CN1754692A - Floor material decorative board with excellent impact and scratch resistance - Google Patents

Floor material decorative board with excellent impact and scratch resistance Download PDF

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Publication number
CN1754692A
CN1754692A CNA2005101056293A CN200510105629A CN1754692A CN 1754692 A CN1754692 A CN 1754692A CN A2005101056293 A CNA2005101056293 A CN A2005101056293A CN 200510105629 A CN200510105629 A CN 200510105629A CN 1754692 A CN1754692 A CN 1754692A
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Prior art keywords
layer
transparent
polypropylene
resin layer
based resin
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CN1754692B (en
Inventor
松川康宏
增田洋史
中山宽章
木村贤
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2471/00—Floor coverings

Abstract

To provide a decorative sheet for flooring material which exerts excellent impact resistance without forming a backer layer and also excellent scratch resistance. This decorative sheet for flooring material is produced by forming respective layers of a picture pattern, a transparent adhesive, a transparent polypropylene-based resin and a transparent surface-protective layer comprising an ionizing radiation-curing resin or two-pack curing urethane-based resin in this order on a substrate sheet made of a polyolefin-based resin, and is characterized in that: (1) the transparent polypropylene-based resin layer is >=150 [mu]m in thickness; (2) its universal hardness is >=35 N/mm<SP>2</SP>; and (3) that of the transparent surface-protective layer is >=100 N/mm<SP>2</SP>.

Description

The floor material decorative board of resistance to impact and scratch-resistant excellence
Technical field
The present invention relates to the floor material decorative board of impact resistance and mar-proof performance excellence.
Background technology
At present, as the constituent material of resinous floor material decorative board, use vinylchloride resin plate mostly.When using vinylchloride resin plate, by regulating the addition of plasticizer, the hardness of adjustable plate (hard～soft), and the easy in addition advantage of implementing the processing of impression embossment easily.
But Corvic can be emitted harmful graphite, chlorine class gas etc. when burning, therefore, in recent years, uses the polyalkenes hydrocarbon resins of not emitting chlorine class gas to replace Corvic gradually.
As the floor decorative panel that uses the polyalkenes hydrocarbon resins, for example, open in the flat 8-1883 communique Japanese patent laid-open 8-13740 communique and spy and to disclose, on the sark layer that forms by the polyalkenes hydrocarbon resins, lamination forms the printed panel of printing flower-pattern layer and bottom successively on single face, the transparent panel that lamination is made of ionomer resin on printed panel again, the floor material decorative board of 3 layers of making constituting by sark layer/printed layers/transparent panel of lamination simultaneously.The sark layer of this floor material decorative board is bonded in various being connect has just formed decorating material for flooring on the material.In addition, the sark layer is the enhancement layer that is provided with in order to give hardness, intensity etc. to floor material decorative board.
Floor material decorative board with sark layer shows hardness, intensity of regulation etc. easily, brings into play outstanding impact resistance.
But, have the floor material decorative board of sark layer, need in manufacturing process the sark layer segment is bonded on part beyond it that () operation for example, printed panel is easy to generate the problem of product defects (product loss) in this operation.
Therefore, wish to develop the hardness that when not forming the sark layer, also possesses regulation, intensity etc., bring into play the floor material decorative board of outstanding impact resistance.
Except outstanding impact resistance, also require further to improve mar-proof performance (marresistance energy) now.This be because, in the existing glued board earth material, because the scratch that tenon processing, ditch processing etc. produce, indenture etc., (sanding) almost can eliminate by sand milling, and can not implement sand milling in the flooring board that bonding decorative panel forms on by adhesive sheet, therefore, because processing etc. are gone up the scar that the scar that generates can become final products on surface (decorative cover).
Summary of the invention
Main purpose of the present invention provides a kind of floor material decorative board, and it also brings into play outstanding impact resistance and outstanding mar-proof performance when not forming the sark layer.
The present inventor has carried out concentrating on studies repeatedly in order to achieve the above object, found that by forming specific polypropylene-based resin and sealer to achieve the above object, thereby has finished the present invention.
That is, the present invention relates to the following decorating material for flooring that has the floor material decorative board of outstanding impact resistance and mar-proof performance and use this decorative panel.
1. floor material decorative board; on the backing material plate that constitutes by the polyalkenes hydrocarbon resins; form design pattern layer, transparent bond layer, transparent polypropylene-based resin layer successively, reach the transparent sealer that constitutes by ionizing radiation gel-type resin or two solution curing type carbamate resinoids, it is characterized in that:
(1) thickness of transparent polypropylene-based resin layer is more than the 150 μ m,
(2) universal hardness of transparent polypropylene-based resin layer is 35N/mm 2More than,
(3) universal hardness of transparent sealer is 100N/mm 2More than.
2. floor material decorative board; on the backing material plate that constitutes by the polyalkenes hydrocarbon resins; form design pattern layer, transparent bond layer, transparent polypropylene-based resin layer successively, reach the transparent sealer that constitutes by ionizing radiation gel-type resin or two solution curing type carbamate resinoids, it is characterized in that:
(1) transparent polypropylene-based resin layer is made of for 2 layers upper strata acrylic resin layer and lower floor's acrylic resin layer,
(2) thickness of upper strata acrylic resin layer is more than the 100 μ m,
(3) universal hardness of upper strata acrylic resin layer is 35N/mm 2More than,
(4) thickness of lower floor's acrylic resin layer is more than the 50 μ m,
(5) universal hardness of lower floor's acrylic resin layer is 20N/mm 2More than,
(6) universal hardness of transparent sealer is 100N/mm 2More than.
3. above-mentioned 2 described floor material decorative boards is characterized in that, the thickness of upper strata acrylic resin layer is 100～300 μ m.
4. above-mentioned 1～3 each described floor material decorative board is characterized in that, also is formed with painted hidden layer between backing material plate and design pattern layer.
5. above-mentioned 1～4 each described floor material decorative board is characterized in that, is formed with concavo-convex on the interarea of transparent sealer.
6. a decorating material for flooring is characterized in that, with the backing material plate side bonds of above-mentioned 1～5 each described floor material decorative board on by adhesives.
Description of drawings
Fig. 1 is the schematic diagram of the decorating material for flooring of making among the embodiment 1.
Fig. 2 is the schematic diagram of the decorating material for flooring of making among the embodiment 3.
Symbol description
1 transparent sealer; 2 transparent polypropylene-based resin layers (being the upper strata polypropylene layer in Fig. 2); 3 design pattern layers and transparent bond layer; 4 backing material plates; 5 bond layers; 6 lauan glued boards; 7 lower floor's polypropylene layers.
The specific embodiment
Below, describe floor material decorative board of the present invention and decorating material for flooring in detail.
Floor material decorative board
Floor material decorative board of the present invention is; on the backing material plate that constitutes by the polyalkenes hydrocarbon resins; form design pattern layer, transparent bond layer, transparent polypropylene-based resin layer successively, and, it is characterized in that by the floor material decorative board that the transparent sealer that ionizing radiation gel-type resin or two solution curing type carbamate resinoids constitute is formed:
(1) thickness of transparent polypropylene-based resin layer is more than the 150 μ m,
(2) universal hardness of transparent polypropylene-based resin layer is 35N/mm 2More than,
(3) universal hardness of transparent sealer is 100N/mm 2More than.
(backing material plate)
Use the plate that constitutes by polypropylene-based resin as backing material plate.Usually use the film that constitutes by polypropylene-based resin to get final product.
Be not particularly limited as polypropylene-based resin, can use at the normally used material in decorative panel field.For example, can enumerate that polyethylene, polypropylene, rare, the poly-methylpent of poly-fourth are rare, the rare copolymer of ethene-third, ethene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethene-third be rare-the rare copolymer of Ding, polyalkenes hydro carbons thermoplastic elastomer (TPE) etc.Wherein, special optimization polypropylene, polyalkenes hydro carbons thermoplastic elastomer (TPE) etc.
Also preferred is the homopolymers or the copolymer of main component with the polypropylene, for example can enumerate equal polypropylene resin, random polypropylene resin, block polypropylene resin and contain crystalling propylene portion and the alpha-olefin of third rare carbon number 2～20 in addition.In addition, also preferably contain ethene, the 1-fourth is rare, the 4-methyl-1-pentene is rare, third rare-alpha-olefin copolymer that oneself 15 moles of % of comonomer rare or the 1-octene of 1-are above etc.
Polyalkenes hydro carbons thermoplastic elastomer (TPE) is, using high crystalline and dystectic aromatic polyester on the hard segment, using the block polymer of the amorphism polyethers below the glass transition temperature-70 ℃ on the soft segment.Preferred especially, hard segment that will constitute by isotactic polypropylene and the soft segment that constitutes by random polypropylene, the material that mixes at 80: 20 with weight ratio.
The polyalkenes hydrocarbon resins makes the film shape and gets final product with rolling process, plavini, T mould extrusion molding.
The thickness of backing material plate is not particularly limited, and can set according to product performance, is generally 40～150 μ m, is preferably about 50～100 μ m.
Can cooperate additive as required in the backing material plate.For example can enumerate fillers such as calcium carbonate, clay as additive, fire retardants such as magnesium hydroxide, antioxidant, lubrication prescription, blowing agent, colouring agent (with reference to following) etc.The combined amount of additive can suitably be set according to product performance.
Be not particularly limited as colouring agent, can use known colouring agents such as pigment, dyestuff.For example can enumerate inorganic pigments such as titanium white, zinc white, di-iron trioxide, cinnabar (vermilion), ultramarine, cobalt blue (cobalt blue), titan yellow, chrome yellow, carbon black; Isoindoline ketone (isoindolinone), hansa yellow-A, quinacridone (quinacridone), permanent red 4R (permanent red 4R), phthalocyanine blue (phthalocyanine blue), indanthrene blue RS (Indanthrene blue RS), nigrosine organic pigments (also comprising dyestuff) such as (aniline black); Metallic pigments such as aluminium, brass: pearly luster (pearl) pigment that titanium dioxide covering mica, basic lead carbonate etc. are made of the paper tinsel powder etc.The coloring mode of backing material plate has transparent painted and opaque coloured (hidden painted), can select arbitrarily therein.For example, will be painted when hidden by the background color of adhesives (base material of bonding ornament materials), select opaque painted getting final product.On the other hand, want with the naked eye to see ground patterns, select transparent painted getting final product by adhesives.
On the single face or two sides of backing material plate, also can implement surface treatments such as Corona discharge Treatment, ozone treatment, plasma treatment, ionizing radiation processing, dichromic acid processing as required.For example, when carrying out Corona discharge Treatment, the surface tension that makes the backing material plate surface is above the getting final product of above, the preferred 40dyne of 30dyne.Surface treatment gets final product according to the conventional method of various processing.
On the single face or two sides of backing material plate, bottom also can be set as required (for example, make by the bonding the inside bottom that carries out easily of adhesives; The bottom that the design pattern layer is formed easily).By bottom is set, can improve interlayer bonding force with adjoining course (for example, by adhesives).
Bottom can be by known silane coupling agent being coated on backing material plate single face or the two sides on form.As silane coupling agent, for example can enumerate, the carbamates silane coupling agent that constitutes by acrylic acid modified carbamate resins, the silane coupling agent that constitutes by carbamate-cellulosic resin (for example, in the mixture of carbamate and nitrated silk floss, adding the resin that hexamethylene diisocyanate constitutes) etc.
The coating weight of silane coupling agent is not particularly limited, and is generally 0.1～100g/m 2, be preferably 0.1～50g/m 2About.
The thickness of priming coat is not particularly limited, and is generally 0.01～10 μ m, is preferably about 0.1～1 μ m.
(design pattern layer)
On backing material plate (with by the opposing face of the bonding plane of adhesives, in following each layer, all refer to an identical therewith side) be formed with the design pattern layer.
That it is had is ornamental by pay desired pattern to decorative panel for the design pattern layer, and the kind of pattern etc. is not particularly limited.For example, can enumerate grain pattern, bag pattern, sand streak pattern, tiling pattern, heap brick pattern, woven design pattern, leather pattern, geometrics, literal, symbol, abstract design etc.
The formation method of design pattern layer is not particularly limited, for example, use known colouring agent (dyestuff or pigment) and adhesives resin in solvent (or decentralized medium), to dissolve painted China ink, smears that (or dispersion) obtains together, utilize print process to form and get final product.
For example can enumerate carbon black, titanium white, zinc white, di-iron trioxide, Prussian blue (prussian blue), cadmium red inorganic pigments such as (cadmium red) as colouring agent; Organic pigments such as AZOpigments, color lake class dyestuff, anthraquinone (anthraquinone) pigment, quinacridone (quinacridone) pigment, phthalocyanine (phthalocyanine) pigment, isoindoline ketone (isoindolinone) pigment, dioxazine (dioxazine) pigment; Metal powder pigment such as aluminium powder, bronze powder; Titanium oxide covers pearlescent pigments such as mica, bismoclite; Fluorescent pigment; Phosphorescent pigment etc.These colouring agents can use separately, also can mix two or more uses.Can also cooperate filler, Bio-Glas extender pigment, nertralizer, surfactants etc. such as (organic beads) such as silica in these colouring agents again.
As adhesive resin, for example can enumerate acrylic resin, styrene resin, mylar, carbamate resinoid, chlorination polyalkenes hydrocarbon resins, vinyl chloride-vinyl acetate copolymer resinoid, polyvinyl butyral resin, alkyd based resin, petroleum resinoid, ketone resin, epoxy resin, melmac, fluororesin, silicones, cellulose derivative, rubber resin etc.These resins can use separately, also can mix two or more uses.
As solvent (or dispersant), for example can enumerate petroleum-type organic solvents such as hexane, heptane, octane, toluene, dimethylbenzene, ethylo benzene, cyclohexane, hexahydrotoluene; Ester class organic solvents such as ethyl acetate, butyl acetate, acetic acid-2-methoxy-ethyl ester, acetic acid-2-ethoxy-ethyl ester; Alcohol organic solvent such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, isobutanol, ethylene glycol, propane diols; Organic solvent of ketone such as acetone, butanone, methylisobutylketone, cyclohexanone; Ether organic solvents such as diethyl ether, diox, oxolane; Chlorine class organic solvents such as carrene, carbon tetrachloride, trichloro-ethylene, tetrachloro-ethylene; Inorganic solvents such as water etc.These solvents (or dispersant) can use separately, also can mix two or more uses.
Be used to form the print process of design pattern layer, for example can enumerate intaglio method, offset printing method, silk screen print method, aniline printing method, videograph, ink jet printing method etc.In addition, on whole surface, form the method for design pattern layer, for example can enumerate rolling method, cutter and be coated with method, airblade coating method, filtering type rubbing method (tie coat), scraper rubbing method, spot printing method (commacoat method), engagement rubbing method (kiss coat method), flow coat method (flow coat), tiltedly be coated with method various coating processes such as (tip coat).Can use part vapour deposition method, etching method of Freehandhand-drawing method, creeping method, photo method, duplicating method, laser beam impasto, electron beam impasto, metal etc. etc. in addition, or be used in combination with other formation method.
The thickness of design pattern layer is not particularly limited, and can suitably set according to product performance, and the thickness of the layer during coating is about l～15 μ m, the thickness of dried layer is about 0.1～10 μ m.
(painted hidden layer)
Between backing material plate and design pattern layer, can also form painted hidden layer more as required.From the decorative panel interarea is hidden painted hidden layer is set in hope during by the background color of adhesive linkage.No matter be backing material plate when transparent, or backing material plate when painted, can be formed painted hidden layer by hidden for stabilisation is disguised.
As the printing ink that forms painted hidden layer, can use form the design pattern layer and can hidden painted printing ink.
The formation method of painted hidden layer, the formation method of preferred covering substrates slab integral (on the whole surface).For example, preferably can enumerate above-mentioned rolling method, cutter is coated with method, airblade coating method, mouthful pattern rubbing method, scraper rubbing method, spot printing method (comma coat method), engagement rubbing method (kiss coat method), flow coat method (flow coat), tiltedly is coated with method (tip coat) etc.
The thickness of painted hidden layer is not particularly limited, and can suitably set according to product performance, and the thickness of the layer during coating is about 0.2～l0 μ m, the thickness of dried layer is about 0.1～5 μ m.
(transparent bond layer)
On the design pattern layer, be formed with transparent bond layer.As long as transparency bond layer has the transparency and just is not particularly limited, can be water white transparency, painted transparent, translucent in any.This bond layer is for bonding and form with design pattern layer and transparent polypropylene-based resin layer.
Be not particularly limited as bond layer, can use at the known bonding agent in decorative panel field.
As at the known bonding agent in decorative panel field, for example can enumerate cured resins such as thermoplastic resins such as polyamide, acrylic resin, vinyl acetate resin, thermosetting carbamate resins etc.In addition, can also be suitable for two solution curing type polyurethane resin or the mylar of isocyanates as curing agent.
Bond layer is, for example, by coating adhesive on the design pattern layer, coating constitutes after the transparent polypropylene-based resin of transparent polypropylene-based resin layer (upper strata described later polypropylene layer or lower floor's polypropylene layer), carries out drying, is solidified to form.The condition of baking temperature, drying time etc. is not particularly limited, and can suitably set according to the kind of bonding agent.The coating process of bonding agent is not particularly limited, for example, can adopt rolling method, the mobile rubbing method (curtain flow coater) of curtain formula, foundry pig rubbing method (wire bar coater), spin-coating method, notch board coating, notch board spin-coating method, airblade coating method, engagement rubbing method (kiss coater), scraper-type coating (blade coater), level and smooth coating (smooth coater), spot printing method methods such as (comma coatmethod).
The thickness of bond layer is not particularly limited, and dried thickness is 0.1～30 μ m, is preferably about 1～20 μ m.
(transparent polypropylene-based resin layer)
On transparent bond layer, be formed with transparent polypropylene-based resin layer (individual course).Transparency polypropylene-based resin layer thickness is that 150 μ m are above, universal hardness is 35N/mm 2More than.By forming so transparent polypropylene-based resin layer, can pay the mar-proof performance in high load capacity field to floor material decorative board.
Here, so-called " the mar-proof performance height in high load capacity field " be meant, under the situation of scratching on the decorative panel surface with high load capacity (load that refers to the per unit area correspondence is big), is difficult to form the situation of scratching wound, impression etc.The degree of the mar-proof performance in high load capacity field can wait by gate-type test in for example pencil hardness test (JIS K 5600-5-4), the gram and estimate.
Universal hardness in this specification is the hardness that useful FISCHERSCOPE H100V (FISCHERINSTRUMENT of Co., Ltd. manufacturing) measures in measuring with hardness such as film coated, elasticity raw material.The hardness mensuration of carrying out with this FISCHERSCOPE H100V is so-called ultra micro Vickers hardness (Ultra-micro Vickers Hardness) test method(s).Specifically, with pressure head pressing in sample surface (for example, transparent polypropylene-based resin layer), directly read cup depth under the state of load and measure sample hardness applying.Measured value (universal hardness) is defined as following (with reference to ISO Technical Report).Pressure head uses diamond indenter (Φ 0.4mm ball pressure head), measures compression distance under test load.Universal hardness use the surface area of the impression that test load is generated down with this test load remove ratio represent.
Universal hardness (N/mm 2)=F/S
F: test load (N)
S: the surface area (mm of ball pressure head under the test load (Φ 0.4mm) 2)
The thickness of transparency polypropylene-based resin layer, requirement is more than the 150 μ m, more than the preferred 300 μ m, more preferably more than the 400 μ m.
The universal hardness of transparency polypropylene-based resin layer requires to be 35N/mm 2More than, preferred 40N/mm 2More than.
Transparency polypropylene-based resin layer can be laminated to transparent polypropylene-based resin above the transparent bond layer by for example rolling process, plavini, T mould extrusion molding, or uses the film that has formed.
Transparency polypropylene-based resin layer is individual layer (1 layer) as mentioned above, but also can be multilayer (more than 2 layers) as required.For example, constitute transparent polypropylene-based resin layer by 2 layers of structure by upper strata described below polypropylene layer and lower floor's polypropylene layer as described below, can pay the mar-proof performance in high load capacity field and the mar-proof performance in following underload field to floor material decorative board.
Below, the situation that is 2 layers of structure with regard to transparent polypropylene-based resin layer describes.
A. upper strata polypropylene layer
The upper strata polypropylene layer is in order to obtain mar-proof performance, and especially the mar-proof performance in high load capacity field forms.
The thickness of upper strata polypropylene layer, requirement are more than the 100 μ m, are preferably about 100～300 μ m, are preferably about 250 μ m especially.
The universal hardness of upper strata polypropylene layer requires to be 35N/mm 2More than, preferred 40N/mm 2More than.
B. lower floor's polypropylene layer
Lower floor's polypropylene layer is in order to obtain mar-proof performance, and especially the mar-proof performance in underload field forms.Here, so-called " the scratch-resistant height in underload field " is meant, when scratching on the decorative panel surface, is difficult to form the situation of scratching wound, impression etc. with underload (load that refers to the per unit area correspondence is little).The degree of the mar-proof performance in underload field can wait and estimate by for example Huffman (Hoffman ' s) scratch test.
The formation method of lower floor's polypropylene layer can be identical with the formation method of above-mentioned transparent polypropylene-based resin layer.Also can extrude simultaneously as required and form the upper and lower.
The thickness of lower floor's polypropylene layer, requirement are more than the 50 μ m, are preferably more than the 100 μ m.The upper limit of lower floor's polypropylene layer is not defined, but is generally about 200 μ m.
The universal hardness of lower floor's polypropylene layer requires to be 20N/mm 2Below, preferred 15N/mm 2Below.
Form such lower floor's polypropylene layer again by forming outside the polypropylene layer of upper strata, can pay the mar-proof performance in underload field to floor material decorative board.
When the surface of upper strata polypropylene layer forms following transparent sealer, can carry out surface treatments such as Corona discharge Treatment, ozone treatment, plasma treatment, ionizing radiation processing, dichromic acid processing as required.Surface treatment gets final product according to the common method of each processing.
In addition, bottom (bottom that the formation of sealer is carried out easily) can also be set as required on the surface.
Bottom can form by single face or the known silane coupling agent of two sided coatings at backing material plate.As silane coupling agent, for example can enumerate the carbamates silane coupling agent that constitutes by acrylic acid modified carbamate resins, silane coupling agent that constitutes by the copolymer of acrylic acid and carbamate etc.
The coating weight of silane coupling agent is not particularly limited, and is generally 0.1～100g/m 2, be preferably 0.1～50g/m 2About.
The thickness of priming coat is not particularly limited, and is generally 0.01～10 μ m, is preferably about 0.1～1 μ m.
(transparent sealer)
Be formed with the transparent sealer that constitutes by ionizing radiation gel-type resin or two solution curing type carbamates on the transparency polypropylene-based resin layer.By forming the transparent sealer that constitutes by ionizing radiation gel-type resin or two solution curing type carbamates, can improve the wearability, resistance to impact, stain resistance, marresistance, against weather of decorative panel etc.
Be not particularly limited as the ionizing radiation gel-type resin, can use in molecule, to contain and to carry out the prepolymer (containing oligomer) of free-radical polymerised pair of key of cross-linking reaction and/or monomer transparent resin as main component by ionizing radiations such as irradiation ultraviolet radiation, electron beams.These prepolymers or monomer can use separately, also can mix multiple use.Curing reaction is often referred to cross-linking and curing reaction.
Specifically, as above-mentioned prepolymer or monomer, can enumerate in the molecule radical polymerization mould assembly unsaturated groups such as containing (methyl) acryloyl group, (methyl) allyl acyloxy, the compound of cationically polymerizable functional groups such as epoxy radicals.In addition, the prepolymer of the polyene that the combines/polythiol class of also preferred polyene and polythiol.Here, (methyl) acryloyl group is meant acryloyl group or methacryl.
As the prepolymer that contains radical polymerization mould assembly unsaturated group, for example can enumerate polyester (methyl) acrylate, carbamate (methyl) acrylate, epoxy (methyl) acrylate, melamine (methyl) acrylate, three azines (methyl) acrylate, silicon (methyl) acrylate etc.These molecular weight is preferably about 250～100000 usually.
As the monomer that contains radical polymerization mould assembly unsaturated group,, can enumerate methyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, phenoxy group ethyl (methyl) acrylate etc. for example as monofunctional monomer.In addition, as polyfunctional monomer, for example can enumerate diethylene glycol two (methyl) acrylate, propane diols (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethylene oxide three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.
As the prepolymer that contains the cationic polymerization type functional group, for example can enumerate epoxy resin such as bisphenol-type epoxy resin, phenolic epoxy compound, the resinoid prepolymers of vinethene such as fatty acid vinethene, fragrant same clan vinethene.In addition, as polythiol, for example can enumerate polythiols such as trimethylolpropane tris mercaptoacetate (tri-methylol propane tri-thioglycolate), pentaerythrite four mercaptoacetates.As polyene, for example can enumerate the material that generates by two pure and mild vulcabond, add allyl alcohol at the polyurethane two ends.
As the ionizing radiation that is used to solidify the ionizing radiation gel-type resin, use the electromagnetic wave or the charged particle of energy with the molecule generation curing reaction that can make in the ionizing radiation gel-type resin (composition).Usually use ultraviolet ray or electron beam, can also use visible light, X ray, ion irradiation etc.
As ultraviolet light source, for example can use light sources such as ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc lamp, invisible light modulation (black light), metal halide lamp.Ultraviolet wavelength is preferred 190～380nm usually.
As electron beam source, for example can use section Kroll husband-Wal step on (Cockcroft-walton) type, Fan Dige pressgang (Van de Graaff) type, resonance transformer type, insulating core transformer type or linear pattern, various electron-beam accelerators such as that rice (Dynamitron) type, high-frequency type.Wherein, especially preferably can shine the accelerator of electron beam with 100～1000keV, preferred 100～300keV energy.
There is no particular limitation as two solution curing type carbamate resinoids, wherein, can use as main component and contain the polyol composition (acrylic acid polyol, polyester polyol, polyether polyhydroxy-compound, epoxy polyol etc.) of OH base, contain the material of isocyanate prepolymer composition (toluene di-isocyanate(TDI), hexamethylene diisocyanate, meta-xylene isocyanates (metaxylene diisocyanate) etc.) as curing agent component.
These sealers can also contain colouring agents such as plasticizer, stabilizing agent, filler, dispersant, dyestuff, pigment, solvent etc. as required.
Sealer can for example pass through, on transparent polypropylene-based resin layer, and known coating processes such as the method that photogravures, rolling method, after ionizing radiation gel-type resin or the coating of two solution curing type carbamate resinoids, cured resin forms.The ionizing radiation gel-type resin comes cured resin by irradiating electron beam.
The thickness of sealer is not particularly limited, and can suitably set according to the characteristic of final products, is generally 0.1～50 μ m, is preferably about 1～20 μ m.
The hardness of sealer is to count 100N/mm with above-mentioned universal hardness 2More than, preferred 150N/mm 2More than.The universal hardness of sealer is discontented with 100N/mm 2The time, the problem that can not give full play to mar-proof performance is arranged.In addition, the universal hardness that has formed the decorative panel integral body that comprises sealer is preferably 45N/mm 2More than, more preferably 50N/mm 2More than.
Can be formed with concavo-convex on the interarea of sealer (being exposed to the surface in the atmosphere).Usually process by embossment and form concavo-convex apperance.The embossment processing method is not particularly limited, and for example can enumerate interarea thermoplastic with transparent acrylate resin layer as method for optimizing, with the method for cooling off behind the embossment version pressurization figuration.Use known vane type or rotary-type embossment machine in the embossment processing.Concaveconvex shape has for example grain board conduit ditch, stone plate surface concavo-convex (granite fault plane etc.), cloth superficial makings, pear-skin texture pattern, sand streak, stria (hairline), ten thousand lines ditches etc.
Decorating material for flooring
Floor material decorative board of the present invention is by becoming decorating material for flooring with various the joint by adhesives.Material by adhesives is not particularly limited, and for example can enumerate materials such as inorganic non-metallic class, metal species, wooden class, plastics class.
Specifically, the inorganic non-metallic class can be enumerated and for example copy system cement, extrude ceramic materials such as non-ceramic sintering material, earthenware, pottery, porcelain, stone implement, glass, enamel such as cement, blast furnace cement, ALC (lightweight cellular concrete), GRC (glass fiber-reinforced concrete), slurry cement, wood chip cement, asbestos cement, calcium silicates, gypsum, gypsum slag etc.
For example can enumerate metal materials (metal foil) such as iron, aluminium, copper in the metal species.
For example can enumerate the veneer made by Japanese cedar (cryptomeria), Japan cypress, Oak Tree, lauan, teak etc., plywood, sawdust-board (particle board), fiberboard, composite material etc. in the wooden class.
Can enumerate for example resin materials such as polypropylene, ABS resin, phenolic resin in the plastics class.
These shapes by convered structure are not particularly limited, and consider that usually the setting of material earthward makes dull and stereotyped getting final product.
After being engaged by adhesives, for example, also can carry out joint tongue processing with severing, dovetailer (tenoner) according to the characteristic of final products, pay the bar ditch of V-shape, carry out the chamfered edge on four limits.
Floor material decorative board of the present invention even do not form the sark layer, also can be brought into play outstanding impact resistance, and can also bring into play outstanding mar-proof performance.
In addition,, make the manufacturing engineering of floor material decorative board easy, and can also remove the manufacturing defect that produces in the present sark layer formation operation owing to need not to form the sark layer.
Enumerate embodiment below, more detailed description the present invention.
Embodiment 1
(making of floor material decorative board)
Go up the enforcement printing at the coloured polypropylene film (backing material plate) of 0.06mm thickness and form the design pattern layer.
Then, hardness is divided into the transparent polypropylene-based resin film of two-part 0.3mm (300 μ m) thickness, stacked bonding with the carbamates dry type with bonding agent, form transparent polypropylene-based resin layer.
Then, on transparent polypropylene-based resin layer, form universal hardness 170N/mm 2Electronic beam solidified transparent sealer (15 μ m).
Then, implement embossment processing, Manufacture of Floor material decorative panel from transparent sealer one side.
(making of decorating material for flooring)
At the backing material plate side bonds 12mm sal glued board (Lauanplywood) of floor material decorative board, Manufacture of Floor ornament materials.Bonding agent uses urethane-modified ethene vinyl acetate class emulsion bonding agent (100g/m 2Wet).
(the mar-proof performance of decorating material for flooring)
To the carrying out of the decorating material for flooring made mar-proof performance evaluation.Gate-type (Clemen) test is used for estimating the mar-proof performance in high load capacity field in following pencil hardness test and the gram.In addition, Huffman (Hoffman ' s) scratch test is used for thinking poorly of the mar-proof performance in load field.Each test method is as described below.
1. pencil hardness test (high load capacity evaluation)
Test with pencil scratching tester.When testing machine is in horizontal level, set the nib that makes pencil is given 1000g to decorative panel load for.Test according to JIS K 5600-5-4 benchmark in addition.
2. Huffman scratch test (underload evaluation)
Test with the Huffman scratch test machine that U.S. BYK-GARDNER society makes.Specifically, cut blade (the columniform blade of Φ 7mm) is arranged to respect to decorating the angle contact of material surface with 45 ° testing machine be moved on the decoration material.Improve load (hammer) gradually, test repeatedly up to decorating the generation scratch of material surface, impression etc.
3. gate-type test (high load capacity evaluation) in the gram
Test according to JIS K 5600-5-5 benchmark.As scratching the pin of decorating the material surface, used the pin of diamond system.
Their result of the test is as shown in table 1 below.
Table 1
The HU of PP layer 15 20 25 30 35 40 45
The HU of decorative panel 25 30 35 40 45 50 55
Pencil hardness *1 6B 4B 3B 2B HB HB HB
The Huffman cut *2 400 400 400 400 400 400 400
Gate-type is scratched in the gram *3 70 80 80 80 90 90 90
HU: universal hardness (N/mm 2) PP: polypropylene
*1: the hardness that albefaction and indenture do not take place
*2: the peak load (g) that albefaction does not take place
*3: do not take place below the peak load (g) of albefaction, these units are also all identical.
Embodiment 2
The universal hardness of transparent polypropylene-based resin layer is fixed on 40N/mm 2, thickness is divided into outside two parts, other and embodiment 1 identical Manufacture of Floor ornament materials.
Mar-proof performance to the decorating material for flooring made is estimated.Evaluation result is as shown in table 2 below.
Table 2
PP layer thickness (μ m) 60 80 100 150 300 400 500
Pencil hardness 3B 3B 2B HB HB HB HB
Embodiment 3
(making of floor material decorative board)
Go up the enforcement printing at the coloured polypropylene film (backing material plate) of 0.06mm thickness and form the design pattern layer.
Then, with universal hardness 40N/mm 2The upper strata polypropylene layer and film (2 layers of structure: thickness 0.3mm), stacked bonding of hardness lower floor's polypropylene layer coextrusion of being divided into two-part 0.15mm thickness with bonding agent with the carbamates dry type.
Then, formed universal hardness 170N/mm in last time on the polypropylene layer 2Electronic beam solidified transparent sealer (15 μ m).
Then, implement embossment processing, Manufacture of Floor material decorative panel from transparent sealer one side.
(making of decorating material for flooring)
At the backing material plate side bonds 12mm sal glued board (Lauanplywood) of floor material decorative board, Manufacture of Floor ornament materials.Bonding agent uses urethane-modified ethene vinyl acetate class emulsion bonding agent (100g/m 2Wet).
(the mar-proof performance of decorating material for flooring)
Mar-proof performance (gate-type is scratched in pencil hardness, Huffman cut, the gram) to the decorating material for flooring made is estimated.Evaluation result is as shown in table 3 below.
Table 3
The HU of upper strata PP layer 40
The HU of the PP of lower floor layer 15 20 30 35 40
The Huffman cut 600 600 400 400 400
Pencil hardness HB HB HB HB HB
Gate-type is scratched in the gram 90 90 90 90 90
Embodiment 4
The HU of upper strata polypropylene layer is fixed as 40N/mm 2, lower floor's polypropylene layer HU be fixed as 15N/mm 2Carry out coextrusion, the thickness that upper strata/lower floor is added up to be 0.3mm ground to outside both compressing tablets, other is identical with embodiment 3, the Manufacture of Floor ornament materials.
(the mar-proof performance of decorating material for flooring)
Mar-proof performance (gate-type is scratched in pencil hardness, Huffman cut, the gram) to the decorating material for flooring made is estimated.Evaluation result is as shown in table 4 below.
Table 4
The thickness of upper strata PP layer 300 280 250 200 150 100 100
The thickness of the PP of lower floor layer 0 20 50 100 150 200 50
The Huffman cut 400 400 600 600 600 800 700
Pencil hardness HB HB HB HB HB B B
Gate-type is scratched in the gram 90 90 90 90 90 80 80
Evaluation result when the thickness that merges the thickness of having represented upper strata PP layer at the end of table 4 and be 100 μ m, the PP of lower floor layer is 50 μ m.Evaluation result shows, even the thickness of upper strata PP layer is the thickness of 100 μ m, the PP of lower floor layer when being 50 μ m, it also has very high serviceability as decorating material for flooring.
Embodiment 5
The HU:15N/mm that is fixed as with lower floor's polypropylene layer 2, thickness 50 μ m; Upper strata polypropylene layer (HU:40N/mm 2) thickness be divided into two parts and carry out coextrusion, outside the compressing tablet, other is identical with embodiment 3, the Manufacture of Floor ornament materials.
(the mar-proof performance of decorating material for flooring)
Mar-proof performance (gate-type is scratched in pencil hardness, Huffman cut, the gram) to the decorating material for flooring made is estimated.Evaluation result is as shown in table 5 below.
Table 5
The thickness of upper strata PP layer 250 350 450
The thickness of the PP of lower floor layer 50 50 50
The Huffman cut 600 500 500
Pencil hardness HB HB HB
Gate-type is scratched in the gram 90 90 90
(resistance to impact of decorating material for flooring)
The resistance to impact of the decoration material (3 kinds) of his-and-hers watches 5 records is estimated with Du Pont's shock machine (according to JIS K 5600-5-3 benchmark).Specifically, measure indenture to the surface of decorating material, estimate by hammer from the height whereabouts predetermined weight of 30cm.Evaluation result is as shown in table 6 below.
Table 6
The thickness of upper strata PP layer 250 350 450
The thickness of the PP of lower floor layer 50 50 50
Du Pont's indenture amount: μ m 350 300 250
In addition, existing flooring board with sark (backer), the indenture amount that records by identical impact test is about 250 μ m, has much at one impact resistance with decorating material for flooring of the present invention as can be known.Existing glued board earth material, the surface is hard, is difficult to shock absorbing, therefore films and breaks easily, and its indenture amount is about 400 μ m.
Embodiment 6
Electronic beam solidified transparent sealer is replaced with the transparent sealer that is made of two solution curing type carbamate resinoids, carried out embodiment 1～5.
Each evaluation result is in identical level with result shown in the result shown in table 1～table 6.As can be known, no matter sealer is made of electronic beam solidified resin, or is made of two solution curing type carbamate resinoids, all has identical effect.

Claims (6)

1. floor material decorative board; on the backing material plate that constitutes by the polyalkenes hydrocarbon resins; be formed with design pattern layer, transparent bond layer, transparent polypropylene-based resin layer successively, reach the transparent sealer that constitutes by ionizing radiation gel-type resin or two solution curing type carbamate resinoids, wherein:
(1) thickness of transparent polypropylene-based resin layer is more than 150 μ m;
(2) universal hardness of transparent polypropylene-based resin layer is at 35N/mm 2More than;
(3) universal hardness of transparent sealer is at 100N/mm 2More than.
2. floor material decorative board; on the backing material plate that constitutes by the polyalkenes hydrocarbon resins; be formed with design pattern layer, transparent bond layer, transparent polypropylene-based resin layer successively, reach the transparent sealer that constitutes by ionizing radiation gel-type resin or two solution curing type carbamate resinoids, wherein:
(1) transparent polypropylene-based resin layer is made of for 2 layers upper strata acrylic resin layer and lower floor's acrylic resin layer;
(2) thickness of upper strata acrylic resin layer is more than the 100 μ m;
(3) universal hardness of upper strata acrylic resin layer is 35N/mm 2More than;
(4) thickness of lower floor's acrylic resin layer is more than the 50 μ m;
(5) universal hardness of lower floor's acrylic resin layer is 20N/mm 2More than;
(6) universal hardness of transparent sealer is 100N/mm 2More than.
3. floor material decorative board as claimed in claim 2 is characterized in that, the thickness of upper strata acrylic resin layer is 100～300 μ m.
4. as each described floor material decorative board in claim 1 or 2, it is characterized in that, between backing material plate and design pattern layer, also be formed with painted hidden layer.
5. as each described floor material decorative board in claim 1 or 2, it is characterized in that, on the interarea of transparent sealer, be formed with concavo-convex.
6. a decorating material for flooring is characterized in that, with backing material plate one side bonds of each described floor material decorative board in described 1 or 2 on by adhesives.
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