CN100566995C - Decorating material for flooring - Google Patents
Decorating material for flooring Download PDFInfo
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- CN100566995C CN100566995C CNB2007100913414A CN200710091341A CN100566995C CN 100566995 C CN100566995 C CN 100566995C CN B2007100913414 A CNB2007100913414 A CN B2007100913414A CN 200710091341 A CN200710091341 A CN 200710091341A CN 100566995 C CN100566995 C CN 100566995C
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- layer
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- flooring
- synthetic resin
- transparent
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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
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
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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
- B32B2317/00—Animal or vegetable based
- B32B2317/16—Wood, e.g. woodboard, fibreboard, woodchips
Abstract
The invention provides the decorating material for flooring of a kind of flatness and the damaging excellence of anti-depression.This decorating material for flooring has decorative layer at the wood substrate superimposed layer; this decorative layer lamination successively has synthetic resin layer, substrate sheets, pattern layer, transparent adhesive phase, transparent resin bed and transparent sealer, makes synthetic resin layer contact with wood substrate.This decorating material for flooring is characterised in that: (1) is selected from least a in substrate sheets and the transparent resin bed to have according to JIS K6734 is tensile modulus of elasticity below the 1000MPa; (2) to have according to JIS K6734 be tensile modulus of elasticity more than the 1000MPa to synthetic resin layer.
Description
Technical field
The present invention relates to decorating material for flooring.
Background technology
All the time, as the constituent material of resinous decorating plate for flooring, use the Corvic sheet mostly.As the manufacture method of Corvic sheet, can be set forth in the method (patent documentation 1) of adding plasticizer in the Corvic.Under the situation of using sheet, have by adjusting the addition of plasticizer, can easily adjust Corvic sheet hardness (hard～soft), and implement the advantage of embossing processing easily.
But Corvic might be emitted harmful graphite when burning, chlorine is gas.In recent years, the polyolefin-based resins replacement Corvic that chlorine is gas is not emitted in use when burning.
But in decorating material for flooring, major requirement flatness and anti-depression are damaging.
In order to improve the flatness of decorating material for flooring, use the high decorative layer of hardness all the time.
But the decorative layer that hardness is high for example but exists owing to impacted, and is easy to generate crack and depression, the damaging inadequate problem of promptly anti-depression.
Patent documentation 1: TOHKEMY 2004-019343
Summary of the invention
Main purpose of the present invention is to provide the decorating material for flooring of a kind of flatness and the damaging excellence of anti-depression.
The inventor furthers investigate repeatedly, found that by using specific decorative layer, and can achieve the above object, the present invention is accomplished.
That is, the present invention relates to following decorating material for flooring.
Described in this manual JIS is JIS.
1. decorating material for flooring; at the wood substrate superimposed layer decorative layer is arranged; this decorative layer lamination successively has synthetic resin layer, substrate sheets, pattern layer, transparent adhesive phase, transparent resin bed and transparent sealer; make synthetic resin layer contact, it is characterized in that with wood substrate:
(1) being selected from least a in substrate sheets and the transparent resin bed, to have according to JISK6734 be tensile modulus of elasticity below the 1000MPa;
(2) to have according to JIS K6734 be tensile modulus of elasticity more than the 1000MPa to synthetic resin layer.
2. above-mentioned 1 described decorating material for flooring is characterized in that: be selected from least a layer in synthetic resin layer, substrate sheets and the transparent resin bed, contain polyolefin-based resins as resinous principle.
3. as above-mentioned 1 described decorating material for flooring, it is characterized in that: synthetic resin layer contains the crystallization nucleator.
4. as above-mentioned 1 described decorating material for flooring, it is characterized in that: the thickness of decorative layer is 200～300 μ m.
The invention effect
The flatness of decorating material for flooring of the present invention and the damaging excellence of anti-depression.
And, decorating material for flooring of the present invention, even under the thickness of decorative layer is situation below the 300 μ m, it is damaging also to have excellent flatness and anti-depression.Because thickness is the following easy severings of decorative layer of 300 μ m, so can be by a large amount of productions of continuous laminating decorating material for flooring of the present invention.In addition, in decorating material for flooring of the present invention, be more than the 200 μ m by the thickness that makes decorative layer, except that flatness and anti-depression are damaging, can also give resistance to water.
Description of drawings
Fig. 1 is the schematic diagram (sectional view) of the decorating material for flooring of making in embodiment 1.
Fig. 2 is the regulation according to JIS K6734 " plastics-RPVC sheet-size and characteristic-part 2: thickness is less than the sheet of 1mm ", when measuring tensile modulus of elasticity as the top figure of the test sample of determination object.
Symbol description
1: transparent sealer; 2: transparent resin bed; 3: transparent adhesive phase; 4: the pattern layer; 5: substrate sheets; 6: adhesive phase; 7: synthetic resin layer: 8: priming coat.
The specific embodiment
Decorating material for flooring of the present invention, at the wood substrate superimposed layer decorative layer is arranged, this decorative layer lamination successively has synthetic resin layer, substrate sheets, pattern layer, transparent adhesive phase, transparent resin bed and transparent sealer, make synthetic resin layer contact with wood substrate, it is characterized in that: (1) is selected from least a in substrate sheets and the transparent resin bed to have according to JIS K6734 is tensile modulus of elasticity below the 1000MPa; (2) to have according to JIS K6734 be tensile modulus of elasticity more than the 1500MPa to synthetic resin layer.
According to the present invention, when being selected from least a in substrate sheets in the decorative layer and the transparent resin bed to have according to JIS K6734 being tensile modulus of elasticity below the 1000MPa, the crack that can prevent decorating material for flooring effectively.That is it is damaging that, decorating material for flooring can access excellent anti-depression.At least a tensile modulus of elasticity according to JIS K6734 in special preferred substrates sheet and the transparent resin bed is 600～1000MPa.
In addition, according to the present invention,, flatness is improved by between wood substrate and substrate sheets, synthetic resin layer being set.And, utilizing above-mentioned synthetic resin layer, can prevent effectively owing to cause the depression of decorating material for flooring from the impact of outside.That is, can further to improve anti-depression damaging for above-mentioned synthetic resin layer.Particularly in the present invention, be more than the 1000MPa by the tensile modulus of elasticity that makes synthetic resin layer, it is damaging that decorating material for flooring can access excellent flatness and anti-depression.The tensile modulus of elasticity according to JIS K6734 of preferred above-mentioned synthetic resin layer is more than the 1500MPa, more preferably 1500～2500MPa.
In addition, the tensile modulus of elasticity in this specification is the value of measuring according to the regulation of JIS K6734 " plastics-RPVC sheet-size and characteristic-part 2: thickness is less than the sheet of 1mm ".
Particularly, use cupping machine (TENSILON universal testing machine RTC-1250A), with the speed stretching and punching of 50mm/min become shape shown in Figure 2 test sample (synthetic resin layer and be selected from substrate sheets and transparent resin bed at least a layer) two ends (A of Fig. 2 and B) time, measure the value of trying to achieve the tensile modulus of elasticity (MPa) of above-mentioned test sample when middle body cuts off.
As mentioned above, decorating material for flooring of the present invention is selected from least a layer in substrate sheets and the transparent resin bed and the tensile modulus of elasticity of synthetic resin layer and is set in the particular range.Because the tensile modulus of elasticity of these layers suitably is set in the above-mentioned scope, so at least a layer that decorating material for flooring of the present invention is preferably selected from synthetic resin layer, substrate sheets and the transparent resin bed contains polyolefin-based resins as resinous principle.Particularly, possesses the above tensile modulus of elasticity of 1000MPa easily because above-mentioned synthetic resin layer also contains the crystallization nucleator.
Here, so-called crystallization nucleator refers to itself and is scattered in equably in the resin combination that is used to form synthetic resin layer, becomes the nuclei of crystallization of crystallization starting point, promotes the additive of resinous principle crystallization.Contain at above-mentioned synthetic resin layer under the situation of crystallization nucleator, in above-mentioned synthetic resin layer, generate evenly fine crystallization, so the crystallization degree of above-mentioned synthetic resin layer increases, optical property such as engineering properties such as tensile modulus of elasticity, heat distortion temperature and transparency is improved.
In addition, the decorative layer thickness in the decorating material for flooring of the present invention is preferably 200～300 μ m.
By making decorative layer thickness is below the 300 μ m, because severing decorative layer easily, so be easy to produce in a large number.That is, continuous laminating decorative layer on wood substrate adopts the method that meets wood substrate size ground severing decorative layer then, makes decorating material for flooring of the present invention.
In addition, be more than the 200 μ m by making decorative layer thickness, except that flatness, anti-depression are damaging, can also give decorating material for flooring with excellent in water resistance.
Below, the above-mentioned decorating material for flooring of illustration describes.
Synthetic resin layer
By between wood substrate and substrate sheets, adding synthetic resin layer, can improve the flatness of decorating material for flooring.
Preferred above-mentioned synthetic resin layer contains polyolefin-based resins as resinous principle.
As polyolefin-based resins, can enumerate for example polyethylene (high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE)), polypropylene etc.These can use more than a kind or 2 kinds.Wherein, special optimization polypropylene.As polypropylene, can enumerate for example homo-polypropylene, random polypropylene, block polypropylene etc.Wherein, preferred especially homo-polypropylene.
In addition, as the resinous principle of above-mentioned synthetic resin layer, also can use said polyolefins is resin resinous principle in addition.Can enumerate for example vinyl chloride resin, polystyrene, polyamide, polyimide resin, polyamide-imide resin, fluororesin, polyurethane resin, polysulfones, Merlon, polyacetals, polyphenylene ether, methacrylic resin, AS resin acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, PEN (PEN), PETG (PET), polybutylene terephthalate (PBT) (PBT), polyarylate, amorphism PETG (so-called A-PET) (Mitsubishi Chemical Ind, trade name Novaclear (ノ バ Network リ ア one)), pet copolymer (PETG) etc.Wherein, preferred especially A-PET.In addition, for obtaining stable on heating purpose, preferred A-PET and PEN are shared.
Said polyolefins in the above-mentioned synthetic resin layer is that the content of resin is preferably 90～100 weight %, more preferably 95～100 weight %.
In addition, preferred above-mentioned synthetic resin layer contains the crystallization nucleator.By containing the crystallization nucleator, can further improve the tensile modulus of elasticity of synthetic resin layer.As above-mentioned crystallization nucleator, can use for example two (to the methyl benzal) D-sorbites, phosphoric acid 2,2 '-di-2-ethylhexylphosphine oxide (4,6-two-tert-butyl-phenyl) sodium, the slaine of rosin, the slaine of rosin derivative, benzoic slaine etc.As the slaine of rosin, the slaine and the benzoic slaine of rosin derivative, can enumerate sodium salt, mantoquita, zinc salt etc.These crystallization nucleators can use more than a kind or 2 kinds.Particularly in the present invention, as the crystallization nucleator, the preferred use is selected from two (to the methyl benzal) D-sorbites and phosphoric acid 2, in 2 '-di-2-ethylhexylphosphine oxide (4,6-two-tert-butyl-phenyl) sodium at least a kind.Content about above-mentioned crystallization nucleator, can suitably set, make that the tensile modulus of elasticity according to JISK6734 of above-mentioned synthetic resin layer is more than the 1000MPa, but the resinous principle of the above-mentioned synthetic resin layer of relative 100 weight portions, be generally 0.05～0.4 weight portion, be preferably 0.1～0.3 weight portion.
Above-mentioned synthetic resin layer can adopt for example rolling process, plavini, T mould extrusion molding etc., contains the resin combination of above-mentioned resinous principle at the substrate sheets superimposed layer.In addition, also can use ready-made film as above-mentioned synthetic resin layer.
There is no particular limitation for the thickness of above-mentioned synthetic resin layer, is generally 50～210 μ m, is preferably about 100～200 μ m.
Substrate sheets
As substrate sheets, there is no particular limitation, from can easily the tensile modulus of elasticity according to JIS K6734 being set at the viewpoint below the 1000MPa, preferably contains the film of polyolefin-based resins as resinous principle.The content of the vistanex in the substrate sheets is preferably 90～100 weight %, more preferably 95～100 weight %.
As said polyolefins is resin, and there is no particular limitation, can use at the normally used resin in cosmetic sheet field.Can enumerate for example polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butylene copolymer, polyolefin thermoplastic elastomer (TPE) etc.These can use more than a kind or 2 kinds.Wherein, special optimization polypropylene, polyolefin thermoplastic elastomer (TPE) etc.
As said polyolefins is resin, and also preferred is the homopolymerization or the copolymer of main component with the polypropylene.Can enumerate carbon number beyond for example sym-propene polymer resin, random polypropylene resin, block polypropylene resin and the crystalling propylene portion and propylene and be the copolymer of 2～20 alpha-olefin.In addition, also preferably contain 15 moles of % above ethene, butene-1, the propylene-alpha-olefin copolymers of the comonomer of 4-methylpentene-1, hexene-1 or octene-1 etc.
Said polyolefins based thermoplastic elastomer is, has as the high crystalline of hard segment (hard segment) and dystectic aromatic polyester with as the glass transition temperature of the soft chain segment block polymer for the amorphism polyethers below-70 ℃.Especially preferably mix the soft chain segment that hard segment that isotactic polypropylene forms and random polypropylene form and the elastomer that obtains with weight ratio 80: 20.
As required, can in substrate sheets, cooperate known additive.As above-mentioned additive, can enumerate for example fire retardants such as filler such as calcium carbonate, clay, magnesium hydroxide, antioxidant, lubricant, blowing agent, colouring agent (with reference to following) etc.These can use more than a kind or 2 kinds.The use level of above-mentioned additive can suitably be set according to article characteristic.
As colouring agent, there is no particular limitation, can use known colouring agents such as pigment, dyestuff.Can enumerate for example inorganic pigment of titanium white, zinc white, iron oxide red, bright red, ultramarine, cobalt blue, titan yellow, chrome yellow, carbon black etc., the organic pigment (also comprising dyestuff) of isoindoline, hansa yellow A, quinoline a word used for translation ketone, permanent red 4R, phthalocyanine blue, indanthrene blue-RS, nigrosine etc., metallic pigments such as aluminium, brass, pearly luster (pearl) pigment that the paper tinsel powder of the mica of covering titanium dioxide, basic lead carbonate etc. is formed etc.These can use more than a kind or 2 kinds.The coloring mode of substrate sheets has transparent painted and opaque coloured (hidden painted), can select arbitrarily.For example, to being undertaken to select opaque coloured under the painted hidden situation by the background color of enclosure material (base material of bonding cosmetic sheet).On the other hand, under hope can be estimated by the situation of the bottom decorative pattern of enclosure material, can select transparent painted.
Above-mentioned substrate sheets can adopt resin combination that for example rolling process, plavini, T mould extrusion molding etc. will contain above-mentioned resinous principle etc. to form membranaceous and obtains.
There is no particular limitation for the thickness of above-mentioned substrate sheets, is generally 50～150 μ m, is preferably about 60～80 μ m.
As required, can implement surface treatments such as Corona discharge Treatment, ozone treatment, plasma treatment, ionizing radiation processing, dichromic acid processing to the single face or the two sides of substrate sheets.For example, when carrying out Corona discharge Treatment, the surface tension that can make the substrate sheets surface is more than the 35dyne, to be preferably more than the 40dyne.Surface treatment can be carried out according to the usual method of each processing.
As required, can be provided with on the single face of substrate sheets or two sides priming coat (for example, be used for being colored easily material bonding back side priming coat, be used for forming easily the priming coat of pattern layer).By priming coat is set, can improve interlayer adhesion with adjoining course (for example by enclosure material).
Priming coat can form by single face or the known silane coupling agent of two sided coatings in substrate sheets.As silane coupling agent, the silane coupling agent that the polyurethane resin that can enumerate composition such as acrylic acid modified polyurethane resin for example is silane coupling agent, be made up of polyurethane-cellulose-based resin (for example adding the resin that hexamethylene diisocyanate obtains in the mixture of polyurethane and nitrocotton) etc.These can use more than a kind or 2 kinds.
There is no particular limitation for the coating weight of silane coupling agent, is generally 0.1～100g/m
2, be preferably 0.1～50g/m
2About.
There is no particular limitation for the thickness of priming coat, is generally 0.01～10 μ m, is preferably about 0.1～1 μ m.
Adhesive phase
As required, can on the substrate sheets binding face of synthetic resin layer, form adhesive phase.
As adhesive, there is no particular limitation, can enumerate for example polyamide, acrylic resin, vinyl acetate resin, polyurethane resin etc.These can use more than a kind or 2 kinds.
Adhesive phase, makes it dry, is solidified to form after coating constitutes the adhesive of adhesive phase for example by coating adhesive on synthetic resin layer.Baking temperature, drying time etc. condition there is no particular limitation, can suitably set according to the kind of adhesive.There is no particular limitation for the coating process of adhesive, for example can adopt the flow coating, wire drawing (wirebar) coating, upset coating, intaglio plate coating, intaglio plate upset coating, pneumatic coating, contact coating, scraper plate coating, level and smooth coating, point of roller coat cloth, curtain formula to be coated with methods such as (コ Application マ コ one ト).
There is no particular limitation for the thickness of adhesive phase, and dried thickness is 0.1～30 μ m, is preferably about 1～20 μ m.
Priming coat
As required, can on the wood substrate binding face of synthetic resin layer, form priming coat.Priming coat can form by the known silane coupling agent of coating.
As silane coupling agent, the silane coupling agent that for example can enumerate the polyurethane resin of forming by acrylic acid modified polyurethane resin etc. and be silane coupling agent, form by polyurethane-cellulose-based resin (for example, in the mixture of polyurethane and nitrocotton, adding the resin that hexamethylene diisocyanate obtains) etc.These can use more than a kind or 2 kinds.
There is no particular limitation for the coating weight of silane coupling agent, is generally 0.1～100g/m
2, be preferably 0.1～50g/m
2About.
There is no particular limitation for the thickness of priming coat, is generally 0.01～10 μ m, is preferably about 0.1～1 μ m.
The pattern layer
(face opposite with the wood substrate binding face is in following each layer middle finger phase the same side) is formed with the pattern pattern layer on substrate sheets.
The pattern pattern layer is a design layer of giving desired pattern on cosmetic sheet, and there is no particular limitation for pattern kind etc.Can enumerate for example wood grain decorative pattern, bag decorative pattern, sand streak decorative pattern, ceramic tile applique line, brick decorative pattern, woven design decorative pattern, dermatoglyph decorative pattern, geometry pattern, literal, mark, abstract patterns etc.
There is no particular limitation for the formation method of pattern pattern layer, for example can be by using the formation such as print process of dissolving simultaneously (or dispersion) known colouring agent (dyestuff or pigment) and adhesive resin obtain in solvent (or decentralized medium) coloring printing ink, coating agent etc.
As colouring agent, for example can enumerate inorganic pigments such as carbon black, titanium white, zinc white, iron oxide red, Prussian blue, cadmium red, organic pigments such as AZOpigments, mordant pigment, anthraquinone pigment, quinoline a word used for translation ketone pigment, phthalocyanine color, isoindoline pigment, triazine dioxin pigment, metal powder pigment such as aluminium powder, bronze powder, pearlescent pigments such as the mica of capping oxidation titanium, oxidation chlorination bismuth, fluorescent pigment, phosphorescent pigment etc.These colouring agents can separately or mix use more than 2 kinds.In these colouring agents, can also cooperate extender pigments such as filler, Bio-Glas, nertralizer, surfactants etc. such as silica.
As adhesive resin, for example can enumerate acrylic resin, phenylethylene resin series, polyester based resin, polyurethane series resin, chloridized polyolefin and be resin, vinyl chloride-vinyl acetate copolymer and be resin, polyvinyl butyral resin, alkyd and be resin, petroleum line resin, ketone and be resin, epoxy and be resin, melamine and be resin, fluorine resin, silicon and be resin, cellulose derivative, rubber is resin etc.These resins can separately or mix more than 2 kinds and use.
As solvent (or decentralized medium), can enumerate for example hexane, heptane, octane, toluene, dimethylbenzene, ethylbenzene, cyclohexane, oil such as hexahydrotoluene are organic solvent, ethyl acetate, butyl acetate, acetic acid-2-methoxyl group ethyl ester, acetic acid-esters such as 2-ethoxy ethyl ester are organic solvent, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, isobutanol, ethylene glycol, alcohol such as propane diols are organic solvent, acetone, MEK, methyl iso-butyl ketone (MIBK), ketone such as cyclohexanone are organic solvent, diethyl ether diox, ethers such as oxolane are organic solvent, carrene, carbon tetrachloride, trichloro-ethylene, chlorine-based organic solvents such as tetrachloro-ethylene, inorganic solvents such as water etc.These solvents (or decentralized medium) can separately or mix use more than 2 kinds.
As the printing process that is used to form the pattern layer, can enumerate for example woodburytype, hectographic printing method, screen painting method, aniline printing (flexography) method, videograph, ink jet printing method etc.
There is no particular limitation for the thickness of pattern pattern layer, can suitably set according to article characteristic, and the bed thickness during coating is about 1～15 μ m, and dried bed thickness is about 0.1～10 μ m.
Painted hidden layer
As required, can also between substrate sheets and pattern layer, form painted hidden layer.From the outer surface of cosmetic sheet is hidden painted hidden layer is set in hope during by the background color of enclosure material.When being the transparency, substrate sheets certainly much less,, also can be formed when painted by hidden so that disguised stabilisation in substrate sheets.
As the printing ink that forms painted hidden layer, can use the printing ink that forms the pattern layer, this printing ink can be hidden painted.
The formation method of painted hidden layer, the preferably method that can form in the mode that covers whole substrate sheets (full coat (ベ ) shape comprehensively).For example, as preferable methods, can enumerate above-mentioned roller rubbing method, scraper plate rubbing method, pneumatic rubbing method, mould coating (ダ イ コ one ト) method, incision (rip) rubbing method, some rubbing method, contact rubbing method, mobile rubbing method, dip coated method etc.
There is no particular limitation for the thickness of painted hidden layer, can suitably set according to article characteristic, and the bed thickness during coating is about 0.2～10 μ m, and dried bed thickness is about 0.1～5 μ m.
Transparency adhesive phase
On the pattern layer, be formed with transparent adhesive phase.Transparency adhesive phase, so long as the layer of the transparency, there is no particular limitation, comprises water white transparency, painted transparent, translucent etc. any one.For bonding patterns flower-pattern layer and transparent resin bed, form this adhesive phase.
As adhesive, there is no particular limitation, can use known adhesive in the cosmetic sheet field.
As known adhesive in the cosmetic sheet field, can enumerate for example thermoplastic resins such as polyamide, acrylic resin, vinyl acetate resin, curable resins such as thermosetting polyurethane resin etc.In addition, also can use with bi-component curable polyurethane resin or the mylar of isocyanates as curing agent.These can use more than a kind or 2 kinds.As above-mentioned bi-component curable polyurethane resin, the same resin of bi-component curable polyurethane resin that can use Yu in following transparent sealer, illustrate.
Transparency adhesive phase, for example coating adhesive on the pattern layer is coated with the resin that constitutes transparent resin bed, makes it dry then, is solidified to form.Baking temperature, drying time etc. condition there is no particular limitation, can suitably set according to the kind of adhesive.There is no particular limitation for the coating process of adhesive, for example can adopt roller coat cloth, curtain formula flow coating, wire drawing coating, upset coating, intaglio plate coating, intaglio plate upset coating, pneumatic coating, contact coating, scraper plate coating, level and smooth coating, put methods such as coating.
There is no particular limitation for the thickness of transparency adhesive phase, and dried thickness is 0.1～30 μ m, is preferably about 1～20 μ m.
Transparency resin bed
On transparent adhesive phase, be formed with transparent resin bed.Transparency resin bed, so long as the layer of the transparency, there is no particular limitation, comprise water white transparency, painted transparent, translucent etc. any one.
As transparent resin bed, there is no particular limitation, from can easily the tensile modulus of elasticity according to JISK6734 being set at the viewpoint below the 1000MPa, preferably contains the resin bed of polyolefin-based resins as resinous principle.
As polyolefin-based resins, can use with said polyolefins be the same resin of resin.
Said polyolefins in the above-mentioned transparent resin bed is the content of resin, is preferably 90～100 weight %, more preferably 95～100 weight %.
The thickness of transparency resin bed is generally 40～250 μ m, is preferably about 60～100 μ m.
Transparency resin bed can adopt lamination on transparent adhesive phase such as rolling process, plavini, T mould extrusion molding for example to contain the resin combination of above-mentioned resinous principle, also can use ready-made film.
As required, can promptly form on the face of transparent sealer described later, implement surface treatments such as Corona discharge Treatment, ozone treatment, plasma treatment, ionizing radiation processing, dichromic acid processing on the surface of transparent resin bed.Surface treatment can be carried out according to the usual method of each processing.
In addition, as required, priming coat (being used to make the formation of sealer to be easy to priming coat) can be set also on the surface.
Priming coat can be coated with known silane coupling agent by the surface at transparent resin bed and form.As silane coupling agent, resin system silane coupling agent of can enumerate the polyurethane resin of for example forming and be silane coupling agent, forming by the block copolymer of acrylic acid and polyurethane etc. by acrylic acid modified polyurethane resin etc.
There is no particular limitation for the coating weight of silane coupling agent, is generally 0.1～100g/m
2, be preferably 0.1～50g/m
2About.
There is no particular limitation for the thickness of priming coat, is generally 0.01～10 μ m, is preferably about 0.1～1 μ m.
Transparency sealer
By forming transparent sealer, can compensate the injured easy degree in cosmetic sheet surface, marresistance is improved.
As the material that uses in transparent sealer, there is no particular limitation, and in the present invention, preferably using the bi-component curable polyurethane is resin.The bi-component curable polyurethane is a resin, so long as be host with the polyalcohol, be the resin of curing agent with the isocyanates, there is no particular limitation.
At the bi-component curable polyurethane is the qualification that the polyalcohol that uses in the resin and isocyanates do not have, but, can be set forth in polyethylene glycol that molecule has 2 above hydroxyls, polypropylene glycol, acrylic polyalcohol, PEPA, PPG, polycarbonate polyol etc. as polyalcohol.As isocyanates, can enumerate the isocyanates of aliphatic or ester ring type.As the ester ring type isocyanates, can enumerate for example IPDI (IPDI), hydrogenation MDI (hydrogenated diphenyl methane diisocyanate) etc.As aliphatic isocyanates, can enumerate 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate etc.
Reduce the aspect of effects such as VOC from further raising, the preferably clear sealer is formed by waterborne compositions.As waterborne compositions, can use the composition that contains aqueous binder.Above-mentioned aqueous binder can be any one a form such as resin aqueous solution, resin aqueous emulsion.The resin of Shi Yonging can use the same material of aqueous binder with the waterborne compositions that uses in above-mentioned formation patterned layer in these.
In addition, in the present invention, also can use the ionizing radiation gel-type resin as transparent sealer.When using the ionizing radiation gel-type resin, can access more excellent marresistance and weatherability etc.
The ionizing radiation gel-type resin can use known product or commercially available product.Particularly, use contains at least a composition in prepolymer, oligomer and the monomer that has polymerism unsaturated bond or epoxy radicals in molecule.
As above-mentioned prepolymer or oligomer, for example methyl acrylic esters such as polyester methacrylate, polyethers methacrylate, polyalcohol methacrylate, melamine methacrylate are arranged, the urethane acrylate class, esters of acrylic acids such as polyester acrylate, polyether acrylate, urethane acrylate, polyalcohol acrylate, melamine acrylate.
As monomer, styrenic monomers such as styrene, AMS are arranged, esters of acrylic acids such as methyl acrylate, 2-EHA, acrylic acid methoxyl group ethyl ester, acrylic acid butoxy ethyl ester, butyl acrylate, phenyl acrylate, methyl acrylic esters such as methyl methacrylate, EMA, propyl methacrylate, methacrylic acid ethyoxyl methyl esters, phenyl methacrylate, lauryl methacrylate.
Substituted-amino alcohol ester as unsaturated acids, acrylic acid-2-(N, N-diethylamino) ethyl ester, methacrylic acid-2-(N, N-diethylamino) ethyl ester, acrylic acid-2-(N are arranged, the N-dibenzyl amino) methyl esters, acrylic acid-2-(N, N-diethylamino) propyl ester etc.
In addition, acrylamide is arranged, unsaturated carboxylic acid acid amides such as Methacrylamide, glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, 1, the 6-hexanediyl ester, the ethyl card must acrylate (ethyl carbitol acrylate), diethylene glycol diacrylate, compounds such as triethylene glycol diacrylate, propylene glycol diacrylate, EDIA, the diethylene glycol dimethylacrylate, multi-functional compounds such as polyethyleneglycol diacrylate and/or have the poly-thiol compound of 2 above mercaptos in molecule for example have the trimethylolpropane tris thioglycol, trimethylolpropane tris sulfo-propyl alcohol, dipentaerythritol four thioglycols etc.In addition, in the acrylic ester monomer more than 3 functional groups, three acrylic acid trihydroxy methyl propyl ester, pentaerythrite six acrylate, dipentaerythritol hexamethyl acrylate etc. are arranged.
By the transparent sealer of ionizing radiation gel-type resin to form method unqualified, for example can form by the irradiation ionizing radiation of filming to the composition (coating) that contains the ionizing radiation gel-type resin.Ionizing radiation acts on ionizing radiation gel-type resin contained in the coating, as the optical free radical polymerization initiator or the sensitizer of additive, have the energy that Raolical polymerizable is begun, can enumerate electromagnetic waves such as ultraviolet ray, X ray, gamma-rays.Wherein, from the ability to cure of filming, the simplicity of irradiation unit, the practicality of electron ray is the highest.When irradiation electronics line, for example,, the overlay film crosslinking curing is got final product by under the condition of 175keV and 5Mrad (50kGy), shining electron ray.In addition, forming by the ionizing radiation gel-type resin under the situation of transparent sealer,, priming coat (the particularly priming coat of polyurethane series resin) is set on transparent resin bed preferably as pre-substrate.
The thickness of sealer is unqualified, is generally 0.1～50 μ m, is preferably 1～20 μ m especially.
Weather resisting agent
As required, at least a layer of the layer of formation decorative layer of the present invention can contain weather resisting agent.As weather resisting agent, preferred ultra-violet absorber, hindered amine are light stabilizer etc.These weather resisting agent can separately or be mixed more than 2 kinds and be used.For example, contain under the situation of polypropylene as resinous principle,, preferably make and contain above-mentioned weather resisting agent in the above-mentioned synthetic resin layer for the purpose that obtains weatherability at above-mentioned synthetic resin layer.
As above-mentioned ultra-violet absorber, for example can enumerating, benzophenone series ultra-violet absorber, BTA are that ultra-violet absorber, triazine are ultra-violet absorber etc.Unqualified as above-mentioned light stabilizer, for example can suitably use hindered amine is light stabilizer.
The content of above-mentioned photostabilizer that constitutes in the layer of above-mentioned decorative layer is not particularly limited.For example, in above-mentioned synthetic resin layer, contain under the situation of ultra-violet absorber, the concentration that is used to form the ultra-violet absorber in the resin combination of above-mentioned synthetic resin layer can be set at about 1000～10000ppm.In above-mentioned synthetic resin layer, contain under the situation of light stabilizer, the concentration that is used to form the light stabilizer in the resin combination of above-mentioned synthetic resin layer can be set at about 1000～10000ppm.
Decorating material for flooring
Decorating material for flooring of the present invention is for example made by the above-mentioned decorative layer of pantostrat pressure roller shape on wood substrate.
As the method for pressing decorative layer on the wood substrate upper strata, preference, is exerted pressure from the decorative layer side with roller at this coated face side mounting decorative layer as by coating adhesive on wood substrate, thereby with the method for both laminations.In addition, in decorating material for flooring of the present invention, forming under the situation of adhesive phase on the wood substrate by coating adhesive, this adhesive phase is not included in the notion of above-mentioned decorative layer.
As the wood substrate that uses in the present invention, can enumerate the veneer for example made, plywood, sawdust-board, fiberboard, integrated sheet material etc. by China fir, Japan cypress, oak, sal, teak etc.
Behind the lamination, get final product according to the big or small severing decorative layer of wood substrate.
In addition, as required, can use tenonen to implement the actual processing on four limits, give the bar groove of V-shape etc. to decorating material for flooring of the present invention.Can also implement CONTACT WITH FRICTION behind coating composition handles.As above-mentioned coating, there is no particular limitation, and the bi-component curable polyurethane of preferred water system is a pigmented finiss.
Embodiment
Expression experimental example and comparative example further specifically describe the present invention below.But the present invention is not limited to embodiment.
Embodiment 1
Adopt following method to make the decorative layer of structure shown in Figure 1.
Adopt woodburytype, on the substrate sheets of forming by the thick coloured polypropylene film of 60 μ m 5 (the independent tensile modulus of elasticity of this sheet is 600MPa), the coating acrylic acid-polyurethane is resin (resin that the hexamethylene diisocyanate of interpolation 5 weight portions forms in 100 a parts by weight of acrylic polyol esters) solution, makes that the solid constituent amount is 2g/m
2, form printing priming coat (not shown).
Use on the priming coat (not shown) in printing, employing is the woodburytype of resin (resin that the hexamethylene diisocyanate of interpolation 5 weight portions obtains in 100 parts by weight of acrylic polyol esters) solution as printing-ink with acrylic acid-polyurethane, forms the grain pattern flower-pattern layer 4 of 4 μ m.
Adopt woodburytype, with the face of the pattern layer 4 opposite side of substrate sheets 5 on, the solution of coating polyurethane-cellulose-based resin makes that the solid constituent amount is 2g/m
2, form priming coat (not shown).
Wherein, by in the mixed solvent of MEK and methyl iso-butyl ketone (MIBK), adding polyurethane and nitrocotton, add the hexamethylene diisocyanate of 5 weight portions again with respect to the mixture of the polyurethane of 100 weight portions and nitrocotton, prepare the solution of above-mentioned polyurethane-cellulose-based resin.
On pattern layer 4, the coating polyurethane resin is an adhesive, makes that the solid constituent amount is 8g/m
2, extrude polypropylene-based resin with T mould extruder heating and melting again, form the transparent resin bed 2 of thick transparent adhesive phase 3 of 8 μ m and thickness 80 μ m.These resin bed 2 independent tensiles modulus of elasticity are 600MPa.
After the surface enforcement Corona discharge Treatment to transparent resin bed 2, adopt woodburytype, at coating acrylic acid-polyurethane on the Corona discharge Treatment face is resin (adding the resin that 5 weight portion hexamethylene diisocyanates obtain in 100 parts by weight of acrylic polyol esters) solution, makes that the solid constituent amount is 1g/m
2, form transparent sealer and form with priming coat (not shown).
Adopt rolling method, on transparent sealer formed with priming coat (not shown), coating and drying polyurethane acrylic ester electron ray curing type resin made that the solid constituent amount is 15g/m
2, form uncured electron ray curing type resin bed.Then, be in the environment of 200ppm at oxygen concentration, be under the condition of 125KeV, 5Mrad at accelerating potential, to uncured resin layer irradiation electron ray, make resin solidification, form the thick electron ray curing type resin bed of 15 μ m (transparent sealer 1).
Then, adopt embossing processing, from transparent sealer 1, forming the degree of depth is the ridge design of the wood grain catheter shape of 50 μ m.
And in priming coat (not shown) side of substrate sheets 5, the coating polyurethane resin is an adhesive, makes that the solid constituent amount is 8g/m
2, form adhesive phase 6.The thickness of adhesive phase 6 is 8 μ m.Then, adopt the dry lamination method, at the thick synthetic resin layer 7 of adhesive phase 6 superimposed layers, 120 μ m.Use T mould extruder, make that to contain homo-polypropylene, two (to the methyl benzal) D-sorbite (crystallization nucleator), triazine be that ultra-violet absorber and hindered amine are the composition heating and melting of light stabilizer, make above-mentioned synthetic resin layer 7.Wherein, the consumption of two (to the methyl benzal) D-sorbite is, is 0.1 weight portion with respect to the homo-polypropylene of 100 weight portions.In addition, triazine is that the consumption of ultra-violet absorber is, in resin combination, triazine is that the concentration of ultra-violet absorber is the amount of 2000ppm.In addition, hindered amine is that the consumption of light stabilizer is, in resin combination, hindered amine is that the concentration of light stabilizer is the amount of 1000ppm.
Synthetic resin layer 7 independent tensiles modulus of elasticity are 1500MPa.
Make decorative layer by above process.
The thickness of the decorative layer of making is 300 μ m.
With synthetic resin layer 7 sides is the above-mentioned decorative layer that obtains of mode roller shape winding of following (volume is inboard).
Then, by being that the ethene improved-vinyl acetate of coating is an emulsion binding agent on the sal plywood of 12mm at thickness, forming thickness is the adhesive phase of 10 μ m.
Then, be last with the adhesive phase side, arrange many above-mentioned sal plywood, pass through then above-mentioned decorative layer continuous laminating on above-mentioned adhesive phase, to make and decorate plywood.
Decorate the decorative layer of plywood according to the big or small severing of sal plywood, use tenonen to implement the actual processing on four limits then, form the bar groove of V-shape simultaneously at long side direction and short side direction from transparent sealer to the sal plywood degree of depth.And, the side surface part of the long side direction of lamination plywood is carried out chamfering.
At the bar slot part of V-shape and the bi-component curable polyurethane of chamfered section coating water system is pigmented finiss, carries out CONTACT WITH FRICTION then and handles.
Make decorating material for flooring by above process.
Flatness, the damaging and resistance to water of anti-depression of the decorating material for flooring that table 1 expression obtains.
Comparative example 1
Except that the lamination synthetic resin layer 7 not, adopt method similarly to Example 1 to make decorative layer.The thickness of decorative layer is 180 μ m.
The decorative layer that use obtains adopts method similarly to Example 1, makes decorating material for flooring.
Flatness, the damaging and resistance to water of anti-depression of the decorating material for flooring that table 1 expression obtains.
Comparative example 2
In the making of synthetic resin layer 7, the composition of extruding except that heating and melting does not contain two (to the methyl benzal) D-sorbites (crystallization nucleator), adopts method similarly to Example 1, makes decorating material for flooring.
Synthetic resin layer 7 independent tensiles modulus of elasticity are 900MPa.
Flatness, the damaging and resistance to water of anti-depression of the decorating material for flooring that table 1 expression obtains.
Test example 1 (flatness)
The flatness on the decorative layer surface of the decorating material for flooring that affirmation obtains in embodiment and comparative example.Particularly, decorating material for flooring is set, makes that the light inject flooring material ornament materials surface is skew ray, perusal wood substrate and/or transparent adhesive phase concavo-convex whether by hidden.
Is zero with the concavo-convex of wood substrate and/or transparent adhesive phase by hidden average evaluation, concavo-convexly by hidden average evaluation be not *.
Test example 2 (anti-depression is damaging)
The decorative layer portion of the decorating material for flooring that in embodiment and comparative example, obtains, the diameter of pushing 45 ° of inclinations with the 50N loading is the iron cylinder anchor clamps of 20mm, the depression of decorative layer portion this moment is confirmed in range estimation.
The inapparent average evaluation that will cave in is zero, the significant average evaluation that caves in for *.
Test example 3 (resistance to water)
In the bar slot part of the decorating material for flooring that in embodiment and comparative example, obtains, use the fixedly ring of polyethylene system of jointing material.At the inner running water that adds of the ring of above-mentioned polyethylene system, to place after 144 hours, the outward appearance of decorating material for flooring is confirmed in range estimation.
With the average evaluation that does not have in appearance to change is zero, produce the average evaluation that shrinks to be *.
Table 1
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Flatness | ?○ | ?× | ?○ |
| Anti-depression is damaging | ?○ | ?× | ?× |
| Resistance to water | ?○ | ?× | ?○ |
Claims (4)
1. decorating material for flooring; at the wood substrate superimposed layer decorative layer is arranged; this decorative layer lamination successively has synthetic resin layer, substrate sheets, pattern layer, transparent adhesive phase, transparent resin bed and transparent sealer; make synthetic resin layer contact, it is characterized in that with wood substrate:
(1) being selected from least a in substrate sheets and the transparent resin bed, to have according to JISK6734 be tensile modulus of elasticity below the 1000MPa;
(2) to have according to JIS K6734 be tensile modulus of elasticity more than the 1000MPa to synthetic resin layer,
Described synthetic resin layer contains polyolefin-based resins as resinous principle.
2. decorating material for flooring as claimed in claim 1 is characterized in that:
Be selected from least a layer in substrate sheets and the transparent resin bed, contain polyolefin-based resins as resinous principle.
3. decorating material for flooring as claimed in claim 1 is characterized in that:
Synthetic resin layer contains the crystallization nucleator.
4. decorating material for flooring as claimed in claim 1 is characterized in that:
The thickness of decorative layer is 200～300 μ m.
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| JP2006097949 | 2006-03-31 | ||
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| KR101134231B1 (en) | 2008-03-21 | 2012-04-09 | 다이니폰 인사츠 가부시키가이샤 | Decorative sheet for flooring material and method for preparation thereof |
| JP5176640B2 (en) * | 2008-03-27 | 2013-04-03 | 大日本印刷株式会社 | Flooring decorative sheet and flooring decorative material |
| EP2168762B1 (en) | 2008-09-30 | 2017-02-15 | Dai Nippon Printing Co., Ltd. | Decorative sheet for floor material and decorative material for floor |
| JP4840461B2 (en) * | 2008-09-30 | 2011-12-21 | 大日本印刷株式会社 | Decorative sheet for flooring |
| WO2010137393A1 (en) * | 2009-05-25 | 2010-12-02 | 株式会社ニッシンイクス | Flooring material |
| JP5373586B2 (en) * | 2009-12-21 | 2013-12-18 | 住江織物株式会社 | Flooring |
| JP5589510B2 (en) * | 2010-03-31 | 2014-09-17 | 大日本印刷株式会社 | Cosmetic material and decorative sheet |
| JP5699510B2 (en) * | 2010-09-30 | 2015-04-15 | 大日本印刷株式会社 | Floor decorative material |
| JP5702107B2 (en) * | 2010-10-15 | 2015-04-15 | 住江織物株式会社 | Floor material with excellent adhesive workability |
| JP6069868B2 (en) * | 2011-03-31 | 2017-02-01 | 大日本印刷株式会社 | Floor decorative sheet and floor decorative material |
| JP6064421B2 (en) * | 2011-09-26 | 2017-01-25 | 大日本印刷株式会社 | Floor decorative material |
| JP6403937B2 (en) * | 2012-09-07 | 2018-10-10 | 大日本印刷株式会社 | Floor decorative material |
| JP6520128B2 (en) * | 2014-01-10 | 2019-05-29 | 大日本印刷株式会社 | Decorative sheet and decorative board |
| KR102014667B1 (en) * | 2014-01-10 | 2019-08-26 | 다이니폰 인사츠 가부시키가이샤 | Decorative sheet and decorative plate, and processes for producing same |
| JP6520129B2 (en) * | 2014-01-10 | 2019-05-29 | 大日本印刷株式会社 | Decorative sheet and method of manufacturing the same, and decorative plate and method of manufacturing the same |
| JP5839066B2 (en) * | 2014-03-19 | 2016-01-06 | 大日本印刷株式会社 | Decorative sheet and decorative member using the same |
| JP2016089379A (en) * | 2014-10-30 | 2016-05-23 | 株式会社トッパン・コスモ | Decorative floor sheet |
| JP6696726B2 (en) * | 2014-12-10 | 2020-05-20 | 大日本印刷株式会社 | Floor cosmetics |
| CN105090193A (en) * | 2015-08-12 | 2015-11-25 | 天津航天液压装备有限公司 | Rubber softening technology for surface of wooden part |
| JP6862661B2 (en) * | 2016-03-02 | 2021-04-21 | 凸版印刷株式会社 | Decorative sheet and manufacturing method of decorative sheet |
| CN110352132A (en) * | 2017-02-28 | 2019-10-18 | 大日本印刷株式会社 | Cosmetic sheet and decorative panel |
| EP3675091A4 (en) * | 2017-08-21 | 2021-05-05 | Lintec Corporation | Peel detection label |
| CN109537847A (en) * | 2019-01-15 | 2019-03-29 | 圣象地板（句容）有限公司 | A kind of cured polypropylene screen facing multi-layer composite floor of EB and its production technology |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR200344732Y1 (en) * | 1997-08-16 | 2004-07-06 | 고려화학 주식회사 | Flooring using wood powder |
| JP2001105534A (en) | 1999-10-14 | 2001-04-17 | Dainippon Printing Co Ltd | Decorative plate, decorative door, finishing carpentry member, and floor plate |
| JP2001145935A (en) * | 1999-11-18 | 2001-05-29 | Chuo Kaseihin Kk | Injection-molded molding of regenerated polyethylene terephthalate resin |
| JP4839541B2 (en) * | 2001-07-25 | 2011-12-21 | 凸版印刷株式会社 | Floor decorative sheet |
| JP2003033903A (en) * | 2001-07-25 | 2003-02-04 | Toppan Printing Co Ltd | Decorative material |
| KR100554838B1 (en) * | 2003-06-05 | 2006-03-03 | 주식회사 엘지화학 | Wood flooring composed of WPL, base and soundproof layer |
| JP2005096213A (en) * | 2003-09-24 | 2005-04-14 | Sekisui Film Kk | Surface film for building material |
| JP4393880B2 (en) * | 2004-01-27 | 2010-01-06 | 株式会社カネカ | Synthetic resin foam molding having a thin groove |
| JP2006046053A (en) * | 2004-07-08 | 2006-02-16 | Dainippon Printing Co Ltd | Floor material |
| JP2006068906A (en) * | 2004-08-31 | 2006-03-16 | Kaneka Corp | Synthetic resin foam and its manufacturing method |
| KR100799928B1 (en) * | 2006-01-19 | 2008-01-31 | 이성철 | Wooden flooring and the manufacturing method thereof |
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| JP5509516B2 (en) | 2014-06-04 |
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