　 The floor decorative material according to claim 6, wherein the backer layer has a thickness of 100 μm or more.
  8. 前記木質基材は、合板である請求項１～７のいずれか一項に記載の床用化粧材。　 The floor decorative material according to any one of claims 1 to 7, wherein the wood base material is plywood.
PCT/JP2020/037222 2019-09-30 2020-09-30 Decorative material for floor WO2021066035A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016168842A (en) * 2015-03-09 2016-09-23 大日本印刷株式会社 Decorative sheet and decorative plate
WO2018159660A1 (en) * 2017-02-28 2018-09-07 大日本印刷株式会社 Decorative sheet and decorative panel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016168842A (en) * 2015-03-09 2016-09-23 大日本印刷株式会社 Decorative sheet and decorative plate
WO2018159660A1 (en) * 2017-02-28 2018-09-07 大日本印刷株式会社 Decorative sheet and decorative panel

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