WO2016093313A1 - 床用化粧材 - Google Patents

床用化粧材 Download PDF

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Publication number
WO2016093313A1
WO2016093313A1 PCT/JP2015/084663 JP2015084663W WO2016093313A1 WO 2016093313 A1 WO2016093313 A1 WO 2016093313A1 JP 2015084663 W JP2015084663 W JP 2015084663W WO 2016093313 A1 WO2016093313 A1 WO 2016093313A1
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WO
WIPO (PCT)
Prior art keywords
layer
resin
resin layer
decorative material
floor
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PCT/JP2015/084663
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English (en)
French (fr)
Japanese (ja)
Inventor
孝志 土井
浩久 吉川
正文 清水
白行 野口
Original Assignee
大日本印刷株式会社
株式会社カネカ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 大日本印刷株式会社, 株式会社カネカ filed Critical 大日本印刷株式会社
Priority to KR1020217039045A priority Critical patent/KR102471547B1/ko
Priority to CN201580066542.1A priority patent/CN107002419B/zh
Priority to KR1020177015103A priority patent/KR20170094175A/ko
Publication of WO2016093313A1 publication Critical patent/WO2016093313A1/ja

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    • 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
    • E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • E04F15/107—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials composed of several layers, e.g. sandwich panels
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/16—Flooring, e.g. parquet on flexible web, laid as flexible webs; Webs specially adapted for use as flooring; Parquet on flexible web
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0228—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2471/00—Floor coverings

Definitions

  • the present invention relates to a floor decorative material.
  • wooden flooring materials have been widely used as flooring materials mainly for residential use, and the wooden flooring materials are generally laminated with a wooden material such as a veneer and then decorated with a decorative sheet or paint. It is used for.
  • Residential use such as toilets, bathrooms, kitchens, etc., are in a humid environment, so wooden flooring materials are prone to mold and warp, and are made of resin called a resin floor with excellent moisture resistance.
  • air conditioners such as air conditioners are rarely installed in toilets and washbasins, and the cushion floor has problems such as cooling down in the winter. In order to alleviate this cold in winter, it is conceivable to use a foamed flooring material having a foamed layer (for example, Patent Document 1).
  • the foam flooring is a non-wood flooring, it can be said to be a flooring that can solve the above problems because it is excellent in moisture resistance, water resistance and heat insulation.
  • heavy toilets, toilets and other building materials, and electrical appliances such as washing machines and refrigerators are placed around the water, so there is a problem with load resistance and scratch resistance against dents on the floor surface due to long-term loads.
  • Hardness of the floor material surface is important for load resistance and scratch resistance, but if it is too hard, impact resistance will be reduced, so the floor material has conflicting load resistance, scratch resistance and impact resistance. It is required to satisfy the performance at the same time.
  • the temperature change and the humidity change are larger in the area around the water than in other parts of the dwelling, the problem of warpage accompanying these changes is likely to occur.
  • the present invention has excellent heat insulation, water resistance, moisture resistance, shape stability, excellent surface properties such as impact resistance, load resistance, and scratch resistance, and is easy to install.
  • An object of the present invention is to provide an excellent flooring decorative material.
  • the present invention provides the following floor decorative material.
  • a foamed resin layer, a support layer, and a decoration layer are provided in this order, the foaming resin layer has a foaming ratio of 5 to 20 times, and a compression elastic modulus is 20 MPa or more.
  • the floor decorative material has excellent heat insulation, water resistance, moisture resistance, shape stability, excellent surface characteristics such as impact resistance, load resistance, and scratch resistance, and excellent workability. Can be provided.
  • the floor decorative material of the present invention has a foamed resin layer, a support layer, and a decorative layer in this order, the foamed resin layer has a foaming ratio of 5 to 20 times, and a compression modulus of 20 MPa or more,
  • the support layer has a tensile elastic modulus of 180 MPa or more.
  • FIGS. 1 and 2 are schematic views showing a cross section of a preferred floor decorative material 10 of the present invention.
  • the floor decorative material 10 of the present invention has a foamed resin layer 1, a support layer 2, and a decoration layer 3 in this order.
  • FIG. 1 the floor decorative material 10 of the present invention
  • the base resin layer 4 is provided between the support layer 2 and the decorative layer 3, and the adhesive layer 7, the transparent resin layer 5, and the decorative layer 3 are provided. It has a surface protective layer 6, and has a foamed resin layer 1, a support layer 2, a base resin layer 4, a decorative layer 3, an adhesive layer 7, a transparent resin layer 5, and a surface protective layer 6 in this order. .
  • the support body layer 2 becomes a 3 layer structure, and becomes a structure which has the 1st thermoplastic resin layer 21, the glass component layer 22, and the 2nd thermoplastic resin layer 23 in order. ing.
  • the foamed resin layer is a layer that mainly imparts heat insulation, load resistance, and impact resistance to the flooring decorative material of the present invention.
  • the foamed resin layer is formed by foaming a foamed resin composition, and has a foaming ratio of 5 to 5. It is a layer that is 20 times and has a compression modulus of 20 MPa or more.
  • the expansion ratio in the foamed resin layer needs to be 5 to 20 times.
  • the expansion ratio is preferably 5 to 15 times, and more preferably 5 to 12 times.
  • the compression elastic modulus of the foamed resin layer is required to be 20 MPa or more. If the compression modulus is less than 20 MPa, excellent load resistance and impact resistance cannot be obtained. From the viewpoint of obtaining excellent load resistance and impact resistance, the compressive elastic modulus is preferably 20 to 100 MPa, and more preferably 20 to 50 MPa.
  • the compressive elastic modulus is a value obtained by measuring a foamed molded product according to a method described in JIS A9511: 1999 “foamed plastic heat insulating material”.
  • a rectangular parallelepiped test piece having a length of 100 mm ⁇ width of 100 mm ⁇ thickness of 30 mm was cut out from the foamed resin layer, and the test piece was measured for compression elastic modulus at a compression speed of 10 mm / min using a Tensilon measuring instrument. I do. Five test pieces are prepared, the compression elastic modulus is measured for each test piece as described above, and the value obtained by arithmetically averaging them is defined as the compression elastic modulus.
  • the foaming method of the foamed resin composition is not particularly limited, and any known method can be adopted, but foaming by a bead method is preferable from the viewpoint of obtaining a homogeneous foamed resin layer.
  • the bead method uses foamed resin particles (pre-foamed particles) as raw materials, fills the foamed resin particles into a cavity of a mold, and performs secondary foaming of the filled pre-foamed particles with steam, This is a method of obtaining a foamed resin layer by integrating the two by heat fusion.
  • the resin used for the expanded resin particles is preferably a thermoplastic resin.
  • Thermoplastic resins include polyethylene, propylene, polystyrene, polyolefin resin such as ethylene-vinyl acetate copolymer resin (EVA), ethylene- (meth) acrylic acid resin, acrylonitrile-butadiene-styrene copolymer (ABS resin) , Acrylonitrile-styrene copolymer, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl resin such as polyvinyl alcohol resin, polyester resin such as polyethylene terephthalate resin (PET resin), nylon, polyacetal resin, acrylic resin, polycarbonate resin, polyurethane
  • PET resin polyethylene terephthalate resin
  • Preferable are simple substances and copolymers of thermoplastic resins such as resins, or mixed resins thereof. Among these, considering the strength of the resin itself, a polyolefin resin is preferable,
  • the styrene monomer that forms the polystyrene resin is not particularly limited, and any known styrene monomer can be used. Examples include styrene, ⁇ -methyl styrene, vinyl toluene, chlorostyrene, ethyl styrene, isopropyl styrene, dimethyl styrene, bromostyrene, and the like. These styrenic monomers may be one kind or a mixture of plural kinds. A preferred styrene monomer is styrene.
  • the foamed resin particles are usually made into resin particles by polymerizing the seed particles made of the resin forming the foamed resin particles by absorbing a monomer such as a styrene monomer together with a plasticizer as necessary, and at the same time as the polymerization or After polymerization, the resin particles are obtained by impregnating the resin particles with a foaming agent and then foaming.
  • the foamed resin particles can also be obtained by a method in which particles obtained by suspension polymerization of a monomer such as a styrene monomer in an aqueous medium are impregnated with a foaming agent.
  • foaming agent examples include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosotephthalamide, N, N′-di Nitroso compounds such as nitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide and toluenesulfonyl hydrazide; calcium Preferred examples include azide compounds such as azide, 4,4′-diphenyldisulfonyl azide, and p-toluenesulfonyl azide.
  • inorganic foaming agents such as sodium hydrogen carbonate
  • blowing agent in addition to aliphatic hydrocarbons such as propane, normal butane, isopentane, normal pentane, and neopentane, fluorinated hydrocarbons such as difluoroethane and tetrafluoroethane that have zero ozone destruction coefficient
  • fluorinated hydrocarbons such as difluoroethane and tetrafluoroethane that have zero ozone destruction coefficient
  • volatile foaming agents such as These foaming agents can be used alone or in combination.
  • the addition amount of the foaming agent may be appropriately determined according to the desired expansion ratio and compression modulus, but is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin. .
  • Plasticizers include fatty acid ester compounds such as propylene glycol fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters; phthalic acid esters such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), and diisononyl phthalate (DINP).
  • fatty acid ester compounds such as propylene glycol fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters
  • phthalic acid esters such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), and diisononyl phthalate (DINP).
  • adipate compounds such as diisobutyl adipate and dioctyl adipate
  • sebacate compounds such as dibutyl sebacate and di-2-ethylhexyl sebacate
  • glycerin fatty acid ester compounds such as glycerin tristearate and glycerin tricaprylate
  • liquid paraffin Preferred examples include natural fats and oils such as coconut oil, palm oil and rapeseed oil.
  • the plasticizer may be added when the monomer is polymerized, or may be added when the foaming agent is impregnated.
  • the addition amount of the plasticizer may be appropriately determined according to the desired expansion ratio and compression modulus, but is preferably 0.2 parts by mass or more and less than 3 parts by mass with respect to 100 parts by mass of the resin, 0.4 parts by mass More preferably, it is less than 1.6 parts by mass. If the added amount of the plasticizer is 0.2 parts by mass or more, the secondary transition temperature becomes low, so it is advantageous for pre-foaming and molding at low temperature. If it is less than 3 parts by mass, the foam is difficult to shrink and good. A nice look.
  • the foamed resin particles have a flame retardant, a flame retardant aid, a lubricant, a binding inhibitor, a fusion accelerator, an antistatic agent, a spreading agent, a cell conditioner, a crosslinking agent, within a range that does not impair physical properties.
  • Additives such as fillers and colorants may be included.
  • the above-mentioned foamed resin particles are filled in a mold cavity, and the filled pre-foamed particles are used at a temperature of 100 to 150 ° C., preferably 100 to 120 ° C. using a heat medium such as steam,
  • a foamed resin layer can be obtained by integrating the pre-expanded particles by heat fusion while performing secondary foaming with a heating time of 10 to 40 seconds.
  • the average particle diameter of the foamed resin particles generally used is preferably 0.2 to 4 mm, more preferably 0.5 to 2 mm.
  • the foamed resin layer is not limited to the above-mentioned bead method, and the resin composition for forming the foamed resin layer includes a resin for a foamed resin layer, a foaming agent, a plasticizer, an inorganic filler, and other additives as necessary. It is also possible to obtain a product by forming a non-foamed resin layer by a film forming method such as an extrusion film forming method using a T-die or a calender film forming method, and then foaming at about 220 to 250 ° C. using a heating foaming furnace it can.
  • a film forming method such as an extrusion film forming method using a T-die or a calender film forming method
  • a commercially available heat insulating board such as a bead method polystyrene foam heat insulating plate, an extrusion method polystyrene foam heat insulating plate, or the like can be used as long as it is within a predetermined expansion ratio and tensile modulus.
  • the thickness of the foamed resin layer is somewhat from 3 to 15 mm, more preferably from 5 to 15 mm, and even more preferably from 5 to 12 mm, although it is somewhat dependent on the expansion ratio.
  • the thickness of the foamed resin layer is within the above range, excellent heat insulation, load resistance and impact resistance can be obtained.
  • the thickness of a foamed resin layer is thicker than the support layer mentioned later. By being thicker than the support layer, excellent heat insulation, load resistance, and impact resistance can be obtained, and stress warpage due to difference in elongation from other layers such as support layer is unlikely to occur. Become.
  • the support layer is a layer mainly imparting shape stability, water resistance, moisture resistance, impact resistance, and scratch resistance to the floor decorative material of the present invention, and is a layer having a tensile modulus of 180 MPa or more. .
  • the support layer needs to have a tensile modulus of 180 MPa or more. If the tensile modulus is less than 180 MPa, scratch resistance cannot be obtained. From the viewpoint of obtaining excellent water resistance, moisture resistance, and scratch resistance, the tensile modulus is preferably 180 to 3000 MPa, more preferably 250 to 1000 MPa, and further preferably 250 to 500 MPa. Further, when the tensile elastic modulus is within the above range, stress warpage due to a difference in elongation due to moisture or the like with other layers such as a foamed resin layer is less likely to occur.
  • the support layer preferably has a thermoplastic resin layer.
  • the thermoplastic resin forming the thermoplastic resin layer include polyvinyl resins such as polyvinyl chloride resin, polyvinyl acetate resin, and polyvinyl alcohol resin, polyethylene, propylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), and ethylene.
  • -Polyolefin resins such as (meth) acrylic acid resins, polyester resins such as polyethylene terephthalate resins (PET resins), thermoplastic resins such as acrylic resins, polycarbonate resins, and polyurethane resins, copolymers, and mixtures thereof A resin is preferred. Of these, polyvinyl resin is preferable.
  • the support layer may be composed of one layer or a laminate composed of two or more layers, but is a laminate composed of two or more layers, and has at least one layer. It is preferable that contains a glass component. That is, the support layer is a laminate composed of two or more layers, preferably at least one layer is a thermoplastic resin layer and the other layer is a glass component layer containing a glass component. With such a configuration, excellent impact resistance is obtained, and shape stability is improved.
  • the glass component layer containing a glass component the layer comprised by glass fiber etc. is mentioned preferably, for example.
  • the support layer is preferably a laminate in which a thermoplastic resin layer and a glass component layer are alternately laminated, and in particular, the first thermoplastic resin layer as shown in FIG. It is preferable that it is a laminated body which has a glass component layer and a 2nd thermoplastic resin layer in order.
  • the types of resins forming the thermoplastic resin layer may be the same or different, and the thicknesses may be the same or different. Also good.
  • the thickness of the support layer is preferably 1 to 10 mm, and more preferably 1 to 5 mm.
  • the thickness of the support layer is within the above range, excellent water resistance, moisture resistance, impact resistance, and scratch resistance can be obtained. Moreover, it becomes difficult to produce the stress curvature resulting from the difference in elongation by temperature etc. with other layers, such as a foamed resin layer.
  • the thickness of a support body layer is thinner than a foamed resin layer. Stress warpage due to a difference in elongation due to moisture or the like with other layers such as a foamed resin layer layer is less likely to occur.
  • the decorative layer is a layer that imparts decorativeness to the decorative material for floors of the present invention, and may be a concealing layer (solid printing layer) that is uniformly colored, or various patterns using ink and a printing machine. It may be a pattern layer formed by printing, or a combination of a hiding layer and a pattern layer.
  • a concealing layer By providing a concealing layer, it is possible to conceal the base on which the flooring decorative material is provided, and when the base material layer is colored or uneven in color, the surface color is adjusted by giving the intended color. Can do.
  • a pattern layer a grain pattern imitating the surface of a rock such as a wood grain pattern, marble pattern (for example, travertine marble pattern), a fabric pattern imitating a texture or cloth pattern, tiled pattern, brickwork
  • a pattern such as a pattern or a combination of these, a parquet, a patchwork, or the like can be applied to the decorative sheet.
  • These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates constituting the pattern. Is done.
  • a binder resin in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used.
  • the binder resin is not particularly limited, and preferred examples include urethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, acrylic resins, polyester resins, and nitrocellulose resins. It is done. Any of these binder resins can be used alone or in admixture of two or more.
  • Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow , Organic pigments such as phthalocyanine blue, or metallic pigments made of scaly foils such as dyes, aluminum and brass, pearlescent pigments made of scaly foils such as titanium dioxide-coated mica and basic lead carbonate, etc. Preferably mentioned.
  • the thickness of the decoration layer is usually 0.5 to 10 ⁇ m, preferably 1 to 5 ⁇ m. If the thickness of the decorative layer is within the above range, an excellent design can be imparted to the decorative material for flooring, and concealment can be imparted.
  • the base resin layer is a layer provided as desired, and is preferably a layer formed of a thermoplastic resin.
  • a thermoplastic resin what was illustrated as a thermoplastic resin provided in said foamed resin layer can be mentioned preferably. Of these, polyolefin resins are preferable, and polyethylene resins and propylene resins are more preferable.
  • the base resin layer may be transparent or colored, and is preferably colored from the viewpoint of concealing the base on which the floor decorative material is provided.
  • Preferred examples of the colorant used include those exemplified as the colorant used in the decorative layer.
  • the thickness of the base resin layer is preferably 10 to 150 ⁇ m, more preferably 30 to 100 ⁇ m, and further preferably 40 to 80 ⁇ m. When the thickness of the base resin layer is within the above range, handling is easy, and the floor covering material does not become thicker than necessary.
  • additives such as a filler, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer may be added to the base resin layer as necessary.
  • the transparent resin layer is an arbitrary layer provided for protecting the decorative layer, and is preferably a layer formed of a thermoplastic resin.
  • a thermoplastic resin what was illustrated as a thermoplastic resin provided in said foamed resin layer can be mentioned preferably. Of these, polyolefin resins are preferable, and polyethylene resins and propylene resins are more preferable.
  • the transparent resin layer is a transparent resin layer so that the decorative layer can be seen through.
  • transparent is a concept including colorless and transparent as well as colored and translucent.
  • various additives such as fillers, flame retardants, lubricants, antioxidants, ultraviolet absorbers, light stabilizers and the like may be added to the transparent resin layer as long as the transparency is not impaired. Good.
  • the thickness of the transparent resin layer is preferably 10 to 150 ⁇ m, more preferably 30 to 100 ⁇ m, and further preferably 50 to 100 ⁇ m.
  • the decorative layer can be protected, the handling is easy, and the floor decorative material does not become thicker than necessary.
  • the surface protective layer is a layer provided as desired, which imparts surface characteristics such as impact resistance, load resistance, and scratch resistance to the floor decorative material of the present invention.
  • the surface protective layer is provided on the outermost surface of the floor decorative material of the present invention.
  • the surface protective layer is preferably constituted by applying a resin composition containing a curable resin on a decorative layer, or a preferably provided transparent resin layer or adhesive layer, and curing the resin composition. By containing the curable resin that has been crosslinked and cured, the surface characteristics of the decorative material for flooring can be improved.
  • Preferred examples of the curable resin used for forming the surface protective layer include ionizing radiation curable resins and thermosetting resins. A plurality of these are used, for example, ionizing radiation curable resins and thermosetting resins are used in combination.
  • the so-called hybrid type may be used.
  • ionizing radiation curable resins are preferable, and the viewpoint that they can be applied without a solvent and are easy to handle. Therefore, an electron beam curable resin is more preferable.
  • the ionizing radiation curable resin refers to a resin having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.
  • the polymerizable monomer a (meth) acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable.
  • the polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.
  • an oligomer having a radical polymerizable unsaturated group in the molecule for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate The system etc. are mentioned.
  • other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain.
  • an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule or a novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.
  • oligomers having a cationic polymerizable functional group there are oligomers having a cationic polymerizable functional group.
  • a monofunctional (meth) acrylate can be appropriately used in combination with the polyfunctional (meth) acrylate and the like within a range that does not impair the object of the present invention, for the purpose of reducing the viscosity.
  • These monofunctional (meth) acrylates may be used alone or in combination of two or more.
  • Thermosetting resins include epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, carboxyl functional acrylic resin, amide functional copolymer Preferred examples include coalescence and urethane resin.
  • thermosetting resin a two-component curable resin is also preferably exemplified, and a two-component curable resin of a polyol and an isocyanate is preferable.
  • the polyol include acrylic polyol, polyester polyol, and epoxy polyol.
  • the isocyanate may be any polyisocyanate having two or more isocyanate groups in the molecule.
  • 2,4-tolylene diisocyanate TDI
  • xylene diisocyanate XDI
  • naphthalene diisocyanate 4 Aliphatics such as aromatic isocyanates such as' -diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate
  • Polyisocyanates such as (alicyclic) isocyanates are used.
  • adducts or multimers of these various isocyanates for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers, and the like are also used.
  • the resin composition constituting the surface protective layer can contain various additives as long as the performance is not impaired.
  • the various additives include ultraviolet absorbers (UVA), light stabilizers (HALS, etc.), polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents. , Coupling agents, plasticizers, antifoaming agents, fillers, solvents and the like.
  • the thickness of the surface protective layer is preferably 3 to 20 ⁇ m, more preferably 5 to 20 ⁇ m. When the thickness of the surface protective layer is within the above range, excellent surface characteristics can be obtained.
  • the adhesive layer is a layer provided as necessary when laminating the resin layer when providing the base resin layer and the transparent resin layer.
  • Preferred examples of the adhesive used in the adhesive layer include urethane adhesives, acrylic adhesives, acrylic / urethane adhesives, polyester adhesives, polyester urethane adhesives, polyamide adhesives, polystyrene adhesives, and cellulose adhesives. . These adhesives can be used singly or as a mixture of two or more.
  • the thickness of the adhesive layer is preferably 3 to 30 ⁇ m, and more preferably 3 to 15 ⁇ m. When the thickness of the adhesive layer is within the above range, good adhesiveness is obtained, and the floor decorative material does not become thicker than necessary.
  • the floor decorative material of the present invention having each of the above layers is excellent in impact resistance, heat insulation, water resistance, moisture resistance, load resistance, scratch resistance, and excellent workability. It is suitable for flooring for residential use, especially watering applications such as toilets, washbasins and kitchens.
  • the thickness of the floor decorative material of the present invention is preferably 5 to 25 mm, more preferably 7 to 20 mm from the viewpoint of obtaining excellent impact resistance, heat insulation, water resistance, moisture resistance, load resistance, and scratch resistance. 8 to 15 mm is more preferable. In consideration of easiness of construction, it is preferable to have the same thickness as the wooden flooring material provided in places other than around the water such as a living room or a corridor.
  • the thickness of the wood flooring material is usually 8 mm, 12 mm, 15 mm, etc., and 12 mm is a standard thickness.
  • the floor decorative material of the present invention can be produced, for example, through the following steps.
  • a foamed resin layer is prepared.
  • the foamed resin layer is produced by foaming the bead method or the resin composition for the foamed resin layer so that the expansion ratio is 5 to 20 times and the compression modulus is 20 MPa or more.
  • the expansion ratio and compression modulus of the foamed resin layer can be appropriately adjusted depending on the foaming temperature at the time of foaming, the type of resin, the amount of foaming agent and plasticizer used, and the like.
  • a decorative layer is formed using the ink composition on the support layer or a base resin layer provided as necessary.
  • the ink composition may be applied by a method such as gravure printing, offset printing, screen printing, flexographic printing, or ink jet printing.
  • a concealing layer solid printing layer
  • it may be formed by various coating methods such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating.
  • Adhesion between the foamed resin layer obtained in the step of preparing the foamed resin layer and the support layer on which the decorative layer is formed can be performed using, for example, a heat-sensitive adhesive, a pressure-sensitive adhesive, a hot melt adhesive, and the like. It can be carried out.
  • a hot melt adhesive for example, a reactive hot melt adhesive such as a urethane-based reactive hot melt (hereinafter referred to as “PUR”) is preferably exemplified. This PUR contains a functional group (isocyanate group) that reacts with moisture in the components, and reacts with moisture attached to the substrate and the decorative sheet and moisture given through them after cooling and curing. After the reaction, it does not melt even when heated and has a high adhesive strength.
  • the transparent resin layer is preferably provided by a dry lamination method via an adhesive layer after forming a decorative layer.
  • a decorative layer is formed on the base substrate layer by the above-mentioned method, and then dry lamination such as a two-component curable urethane resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer using a blocked isocyanate as a curing agent, for example.
  • An adhesive layer is formed by applying an adhesive, and a transparent resin layer can be provided by a dry lamination method.
  • the surface protective layer is a curable resin composition after the decoration layer forming step, or when the transparent resin layer is laminated, after the resin layer lamination step, on the decoration layer or on the transparent resin layer.
  • the uncured resin layer can be formed by applying heat to the uncured resin layer or irradiating it with ionizing radiation such as an electron beam or ultraviolet rays to cure the uncured resin layer.
  • the heating temperature in the case of thermosetting is appropriately determined according to the resin used.
  • the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but it is preferable to cure the uncured resin layer usually at an acceleration voltage of about 70 to 300 kV.
  • the irradiation dose is preferably such that the crosslinking density of the resin layer 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, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
  • ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted.
  • an ultraviolet-ray source For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
  • the floor decorative materials obtained in each Example and Comparative Example were evaluated and measured by the following methods.
  • the “scratch hardness (pencil method) test” in accordance with JIS K5600-5-4 was conducted 5 times by scratching the surface of the flooring decorative material with a load of 500 g, and the hardness of the pencil with no scars occurring 3 times or more.
  • the pencil hardness was evaluated based on the following criteria. ⁇ It was B or more, and there was extremely excellent scratch resistance. ⁇ 2B or more and excellent scratch resistance. X 3B or less and poor scratch resistance.
  • Example 1 On a colored polypropylene resin film (thickness: 60 ⁇ m, color: white), a 2 ⁇ m-thick decorative layer was formed by gravure printing using an ink composition (acrylic urethane). Next, a transparent polypropylene resin film (thickness: 80 ⁇ m) was dry laminated on the decorative layer using an urethane dry laminate adhesive. On the transparent polypropylene resin film, an electron beam curable resin composition (acrylate system) is applied by gravure printing at an application amount of 15 g / m 2 to form a coating film, and an electron is applied under conditions of 175 keV and 5 Mrad (50 kGy).
  • an electron beam curable resin composition (acrylate system) is applied by gravure printing at an application amount of 15 g / m 2 to form a coating film, and an electron is applied under conditions of 175 keV and 5 Mrad (50 kGy).
  • the coating film was cross-linked and cured by irradiation with a line to form a surface protective layer (thickness: 15 ⁇ m), and a decorative sheet (thickness; 160 ⁇ m) was produced.
  • a medium density polyethylene resin sheet (tensile elastic modulus: 200 MPa, thickness: 3 mm) is prepared as a support layer, and the support is provided so as to face the colored polypropylene resin film (base resin layer) of the decorative sheet.
  • the body layer and the decorative sheet were attached by dry lamination via an urethane dry laminate adhesive.
  • polystyrene resin (foaming agent; butane (7 parts by mass with respect to 100 parts by mass of polystyrene resin), plasticizer; liquid paraffin (0.15 parts by mass with respect to 100 parts by mass of polystyrene resin)) is used as the foamed resin layer.
  • a foamed resin layer (foaming ratio: 10 times, compression elastic modulus: 43 MPa, thickness: 9 mm) prepared by using the bead method is prepared, and the support layer and the foamed resin layer on which the decorative sheet is attached, Adhesion was carried out using a urethane-based reactive hot melt adhesive to produce a flooring decorative material. Table 1 shows the results of evaluating the obtained floor decorative material.
  • Example 2 a floor decorative material was produced in the same manner as in Example 1 except that the foamed resin layer and the support layer shown in Table 1 were used. Table 1 shows the results of evaluating the obtained floor decorative material.
  • the floor decorative material has excellent heat insulation, water resistance, moisture resistance, shape stability, excellent surface characteristics such as impact resistance, load resistance, and scratch resistance, and excellent workability. Can be obtained.
  • the flooring decorative material of the present invention is suitably used as a flooring material for residential use, particularly as a flooring material for use around water such as toilets, washbasins and kitchens.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Floor Finish (AREA)
  • Laminated Bodies (AREA)
PCT/JP2015/084663 2014-12-10 2015-12-10 床用化粧材 WO2016093313A1 (ja)

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CN201580066542.1A CN107002419B (zh) 2014-12-10 2015-12-10 地板用装饰材料
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JP2018167510A (ja) * 2017-03-30 2018-11-01 積水化成品工業株式会社 複合発泡体、及び、複合発泡体の作製方法
WO2024068988A1 (en) * 2022-09-30 2024-04-04 Champion Link International Corporation Panel, composition for impregnating or coating a panel, and a method for producing a panel

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KR101760755B1 (ko) 2017-05-10 2017-07-24 주식회사 스타코리아 내마모성이 강화된 강마루 바닥판재의 제조방법
KR101788542B1 (ko) 2017-05-15 2017-10-20 주식회사 스타코리아 산업부산물을 이용한 친환경 마루바닥재의 제조방법
KR101788541B1 (ko) 2017-05-15 2017-10-23 주식회사 스타코리아 방염성 및 난연성이 우수한 친환경 마루바닥재의 제조방법
KR20230126354A (ko) 2022-02-23 2023-08-30 공주대학교 산학협력단 건물 지붕외피 단열재 및 바닥내장 단열재 겸용 음각 트러스 데크플레이트 일체형 단열시스템

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JP6696726B2 (ja) 2020-05-20
KR102471547B1 (ko) 2022-11-29
KR20210149891A (ko) 2021-12-09
CN111962820A (zh) 2020-11-20
CN107002419A (zh) 2017-08-01
CN107002419B (zh) 2021-01-05
KR20170094175A (ko) 2017-08-17

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