CN100529300C - Laminated wood for floor member - Google Patents
Laminated wood for floor member Download PDFInfo
- Publication number
- CN100529300C CN100529300C CNB2005101370100A CN200510137010A CN100529300C CN 100529300 C CN100529300 C CN 100529300C CN B2005101370100 A CNB2005101370100 A CN B2005101370100A CN 200510137010 A CN200510137010 A CN 200510137010A CN 100529300 C CN100529300 C CN 100529300C
- Authority
- CN
- China
- Prior art keywords
- layer
- laminate
- floor board
- synthetic resin
- resin layer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
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- 239000000057 synthetic resin Substances 0.000 claims abstract description 153
- 238000009408 flooring Methods 0.000 claims abstract description 64
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- 238000002156 mixing Methods 0.000 description 2
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
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- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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Images
Landscapes
- Floor Finish (AREA)
Abstract
The invention discloses a sheet material for flooring material comprising a synthetic resin layer and a decorative layer formed on the synthetic resin layer, wherein, the synthetic resin layer is divided into more than two separated areas. The invention also discloses a laminate for flooring material, which is formed by laminating the sheet material for flooring material on a wooden base material.
Description
The application be that March 31, application number in 2004 are 200410033233.8 the applying date, denomination of invention divides an application for the Chinese invention patent application of " laminate for floor board material ".
Technical field
The laminate for floor board material that the present invention relates to anti-caster, resistance to impact and have excellent water-resistance.
Background technology
In the past, as flooring material, what be widely known by the people was the flooring material that applying wooden decorative veneer also is coated with on veneer, perhaps that veneer and medium density fibreboard (MDF) is stacked, further the flooring material of applying wooden decorative veneer and coating on MDF.In addition, implement the fluting and the chamfer machining of the degree of depth that arrives veneer and MDF and slot part is set and chamfered section from wooden decorative plate side, thereby the flooring material that improves design of patterns also is widely known by the people.
But the wooden decorative veneer is cut thin obtaining with unstained natural timber, and from the exhausted problem of timber resources, the kinematic mounting of protection world resource, along with the timber price promotion, material has also reduced, and is difficult to obtain the picture timber of high-quality in the past always.
For this reason, as the substituent of wooden decorative veneer, can use the decoration sheet that beautiful patterns such as wood grain decorative pattern are printed.As its representative, can enumerate substituent, the substituent of applying decoration sheet on the aforementioned medium density fibreboard face of the duplexer of stacked veneer and medium density fibreboard (MDF) at applying decoration sheet on the veneer.But the former is the same when using the wooden decorative veneer, often sees caster-resistant and poor impact resistance, when slot part and chamfered section are set on the wooden decorative veneer, produces burr and hangnail etc., and their can scratch socks and stocking and jump silk.Have, the latter is the same when using the wooden decorative veneer again, often sees that because the MDF poor water resistance, the immersion of water has damaged dilation, the design of MDF.
In contrast, open in 2003-239517 number the spy, proposed veneer, synthetic resin layer and decorative layer stackedly, can make this synthetic resin layer as good laminate for floor board material such as specific physics value and caster-resistant, resistance to impact, water resistance.
But, if laminate for floor board material is subjected to the influence of the heat of the means of heating, will often see and produce following influence: veneer or synthetic resin layer produce thermal contraction or thermal expansion and laminate for floor board material are sent out stick up and when the decorative layer surface of laminate for floor board material implemented design, direction along the fiber on the top layer of veneer produces concaveconvex shape etc.In addition, also require further to improve the caking property of synthetic resin layer and decorative layer.
Thereby, wish to develop that size that variations in temperature causes changes less and as the laminate for floor board material of more cheap building materials.
Summary of the invention
The inventor etc. are by stacking gradually synthetic resin layer and the decorative layer with specific physics value on wood substrate, can obtain when possessing many rerum naturas such as caster-resistant, resistance to impact, marresistance, mar proof, stain resistance the laminate for floor board material that the size that variations in temperature causes changes less and the caking property of synthetic resin layer and decorative layer is further improved.Thereby the present invention is based on this discovery and does.
The 1st mode of the present invention
According to first mode of the present invention, can be provided on the base material that constitutes by timber, stack gradually the laminate for floor board material that synthetic resin layer and decorative layer constitute, the yield point load of the aforementioned synthetic resin layer of this laminate for floor board material is more than the 9kgf, and tensile elasticity rate is 50kgf/mm
2More than, the surrender elongation is 3～8%,
The result of the anti-caster test of carrying out on the surface of the decorative layer side of aforementioned laminate for floor board material is, the recessed degree of depth of aforementioned surfaces is below the 100 μ m,
The test of aforementioned castor use be equipped with rotatable castor fixed part, 3 castors installing on aforementioned castor fixed part, the movable type that is connected with aforementioned castor fixed station increase the weight of portion and sample fixed station, carry out as follows:
Aforementioned laminate for floor board material is fixed on the aforementioned sample fixed station,
Increase the weight of portion by aforementioned movable type, make aforementioned 3 castors increase the weight of to contact with the surface of the decorative layer side of aforementioned laminate for floor board material,
Start aforementioned castor fixed part, make aforementioned 3 castors after rotation on the surface of the decorative layer side of aforementioned laminate for floor board material,
Be determined at the degree of depth of the depression that produces on the aforementioned surfaces,
The average diameter 75mm of aforementioned castor, thickness 25mm,
Surface to the cosmetic side of aforementioned laminate for floor board material applies weight, is 70kg,
Aforementioned 3 castors rotate 100 times with the speed of 20rpm counter-rotating in per 5 minutes 1 time.
According to the 1st mode of the present invention, can be provided in possess caster-resistant, many rerum natura such as marresistance, mar proof, stain resistance the time, the size that temperature change causes changes few laminate for floor board material.
The 2nd mode of the present invention
The 2nd mode of the present invention can be provided in the laminate for floor board material that stacks gradually synthetic resin layer and decorative layer formation on the wood substrate, it is more than 75 ℃ that the pin of the aforementioned synthetic resin layer of this laminate for floor board material is gone into temperature, yield point load is more than the 10kgf, and tensile elasticity rate is 100kgf/mm
2More than, the yield extension rate is 4～8%.
The 2nd mode of the present invention can provide caster-resistant, marresistance, mar proof, stain resistance, resistance to impact, have excellent water-resistance, decorating material for flooring especially excellent heat resistance, that can effectively suppress the generation of shrinkage phenomenon.
The 3rd mode of the present invention
The 3rd mode of the present invention is the flooring material sheet material that is made of synthetic resin layer and the decorative layer that forms thereon,
Aforementioned synthetic resin layer has individual layer or the layer structure more than 2 layers,
When aforementioned synthetic resin layer is individual layer, aforementioned individual layer is formed by amorphism PETG and pet copolymer, perhaps aforementioned synthetic resin layer is more than 2 layers the time, its at least one deck form by amorphism PETG and pet copolymer
The part of the ethylene glycol of aforementioned pet copolymer is by 1, and the 4-cyclohexanedimethanol replaces.
The flooring material that the 3rd mode of the present invention can provide the caking property of synthetic resin layer and decorative layer to be improved is used sheet material and is used the laminate for floor board material of this sheet material.
The 4th mode of the present invention
The 4th mode of the present invention is the laminate for floor board material that stacks gradually synthetic resin layer and decorative layer formation on wood substrate, and aforementioned synthetic resin layer is divided into 2 above isolated areas.
According to the 4th mode of the present invention, because synthetic resin layer is divided into isolated area more than 2, so can effectively absorb the thermal expansion difference of wood substrate and synthetic resin layer, the result can effectively suppress or prevent the warpage of thermal expansion difference cause.In addition, the 4th mode of the present invention can provide the caking property of synthetic resin layer and decorative layer flooring material usefulness sheet material that is improved and the laminate for floor board material that uses this sheet material.
Description of drawings
Fig. 1 is the sectional drawing that the basic layer of expression laminate for floor board material of the present invention constitutes.
Fig. 2 is the sectional drawing of the 1st the concrete embodiment of the expression decorative layer that constitutes laminate for floor board material of the present invention.
Fig. 3 is the sectional drawing of the 2nd the concrete embodiment of the expression decorative layer that constitutes laminate for floor board material of the present invention.
Fig. 4 is the sectional drawing of the 3rd the concrete embodiment of the expression decorative layer that constitutes laminate for floor board material of the present invention.
Fig. 5 is the sectional drawing of the 4th the concrete embodiment of the expression decorative layer that constitutes laminate for floor board material of the present invention.
Fig. 6 is the figure of the relation of the expression cup depth of various test body B and yield point load.
Fig. 7 is the figure of the relation of the expression yield point load of various test body B and tensile elasticity rate.
Fig. 8 is the figure of the relation of the expression yield point load of various test body B and yield extension rate.
Fig. 9 is the sectional drawing of anti-caster experimental rig.
Figure 10 is the sectional drawing of the flooring material of expression the 3rd mode of the present invention with the basic layer formation of sheet material.
Figure 11 is that expression constitutes the sectional drawing of the flooring material of the 3rd mode of the present invention with the embodiment of sheet material.
Figure 12 is the configuration example of zoning of synthetic resin layer of the laminate for floor board material of the 4th embodiment of the present invention.
Figure 13 is the schematic diagram that is illustrated in the cross-section structure when forming slot part on the laminate for floor board material of the 4th embodiment of the present invention.
Figure 14 is the schematic diagram that is illustrated in the cross-section structure when forming slot part on the laminate for floor board material of the 4th mode of the present invention.
The specific embodiment
The 1st mode of the present invention
Adopt accompanying drawing, the 1st mode of the present invention described.
Fig. 1 is the sectional drawing of the basic layer structure of expression laminate for floor board material of the present invention, and laminate for floor board material 1 obtains like this, promptly by adhesive layer synthetic resin layer 3 is set on wood substrate 2, on aforementioned synthetic resin 3 decorative layer 4 is set.By satisfying above-mentioned numerical value, aforementioned synthetic resin layer 3 can satisfy caster-resistant, resistance to impact, water resistance etc.In addition, the result of the anti-caster test that laminate for floor board material of the present invention carries out on the surface of its decorative layer side, requiring does not have crackle to produce in aforementioned surfaces.In addition, according to preferred mode of the present invention, the result of aforementioned anti-caster test is that the depression in the surface degree of depth of the decorative layer side of aforementioned laminate for floor board material is below the 100 μ m, below the preferred 80 μ m.
The anti-caster test
Anti-caster test of the present invention can use the anti-caster experimental rig to carry out.Fig. 9 with the sectional drawing of a mode representing the anti-caster experimental rig describes.Anti-caster experimental rig 1000 is equipped with the portion that increases the weight of 1002 with sliding weight of steelyard 1001 that can gently can be heavy, regulating handle 1003, rotatable castor fixed station 1010,3 castors 1011 installing and sample fixed station 1013 on aforementioned castor fixed part.
The following describes an example of anti-caster test.
The laminate for floor board material 1012 of test is fixed on the sample fixed station 1013,
The portion of increasing the weight of 1002 is applied the sliding weight of steelyard (counterweight) 1001 of 70kg,, 3 castors 1011 that are fixed on the rotatable castor fixed station 1010 is contacted with the surface of the decorative layer side of laminate for floor board material 1020 by regulating handle 1003,
Make castor fixed station 1010 running, make lip-deep aforementioned 3 castors 1011 in the decorative layer side of laminate for floor board material 1012 with the speed of 20rmp counter-rotating in per 5 minutes 1 time, rotate 1000 times, afterwards, evaluation has or not on aforementioned surfaces and cracks.
The anti-caster experimental rig can obtain from anti-caster experimental rig L6-04 (shallow wild machinery production Co., Ltd.).In addition, the average diameter of the castor of use is 75mm, thickness 25mm.This castor can obtain with 420SA-N (wheel: nylon system) from HANMMER CASTER society.
Synthetic resin layer
Synthetic resin layer both can be that individual layer also can be a composite bed, and as its physical characteristic, requiring yield point load is more than the 9kgf, and more than the preferred 12kgf, tensile elasticity rate is 50kgf/mm
2More than, the yield extension rate is 3～8%, preferred 3～5%.The following of the thickness of synthetic resin layer is limited to more than the 200 μ m, more than the preferred 250 μ m, on be limited to below the 800 μ m, below the preferred 500 μ m.Instantiation as the resin that constitutes synthetic resin layer, (for example can enumerate the high polyalkylene terephthalates of the PETG PETG of biaxial tension (preferred), heat resistance, the part of ethylene glycol is with 1, the PETG that the 4-cyclohexanedimethanol replaces: polyester resins such as trade name PET-G (イ-ス ト マ Application ケ ミ カ Le カ Application パ ニ-society's system), polybutylene terephthalate (PBT), Merlon, polyacrylate etc.These resins both can be single things, also can be mixtures.
Decorative layer
As the instantiation of the base material that constitutes decorative layer, can use paper such as strengthening paper between the paper, paper of thin paper, first-class paper, kraft, Japan paper, titanium paper, resin impregnation; Fibers such as wood fibre, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber constitute weaves cotton cloth and the duplexer more than a kind or 2 kinds of plastic sheet materials such as nonwoven or polyolefin, polyester, polyacrylic acid, polyamide, poly-urethane, polystyrene etc.The thickness of these base materials is that 20～300 μ m are proper.In addition, the used base material of decorative layer adds pigment in both can necessary in the past layer and waits painted as required, also can implement the processing that Corona discharge Treatment, plasma treatment, ozone treatment etc. are easy to bond to the face of necessity.
The pattern of decorative layer
Fig. 2 is the sectional drawing of the concrete embodiment of the expression decorative layer that constitutes laminate for floor board material of the present invention; decorative layer 4 ' is following layer; promptly on the one side of transparent olefin hydrocarbons thermoplasticity resin sheet 40, implement embossing processing; ridge design 41 is set; implement from it and smear processing; fill in the depressed part of aforementioned ridge design 41 smear printing ink 42 after; scratch coat 43 is set exposing on whole of face; on this scratch coat 43, form sealer 44, on the another side of aforementioned olefin hydrocarbons thermoplasticity resin sheet 40, form design layer 46 simultaneously by scratch coat 45; all print layer 47.
Fig. 3 is the sectional drawing of a concrete embodiment of the expression decorative layer that constitutes laminate for floor board material of the present invention; decorative layer 4 " be following layer; promptly on the one side of painted olefin hydrocarbons thermoplasticity resin sheet 40 ', scratch coat 45 is set; printing forms all print layer 47 successively on this scratch coat 45; design layer 46; further on aforementioned design layer 46; by the stacked adhesive layer 48 that forms with cementing agent of known dry types such as biliquid curable urethane resin; with known dry type layered manner and T shape mould extrusion molding; stacked transparent olefin hydrocarbons thermoplasticity resin sheet 40 or transparent olefin hydrocarbons thermoplasticity resin bed 40 "; at transparent olefin hydrocarbons thermoplasticity resin sheet 40 or transparent olefin hydrocarbons thermoplasticity resin bed 40 " expose on whole of face scratch coat 43 be set, on this scratch coat 43, form sealer 44.On the face down (Fig. 3 does not illustrate) of painted olefin hydrocarbons thermoplasticity resin sheet 40 ', need bottom, form synthetic resin layer.
Fig. 4 is the sectional drawing of a concrete embodiment of the expression decorative layer that constitutes laminate for floor board material of the present invention; decorative layer 4 ' " be following layer; promptly on a face of painted olefin hydrocarbons thermoplasticity resin sheet 40 ', scratch coat 45 is set; printing forms all print layer 47 successively on this scratch coat 45; design layer 46; further on aforementioned design layer 46, pass through the stacked adhesive layers 48 that form with cementing agent of known dry type such as biliquid curable urethane resin; with known dry type layered manner and T shape mould extrusion molding; stacked transparent olefin hydrocarbons thermoplasticity resin sheet 40 or transparent olefin hydrocarbons thermoplasticity resin bed 40 "; at transparent olefin hydrocarbons thermoplasticity resin sheet 40 or transparent olefin hydrocarbons thermoplasticity resin bed 40 " the surface on implement embossing processing; ridge design 41 is set; implement from it and smear processing; fill in the depressed part of aforementioned ridge design 41 smear printing ink 42 after; scratch coat 43 is set exposing on whole of face, on this scratch coat 43, forms sealer 44.On the face down (Fig. 4 does not illustrate) of painted olefin hydrocarbons thermoplasticity resin sheet 40 ', need bottom, form synthetic resin layer.
Up to the present, just use the decorative layer of decorating with base material 4 to describe, but decorative layer 4 is not limited to these, for example, prominent plate is also passable always.At this moment; can use such decorative layer; promptly usually at UV (ultraviolet hardening) resin of prominent plate surface coating as protective clear layer; perhaps further on prominent plate surface, pass through the urethanes cementing agent; to decorative layer 4 ', 4 as shown in Figures 2 and 3 " implement processing such as applying so that this decoration 4 ', 4 " aforementioned surfaces topping 44 expose.
Decorative layer 4 ' shown in Fig. 2～4,4 ", 4 ' " be the specific embodiment that expression constitutes the decorative layer 4 of laminate for floor board material of the present invention, only otherwise break away from aim of the present invention, unqualified to this.For example, also can be the decorative layer of following formation, promptly on a face of thin paper, print formation all print layer, design layer successively, on whole of this design layer of formation, sealer is set.
1) scratch coat
In order to improve aforementioned olefin hydrocarbons thermoplasticity resin sheet 40 or aforementioned olefin hydrocarbons thermoplasticity resin bed 40 " with the adhesion strength of aforementioned surfaces topping 44, aforementioned scratch coat 43 is set, from the adhesion strength aspect, wish to be provided with aforementioned scratch coat 43.In addition, in order to improve olefin hydrocarbons thermoplasticity resin sheet 40 or 40 ' and the caking property of printed layers such as design layer 46, all print layer 47, aforementioned scratch coat 45 shown in Fig. 2～4 is set, use and form equally with aforementioned scratch coat 43 the same resins, meaning equally with aforementioned bottom 43, thereby is preferred.
Aforementioned bottom 43,45 as mentioned above, be in order to improve olefin hydrocarbons thermoplasticity resin sheet 40,40 ', 40 " the caking property on surface; as use therein resin; can enumerate ester resin, urethane resin, acrylic resin, polycarbonate resin, ethylene chloride-ethylene acetate ester copolymer, polyvinylbutyral resin, Nitro cellulose resin etc.; 2) these resins can separately or mix as coating composition; perhaps as ink composite, the coating means suitable with rolling method or woodburytype etc. form.
2) ridge design
3) design layer and all print layer
Generally can use known print processes such as intaglio printing, lithographic printing, serigraphy to form aforementioned design layer 46 and aforementioned all print layer 47.As aforementioned design layer 46, can enumerate wood grain decorative pattern, bag decorative pattern, woven design decorative pattern, dermatoglyph decorative pattern, geometrical pattern, literal, mark, lines, various abstract designs etc.As aforementioned all print layer 47, obtain with having concealed printing ink all print.In addition, in Fig. 2～4, demonstrate aforementioned design layer 46 and aforementioned all print layer 47 this two-layer structure are set, no matter the structure of which layer all can.
For the ink composite that in aforementioned design layer 46 and aforementioned all print layer 47, uses,, can mix chloridized polyolefins such as using haloflex, chlorinated polypropylene more than a kind or 2 kinds as carrier; Polyester; The poly-urethane that isocyanates and polyalcohol constitute; Polyacrylic acid.Polyvinyl acetate.Polyvinyl chloride; The ethylene chloride-ethylene acetate ester copolymer; Cellulosic resin; Polyamide-based resins etc. can wherein add uses such as pigment, solvent, various auxiliary agents in the past.But, from environmental problem and with the considerations such as caking property that are printed face, more than a kind or 2 kinds of the poly-urethane that mixed polyester, isocyanates and polyalcohol constitute, polyacrylic acid, polyamide etc.In addition, for smearing printing ink 42, also can form with printing ink with the same with the printing ink of use in all print layer 47 at above-mentioned design layer 46.
4) sealer
The sealer 44 that surface at decorative layer 4 is provided with describes.This sealer 44 is in order to give surface physical properties such as the desired marresistance of laminate for floor board material (referring to Fig. 1), mar proof, water resistance, stain resistance and be provided with; as the resin that forms this sealer 44, use gel-type resins such as thermohardening type resin or ionizing radiation gel-type resin to form proper., highly productive hard from case hardness waits, preferred ionizing radiation gel-type resin.
As the concrete example of thermohardening type resin, can enumerate unsaturated polyester resin, poly-urethane resin (comprising that also the biliquid curing type gathers urethane), epoxy resin, amino-alkyd resin, phenolic resin, urea resin, diallyl phthalate resin, melamine resin, triamido cyanate resin, melamine-urea condensation resin, contain silicones, polyorganosiloxane resin etc.As required, add curing compound such as crosslinking agent, polymerization initiator or add polymerization accelerant and use in the above-mentioned resin.As curing compound, isocyanates or organic sulfonate etc. add in unsaturated polyester resin or the poly-urethane resin, radical initiators such as peroxide such as organic amine etc. add in the epoxy resin, methyl ethyl ketone peroxide or azo isobutyronitrile add in the unsaturated polyester resin.Method as form sealer with above-mentioned thermohardening type resin can be coated with known rubbing methods such as rolling method, groove rolling methods by making above-mentioned thermohardening type resin solutionization, makes it to solidify in drying, forms sealer.As coating weight, in solid content, about 5～30 μ m are proper, preferred 15～25 μ m.
As the concrete example of ionizing radiation gel-type resin, be by the irradiation ionizing radiation, produce cross-linking polymerization, change into the resin of three-dimensional macromolecular structure.Ionizing radiation be meant have electromagnetic wave or can polymerization in the charge particle line, the radioactive ray of the quanta of energy of corsslinking molecular, comprise visible light, ultraviolet ray (near ultraviolet ray, vacuum ultraviolet etc.), X ray, electron ray, ion irradiation etc.Usually use ultraviolet ray or electron ray.As ultraviolet source, can use the light source of extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, carbon arc lamp, black light fluorescent lamp, metal halide lamp.As ultraviolet wavelength, can use the wave-length coverage of about 190～380nm.In addition, as electronic radial source, can use various electron ray accelerators such as Cockcroft-Walton type, model Dege loudspeaker husband type, resonance transformer type, insulating core transformer type or linear pattern, high-frequency and high-voltage type, high-frequency type.As used electron ray, can use about 100～1000keV, the electron ray of preferred 100～300keV.The exposure of electron ray is about 2～15Mrad usually.
The ionizing radiation gel-type resin is to be made of the monomer, prepolymer or the polymer that have cationically polymerizable functional groups such as free-radical polymerised unsaturated group such as (methyl) acryloyl group, (methyl) acryloxy or epoxy radicals in the molecule (following they are generically and collectively referred to as compound).These monomers, prepolymer and polymer can use with monomer, and perhaps multiple mixing is used.In addition, in this manual, (methyl) acrylate uses with the meaning of acrylate or methacrylate.
As prepolymer, can enumerate polyester (methyl) acrylate, urethane (methyl) acrylate, epoxy (methyl) acrylate, melamine (methyl) acrylate, triazine (methyl) acrylate, polyvinylpyrrolidone etc. with free-radical polymerised unsaturated group.Usually use about this prepolymer below 10000 of molecular weight.Molecular weight is owing to be this scope, so can improve the surface physical properties such as marresistance, mar proof, chemical resistance, heat resistance of the resin bed of curing.Can shared above-mentioned acrylate and methacrylate, but aspect the crosslinking curing speed of so-called ionizing radiation, the quick solidifying of acrylate is so under high-speed, short time, can effectively solidify, thereby acrylate is favourable.
As prepolymer, can enumerate epoxy resin such as bisphenol-type epoxy resin, novolac resin, alicyclic type epoxy resin with cationically polymerizable functional group; Vinethene resinoids such as aliphatic series class vinethene, fragrant same clan vinethene, urethanes vinethene, ester class vinethene; The cyclic ether compound; Prepolymers such as spiro-compound.
Example as monomer with free-radical polymerised unsaturated group, can enumerate (methyl) acrylate as the monofunctional monomer of (methyl) acrylate compounds, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid methoxyl group ethyl ester, (methyl) acrylic acid methoxyl group butyl ester, (methyl) acrylic acid butoxy ethyl ester, (methyl) acrylic acid 2-, Octyl Nitrite, N, N-dimethylaminomethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-diethylamino propyl group (methyl) acrylate, N, N-dibenzyl amino ethyl (methyl) acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid Isobornyl, ethyl carbitol (methyl) acrylate, (methyl) acrylic acid phenoxy ethyl, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, MPEG (methyl) acrylate, 2-(methyl) acrylyl oxy-ethyl-2-hydroxypropyl phthalic acid ester, 2-(methyl) acryloyl-oxy propyl group hydrogen terephthalate etc.
In addition, as polyfunctional monomer with free-radical polymerised unsaturated group, can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, two three (ethylene glycol) dimethylacrylates that contract, propane diols two (methyl) acrylate, DPG (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, tetraethylene-glycol two (formic acid) acrylate, two three (propane diols) two (methyl) acrylate that contract, bisphenol-A-two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane oxirane three (methyl) acrylate, pentaerythrite four (methyl) acrylate, bipentaerythrite does not have (methyl) acrylate, bipentaerythrite six (methyl) acrylate, glycerine PEO three (methyl) acrylate, three (methyl) acryloxy ethyl phosphonic acid ester etc.Monomer with cationically polymerizable functional group can use the monomer of the prepolymer with above-mentioned cationically polymerizable functional group.
If, will fully solidify, but, add Photoepolymerizationinitiater initiater as sensitive agent in the occasion that irradiation ultraviolet radiation makes it to solidify to above-mentioned ionizing radiation gel-type resin irradiation electron ray.Occasion with resinae of free-radical polymerised unsaturated group, Photoepolymerizationinitiater initiater can be used alone or as a mixture acetophenones, Benzophenones, thioxanthones, benzoin, benzoin methyl ether, rice Chi benzoin benzoate, Michler's keton, diphenyl sulfide, dibenzyl disulfide, oxidation diethyl, the two imidazoles of triphenyl,, N, N-dimethylaminobenzoic acid isopropyl ester etc.In addition, have the occasion of cationically polymerizable functional group's resinae, can use aromatic series diazotising salt, aromatic series sulfonium salt, Metallocenic compound, benzoin sulphonic acid ester, furyl oxygen base sulfoxonium diallyl iodoso salt etc. separately or as mixture.In addition, the addition of these Photoepolymerizationinitiater initiaters is generally with respect to 100 weight portion ionizing radiation gel-type resins, about 0.1～10 weight portion.Have again,, can form with known rubbing method coating such as groove rolling method, rolling method by with this ionizing radiation gel-type resin solubilize as the method that forms topping with this ionizing radiation gel-type resin.The coating weight of this moment is in solid content, and about 5～30 μ m are proper, more preferably 15～25 μ m.
In addition; give the sealer 44 better marresistances that form by the ionizing radiation gel-type resin, the occasion of mar proof, can reach by adding grinding-materials such as pulverous alumina, carborundum, silica, calcium titanate, barium titanate, pyroboric acid magnesium, zinc oxide, silicon nitride, zirconia, chromium oxide, iron oxide, boron nitride, diamond, diamond dust, glass fiber.This grinding-material is that 1～80 weight portion is proper with respect to the ratio of 100 weight portion ionizing radiation gel-type resins.
In addition; up to the present; sealer 44 just is set on the surface of decorative layer 4 always to be described; not only sealer 44 can be set on the surface of decorative layer 4; and can be for example in embodiment shown in Figure 2; decorative layer 4 as the structure shown in Figure 5 that scratch coat 43 and sealer 44 are not set " "; stack gradually this decorative layer 4 " ", the base material 2 that constitutes of synthetic resin layer 3 and veneer; make duplexer; afterwards, scratch coat 43 and sealer 44 are set on the surface of aforementioned duplexer.
Like this; by become the structure that aforementioned scratch coat 43 and aforementioned surfaces topping 33 are set on the surface of aforementioned duplexer; usually be the terminal stage of the operation of purpose to improve design; pass through machining; on laminate for floor board material, form slot part and chamfering; yet in the embodiment of the 1st～the 3rd shown in Fig. 2～4; become the structure that does not have sealer 44 in slot part and chamfered section; but by become the structure that aforementioned scratch coat 43 and aforementioned surfaces topping 44 are set on the surface of aforesaid aforementioned duplexer; from decorative layer 4 " " after side forms slot part and chamfered section (not illustrating); just can on whole of the surface that is provided with slot part and chamfered section (not illustrating), scratch coat 43 and sealer 44 be set; also can form sealer and can improve the marresistance of slot part and chamfered section in slot part and chamfered section; abrasion resistance; stain resistance; surface physical properties such as water resistance.
In addition, on slot part and chamfered section, be coated with coloring pigment, perhaps be coated with pigmented finiss as required, can become slot part with degree of depth and the slot part that the degree of depth is arranged, can improve pattern of groove portions design and water resistance with water resistance with water resistance.In addition, the formation method of slot part and chamfered section is not limited to above-mentioned machining, also can by implementing embossing processing, slot part and chamfered section be set from top layer side.
Wood substrate
As wood substrate, there is no particular limitation to this, can enumerate with China fir, Japanese cypress, beech, pine, willow Eucalyptus, teak, メ ラ ピ-etc. the prominent plate made of various raw materials, wood single-plate, wood gluing plate, light rudimentary hardboard, medium density fibreboard (MDF) etc.Laminating method to flooring material is unqualified, can adopt method that fits to cementing agent on the decoration sheet etc.Cementing agent can carry out suitable selection according to kind of base material etc. from known cementing agent.Except polyvinyl acetate, polyvinyl chloride, vinyl chloride, acetate ethylene copolymer, ethylene acrylic acid co polymer, ionomer, also can enumerate acrylonitrile butadiene rubber, neoprene, natural rubber etc.
The preparation method
According to the 1st mode of the present invention, the preparation method of laminate for floor board material has been proposed.Its preparation method is as follows.
A kind of preparation method of laminate for floor board material is the preparation method who stacks gradually the laminate for floor board material of synthetic resin layer and decorative layer formation on wood substrate, it is characterized in that,
On aforementioned wood substrate, forming yield point load is more than the 9kgf, and tensile elasticity rate is 50kgf/mm
2More than, the yield extension rate is 3～8% aforementioned synthetic resin layer,
On aforementioned synthetic resin layer, form aforementioned decorative layer,
The result of the anti-caster test of carrying out on the surface of the decorative layer side of aforementioned laminate for floor board material is, the cup depth of aforementioned surfaces is below the 100 μ m,
The anti-caster experimental rig is used in aforementioned anti-caster test, this device is equipped with rotatable castor fixed part, 3 castors installing on aforementioned castor fixed part, the portion that increases the weight of and the sample fixed station that is connected with aforementioned castor fixed station, carries out as follows:
Aforementioned laminate for floor board material is fixed on the aforementioned sample fixed station,
Increase the weight of by the aforementioned portion of increasing the weight of, aforementioned 3 castors contacted with the surface of the decorative layer side of aforementioned laminate for floor board material,
Start aforementioned castor fixed part, aforementioned 3 castors are rotated on the surface of the decorative layer side of aforementioned laminate for floor board material, afterwards, estimating has flawless to produce on aforementioned surfaces,
The average diameter 75mm of aforementioned castor, thickness 25mm,
Surface to the decorative layer side of aforementioned laminate for floor board material applies weight, is 70kg,
Aforementioned 3 castors are with the speed of 20rpm, and counter-rotating in per 5 minutes 1 time is rotated 1000 times.
Purposes
Laminate for floor board material of the present invention can be used as constructional materials, and particularly (decorate with) flooring material is used.
The 2nd mode of the present invention
The particular content of the 2nd mode of the present invention
Laminate for floor board material (the preferred decoration used flooring material) is provided, on veneer, stacks gradually in the laminate for floor board material of synthetic resin layer, decorative layer, aforementioned synthetic resin
1. to go into temperature be more than 75 ℃ to pin,
2. yield point load is more than the 10kgf,
3. tensile elasticity rate is 100kgf/mm
2More than,
4. the yield extension rate is 4～8%.
Above-mentioned laminate for floor board material can be provided, and wherein aforementioned synthetic resin layer is to be main component with the amorphism PETG, goes into temperature than the layer of the high polyester of main component as submember toward wherein adding pin.
According to another way, above-mentioned laminate for floor board material can be provided, wherein, aforementioned synthetic resin layer is to be sandwich layer with the amorphism PETG, stacked pin is gone into the layer of temperature than the 3-tier architecture of its high polyester layer on two faces of this sandwich layer.Laminate for floor board material further is provided, and wherein, aforementioned polyester layer is to be main component with the amorphism PETG, goes into temperature than the layer of the high polyester of main component as submember toward wherein adding pin.
Above-mentioned laminate for floor board material can be provided, and wherein one deck at least of aforementioned synthetic resin layer is painted resin bed.
Can propose above-mentioned laminate for floor board material, wherein form slot part from aforementioned decorative layer side.Can propose this this laminate for floor board material, wherein form aforementioned slot part, so that its bottom is positioned at aforementioned synthetic resin layer.Can propose this employing duplexer in addition, wherein the aforementioned synthetic resin of the position, bottom of aforementioned slot part is painted resin bed.This employing duplexer can be proposed, wherein at aforementioned slot part coating composition.
Can propose above-mentioned laminate for floor board material, wherein on the surface of aforementioned decorative layer, form sealer.
In addition, can propose above-mentioned laminate for floor board material, wherein on the surface of this laminate for floor board material, form sealer.
The content of the 2nd mode of the present invention
According to the 2nd mode of the present invention, can be provided in the laminate for floor board material that stacks gradually synthetic resin layer and decorative layer formation on the wood substrate, it is more than 75 ℃ that the pin of the aforementioned synthetic resin layer of laminate for floor board material is gone into temperature, yield point load is more than the 10kfg, and tensile elasticity rate is 100kgf/mm
2More than, the yield extension rate is 4～8%.
For laminate for floor board material 1, because it is more than 75 ℃ that the pin of synthetic resin layer is gone into temperature, so excellent heat resistance, thus in the influence of the heat that is subjected to the heating means and the laminate for floor board material surface produce shrinkage infringement design aspect can effectively improve.
The pin of synthetic resin is gone into the mensuration of temperature and is carried out according to JIS K7196 regulation.It thes contents are as follows.
1. the vertical needle-like pressure head (diameter 0.5mm, above cylindric of length 1mm) of placing on test film surface applies the power of 0.5N.
2. with 5 ℃/minute, the atmosphere temperature degree of test film is raise, invade in the test film until pressure head and finish, the displacement of record temperature and pressure head.
3. getting transverse axis is temperature, and the longitudinal axis is the displacement of pressure head, draws curve (TMA curve), obtains pin from this curve and goes into temperature.
4. in above-mentioned TMA curve,, be intrusion speed that the tangent line of the best part is gone into temperature (T1) with the intersection point that prolongs to low temperature side as pin specifically, extending to high temperature side at the straight line portion of seeing than the low low temperature side of temperature that begins to invade pressure head.
The layer of the laminate for floor board material of the 2nd mode of the present invention constitute can with in the 1st mode of the present invention, illustrate the same, for example can with Fig. 1～illustrated in fig. 5 the same.
Synthetic resin layer
Can form synthetic resin layer with the single or multiple lift form of polyester resins such as PEN, polybutylene terephthalate (PBT), polyarylate.According to preferred mode of the present invention, can be with the amorphism PETG, so-called A-PET (Mitsubishi Chemical's (strain): be main component ノ バ Network リ ア-(trade name)), go into temperature than its high polyester with pin, for example at least a resin that adds for submember in PEN, polybutylene terephthalate (PBT), the polyarylate etc. forms with individual layer.According to another preferred mode, the duplexer that forms with 3-tier architecture is preferred from considerations such as cost or processabilities, be sandwich layer promptly with the amorphism PETG, go into temperature than its high polyester with pin, PEN for example, polybutylene terephthalate (PBT), polyarylate or A-PET (Mitsubishi Chemical's (strain): be main component ノ バ Network リ ア-(trade name)), go into temperature than its high polyester with pin, for example, PEN, polybutylene terephthalate (PBT), at least a in the polyarylate for submember adds, the stacked resin that adds on two faces of this sandwich layer.In addition, aforementioned synthetic resin layer is made the occasion of 3-tier architecture, the resin bed that is provided with on two faces of the sandwich layer that is made of the amorphism PETG can be same resin, same thickness, is preferred on preventing to curl.
Other layer is formed
Except the synthetic resin layer of the laminate for floor board material of the 2nd mode of the present invention, with in the 1st mode of the present invention, illustrate the same.
The 3rd mode of the present invention
The particular content of the 3rd mode of the present invention
The 3rd mode of the present invention proposes a kind of decorative sheet for floor material, it is the decorative sheet for floor material of synthetic resin layer and the stacked formation of decorative layer, it is characterized in that (1) this synthetic resin layer has individual layer or the layer structure more than 2 layers, (2) a) during individual layer, this individual layer, perhaps b) in the time of more than 2 layers, the superiors at least of this synthetic resin layer are the mixed layers that contains A-PET and PETG.
Preferred propose above-mentioned decorative sheet for floor material, wherein (1) this synthetic resin layer has the layer structure more than 3 layers, and (2) the superiors and orlop at least are the mixed layers that contains A-PET and PETG.In addition, propose above-mentioned decorative sheet for floor material, wherein (1) this synthetic resin layer has the layer structure of 3 layers of formation, and (2) the superiors and orlop are the mixed layers that contains A-PET and PETG, and sandwich layer is the layer that is made of A-PET.
According to another way, above-mentioned decorative sheet for floor material is proposed, wherein synthetic resin layer and decorative layer are undertaken stacked by urethanes adhesive layer and/or urethanes scratch coat.The above-mentioned decorative sheet for floor material of preferred proposition, wherein mixed layer is made of A-PET and these 2 kinds of compositions of PETG in fact, adds up to 100 weight portions in both, contains PETG20～90 weight %.
Propose above-mentioned decorative sheet for floor material in addition, wherein the thickness of synthetic resin layer is 200～600 μ m.
The laminate for floor board material of stacked above-mentioned decorative sheet for floor material on wood materials is further proposed.
The content of the 3rd mode of the present invention
Layer structure
By Figure 10, flooring material of the present invention is described with sheet material.Figure 10 is the sectional drawing of expression flooring material of the present invention with the basic layer structure of sheet material.Be appreciated that the flooring material sheet material 101 that forms synthetic resin layer 103 and decorative layer 104 stacked formations according to Figure 10.In addition, according to Figure 10, this flooring material sheet material 101 is stacked on wood substrate 102, forms laminate for floor board material of the present invention.
Further flooring material of the present invention is described with sheet material by Figure 11.Figure 11 is that expression constitutes the sectional drawing of flooring material of the present invention with the embodiment of sheet material.This formation has such structure, promptly stacks gradually adhesive layer 104, scratch coat 105, substrate layer 106, design layer 107, adhesive layer 108, transparent resin bed 109, scratch coat 110 and sealer 111 on synthetic resin layer 103.Implement embossing processing 133 from sealer 111, form concaveconvex shape.In addition, constitute synthetic resin layer 103 by A-PET and PETG (121), sandwich layer is made of A-PET (122), and orlop is made of A-PET and PETG (123).
Synthetic resin layer
A sheet material of the present invention particularly synthetic resin layer has 1 layer (individual layer) or the layer structure more than 2 layers, and the mixed layer of A-PET and PETG is contained in its superiors.That is, during individual layer, this individual layer, in the time of perhaps more than 2 layers, the layer near decorative layer must be above-mentioned mixed layer.These the superiors are stacked by adhesive layer and/or scratch coat to be decorative layer.In the present invention, be above-mentioned mixed layer by making its superiors, can further improve caking property with decorative layer.During individual layer, this individual layer is a mixed layer.
Synthetic resin layer both can be an individual layer as previously mentioned, also can be by constituting more than 2 layers.Be more than 2 layers the time, its laminating method can adopt known method such as extrusion molding.
In addition, in sheet material of the present invention, have the occasion of the layer structure more than 3 layers, preferably the superiors and orlop are the mixed layers that contains A-PET and PETG at least.Thus, not only can improve the caking property with decorative layer, but also can improve the caking property of synthetic resin layer and flooring material.The superiors are with aforementioned the same, are near the layer of decorative layer.Orlop is meant the layer (that is, constituting the layer at the back side of sheet material of the present invention) of the most approaching stacked wood materials.
As preferred embodiment of the present invention, can enumerate following flooring material sheet material, promptly (1) this synthetic resin layer has the layer structure of 3 layers of formation, and (2) the superiors and orlop are the mixed layers that contains A-PET and PETG, and sandwich layer is the layer that A-PET constitutes.
The mixed layer of sheet material of the present invention contains A-PET and PETG.These can use known products or commercially available product.As A-PET,, can suitably use commercially available A-PET (Mitsubishi Chemical's (strain): ノ バ Network リ ア-(trade name)) etc. so long as the amorphism PETG is unqualified to this.PETG is with 1, and the 4-cyclohexanedimethanol replaces the pet copolymer of a part of ethylene glycol, can use commercially available product " PETG6763 " (イ-ス ト マ Application ケ ミ カ Le system).
Mixed layer can comprise other resinous principle.Can enumerate polyester resins such as PEN, polybutylene terephthalate (PBT), polyarylate.In the present invention, especially preferably make the mixed layer of 2 kinds of compositions that constitute by A-PET and PETG.In the occasion of 2 kinds of compositions, also can contain other additive except that mylar.
A-PET in the mixed layer and the content of PETG can suitably be set according to the grade of each composition, the service condition of sheet material of the present invention etc.Sheet material of the present invention is in above-mentioned 2 one-tenth subsystems, and in the total 100 weight % of A-PET and PETG, PETG is 20～90 weight %, more preferably 40～60 weight %.
Thickness (occasion more than 2 layers is the thickness that adds up to) to the synthetic resin layer of sheet material of the present invention is unqualified, but, can be decided to be more than the 200 μ m preferred about 200～600 μ m from considerations such as caster-resistant, marresistances.The thickness of each layer of the occasion more than 2 layers can grade according to the one-tenth of each layer, suitably determines.
According to preferred mode of the present invention, a kind of flooring material sheet material is proposed, be the flooring material sheet material that constitutes by synthetic resin layer and the decorative layer that forms thereon, it is characterized in that
Aforementioned synthetic resin layer has individual layer or the layer structure more than 2 layers,
Aforementioned synthetic resin layer is the occasion of individual layer, aforementioned individual layer is formed by amorphism PETG and pet copolymer, aforementioned synthetic resin is the occasion more than 2 layers, wherein one deck is formed by amorphism PETG and pet copolymer at least
Aforementioned pet copolymer is with 1, and the 4-cyclohexanedimethanol replaces the pet copolymer of a part of ethylene glycol.
The another way according to the present invention proposes a kind of above-mentioned flooring material sheet material, and aforementioned synthetic resin layer has the layer structure more than 3 layers,
The superiors and the orlop of aforementioned layer structure more than 3 layers are formed by amorphism PETG and pet copolymer,
Aforementioned pet copolymer is with 1, and the 4-cyclohexanedimethanol replaces the pet copolymer of a part of ethylene glycol.
Further propose above-mentioned flooring material sheet material, the sandwich layer that is clipped in the aforementioned the superiors and the aforementioned orlop is formed by the amorphism PETG.
In addition, propose above-mentioned flooring material sheet material, the content of aforementioned pet copolymer is 20～90 weight % with respect to the gross weight of aforementioned amorphism PETG and aforementioned poly terephthalic acid glycol copolymer.
Decorative layer
Can make the decorative layer of sheet material of the present invention become the structure the same, can preferably adopt the structure of following explanation with known decorative layer.In addition, as required, also can become and the same structure that in the 1st mode of the present invention, illustrates.
Tack coat
Can from known or commercially available cementing agent, grade, suitably select adhesive layer according to the one-tenth that constitutes the design layer or the second transparent resin bed.Except that polyolefin resins such as polyethylene, polypropylene, can also enumerate heat-curing resins such as polyester resin, poly-urethanes resin, epoxylite.
Wherein, in the present invention, can further improve aspect such as heat resistance, preferred urethanes resinoid bond.It is host that the urethanes resinoid bond can be enumerated with the polyalcohol, is the biliquid curable urethane resin of crosslinking agent (curing compound) with the isocyanates.
As above-mentioned polyalcohol, be the polyalcohol that in molecule, has the hydroxyl more than 2.Can use polyethylene glycol, polypropylene glycol, acryloyl group polyalcohol, polyester polyalcohols, polyether polyols, Merlon polyalcohols etc.
In addition, as above-mentioned isocyanates, can use the multicomponent isocyanate that has 2 above NCOs in the molecule.Can use 2,4-toluene di-isocyanate(TDI), XDI, 4, aromatic isocyanate classes such as 4-methyl diphenylene diisocyanate; Aliphatic series such as the toluene di-isocyanate(TDI) of hexamethylene diisocyanate, IPDI, hydrogenation, the methyl diphenylene diisocyanate of hydrogenation (and even alicyclic) isocyanates.In addition, also can use the addition product or the polymer of above-mentioned various isocyanates.Can enumerate the addition product of toluene di-isocyanate(TDI), the trimer of toluene di-isocyanate(TDI) etc.
In addition, as required, also can implement known easy binder-treatment such as Corona discharge Treatment, plasma treatment, ungrease treatment, surperficial asperities processing to adhesive surface.
As adhesive method, can implement according to known method according to kind of used cementing agent etc.Can adopt following method: use polyolefin resins such as polyethylene, polypropylene, with melt extrude the method that (extrusion) is coated with on design layer; As required, coating toward polyester resin, gather the cementing agent that adds polymerization accelerants such as polymerization initiator, cobalt naphthenate, dimethylaniline such as crosslinking agents such as isocyanates, amine, methyl ethyl ketone peroxide, hydrogen peroxide, azepine bis-isobutyronitrile etc. in the heat-curing resins such as urethanes resin, epoxylite, carry out the stacked method of dry type.In addition, in the present invention, also can use the sticking cementing agent of hot pressing, by thermocompression bonded, stacked design layer and transparent resin bed.
In addition, in the present invention, as required, also can implement known easy binder-treatment such as Corona discharge Treatment, plasma treatment, ungrease treatment, surperficial asperities processing to adhesive surface.
The thickness of adhesive layer is different because of the kind of the cementing agent of transparent topping, use etc., usually about 0.1～30 μ m.
Scratch coat
Scratch coat is in order to improve the surperficial caking property of substrate layer or transparent resin bed.As use therein resin, can enumerate ester resin, urethane resin, acrylic resin, polycarbonate resin, ethylene chloride-ethylene acetate ester copolymer, polyvinylbutyral resin, Nitro cellulose resin etc., these resins can separately or mix as coating composition, perhaps as ink composite, the coating means suitable with rolling method or woodburytype etc. form.
Substrate layer
Substrate layer can use paper such as strengthening paper between the paper, paper of thin paper, first-class paper, kraft, Japan paper, titanium paper, resin impregnation; Fibers such as wood fibre, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber constitute weaves cotton cloth and the duplexer more than a kind or 2 kinds of synthetic resin sheet materials such as nonwoven or polyolefin, polyester, polyacrylic acid, polyamide, poly-urethane, polystyrene etc., and its thickness is that 20～300 μ m are proper.In addition, for aforementioned decoration base material used in above-mentioned decorative layer, as required, added pigment in both can be the in the past necessary layer and wait painted, also can implement the processing that Corona discharge Treatment, plasma treatment, ozone treatment etc. are easy to bond the face of necessity.
Design layer
Design layer is made of decorative pattern ink lay and full ink lay.Generally can use known print process such as intaglio printing, lithographic printing, serigraphy to form design layer.As the decorative pattern ink lay, can be wood grain decorative pattern, bag decorative pattern, woven design decorative pattern, dermatoglyph decorative pattern, geometrical pattern, literal, mark, lines, various abstract designs etc.As full ink lay, be with layer with concealed printing ink all print.In this embodiment, decorative pattern ink lay and full ink lay can be set, and this is two-layer, and no matter the structure of which layer all can.
For the printing ink that in design layer, uses,, can mix chloridized polyolefins such as using haloflex, chlorinated polypropylene more than a kind or 2 kinds as carrier; Polyester; The poly-urethane that isocyanates and polyalcohol constitute; Polyacrylic acid, polyvinyl acetate; Polyvinyl chloride; The ethylene chloride-ethylene acetate ester copolymer; Cellulosic resin; Polyamide-based resins etc. can wherein add pigment, solvent, various auxiliary agents etc. and printing inkization in the past and use.In the present invention, from environmental problem and with the considerations such as caking property that are printed face, more than a kind or 2 kinds of the poly-urethane that mixed polyester, isocyanates and polyalcohol constitute, polyacrylic acid, polyamide etc.In addition, for smearing printing ink, also can form with the printing ink the same with the printing ink that in above-mentioned design layer, uses.
Transparent resin layer
The transparency resin bed so long as the transparency, unqualified to this.As transparent resin bed, can preferably use the transparent resin that forms by thermoplastic resin.
Can enumerate soft, semi-rigid or rigid polyvinyl chloride, PETG, polybutylene terephthalate (PBT), polyamide, polyethylene, polypropylene, ethylene vinyl acetate copolymer, ethylene acrylic acid co polymer, ethylene acrylate copolymer, ionomer, acrylate, methacrylate etc. particularly.Wherein, in the present invention, as the second transparent resin bed, polyolefin resins such as optimization polypropylene.
Transparency resin bed as required also can be painted.At this moment, adding coloured material (pigment or pigment) in can aforesaid in the past thermoplastic resin comes painted.As coloured material, can use pigment or the dyestuff in aforementioned painted semitransparent layer, enumerated.They can be selected more than a kind or 2 kinds.In addition, the addition of coloured material also can suitably be set according to desirable colourity.
As required, transparent resin bed also can contain filler, delustering agent, blowing agent, fire retardant, sliding agent, antistatic additive, antioxidant, ultra-violet absorber, light stabilizer.Scavenger of free radicals, soft composition various additives such as (for example rubber).
Sealer
As the thermohardening type resin, can enumerate unsaturated polyester resin, poly-urethane resin (comprising that also the biliquid curing type gathers urethane), epoxy resin, amino-alkyd resin, phenolic resin, urea resin, diallyl phthalate resin, melamine resin, triamido cyanate resin, melamine-urea cocondensation resin, contain silicones, polyorganosiloxane resin etc.
As required, in above-mentioned resin, add curing compound, polymerization accelerants such as crosslinking agent, polymerization initiator.As curing compound, isocyanates or organic sulfonate etc. add in unsaturated polyester resin or the poly-urethane resin, radical initiators such as peroxide such as organic amine etc. add in the epoxy resin, methyl ethyl ketone peroxide or azo isobutyronitrile add in the unsaturated polyester resin.
As the method that forms sealer with above-mentioned thermohardening type resin, can enumerate by making above-mentioned thermohardening type resin solutionization, be coated with this solution with known rubbing methods such as rolling method, groove rolling methods, dry method of also solidifying.As the coating weight of above-mentioned solution, in solid content, about 5～30 μ m are proper, preferred 15～25 μ m.
The ionizing radiation gel-type resin is so long as by the irradiation ionizing radiation, produces cross-linking polymerization and changes into the resin of three-dimensional macromolecular structure, and is unqualified to this.Ionizing radiation be meant have electromagnetic wave or can polymerization in the charge particle line, the radioactive ray of the quanta of energy of corsslinking molecular, comprise visible light, ultraviolet ray (near ultraviolet ray, vacuum ultraviolet etc.), X ray, electron ray, ion irradiation etc., ultraviolet ray or electron ray are used in special hope.As ultraviolet source, can use the light source of extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, carbon arc lamp, black light fluorescent lamp, metal halide lamp.As ultraviolet wavelength, can use the wave-length coverage of about 190～380nm.In addition, as electronic radial source, can use various electron ray accelerators such as Cockcroft-Walton type, バ Application デ グ ラ Off ト type, resonance transformer type, insulating core line transformer type, linear pattern, ダ イ Na ミ ト ロ Application type, high-frequency type.As used electron ray, generally can use about 100～1000keV, the electron ray of preferred 100～300keV.The exposure of electron ray is about 2～15Mrad usually.
The ionizing radiation gel-type resin is to be made of the monomer, prepolymer or the polymer that have cationically polymerizable functional groups such as free-radical polymerised unsaturated group such as (methyl) acryloyl group, (methyl) acryloxy or epoxy radicals in the molecule (following they are generically and collectively referred to as compound).These monomers, prepolymer and polymer can use with monomer, and perhaps multiple mixing is used.In addition, in this manual, so-called (methyl) acrylate uses with the meaning of acrylate or methacrylate.
As prepolymer, can enumerate polyester (methyl) acrylate, urethane (methyl) acrylate, epoxy (methyl) acrylate, melamine (methyl) acrylate, triazine (methyl) acrylate, polyvinylpyrrolidone etc. with free-radical polymerised unsaturated group.Usually use about this prepolymer below 10000 of molecular weight.If molecular weight surpasses 10000, then surface physical properties such as the marresistance of resin bed, mar proof, chemical resistance, heat resistance will be not enough.Can shared above-mentioned acrylate and methacrylate, but from the crosslinking curing speed aspect of ionizing radiation, the quick solidifying of acrylate, thus under high-speed, short time, can effectively solidify, thereby acrylate is favourable.
As prepolymer, can enumerate epoxy resin such as bisphenol-type epoxy resin, novolac resin, alicyclic type epoxy resin with cationically polymerizable functional group; Vinethene resinoids such as aliphatic series class vinethene, fragrant same clan vinethene, urethanes vinethene, ester class vinethene; The cyclic ether compound; Prepolymers such as spiro-compound.
As monomer with free-radical polymerised unsaturated group, can enumerate (methyl) methyl acrylate as the monofunctional monomer of (methyl) acrylate compounds, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid methoxyl group ethyl ester, (methyl) acrylic acid methoxyl group butyl ester, (methyl) acrylic acid butoxy ethyl ester, (methyl) acrylic acid 2-, Octyl Nitrite, N, N-dimethylaminomethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-diethylamino propyl group (methyl) acrylate, N, N-dibenzyl amino ethyl (methyl) acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid Isobornyl, ethyl carbitol (methyl) acrylate, (methyl) acrylic acid phenoxy ethyl, phenoxy group polyethylene glycol (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, MPEG (methyl) acrylate, 2-(methyl) acrylyl oxy-ethyl-2-hydroxypropyl phthalic acid ester, 2-(methyl) acryloyl-oxy propyl group hydrogen terephthalate etc.
In addition, as polyfunctional monomer with free-radical polymerised unsaturated group, can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, two three (ethylene glycol) dimethylacrylates that contract, propane diols two (methyl) acrylate, DPG (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, tetraethylene-glycol two (formic acid) acrylate, two three (propane diols) two (methyl) acrylate that contract, bisphenol-A-two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane oxirane three (methyl) acrylate, pentaerythrite four (methyl) acrylate, bipentaerythrite does not have (methyl) acrylate, bipentaerythrite six (methyl) acrylate, glycerine PEO three (methyl) acrylate, three (methyl) acryloxy ethyl phosphonic acid ester etc.Monomer with cationically polymerizable functional group can use the monomer of the prepolymer with above-mentioned cationically polymerizable functional group.
If, will fully solidify, but, add Photoepolymerizationinitiater initiater as sensitive agent in the occasion that irradiation ultraviolet radiation makes it to solidify to above-mentioned ionizing radiation gel-type resin irradiation electron ray.Occasion with resinae of free-radical polymerised unsaturated group, Photoepolymerizationinitiater initiater can be used alone or as a mixture acetophenones, Benzophenones, thioxanthones, benzoin, benzoin methyl ether, rice Chi benzoin benzoate, Michler's keton, diphenyl sulfide, dibenzyl disulfide, oxidation diethyl, the two imidazoles of triphenyl, N, N-dimethylaminobenzoic acid isopropyl ester etc.In addition, have the occasion of cationically polymerizable functional group's resinae, can use aromatic series diazotising salt, aromatic series sulfonium salt, Metallocenic compound, benzoin sulphonic acid ester, furyl oxygen base sulfoxonium diallyl iodoso salt etc. separately or as mixture.
There is no particular limitation to the addition of Photoepolymerizationinitiater initiater, and generally with respect to 100 weight portion ionizing radiation gel-type resins, about 0.1～10 weight portion gets final product.
As the method that forms topping with this ionizing radiation gel-type resin, can form with known rubbing method coating such as groove rolling method, rolling method by with this ionizing radiation gel-type resin solubilize.The coating weight of the solution of this moment is in solid content, and about 5～30 μ m are proper, more preferably 15～25 μ m.
In addition, give the sealer 11 better marresistances that form by the ionizing radiation gel-type resin, the occasion of mar proof, as required, can cooperate inorganic filling material.Can enumerate pulverous alumina, carborundum, silica, calcium titanate, barium titanate, pyroboric acid magnesium, zinc oxide, silicon nitride, zirconia, chromium oxide, iron oxide, boron nitride, diamond, diamond dust, glass fiber etc.
Use amount to inorganic filling material is unqualified, usually with respect to 100 weight portion ionizing radiation gel-type resins, is that 1～80 weight portion gets final product.
The laminating method of each layer
Laminating method to each layer of sheet material of the present invention is unqualified, can adopt the bonding of cementing agent, the whole bag of tricks such as stacked.Special hope is by urethanes cementing agent and/or urethanes scratch coat, stacked synthetic resin layer and decorative layer.The stacked of each layer implements to get final product with common order.For example; if describe with Figure 11; printing forms design layer 107 successively on a face of painted substrate layer 106; further pass through with the stacked adhesive layer 108 that forms with cementing agent of known dry types such as biliquid curable urethane; with known dry type layered manner, T shape mould extrusion molding etc.; stacked transparent resin bed 109 is provided with scratch coat 110 on whole of transparent resin bed 109 on aforementioned design layer 107, forms sealer 111 thereon and gets final product.
In addition, as required,, can form ridge design by implement embossing processing from sealer 111 sides.Ridge design can be by formation such as hot pressing or microgroove processing.As aforementioned ridge design, can enumerate that conduit trough, stone plate surface are concavo-convex, cloth surface texturisation, pears surface, line, microgroove, ten thousand lines grooves etc.
Laminate for floor board material
Laminate for floor board material of the present invention stacked flooring material of the present invention on wood substrate obtains with sheet material.Particularly as shown in figure 10, at the synthetic resin layer side upper strata of sheet material of the present invention cribbing material.As wood substrate, there is no particular limitation, can enumerate with China fir, Japanese cypress, beech, pine, willow Eucalyptus, teak, メ ラ ピ-etc. the prominent plate made of various raw materials, wood single-plate, wood gluing plate, light rudimentary hardboard, medium density fibreboard (MDF) etc.
Laminating method to flooring material is unqualified, can adopt method by cementing agent applying decoration sheet on base material etc.According to kind of base material etc., suitably select cementing agent to get final product from known cementing agent.Except polyvinyl acetate, polyvinyl chloride, vinyl chloride, acetate ethylene copolymer, ethylene acrylic acid co polymer, ionomer, also can enumerate acrylonitrile butadiene rubber, neoprene, natural rubber etc.
Other
The flooring material of the 3rd mode of the present invention with sheet material and the laminate for floor board material that uses this sheet material except that foregoing, also can with in the 1st mode of the present invention, illustrate the same.
The 4th mode of the present invention
The particular content of the 4th mode of the present invention
According to the 4th mode of the present invention, a kind of laminate for floor board material is proposed, be the flooring material of the stacked wood materials of this synthetic resin layer side of the laminate for floor board material that constitutes at synthetic resin layer and decorative layer, it is characterized in that this synthetic resin layer is divided into 2 above distinct area at least.
Propose above-mentioned laminate for floor board material,, this synthetic resin layer and decorative layer can be divided into the isolated area more than 2 wherein by the groove that arrives wood materials from the decorative layer side is set.Propose above-mentioned laminate for floor board material, wherein the thickness of synthetic resin is more than the 200 μ m.
In addition, propose above-mentioned laminate for floor board material, (1) this synthetic resin has individual layer or the layer structure more than 2 layers, (2) a) during individual layer, this individual layer, perhaps b) more than 2 layers the time, at least the superiors of this synthetic resin layer are the mixed layers that contains A-PET and PETG or PEN.Propose above-mentioned laminate for floor board material, wherein (1) this synthetic resin layer has the layer structure more than 3 layers, and (2) the superiors and orlop at least are the mixed layers that contains A-PET and PETG or PEN.
Propose above-mentioned laminate for floor board material, it is characterized in that (1) this synthetic resin layer has the layer structure of 3 layers of formation, (2) the superiors and orlop are the mixed layers that contains A-PET and PETG or PEN, and sandwich layer is the layer that is made of A-PET.
Further, propose above-mentioned laminate for floor board material, it is characterized in that by urethanes adhesive layer and/or urethanes scratch coat, stacked synthetic resin layer and decorative layer.
At last, propose above-mentioned laminate for floor board material, it is characterized in that mixed layer is made of A-PET and PETG or these 2 kinds of compositions of PEN in fact, add up to 100 weight %, contain PETG or PEN20～80 weight % in both.
The content of the 4th mode of the present invention
Layer constitutes
Flooring material of the present invention is divided into 2 above distinct area with the synthetic resin layer of sheet material.In other words, synthetic resin layer is made of a plurality of plastic zoning sheets (following only be called " zoning sheet ").By Figure 12 the mode of flooring material of the present invention with sheet material is described.Figure 12 represents the formulation example (plan view) of flooring material of the present invention with the synthetic resin layer of sheet material.Synthetic resin layer 201 is made of 3 zoning sheets 202,203 and 204.Can be in contact with one another between the zoning sheet, but preferably between the zoning sheet certain clearance 205 be arranged.The thickness (distance between the zoning sheet) in the gap of this moment can be below 2mm, and the following scope of preferred 1mm is suitably set.By setting the gap, can absorb bigger differential expansion.
In Figure 12, can be divided into 3 zoning sheets, but 2 zoning sheets, the zoning sheet more than 3 etc. all can.This division is except being divided into as Figure 12 the nicking shape, and clathrate, horizontal stripe shape all can.
The formation of the synthetic resin layer of zoning sheet
There is no particular limitation to the synthetic resin layer that forms the zoning sheet.Can enumerate method at stacked pre-prepd a plurality of zoning sheets on the decorative layer of wood materials (base material) or decoration sheet, with conventional method after whole upper strata of decorative layer is overlapped into resin bed, cut off synthetic resin layer so that synthetic resin layer is divided into the method for each zoning sheet etc.With Figure 13 a mode that forms such zoning sheet is described.Figure 13 is the sectional drawing of expression laminate for floor board material of the present invention.The following method of preferred employing, as shown in figure 13, use conventional method, whole stacked decorative layer 210 on synthetic resin layer 201, the Manufacture of Floor material is with sheet material 211, and itself and wood substrate 212 is stacked, behind the formation laminate for floor board material 213, for synthetic resin layer being divided into each independently zoning sheet, arrive the groove 214 of synthetic resin layer from the processing of decorative layer side.From the occasion of decorative layer working groove, the same with synthetic resin layer, also decorative layer can be divided into a plurality of zoning sheets.The method of working groove itself can for example get final product with known device processing such as dovetailers according to known method.The occasion of working groove, unqualified to its cross section, V word shape, concavity (square, rectangle) etc. all can.And when forming groove, the part of wood materials is exposed, so in order to protect exposed portions serve, can implement necessary processing (waterproofing work, hydrophobic treatment).
Decorative layer
Decorative layer of the present invention can be understood with the concrete layer formation of sheet material (laminate for floor board material) by flooring material of the present invention shown in Figure 14.According to Figure 14, flooring material of the present invention has the structure that stacks gradually adhesive layer 224, scratch coat 225, substrate layer 226, full ink lay 227, style ink lay 228, adhesive layer 229, transparent resin bed 230, scratch coat and sealer (transparent topping) 231 on synthetic resin layer 223 with sheet material.Implement embossing processing from the sealer side, form the embossed portion 232 of concavity.On the other hand, at the back side of synthetic resin layer, by adhesive layer 222 stacked wood substrates 221.In addition, this bed arrives wood substrate 221 with duplexer from the decorative layer side, and cuspidated groove 220 is set in wood materials, thus, synthetic resin layer is divided into each independently zoning sheet.
Synthetic resin layer
Synthetic resin layer is divided by beyond the following aspect, also can with in the 3rd mode of the present invention, illustrate the same.
A-PET in the mixed layer and the content of PETG can suitably be set according to the grade of each composition, the service condition of sheet material of the present invention etc.Sheet material of the present invention is in above-mentioned 2 one-tenth subsystems, and in the total 100 weight % of A-PET and PETG, PETG is preferably 20～80 weight %.
Thickness (occasion more than 2 layers is the thickness that adds up to) to the synthetic resin layer of sheet material of the present invention is unqualified, but, can be decided to be more than the 200 μ m preferred about 200～500 μ m from considerations such as caster-resistant, marresistances.The thickness of each layer of the occasion more than 2 layers can grade according to the one-tenth of each layer, suitably determines.
The coating of zoning sheet
The preferred mode according to the present invention; the following flooring material that constitutes is proposed with sheet material or laminate for floor board material; with containing the resinoid water-soluble composition of acryloyl group urethane; coating is by aforementioned division place that described synthetic resin layer is divided into the distinct area more than 2 and exposes with by respectively aforementioned synthetic resin layer and aforementioned decorative layer being divided into aforementioned division place separately that 2 above distinct area are exposed.Thus, the wood substrate that can adequately protect.
Water paint
Water paint comprises the acryloyl group urethanes resin as resinous principle.There is no particular limitation to acryloyl group urethanes resin, also can use known product or commercially available product.Can enumerate the reaction product of acryloyl group polyalcohol and isocyanate compound, the acrylic resin by the crosslinked functional group of having and have compound resin of functional group's urethane resin etc.
Acryloyl group urethanes resin preferably mixes the acrylic resin of ketone group containing and contains that the urethane resin of hydrazide group obtains.This is because when having better water resistance, chemical resistance, marresistance etc., can obtain the advantage with the high adaptation of synthetic resin layer (especially olefine kind resin).
By ketone group and hydrazide group crosslinked acrylic resin and urethane resin, with acrylic resin and compoundization of urethane resin.In addition, the resin of this compoundization forms the form of water-based emulsion (urethane/acryloyl group complex emulsions) in the aqueous solution, becomes preferred in the present invention mode.For this water-based emulsion, the compound particle form that the particle of this resin exists with the acrylic resin composition in particle inside is disperseed, and the compound particle form that exists with the urethane resin composition in the particle outside is disperseed.As such complex emulsions, also can use commercially available product.Preferably can enumerate goods name " Port Application コ-ト CG-5000 " (big Japanese ink chemical industry system) etc.
Unqualified to acrylic resin composition in urethane/acryloyl group complex emulsions and urethane resin components in proportions, in both total 100 weight %, the urethane resin composition is preferably 20～40 weight %.By being set in this scope, can further improve caking property with synthetic resin layer.
The resinoid content of acryloyl group urethane in the water paint can suitably limit according to the kind of resin, is preferably about 5～60 weight %, preferred especially 20～40 weight %.
In the present invention, preferably use curing compound,, can improve the degree of cross linking by using curing compound for the acryloyl group urethane resin.As the concrete example of curing compound, can enumerate isocyanates curing compound, epoxies curing compound, melamine class curing compound, aziridines curing compound etc.In the present invention, particularly, preferably use the isocyanates curing compound from can further improving the viewpoint of crosslinked at low temperature performance, atmospheric corrosion resistance, water resistance etc.The content of curing compound also depends on the kind etc. of the curing compound of use, usually, with respect to 100 weight portion acryloyl group urethanes resins, is that 20～70 weight portions get final product.
Water paint preferably contains silicon.By adding silicon, can obtain better defoaming effect, waterproof effect etc.The addition of silicon is that 0.5～5 weight % is relatively good in coating of the present invention.
In water paint of the present invention, also can cooperate the contained additive of known water paint.Can use colorant (pigment, dyestuff), viscosity modifier, other additive.
As the solvent in the water paint, mainly make water, but as required, also can merge the use water-miscible organic solvent.Except that alcohols such as isopropyl alcohol, can also make spent glycol, glycol ether etc.
The solid content of coating of the present invention in the scope of 5～80 weight %, can suitably be determined according to the kind of used composition usually.Coating of the present invention no matter be which kind of form such as solution, emulsion all can, the form of special preferred emulsion.
Other layer constitutes
Except that flooring material with the layer the synthetic resin layer of sheet material, can with in the 3rd mode of the present invention, illustrate the same.
[embodiment]
Embodiment A
By following embodiment A, content of the present invention is described.
The preparation of laminate for floor board material
The laminate for floor board material that preparation is made of following layer.
Decoration sheet and A-PET (0.4mm is thick) layer and lauan veneer (12mm is thick)
Thick and the lauan veneer (12mm is thick) of the PET of decoration sheet and biaxial tension (0.25mm)
Example A1
Prominent plate and lauan veneer (general colored floor board)
Example A2
Prominent plate+MDF (3mm is thick) and lauan veneer (9mm is thick) (giving the colored floor board of anti-rubber tire)
Example A3
Decoration sheet and lauan veneer (12mm is thick)
Example A4
Decoration sheet and A-PET (0.2mm is thick) and lauan veneer (12mm is thick)
In above-mentioned preparation example, decoration sheet is meant the decorative layer of the formation of Fig. 3, A-PET is meant the amorphism ethylene glycol terephthalate, and the PET of biaxial tension is meant the PETG of biaxial tension, and prominent plate is meant cuts thin veneer with unstained natural timber.
Evaluation test
Carry out following evaluation test, it the results are shown in the following Table A.
Test A1: anti-caster test
The laminate for floor board material of the embodiment A 1～routine A4 of above-mentioned preparation is set on following anti-caster experimental rig, tests according to following condition.After the test, visual laminate for floor board material judges that there is flawless on its surface.In addition, measure the concave depth of laminate for floor board material with depth gauge.
The anti-caster experimental rig
Use anti-caster experimental rig L6-04 (shallow wild machinery production Co., Ltd.).The mode of this device is as follows.
Sample fixed station: Φ 80cm, the Acryl system of thickness 8mm
3 castors: the 420SA-N75 of Hammer Caster system (Φ 75mm * 25mm, wheel nylon system)
The rotary speed of castor fixed station: 0～60rpm (variable speed driver drive-type)
Payload portion: can regulate at 40～210kg
Regulating handle:, make castor direction of rotation reversal interval up and down: 1～12 minute (can set) by timer by the handle of rotational load platform
Counter is decided in preset: the setting of revolution and demonstration accumulation revolution
Numeral tachometer: show the castor rotary speed
Sample size: 30cm * 30cm
Test conditions
In above-mentioned anti-caster experimental rig, will be fixed on as the laminate for floor board material of subjects on the test fixed station.By regulating handle, promote the castor fixed station in order to avoid 3 castors contact with the surface of this flooring material duplexer, afterwards, the load platform is applied sliding weight of steelyard so that weight reaches 70kg.
Set the speed of rotary speed 20rpm, counter-rotating in per 5 minutes 1 time, rotate 1000 times, rotate regulating handle, the castor fixed station is dropped on the surface of laminate for floor board material.
Open the starting switch of the rotating driving device of castor fixed station, begin test.After the off-test, rotate regulating handle, the castor fixed station is risen, take out laminate for floor board material, estimate as subjects.
Test A2: anti-Du Pont impact test
According to JIS K5600 Du Pont impact test, the laminate for floor board material of the embodiment A 1～routine A4 of above-mentioned preparation is tested.Specifically, the punch die of r=6.3mm is placed on the surface of above-mentioned laminate for floor board material, the sliding weight of steelyard that makes 500g drops on the punch die of front from the height of 300mm.After the test, visual laminate for floor board material judges that there is flawless on its surface.In addition, measure the concave depth of laminate for floor board material with depth gauge.
Table A
Embodiment B
With regard to the 1st mode of the present invention, describe with following Embodiment B.
The preparation of laminate for floor board material
The adjustment of top layer material B
Carried out on the two sides on the one side of the thick painted polypropylene screen of 60 μ of Corona discharge Treatment the thick urethanes scratch coat of 2 μ m being set, on another side, formed the printed layers of wood grain style simultaneously with biliquid curable urethane class printing-ink.Then, by the urethanes cementing agent, with T shape mould extruder, transparent propylene resin is expressed on the aforementioned printed layers, making thickness is 80 μ m, duplexer in the middle of making.Afterwards; on the aforementioned transparent propene resinoid face of aforementioned middle duplexer, form the thick urethanes scratch coat of 2 μ m; on this urethanes scratch coat; be coated with dry ionizing radiation gel-type resin with the groove rolling method; so that reach the thickness of 15 μ m after the drying; form uncured electronic emission line gel-type resin layer; under the environment below the oxygen concentration 200PPM; to this uncured electronic emission line gel-type resin layer irradiation electron ray (accelerating potential 175KeV; exposure 5Mrad) makes it to solidify; the sealer that formation is made of electronic emission line gel-type resin; in this sealer side,, implement embossing processing simultaneously with the wood grain catheter-like embossing plate of the dark 50 μ m of version; make the decoration sheet that forms the concavo-convex style of wood grain catheter-like, as top layer material B.
Then, will be used on the synthetic resin layer as described below, change resin kind and thickness, prepare 24 kinds,, obtain testing body B1～24 by fitting with aforementioned top layer material B for the laminate for floor board material of test.
Test body B1
On the thick urethanes prime layer side of the 2 μ m that are provided with on the face of the aforementioned painted polypropylene screen of aforementioned top layer material B; by the urethanes cementing agent; the thick esters resin of 300 μ m (Mitsubishi Chemical's system: layer NOVAPEX GM700) is set; simultaneously on this esters resin aspect; by the urethanes cementing agent; the lauan veneer that applying 12mm is thick; further on aforementioned surfaces protection aspect; flowing on the parallel direction with the wood grain style; with the 75mm pitch,, form wide 3.0mm by machining; the V-shaped groove of dark 0.3mm is made the laminate for floor board material for test.
Test body B2-0
Except the thickness of the esters resin layer that makes test body B1 is the 400 μ m, B1 is the same with the test body.
Test body B3
Except the esters resin layer that makes test body B1 is that (Japan's spinning: A4300), B1 is the same with the test body for the PETG film of the thick biaxial tension of 188 μ m.
Test body B4
Except the esters resin layer that makes test body B1 is that (Japan's spinning: A4300), B1 is the same with the test body for the PETG film of the thick biaxial tension of 125 μ m.
Test body B5
Except the esters resin layer that makes test body B1 is that (Japan's spinning: A4300), B1 is the same with the test body for the PETG film of the thick biaxial tension of 100 μ m.
Test body B6
Except the esters resin layer that makes test body B1 is that (Japan's spinning: A4300), B1 is the same with the test body for the PETG film of the thick biaxial tension of 75 μ m.
Test body B7
Except the esters resin layer that makes test body B1 is that (Japan's spinning: A4300), B1 is the same with the test body for the PETG film of the thick biaxial tension of 50 μ m.
Test body B8
Except the esters resin layer that makes test body B1 is that (イ-ス テ マ Application ケ ミ カ Le カ Application パ ニ-system: EasterPETG6763), B1 is the same with the test body for the thick non-crystalline polyester of 400 μ m.
Test body B9
Except the esters resin layer that makes test body B1 is that (イ-ス テ マ Application ケ ミ カ Le カ Application パ ニ-system: EasterPETG6763), B1 is the same with the test body for the thick non-crystalline polyester of 300 μ m.
Test body B10
Except the esters resin layer that makes test body B1 is that (テ Network ノ Port リ マ-system: TECNO ABS810), B1 is the same with the test body for the thick ABS of 300 μ m.
Test body B11
Except the esters resin layer that makes test body B1 is that (テ Network ノ Port リ マ-system: TECNO ABS810), B1 is the same with the test body for the thick ABS of 200 μ m.
Test body B12
Except the esters resin layer that makes test body B1 is that (テ Network ノ Port リ マ-system: TECNO ABS810), B1 is the same with the test body for the thick ABS of 100 μ m.
Test body B13
Except making the esters resin layer of testing body B1 is the thick Merlon of 160 μ m (Mitsubishi's engineering plastics system: ユ-ピ ロ Application S2000), and B1 is the same with the test body.
Test body B14
Except making the esters resin layer of testing body B1 is the thick Merlon of 135 μ m (Mitsubishi's engineering plastics system: ユ-ピ ロ Application S2000), and B1 is the same with the test body.
Test body B15
Except making the esters resin layer of testing body B1 is the thick Merlon of 85 μ m (Mitsubishi's engineering plastics system: ユ-ピ ロ Application S2000), and B1 is the same with the test body.
Test body B16
Except the esters resin layer that makes test body B1 is that (Japanese Port リ ケ system system: ノ バ テ Star Network PPFY3), B1 is the same with the test body for the thick polypropylene of 330 μ m.
Test body B17
Except the esters resin layer that makes test body B1 is that (Japanese Port リ ケ system system: ノ バ テ Star Network PPFY3), B1 is the same with the test body for the thick polypropylene of 200 μ m.
Test body B18
Except the esters resin layer that makes test body B1 is that (Japanese Port リ ケ system system: TX1950), B1 is the same with the test body for the thick polypropylene of 350 μ m.
Test body B19
Except the esters resin layer that makes test body B1 is that (Japanese Port リ ケ system system: TX1950), B1 is the same with the test body for the thick polypropylene of 60 μ m.
Test body B20
Except the esters resin layer that makes test body B1 is that (bright dipping petrochemistry system: F3900), B1 is the same with the test body for the thick polypropylene of 380 μ m.
Test body B21
Except the esters resin layer that makes test body B1 is that (bright dipping petrochemistry system: F3900), B1 is the same with the test body for the thick polypropylene of 200 μ m.
Test body B22
Except the esters resin layer that makes test body B1 is that (bright dipping petrochemistry system: F3900), B1 is the same with the test body for the thick polypropylene of 60 μ m.
Test body B23
Except making the thick polystyrene (A﹠amp of esters resin layer 330 μ m of test body B1; M polystyrene system: HF77), B1 is the same with the test body.
Test body B24
Except making the thick polystyrene (A﹠amp of esters resin layer 60 μ m of test body B1; M polystyrene system: HF77), B1 is the same with the test body.
Evaluation test B
Test B1: anti-Du Pont impact test
Just 24 kinds the test body of adjusting carries out Du Pont's formula impact test from top layer material B side, measures the cup depth of respectively the testing body (unit: μ m), the relation of the rerum natura of cup depth and synthetic resin layer is studied of this moment.Du Pont's formula impact test is the same with evaluation test A1 carries out.
Its result finds relation shown in Figure 6 between the cup depth of each test body B and yield load.
That is, be difficult to see significant depression, cup depth is below the 450 μ m, and the synthetic resin layer of this moment is that yield point load is the above resin kind of 9kgf and the synthetic resin layer of thickness.
According to the chart of the relation of representing yield point load shown in Figure 7 and tensile elasticity rate, tensile elasticity rate is 50kgf/mm
2More than.
Chart according to the relation of yield point load shown in Figure 8 and yield extension, find that the yield extension rate is 3～8%, also be found difficult to see significant depression simultaneously, decorative layer is difficult to break, as this more preferably synthetic resin layer, be that yield point load is more than the 12kgf, the yield extension rate is the synthetic resin layer that 3～5% resin kind and thickness constitute, and has so far finished the present invention.In addition, the numeral of Fig. 6～8 records is numerals of test body B.In addition, among the figure ● expression is best as laminate for floor board material, ▲ expression is no problem on reality is used as laminate for floor board material, and * expression is improper when using as laminate for floor board material.
The adjustment of test body B2-1～B2-6
Carrying out the thick esters resin of the 400 μ m that use among the successful test body B2-0 in the above-mentioned test (Mitsubishi Chemical's system: NOVAPEX GM700) carry out pull and stretch on the layer as synthetic resin layer, with the top layer material B of other top layer material replacement as decorative layer, other 6 kinds of top layer materials and aforementioned resin layer are fitted respectively, obtain testing body B2-1～B2～6.
Test body B2-1
Carried out on the two sides on the one side of the thick painted polypropylene screen of 80 μ of Corona discharge Treatment the thick urethanes scratch coat of 2 μ m being set, on another side, formed the printed layers of wood grain style simultaneously with biliquid curable urethane class printing-ink.Then; on this urethanes scratch coat; be coated with dry ionizing radiation gel-type resin with the groove rolling method; so that reach the thickness of 15 μ m after the drying; form uncured electronic emission line gel-type resin layer; under the environment below the oxygen concentration 200PPM; to this uncured electronic emission line gel-type resin layer irradiation electron ray (accelerating potential 175KeV; exposure 5Mrad) makes it to solidify; the sealer that formation is made of electronic emission line gel-type resin; simultaneously in this sealer side; wood grain catheter-like embossing plate with the dark 50 μ m of version; execution embossing processing; make the top layer material that forms the concavo-convex style of wood grain catheter-like; on the printing aspect of this top layer material; by the urethane cementing agent; the thick esters resin of 400 μ m (Mitsubishi Chemical's system: layer NOVAPEX GM700) is set; simultaneously on this esters resin aspect; by water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system); the lauan veneer that applying 12mm is thick; further on aforementioned surfaces protection aspect; with the flowing on the parallel direction of wood grain style; pass through machining; with pitch 75mm; form wide 3.00mm, the V-shaped groove of dark 0.3mm is made the laminate for floor board material for test.
Test body B2-2
At common tissue paper (30g/m
2) a face on, use urethanes printing ink, form painted full flower-pattern layer successively, the pattern printed layers, the urethanes scratch coat, make the top layer material, on the non-printing surface of this top layer material, by the urethanes cementing agent, the thick esters resin of 400 μ m (Mitsubishi Chemical's system: layer NOVAPEX GM700) is set, simultaneously on this esters resin aspect, by water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system), the lauan veneer that applying 12mm is thick, further on aforementioned urethanes prime layer side, with the flowing on the parallel direction of wood grain style, pass through machining, with pitch 75mm, form wide 3.00mm, the V-shaped groove of dark 0.3mm, afterwards, on whole of the face of implementing machining, coating Port リ メ デ イ Star Network SKS-087 (2) (big Japanese ink chemical industry (strain) system) is so that reach 2.0g/900cm after the drying
2, irradiation ultraviolet radiation makes it to solidify simultaneously, forms scratch coat, and on this scratch coat, coating Port リ メ デ イ Star Network SKS-327Y (big Japanese ink chemical industry (strain) system) is so that reach 2.5g/900cm after the drying
2, irradiation ultraviolet radiation makes it to solidify simultaneously, forms floating coat, use thick loose sand (#400) to grind aforementioned floating coat face then, on this abradant surface, coating Port リ メ デ イ Star Network SK164-40A (big Japanese ink chemical industry (strain) system) is so that reach 1.2g/900cm after the drying
2, irradiation ultraviolet radiation makes it to solidify simultaneously, and coating in the formation is made the laminate for floor board material for test.
Test body B2-3
Except the thickness of the painted polypropylene screen that makes top layer material B is 100 μ m; the thickness of extruding of transparent propylene resin is outside the 100 μ m; make the top layer material the same with top layer material B; on the thick urethanes prime layer side of the 2 μ m that are provided with on the face of the aforementioned painted polypropylene screen of this top layer material; by the urethanes cementing agent; the thick esters resin of 400 μ m (Mitsubishi Chemical's system: layer NOVAPEX GM700) is set; simultaneously on this esters resin aspect; by water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system); the lauan veneer that applying 12mm is thick; further on aforementioned surfaces protection aspect, with the flowing on the parallel direction of wood grain style, pass through machining; with pitch 75mm; form wide 3.00mm, the V-shaped groove of dark 0.3mm is made the laminate for floor board material for test.
Test body B2-4
Except the thickness of the painted polypropylene screen that makes top layer material B is 150 μ m; the thickness of extruding of transparent propylene resin is outside the 150 μ m; make the top layer material the same with top layer material B; on the thick urethanes prime layer side of the 2 μ m that are provided with on the face of the aforementioned painted polypropylene screen of this top layer material; by the urethanes cementing agent; the thick esters resin of 400 μ m (Mitsubishi Chemical's system: layer NOVAPEX GM700) is set; simultaneously on this esters resin aspect; by water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system); the lauan veneer that applying 12mm is thick; further on aforementioned surfaces protection aspect, with the flowing on the parallel direction of wood grain style, pass through machining; with pitch 75mm; form wide 3.00mm, the V-shaped groove of dark 0.3mm is made the laminate for floor board material for test.
Test body B2-5
On the thick prominent plate of 0.2mm, by coating weight 5g/m
2Water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system), the thick esters resin of 400 μ m (Mitsubishi Chemical's system: layer NOVAPEX GM700) is set, simultaneously on this esters resin layer, by water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system), the lauan veneer that applying 12mm is thick, further with the flowing on the parallel direction of wood grain style, pass through machining, with pitch 75mm, form wide 3.00mm, behind the V-shaped groove of dark 0.3mm, on aforementioned prominent plate surface, coating Port リ メ デ イ Star Network SKS-088 (big Japanese ink chemical industry (strain) system) is so that reach 0.4g/900cm after the drying
2, irradiation ultraviolet radiation makes it to solidify simultaneously, forms the filling layer, and on this filling layer, coating ミ ラ ゾ-Le pigment (big Japanese ink chemical industry (strain) system) is so that reach 1.3g/900cm after the drying then
2, irradiation ultraviolet radiation makes it to solidify simultaneously, forms dyed layer, and on this dyed layer, coating Port リ メ デ イ Star Network SKS-087 (2) (big Japanese ink chemical industry (strain) system) is so that reach 2.0g/900cm after the drying
2, irradiation ultraviolet radiation makes it to solidify simultaneously, forms scratch coat, and on this scratch coat, coating Port リ メ デ イ Star Network SKS-327Y (big Japanese ink chemical industry (strain) system) is so that reach 2.5g/900cm after the drying
2, irradiation ultraviolet radiation makes it to solidify simultaneously, forms floating coat, use thick loose sand (#400) to grind aforementioned floating coat face then, on this abradant surface, coating Port リ メ デ イ Star Network SK164-40A (big Japanese ink chemical industry (strain) system) is so that reach 1.29g/900cm after the drying
2, irradiation ultraviolet radiation makes it to solidify simultaneously, and coating in the formation is made the laminate for floor board material for test.
Test body B2-6
On the thick prominent plate of 0.2mm, by coating weight 5g/m
2Water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system); the thick esters resin of 400 μ m (Mitsubishi Chemical's system: layer NOVAPEX GM700) is set; simultaneously on this esters resin layer; by water-soluble urethane emulsion binder (BA-10L of central physics and chemistry industry system); the lauan veneer that applying 12mm is thick; further with the flowing on the parallel direction of wood grain style; pass through machining; with pitch 75mm; form wide 3.00mm; behind the V-shaped groove of dark 0.3mm; on a face of the thick transparent polypropylene film of 80 μ m of the two sides Corona discharge Treatment of preparing in addition on the aforementioned prominent plate surface; the thick urethanes scratch coat of 2 μ m is set; on another side, use biliquid curable urethane class printing-ink simultaneously; after forming the printed layers of wood grain style; on aforementioned urethanes scratch coat; use the groove rolling method; be coated with dry ionizing radiation gel-type resin; so that it is thick to reach 15 μ m after the drying; form uncured electronic emission line gel-type resin layer; under the environment below the oxygen concentration 200PPM; to this uncured electronic emission line gel-type resin layer irradiation electron ray (accelerating potential 175KeV; exposure 5Mrad) makes it to solidify; the sealer that formation is made of electronic emission line gel-type resin; in this sealer side,, implement embossing processing simultaneously with the wood grain catheter-like embossing plate of the dark 50 μ m of version; by the urethanes cementing agent; fitting forms the sheet material of the concavo-convex style of wood grain catheter-like, so that printed layers is positioned at aforementioned prominent plate side, makes the laminate for floor board material for test.
6 kinds of test body B2-1～B2-6 for above-mentioned making, carry out Du Pont's formula impact test (sliding weight of steelyard: 500g from the decorative layer side, height of fall: 300mm, impact diameter: 6.3mm), measure the cup depth (unit: μ m) of respectively testing body B this moment, the crackle of while visual valuation decorative layer, its result concludes and is shown among the table B, makes curve simultaneously in Fig. 6.
Table B
Embodiment C
With regard to the 2nd mode of the present invention, describe with following Embodiment C.
The adjustment of decoration sheet
Carried out on the two sides on the one side of the thick painted polypropylene screen of 60 μ of Corona discharge Treatment the thick urethanes scratch coat of 2 μ m being set, on another side, formed the printed layers of wood grain style simultaneously with biliquid curable urethane class printing-ink.Then,,, transparent propylene resin is expressed on the aforementioned printed layers with T shape mould extruder by the urethanes cementing agent, so that thickness reaches 80 μ m, duplexer in the middle of making.Afterwards; on the aforementioned transparent propene resinoid face of aforementioned middle duplexer; form the thick urethanes scratch coat of 2 μ m; on this urethanes scratch coat; be coated with dry ionizing radiation gel-type resin with the groove rolling method; so that reach the thickness of 15 μ m after the drying; form uncured electronic emission line gel-type resin layer; under the environment below the oxygen concentration 200PPM; to this uncured electronic emission line gel-type resin layer irradiation electron ray (accelerating potential 175KeV; exposure 5Mrad) makes it to solidify; the sealer that formation is made of electronic emission line gel-type resin is simultaneously in this sealer side, with the wood grain catheter-like embossing plate of the dark 50 μ m of version; the decoration sheet that forms the concavo-convex style of wood grain catheter-like is made in execution embossing processing.
The adjustment of laminate for floor board material
Amorphism PETG (hereinafter referred to as amorphism PET) as sandwich layer, with T shape mould extruder, the hybrid resin of amorphism PET/ polyacrylate=50/50 (mass parts) is expressed on the two sides of this sandwich layer, so that the thickness ratio reaches 1/8/1, make the plastic sheet material of supplying with the thick synthetic resin layer of 0.4mm.Then, use polyester urethanes cementing agent, cosmetic sheet with aforementioned plastic sheet material and above-mentioned making, stacked with the dry type layered manner, make duplexer, by water-soluble urethanes emulsion binder, aforementioned plastic face of stacked this duplexer and the thick lauan veneer of 12mm, make laminate for floor board material of the present invention
Except using T shape mould extruder, the hybrid resin of amorphism PET/ PETG=60/40 (mass parts) is expressed on the two sides of amorphism PET, so that the thickness ratio reaches 1/14/1, use outside the thick plastic sheet material of 0.4mm, the same with embodiment 1, make laminate for floor board material of the present invention.
Except that the plastic sheet material that uses the thick polybutylene terephthalate of 0.4mm, the same with embodiment 1, make laminate for floor board material of the present invention.
Example C1
Except that the plastic sheet material that uses the thick amorphism PET of 0.4mm, the same with embodiment 1, make laminate for floor board material as a comparative example.
Example C2
By water-soluble urethanes emulsion binder, the lauan veneer that the decoration sheet of above-mentioned making and 12mm is thick is stacked, to expose the sealer of this decoration sheet, makes laminate for floor board material as a comparative example.
Evaluation test C
Carry out following evaluation test, it the results are shown among the table C.
Test C1: anti-shrinkage is now as evaluation
For the laminate for floor board material of embodiment 1～comparative example 2, to preserve 24 hours in 80 ℃ the thermostat (A) 60 ℃ with (B), there is the pucker-free phenomenon on visual assessment decorative layer surface.
Metewand is as described below.
Estimate A: the pucker-free phenomenon
Estimate B: some shrinkage phenomenons are arranged
Estimate C: the shrinkage phenomenon is arranged
Test C2: caster-resistant and Du Pont's resistance to impact test
For the laminate for floor board material of embodiment 1～comparative example 2, carry out anti-caster test and resistance to impact test.That puts down in writing in test method and the embodiment A is the same.The cup depth of the evaluating and measuring laminate for floor board material of two tests (μ m).
Test C3: physical property measurement test
Be determined at the plastic sheet material that uses in the laminate for floor board material of embodiment 1～comparative example 2 or the various physics values of decoration sheet, specifically measure pin and go into temperature (unit: ℃), yield point load (unit: kgf), tensile elasticity rate (unit: kgf/mm
2), yield extension rate (unit: %).
Table C
Embodiment D
With regard to the 3rd mode of the present invention, describe with following embodiment D.
Embodiment D1
(1)
The making of decorative layer
Carried out on the two sides on the one side of the thick painted polypropylene screen (base material) of 60 μ of Corona discharge Treatment the thick urethanes scratch coat of 2 μ m being set, on another side, formed the printed layers of wood grain style simultaneously with biliquid curable urethane class printing-ink.Then, by the urethanes cementing agent, with T shape mould extruder, the transparent resin bed that transparent propylene resin is constituted is expressed on the design layer, so that thickness reaches 80 μ m, and duplexer in the middle of making.Afterwards; on the transparent resin aspect of aforementioned middle duplexer; form the thick urethanes scratch coat of 2 μ m; on this urethanes scratch coat; be coated with dry ionizing radiation gel-type resin with the groove rolling method; so that reach the thickness of 15 μ m after the drying; form uncured electronic emission line gel-type resin layer; under the environment below the oxygen concentration 200PPM; to this uncured electronic emission line gel-type resin layer irradiation electron ray (accelerating potential 175KeV; exposure 5Mrad) makes it to solidify; the sealer that formation is made of electronic emission line gel-type resin is then from the sealer side, with the wood grain catheter-like embossing plate of the dark 50 μ m of version; the decoration sheet (decorative layer) that forms the concavo-convex style of wood grain catheter-like is made in execution embossing processing.
(2)
The making of synthetic resin layer
Amorphism PETG (hereinafter referred to as amorphism PET) as sandwich layer, on the two sides of this sandwich layer, with the coextrusion of T shape mould extruder, to become the structure (thickness of mixed layer/sandwich layer/mixed layer is than=1/8/1) of carrying secretly, make the thick synthetic resin sheet material (synthetic resin layer) of 0.4mm by the mixed layer of amorphous PET/PETG=60/40.
(3)
Synthetic resin layer and decorative layer stacked
On the back side (urethanes scratch coat) of the decoration sheet of aforementioned (1), use the urethanes cementing agent, carry out stackedly with the dry type layered manner, obtain decorative sheet for floor material.
(4)
The making of flooring material
The sheet material that use obtains in aforementioned (3), by water-soluble urethanes emulsion binder, the synthetic resin sheet face of stacked this sheet material and lauan veneer (thickness 12mm) are made flooring material of the present invention.
Example D1
Except as the A-PET individual layer of synthetic resin layer and embodiment 1, make decoration sheet and flooring material.
Example D2
Except as the PETG individual layer of synthetic resin layer and embodiment 1, make decoration sheet and flooring material.
Evaluation test D
For the decoration sheet of the formation of embodiment E 1～example 2 with above-mentioned making, the peel strength between research synthetic resin layer and the decorative layer.Test method is carried out in the following order, and it the results are shown among the table E.
(1) pre-treatment
Each synthetic resin layer is left standstill under the condition of-10 ℃, 8 ℃, 25 ℃, 40 ℃, 60 ℃, 70 ℃ and 80 ℃, will move under the normal temperature environment through the synthetic resin layer of 48 hours or 7 days.
(2) and decorative layer stacked
On a face of decorative layer, behind the urethanes scratch coat of formation thickness 2 μ m, further use the urethanes cementing agent, with dry type layered manner (70 ℃), stacked with synthetic resin layer.After dry type is stacked, at normal temperatures, through the duplexer of maintenance in 5 days as the test body.
(3) disbonded test
With electronic stripping tester (goods name " RTC1210-A " オ リ Application テ Star Network system), the synthetic resin layer and the decorative layer of each test body are peeled off, measure its peel strength.
Table D
Unit is the N/25m ware width of cloth
(★) refer to find splitting.
With regard to the 4th mode of the present invention, describe with following embodiment E.
The preparation of decoration sheet
On a face of the painted polypropylene screen of 60 μ m of two sides Corona discharge Treatment, use the groove rolling method, coating urethane cellulosic resin (with respect to mixture 100 weight portions of urethane and nitrocotton, interpolation hexamethylene diisocyanate 5 weight portions obtain) is so that solid content is 2g/m
2, form back side scratch coat.On another side, use the groove rolling method, coating acryloyl group urethanes resin (obtaining toward acryloyl group polyalcohol 100 weight portions interpolation hexamethylene diisocyanate 5 weight portions) is so that solid content is 2g/m
2, form the printing scratch coat.
Secondly; use the printing-ink of acryloyl group urethanes resin (obtaining) as adhesive toward acryloyl group polyalcohol 100 weight portions interpolation hexamethylene diisocyanate 5 weight portions; by intaglio printing; form full ink lay and decorative pattern ink lay successively, and form the design layer of wood grain and abstract style.
Then, behind coating urethanes cementing agent on the design layer, use T shape mould extruder from it, heating and melting is extruded propylene resin, so that thickness is 80 μ m, forms transparent resin bed.
Above-mentioned transparent resin bed is implemented Corona discharge Treatment; on its treated side; use the groove rolling method, coating acryloyl group urethanes resin (obtaining toward acryloyl group polyalcohol 100 weight portions interpolation hexamethylene diisocyanate 5 weight portions) forms the sealer scratch coat.
Sealer with scratch coat on, with rolling method coating, dry urethane acrylate electron-like ray curing resin, so that solid content is 15g/m
2After, under the environment below the oxygen concentration 200PPM, uncured electronic emission line gel-type resin layer irradiation electron ray (accelerating potential 175KeV, exposure 5Mrad) made it to solidify, form the sealer that constitutes by electronic emission line gel-type resin.
Then,,, implement embossing processing, obtain forming the decorative layer of the abstract concavo-convex style of wood grain catheter-like or wood grain skin texture with wood grain catheter-like embossing plate or the abstract embossing plate of wood grain skin texture of the dark 50 μ m of version from the sealer side.
The preparation of synthetic resin layer
Amorphism PETG (A-PET) as sandwich layer, on its two sides, with T shape mould extruder, coextrusion A-PET60 weight % and poly-hybrid resin layer to (ethylene naphthalate) 40 weight %, to reach the thickness ratio of hybrid resin layer/sandwich layer/hybrid resin layer=1/14/1, obtain the synthetic resin sheet material (synthetic resin layer) of thickness 0.4mm.
Synthetic resin layer and decorative layer stacked
At the back side of decorative layer, further by the urethanes adhesive layer, with the stacked synthetic resin layer of dry type layered manner.Manufacture of Floor material decoration sheet.
The preparation of laminate for floor board material
On the synthetic resin aspect of the decorative sheet for floor material of aforementioned (3), by the stacked gummed version of water-soluble emulsion class cementing agent (thickness 12mm), the size that is cut into regulation is (behind the 300mm * 1800mm), use dovetailer, four limits are processed, further form the V-shape groove (bar slot part) that arrives the degree of depth of gummed version from the decorative layer side in long dimensional directions of seeing and short dimensional directions from the flooring material plane.Coating biliquid curable urethane class coloring pigment by smearing processing, forms coating layer at bar slot part and chamfered section simultaneously on V-shape groove that forms and chamfered section whole.So make required flooring material.
Example E1
Except the bar slot part does not reach the lauan veneer, form outside the bar slot part of the degree of depth that runs through synthetic resin layer, the same with embodiment 1, the Manufacture of Floor material.
Evaluation test E
Test E1: anti-warpage properties test
For the flooring material of making among embodiment E 1 and the routine E1, measure its " amount of warpage ".For assay method, each flooring material under the condition of 35 ℃ of humidity 60%RH of temperature, is placed after 7 days, and the warpage of further placing under the condition of 0 ℃ of humidity 30%RH after 7 days is compared with the state before the test, measure maximum warpage length, it the results are shown among the following table E.
Table E
Embodiment F
Another optimal way for the 4th mode of the present invention describes with following embodiment F.
Production Example F1
The preparation of water paint
Cooperate, mix each composition; to reach the about 31 weight % (solid content) of acryloyl group urethanes resin (the big Japanese ink chemical industry of goods name " Port Application コ-ト CG-5000 ", urethane/acryloyl group complex emulsions), the about 7 weight % of filler pigment (silica), silicon 2 weight %, isopropyl alcohol 5 weight % and water 54 weight %.On the other hand,, will mix, its 20 weight portion is mixed with aforementioned mixture 100 weight portions as the isocyanates PIC and the water of curing compound with 1: 1 (weight ratio).Obtain the water paint that constitutes by water-based emulsion thus.
Production Example F2
The making of flooring material
Be produced on the decoration sheet that uses in the decorative layer earlier.
(1) making of decoration sheet
On a face of the painted polypropylene screen of 60 μ m of two sides Corona discharge Treatment, use the groove rolling method, coating urethane cellulosic resin (with respect to mixture 100 weight portions of urethane and nitrocotton, interpolation hexamethylene diisocyanate 5 weight portions obtain) is so that solid content is 2g/m
2, form back side scratch coat.On another side, use the groove rolling method, coating acryloyl group urethanes resin (obtaining toward acryloyl group polyalcohol 100 weight portions interpolation hexamethylene diisocyanate 5 weight portions) is so that solid content is 2g/m
2, form the printing scratch coat.
Secondly; use the printing-ink of acryloyl group urethanes resin (obtaining) as adhesive toward acryloyl group polyalcohol 100 weight portions interpolation hexamethylene diisocyanate 5 weight portions; by intaglio printing; form full ink lay and decorative pattern ink lay successively, and form the design layer of wood grain and abstract style.
Then, behind coating urethanes cementing agent on the design layer, use T shape mould extruder from it, heating and melting is extruded propylene resin, so that thickness is 80 μ m, forms transparent resin bed.
Above-mentioned transparent resin bed is implemented Corona discharge Treatment; on its treated side; use the groove rolling method, coating acryloyl group urethanes resin (obtaining toward acryloyl group polyalcohol 100 weight portions interpolation hexamethylene diisocyanate 5 weight portions) forms the sealer scratch coat.
Sealer with scratch coat on, with rolling method coating, dry urethane acrylate electron-like ray curing resin, so that solid content is 15g/m
2After, under the environment below the oxygen concentration 200PPM, uncured electronic emission line gel-type resin layer irradiation electron ray (accelerating potential 175KeV, exposure 5Mrad) made it to solidify, form the sealer that constitutes by electronic emission line gel-type resin.
Then,,, implement embossing processing, obtain forming the decorative layer of the abstract concavo-convex style of wood grain catheter-like or wood grain skin texture with wood grain catheter-like embossing plate or the abstract embossing plate of wood grain skin texture of the dark 50 μ m of version from the sealer side.
(2) making of synthetic resin layer
Amorphism PETG (A-PET) as sandwich layer, on its two sides, with T shape mould extruder, coextrusion A-PET60 weight % and poly-hybrid resin layer to (ethylene naphthalate) 40 weight %, to reach the thickness ratio of hybrid resin layer/sandwich layer/hybrid resin layer=1/14/1, obtain the synthetic resin sheet material (synthetic resin layer) of thickness 0.4mm.
(3) synthetic resin layer and decorative layer is stacked
On the scratch coat of the back side of decorative layer, further by the urethanes adhesive layer, with the stacked synthetic resin layer of dry type layered manner.Manufacture of Floor material decoration sheet.
(4) making of flooring material
On the synthetic resin aspect of the decorative sheet for floor material of aforementioned (3), by the stacked gummed version of water-soluble emulsion class cementing agent (thickness 12mm), the size that is cut into regulation is (behind the 300mm * 1800mm), use dovetailer, four limits are processed, further form the V-shape groove (bar slot part) that arrives the degree of depth of gummed version from the decorative layer side in long dimensional directions of seeing and short dimensional directions from the flooring material plane.In addition, the side surface part of the long dimensional directions of seeing from the flooring material plane forms chamfered section.
The water paint that use obtains in Production Example 1, coating on the V-shape groove of the flooring material of Production Example 2 and chamfered section whole by smearing processing, forms coating layer at bar slot part and chamfered section simultaneously.
Example F1
Except using commercially available water-based urethane coating as water paint, the same with embodiment 1, form coating layer.
Evaluation test F
For the coating layer that in embodiment F 1 and routine F1, forms, respectively with regard to 1) water resistance, 2) humidity resistance, 3) anti-thinner, 4) acid resistance, 5) alkali resistance, 6) fitness test, 7 of セ ロ テ-プ (trade (brand) name)) atmospheric corrosion resistance studies.
1) Water Resistance Test:
Carry out the Kapp permeability test.Make the test body contact 144 hours with water droplet, remove water droplet after, the outward appearance of validation test body has no change.Do not find cosmetic variation as certified products.
2) humidity resistance test:
Implement the JAS damp heat test.After will testing the body horizontal fixed, drip boiled water, place it in the aluminium vessel of the 1L capacity of having poured the 0.5L boiled water into 20 minutes,, under this state, placed 24 hours with dry cloth friction toward the test surface.After 24 hours, confirm that outward appearance has no change.Do not find cosmetic variation as certified products.
3) anti-thinner test:
Behind the slot part surface dropping thinner of test body, place after 4 hours, confirm that outward appearance has no change.Do not find cosmetic variation as certified products.
4) acid resisting test:
Behind slot part surface dropping 10% aqueous hydrochloric acid solution of test body, place after 4 hours, confirm that outward appearance has no change.Do not find cosmetic variation as certified products.
5) alkaline resistance test:
Behind slot part surface dropping 10% sodium hydrate aqueous solution of test body, place after 4 hours, confirm that outward appearance has no change.Do not find cosmetic variation as certified products.
6) fitness test of セ ロ テ-プ (trade (brand) name):
On filming, press sticking セ ロ テ-プ (ニ チ バ Application system), peel in vertical direction, almost can not peel as certified products.
7) atmospheric corrosion resistance test:
Exposure to Sunlight weather color fastness instrument irradiation 500 hours, observing outward appearance has no change.Do not find cosmetic variation as certified products.
The evaluation test result
With all qualified opposite of all items in embodiment F 1, all defective in all items in routine F1.
Claims (16)
1. flooring material sheet material is the flooring material sheet material that is made of synthetic resin layer and the decorative layer that forms thereon, it is characterized in that,
Described synthetic resin layer constitutes by being divided into 2 above distinct area,
Described decorative layer has substrate layer, all print layer, design layer and sealer.
2. flooring material sheet material according to claim 1 is characterized in that, described synthetic resin layer has individual layer or the layer structure more than 2 layers,
When described synthetic resin layer is individual layer, described individual layer is formed by amorphism PETG and pet copolymer, perhaps described synthetic resin layer is more than 2 layers the time, its at least one deck form by amorphism PETG and pet copolymer
The part of the ethylene glycol of described pet copolymer is by 1, and the 4-cyclohexanedimethanol replaces.
3. flooring material sheet material according to claim 1 is characterized in that, described synthetic resin layer has the layer structure more than 3 layers,
The superiors and the orlop of described layer structure more than 3 layers are formed by amorphism PETG and pet copolymer,
The part of the ethylene glycol of described pet copolymer is by 1, and the 4-cyclohexanedimethanol replaces.
4. flooring material sheet material according to claim 1 is characterized in that, is clipped in the middle sandwich layer of the described the superiors and described orlop and is formed by the amorphism PETG.
5. according to each described flooring material sheet material in the claim 1～4, it is characterized in that, with respect to the gross weight of described amorphism PETG and described pet copolymer, the content of described pet copolymer is 20～80 weight %.
6. according to each described flooring material sheet material in the claim 1～4, it is characterized in that described synthetic resin layer and described decorative layer are by urethanes adhesive layer and/or the stacked formation of urethanes scratch coat.
7. according to each described flooring material sheet material in the claim 1～4, it is characterized in that the thickness of described synthetic resin layer is more than the 200 μ m.
8. laminate for floor board material, on wood substrate in the stacked claim 1～7 each described flooring material constitute with sheet material.
9. laminate for floor board material according to claim 8 is characterized in that, by the groove that arrives wood substrate from the decorative layer side is set, described synthetic resin layer and described decorative layer is divided into 2 above distinct area respectively.
10. the described laminate for floor board material of claim 9; it is characterized in that; with containing the coating of the resinoid waterborne compositions of acryloyl group urethane by described division place that described synthetic resin layer is divided into 2 above distinct area and exposes with respectively described synthetic resin layer and described decorative layer are divided into described division place separately that 2 above isolated areas expose.
11. the described laminate for floor board material of claim 10 is characterized in that, contained acryloyl group urethanes resin is made of acrylic resin that contains ketone group and the mixture that contains the urethane resin of hydrazide group in the described waterborne compositions.
12. the described laminate for floor board material of claim 10 is characterized in that described waterborne compositions further contains curing compound.
13. the described laminate for floor board material of claim 10 is characterized in that described waterborne compositions further contains silicon.
14. the described laminate for floor board material of claim 10 is characterized in that described waterborne compositions is an emulsion form.
15. laminate for floor board material according to claim 9 is characterized in that, use therein waterborne compositions contains acryloyl group urethanes resin.
16. laminate for floor board material according to claim 8 is characterized in that, the result of the anti-caster test of carrying out on the surface of the decorative layer side of described laminate for floor board material is, the described depression in the surface degree of depth is below the 100 μ m,
The test of described anti-caster use be equipped with rotatable castor fixed part, 3 castors on described castor fixed part, installing, the portion that increases the weight of that is connected with described castor fixed station and the anti-caster experimental rig of sample fixed station, the following test,
Described laminate for floor board material is fixed on the described sample fixed station,
By the described portion that increases the weight of, make described 3 castors increase the weight of to contact with the surface of decorative layer one side of described laminate for floor board material,
Start described castor fixed part, make described 3 castors after rotation on the surface of the decorative layer side of described laminate for floor board material,
Be determined at the degree of depth of the depression that produces on the described surface,
The average diameter 75mm of described castor, thickness 25mm,
Surface to the cosmetic side of described laminate for floor board material applies weight, is 70kg,
Described 3 castors rotate 1000 times with the speed of 20rpm counter-rotating in per 5 minutes 1 time.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003094612 | 2003-03-31 | ||
| JP94612/2003 | 2003-03-31 | ||
| JP338646/2003 | 2003-09-29 | ||
| JP338642/2003 | 2003-09-29 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100332338A Division CN1537719A (en) | 2003-03-31 | 2004-03-31 | Laminate for floor board material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1796701A CN1796701A (en) | 2006-07-05 |
| CN100529300C true CN100529300C (en) | 2009-08-19 |
Family
ID=36817995
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101370100A Expired - Lifetime CN100529300C (en) | 2003-03-31 | 2004-03-31 | Laminated wood for floor member |
| CNB2005101318008A Expired - Fee Related CN100504008C (en) | 2003-03-31 | 2004-03-31 | Laminate for floor member |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101318008A Expired - Fee Related CN100504008C (en) | 2003-03-31 | 2004-03-31 | Laminate for floor member |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN100529300C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102624352B (en) * | 2010-10-06 | 2015-12-09 | 日本碍子株式会社 | The manufacture method of composite base plate and composite base plate |
| JP6026647B2 (en) * | 2012-05-08 | 2016-11-16 | アーベー グスタフ ケール | Core, panel blank, floor panel and manufacturing method thereof |
| BE1020722A3 (en) | 2012-06-01 | 2014-04-01 | Unilin Bvba | PANEL FOR FORMING A FLOOR COVERING AND METHOD FOR MANUFACTURING SUCH PANELS. |
| FR3033282B1 (en) * | 2015-03-06 | 2017-03-24 | Gerflor | MULTILAYER FLOOR COATING |
| BE1025875B1 (en) * | 2018-01-04 | 2019-08-06 | Unilin Bvba | Methods for manufacturing panels |
| CN111058592A (en) * | 2019-12-31 | 2020-04-24 | 浙江上臣家居科技有限公司 | All-round king-shaped solid wood composite floor and processing technology |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123647A (en) * | 1999-10-29 | 2001-05-08 | Dainippon Printing Co Ltd | Decorative material for floor material and its manufacturing method |
-
2004
- 2004-03-31 CN CNB2005101370100A patent/CN100529300C/en not_active Expired - Lifetime
- 2004-03-31 CN CNB2005101318008A patent/CN100504008C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123647A (en) * | 1999-10-29 | 2001-05-08 | Dainippon Printing Co Ltd | Decorative material for floor material and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1796701A (en) | 2006-07-05 |
| CN100504008C (en) | 2009-06-24 |
| CN1796700A (en) | 2006-07-05 |
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