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CN101519018B - Decorative sheet - Google Patents

Decorative sheet Download PDF

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Publication number
CN101519018B
CN101519018B CN2009101295911A CN200910129591A CN101519018B CN 101519018 B CN101519018 B CN 101519018B CN 2009101295911 A CN2009101295911 A CN 2009101295911A CN 200910129591 A CN200910129591 A CN 200910129591A CN 101519018 B CN101519018 B CN 101519018B
Authority
CN
China
Prior art keywords
cosmetic sheet
sealer
methyl
resin
acrylate
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 - Fee Related
Application number
CN2009101295911A
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Chinese (zh)
Other versions
CN101519018A (en
Inventor
黑田玲子
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Publication of CN101519018A publication Critical patent/CN101519018A/en
Application granted granted Critical
Publication of CN101519018B publication Critical patent/CN101519018B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • 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
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2419/00—Buildings or parts thereof
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • 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
    • B32B2479/00—Furniture

Landscapes

  • Laminated Bodies (AREA)

Abstract

To provide a decorative sheet improved in anti-staining properties along with abrasion resistance and scratch resistance. In the decorative sheet for use in the state laminated on an adherend material, (1) the decorative sheet has at least a base material sheet, a pattern layer, a transparent resin layer, a primer layer and a surface protective layer in succession, (2) the primer layer includes an antistatic agent and (3) the surface protective layer is formed from a composition containing (a) an ionizing radiation polymerizable oligomer, (b) a reactive silicone acrylate and (c) spherical particles with an apparent specific gravity of 0.3-1 g/cm3.

Description

Cosmetic sheet
This case is On September 30th, 2005, application number is 200580033313.6, denomination of invention is Cosmetic sheetDivide an application
Technical field
The present invention relates to the decorative panel of the surface decoration material as building materials such as furniture, building services, the cosmetic sheet that is added with effective pattern and this cosmetic sheet of lamination.
Background technology
By by the surface label attaching spike of enclosure material, can reach wood based panel etc. by purposes such as the surface protection of enclosure material, decorations.And the decorative panel that obtains being attached cosmetic sheet by enclosure material obtains using in various building materials, furniture etc.
Cosmetic sheet is provided with for the protection of the most surperficial sealer.Sealer must have excellent mar proof, marresistance etc.And sealer also must have for the stain resistance (soil resistance) from external contamination.
As the excellent cosmetic sheet such as mar proof, stain resistance, for example, have at the single face of base material film (1) successively lamination and contain the cosmetic sheet (patent documentation 1) that layer (2), synthetic resin layer (3) and the synthetic resin layer (4) different from above-mentioned synthetic resin layer (3) of colouring agent consist of.
In addition, also has the anti-pollution ornament materials, namely base material stain-proofing layer is set and the anti-pollution ornament materials, above-mentioned stain-proofing layer consists of (patent documentation 2) by the organosilicon-modified acrylic polyurethane resin that imports the poly organo alkyl at the side chain of acrylated polyurethane resin.
Patent documentation 1: Japanese kokai publication hei 11-58614 communique
Patent documentation 2: TOHKEMY 2004-17617 communique
But the cosmetic sheet of patent documentation 1 is used the low silicones of surface tension, fluororesin etc. as the most surperficial synthetic resin layer.Therefore, have problems at aspects such as durability.
In addition, cosmetic sheet is normally with web-like or layer-by-layer state keeping, and is too much at the silicones that the cosmetic sheet surface is oozed out at this moment, just is attached to easily the back side of another cosmetic sheet.The cosmetic sheet of patent documentation 1 might have more silicones and ooze out.If the cosmetic sheet back side is polluted by silicones, on plywood etc. during the applying cosmetic sheet, the cohesive that just possibly can't obtain stipulating.
The cosmetic sheet of patent documentation 2 is used organic-silicon-modified resin as stain-proofing layer, by on the cosmetic sheet surface organic-silicon-modified resin being oozed out to obtain stain resistance (repellence of the pollution that particularly produces to the pollution that produced by stationery, by food).Therefore, identical with above-mentioned patent documentation 1, can be because organic-silicon-modified resin ooze out and have problems.
In addition, the cosmetic sheet of patent documentation 2 by surperficial wiping, also can be wiped the organic-silicon-modified resin that forms from the teeth outwards stain-proofing layer simultaneously, therefore is difficult to the long term maintenance stain resistance.
Summary of the invention
Therefore, main purpose of the present invention is to provide a kind of excellent cosmetic sheet of not being stained with performance (stain resistance) and durability that has.
The inventor in view of the problem of prior art, repeatedly the further investigation the result, discovery will have the laminated body of ad hoc structure to be used as cosmetic sheet, can achieve the above object, and has finished thus the present invention.
That is, the present invention relates to following cosmetic sheet.
1. be used in the cosmetic sheet of being used by the enclosure material superimposed layer, it is characterized in that,
(1) this sheet has substrate sheets, patterned layer, transparent resin bed and sealer at least successively,
(2) this sealer is by containing a) ionizing radiation polyreactive oligomers and b) composition of reactive organic silicon acrylic ester forms.
2. above-mentioned 1 described cosmetic sheet is characterized in that, also has priming coat between transparent resin bed and sealer,
(1) this priming coat contains antistatic additive,
(2) this sealer is by containing a) ionizing radiation polyreactive oligomers, b) reactive organic silicon acrylic ester and c) apparent specific gravity is 0.3～1g/cm 3The composition of spherical particle form.
3. in the above-mentioned 2 described cosmetic sheet, the pore capacity of above-mentioned spherical particle is below the 0.5ml/g.
4. in above-mentioned 1～3 in each described cosmetic sheet, above-mentioned surface protectant contains above-mentioned sealer and contains delustering agent.
5. in above-mentioned 2～4 in each described cosmetic sheet, part or all of above-mentioned spherical particle is silica dioxide granule.
6. in above-mentioned 1～5 in each described cosmetic sheet, above-mentioned sealer has utilize embossing processing to produce concavo-convex.
7. in above-mentioned 1～6 in each described cosmetic sheet, above-mentioned ionizing radiation polyreactive oligomers comprises: polyurethane (methyl) acrylate oligomer that (A) has 2 free-radical polymerised unsaturated groups in 1 molecule; (B) in 1 molecule, has aliphatic polyurethane (methyl) acrylate oligomer of 3～15 free-radical polymerised unsaturated groups.
8. in above-mentioned 1～6 in each described cosmetic sheet, above-mentioned ionizing radiation polyreactive oligomers comprises: polyurethane (methyl) acrylate oligomer 40～80 % by weight that (A) have 2 free-radical polymerised unsaturated groups in 1 molecule; (B) in 1 molecule, have aliphatic polyurethane (methyl) acrylate oligomer 60～20 % by weight of 3～15 free-radical polymerised unsaturated groups.
9. in above-mentioned 1～8 in each described cosmetic sheet, at least one in above-mentioned transparent resin bed and the substrate sheets is polyolefin-based resins.
10. decorative panel, its be sealer with each described cosmetic sheet in above-mentioned 1～9 for superficial layer, formed by this cosmetic sheet of enclosure material superimposed layer.
Cosmetic sheet of the present invention because sealer is formed by the composition that contains ionizing radiation polyreactive oligomers and reactive organic silicon acrylic ester, so, can avoid the problem of oozing out, and performance excellent be not stained with performance (stain resistance) and durability.
That is, cosmetic sheet of the present invention because be difficult to adhere to pollutant (what is called is not stained with excellent) at its sealer, and also has lasting effect, so can bring into play excellent stain resistance and durability in long-time.
In addition, cosmetic sheet of the present invention in the situation of using delustering agent, can be brought into play more excellent design (particularly various bright pasters).
The specific embodiment
Cosmetic sheet of the present invention is in the cosmetic sheet of being used by the enclosure material superimposed layer, it is characterized in that,
(1) this sheet has substrate sheets, patterned layer, transparent resin bed and sealer at least successively,
(2) this sealer is by containing a) ionizing radiation polyreactive oligomers and b) composition of reactive organic silicon acrylic ester forms.
Below, each layer described.
Substrate sheets
As substrate sheets, for example, make paper using, nonwoven, thermoplastic resin sheet or these composite etc.
As paper, for example, can enumerate thin paper, brown paper (kraft paper), upper matter paper, kapok paper (linter paper), herbarium paper (baryta paper), template, Japan paper etc.
In addition, as nonwoven, for example, can enumerate the nonwoven of being made by fibers such as mylar, acrylic resin, nylon, vinylon, glass.The weight per unit area of paper or nonwoven, normally 20～100g/m 2About.In addition, paper or nonwoven, for between its fiber or with the reinforcement of the interlaminar strength of other layer and prevent grain raising, for example, also can add (manufacture paper with pulp rear resin impregnated or when manufacturing paper with pulp in fill out) resin such as acrylic resin, styrene butadiene ribber, melmac, polyurethane resin.In addition, making the cosmetic sheet of paper using (or nonwoven) in substrate sheets is facing paper.
As thermoplastic resin sheet, for example, can enumerate acrylic resin, mylar, polyolefin-based resins, Corvic, polystyrene, ABS resin, polycarbonate resin, polyamide etc.Concrete, can enumerate following (1)～(4).
(1) polyolefin-based resins such as polyethylene (high density, middle density, low-density), polypropylene (waiting formalism, a formalism), polybutene, ethylene-propylene copolymer, ethylene-propylene-butylene copolymer, olefin series thermoplastic elastomer.
In addition, above-mentioned olefin series thermoplastic elastomer, form by mixing hard segment and soft chain segment, hard segment is made of the crystalline polyolefin resin, and soft chain segment is made of the elastomer of ethylene-propylene rubber, ethylene-propylene-diene rubber, random polypropylene, SBR styrene butadiene rubbers, hydrogenated styrene-butadiene rubber etc.The mixing ratio of hard segment and soft chain segment is about (hard segment/soft chain segment)=5/95～40/60 (mass ratio).As required, the elastomer composition is undertaken crosslinked by known crosslinking agents such as sulphur, hydrogen peroxide.
(2) acrylic resins (wherein, so-called (methyl) acrylate is the meaning of acrylate or methacrylate) such as poly-(methyl) methyl acrylate, poly-(methyl) butyl acrylate, (methyl) methyl acrylate-(methyl) butyl acrylate copolymer, (methyl) methyl acrylate-styrol copolymer.
(3) mylar such as PETG, polybutylene terephthalate (PBT), ethene-terephthalate-isophthalic acid ester copolymer, PEN, polyester based thermoplastic elastomer, amorphism polyester.
In addition, as polyester based thermoplastic elastomer, the high crystallization of use, dystectic aromatic polyester are arranged in hard segment, using the vitrifying transition temperature in soft chain segment is block polymers such as amorphism polyethers etc. below-70 ℃.In high crystalline, dystectic aromatic polyester, for example, use polybutylene terephthalate (PBT), in this amorphism polyethers, for example, use polytetramethylene glycol.As the amorphism polyester, representational have ethylene glycol-1,4-CHDM-terephthaldehyde's acid copolymer.
(4) other resin
For example, can enumerate polycarbonate resin, Corvic, polyamide, polyphenylene sulfide, polyether-ether-ketone etc.
Substrate sheets, can individual layer or 2 layers with uses such as the above-mentioned paper of superimposed layer, nonwoven, thermoplastic resin sheets.
The thickness of substrate sheets (being gross thickness during laminated body) is unqualified, is generally about 25～500 μ m.
Patterned layer
Patterned layer also has literal, mark, figure etc. beyond the pattern that the natural material of wood grain, joint line etc. has.
The formation method of patterned layer, there is no particular limitation for material, pattern kind etc.Patterned layer is used printing ink, can be formed by intaglio printing, serigraphy, hectographic printing, intaglio plate hectographic printing, ink jet etc.For example, pattern can be enumerated wood grain decorative pattern, bag decorative pattern, sand streak decorative pattern, woven design decorative pattern, tile decorative pattern, brick decorative pattern, dermatoglyph decorative pattern, literal, mark, geometry decorative pattern etc.Also can be with these decorative pattern combinations more than 2 kinds.
The printing ink that uses in patterned layer is by 1) vehicle that consisted of by adhesive etc.; 2) colouring agent such as pigment, dyestuff; The various additives such as the extender pigment that 3) can suitably add as any composition, stabilizing agent, plasticizer, catalyst, curing agent consist of.
As the resin of adhesive, can according to desired physical property, printing adaptability etc., suitably select from thermoplastic resin, thermosetting resin, ionizing radiation curable resin etc.For example, can use the cellulose-based resin of celluloid, cellulose acetate, acetic acid esters propionic ester cellulose etc.; The acrylic resin of poly-(methyl) methyl acrylate, poly-(methyl) butyl acrylate, (methyl) methyl acrylate-(methyl) butyl acrylate-(methyl) acrylic acid 2-hydroxyl ethyl ester copolymer etc.; Monomers such as polyurethane resin, vinyl chloride-vinyl acetate copolymer, mylar, alkyd resins or contain these mixture.
In addition, as colouring agent, can use the inorganic pigment of titanium white, carbon black, iron oxide black, colcother (bengala), chrome yellow, ultramarine etc.; Nigrosine, quinoline Azone are red, the organic pigment of isoindoline ketone Huang, phthalocyanine blue etc.; The flash of light pigment of the mica of titanium dioxide-coated, aluminium etc. can also use various dyestuffs.
Adhesive phase
Cosmetic sheet of the present invention preferably has adhesive phase between patterned layer and transparent resin bed.
Adhesive can grade corresponding to the one-tenth that consists of patterned layer or transparent resin bed, the suitable selection in known adhesive.Beyond the polyolefin-based resins such as polyethylene, polypropylene, can also enumerate polyester based resin, polyurethane series resin, epoxy is the thermosetting resins such as resin.
In the present invention, consider that from can further improving the aspects such as heat resistance optimization polyurethane is resin binder.The polyurethane series resin adhesive for example, can be enumerated take polyalcohol as host, the hypergolic polyurethane resin of (curing agent) take isocyanates as crosslinking agent.
As above-mentioned polyalcohol, be the alcohol that in molecule, has 2 above hydroxyls.For example, can use polyethylene glycol, polypropylene glycol, acrylic polyol, PEPA, PPG, polycarbonate polyol etc.
In addition, as above-mentioned isocyanates, can use the polynary cyanate that in molecule, has 2 above NCOs.For example, can use 2,4-benzal vulcabond, XDI, 4, aliphatic (or alicyclic) isocyanates such as the aromatic diisocyanate classes such as 4-methyl diphenylene diisocyanate, hexamethylene diisocyanate, IPDI, hydrogenation benzal vulcabond, hydrogenation methyl diphenylene diisocyanate.In addition, also can use adduct or the polymer of above-mentioned isocyanates.For example, can enumerate the adduct of benzal vulcabond, 3 polymers of benzal vulcabond etc.
In addition, as required, on adhesive surface, also can apply the known easy adhesion process such as Corona discharge Treatment, Cement Composite Treated by Plasma, ungrease treatment, surface roughening processing.
As adhesive bonding method, can be according to the selections such as adhesive kind of using.For example, use the polyolefin-based resins such as polyethylene, polypropylene, the method that is coated with in patterned layer by melt extruding (extrusion coated method); It is applying adhesive on the thermosetting resin of resin etc. at polyester based resin, polyurethane resin, epoxy, carry out the method for dried lamination, this adhesive is added with the polymerization initiators such as the crosslinking agent, methyl-ethyl-ketone peroxide, hydroperoxides, azodiisobutyronitrile of isocyanates, amine etc., the polymerization accelerants such as cobalt naphthenate, dimethylaniline as required.In addition, can use among the present invention can hot pressing adhesive, by hot pressing lamination patterned layer and transparent resin bed.
The thickness of adhesive phase is according to the kind of transparent protective layer, the adhesive kind of use etc. and different, normally about 0.1～30 μ m.
Transparency resin bed
Transparency resin bed is so long as the transparency is just unqualified.Therefore, comprise water white transparency, painted in transparent, translucent etc. wantonly a kind.
As transparent resin bed, be preferably the resin bed that is formed by thermoplastic resin.Concrete, can enumerate soft, semi-rigid or RPVC, PETG, polybutylene terephthalate (PBT), polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, ionomer, acrylate, methacrylate etc.In the present invention, as transparent resin bed, the polyolefin-based resins of polypropylene etc. particularly preferably.
Transparency resin bed, as required, also can be colored.To thermoplastic resin, can add coloured material (pigment or dyestuff) and carry out painted.As coloured material, can suitably use known pigment or dyestuff.These can select one kind or two or more use.In addition, the addition of coloured material also can suitably be set according to desirable tone.
In transparent resin bed, as required, also can contain the various additives such as filler, flatting agent, blowing agent, fire retardant, lubricant, antistatic additive, antioxidant, ultra-violet absorber, light stabilizer, free radical scavenger, soft composition (such as rubber).
Fire retardant is to give the material that flame resistance is added for knowing clearly.For example, can compatibly use chloralkane (chloride paraffin), tricresyl phosphate, chlorinated oil, tetrachlorobenzene dicarboxylic anhydride, tetrabromo-benzene dicarboxylic anhydride, tetrabromobisphenol A, dibromopropyl phosphate, three (2,3-dibromopropyl) phosphate, antimony oxide, aqueous alumina, barium borate etc.
In order to suppress or to prevent oxidation Decomposition, need to add antioxidant.For example, preferred alkyl phenols, amine, quinones.
Ultra-violet absorber absorbs and causes the ultraviolet ray in the deteriorated wavelength 280～450nm zone of resin (particularly polyolefin-based resins).For example, can enumerate the various ultra-violet absorbers of benzophenone series, salicylate system, BTA system, acrylic etc.
Free radical scavenger prevents because the variable color that daylight produces, fade, be full of cracks, albefaction, strength deterioration etc., improve weatherability.As free radical scavenger, beyond two (2,2,6,6-tetramethyl-4-piperidyl) sebacates, for example, can also use that disclosed hindered amine is that free radical scavenger, piperidines are free radical scavenger etc. in Japanese JP 4-82625 communique.
Transparency resin bed for example, can adopt the method at preformed of adjoining course superimposed layer or film; By melt extruding the method that can form the resin combination of transparent resin bed in the adjoining course coating; Any method in method of adjoining course lamination etc.In the present invention, particularly preferably form transparent resin bed by melt extruding.Particularly transparent resin bed is preferably by melt extruding the coating polyolefin-based resins.
Particularly, be pre-formed adhesive phase in patterned layer, melt extrude at adhesive phase, painting polypropylene based thermoplastic elastomer, can form aptly transparent resin bed thus.The method that melt extrudes is such as known methods such as using the T mould is arranged.
The thickness of transparency resin bed can suitably be set according to the purposes of end article, using method etc., is generally 50～250 μ m, particularly about 20～200 μ m.
At surface (surface) and/or the back side of transparent resin bed, in order to improve the cohesive with adjoining course, can carry out Corona discharge Treatment as required.The method of Corona discharge Treatment and condition can be carried out according to known method.
Priming coat
Surface (surface) and/or the back side at transparent resin bed are preferably formed priming coat.
As the material that is used to form priming coat, for example, except the resinaes such as mylar, polyurethane resin, acrylic resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer, polyvinylbutyral resin, nitrocellulose resin, also can use the compounds such as Alkyl titanate, Ethylenimine (ethylene imine).Particularly as priming coat, preferably use the polyurethane series resin of bi-component curing type.As aliphatic acid isocyanates (aliphatic isocyanates) such as isocyanates use hexamethylene diisocyanates (HMDI), when using acrylic polyol as polyalcohol, can obtain more excellent weatherability, stickiness etc.
Priming coat directly uses above-mentioned material or uses with the state that dissolves in solvent or disperse, can be according to formation such as known printing process, coating processes.
As the priming coat that between transparent resin bed and sealer, forms, preferably contain antistatic additive.Below, the priming coat that contains antistatic additive is described.
Unqualified as antistatic additive, the classification according to ion produces has cation system, anion system, nonionic system, both sexes system etc.In addition, the classification that produces according to molecular weight beyond so-called low molecule-type antistatic additive, is called the Polymer Antistatic Agent of the antistatic behaviour resin of the polymer such as copolymer in addition.Antistatic additive, physical property as requested, purposes etc. are suitably selected.
In these antistatic additive, cation is that antistatic additive is preferred because obtain strong antistatic behaviour easily.Concrete, be, can enumerate quaternary ammonium salt etc. as cation.From the physical property of easy adjustment intermiscibility etc., compare suitable polymer electrolyte, for example comonomer selected with low molecule-type.As antistatic additive, the polymer electrolyte of preferred cationic system, the Polymer Antistatic Agent that the cation that preferably has quaternary ammonium salt is.
The addition of antistatic additive can be according to the suitably settings such as kind of purposes, desired physical property, antistatic additive.As addition, usually to compare with low molecule-type, polymer electrolyte adds manyly.The addition of antistatic additive for example, is 30～120 % by weight with respect to resin portion.
From giving the viewpoint of antistatic property, also contain conductive agent, but carbon dusts etc. exist the outward appearance blackout of cosmetic sheet, the problem of damage design.In addition, tin oxide (ITO) powder, the tin oxide that are doped with antimony are processed titanium dioxide powder etc., have the high problem of gonorrhoea and cost.These inorganic based compounds, usually undesirable as the antistatic additive of cosmetic sheet.
In priming coat, with the interpolation antistatic additive while, add specific extender pigment as inorganic filler, can further improve antistatic behaviour.In addition, add the part of extender pigment, if obtain identical antistatic property, can reduce the addition of antistatic additive, and can reduce the resin part, can realize with cheaper cost the performance of expectation.As extender pigment (antistatic auxiliary agent), for example preferably barium sulfate.Containing in the situation of barium sulfate, not only can improve antistatic behaviour, and can improve weather-proof stickiness.On the other hand, as the calcium carbonate of extender pigment, although can improve antistatic behaviour, because weather-proof stickiness reduces, therefore be difficult to use in the cosmetic sheet.
The addition of above-mentioned barium sulfate is unqualified, and for example, the resin part is generally about 50～500 % by weight relatively.Addition is too much, can make the prime layer side roughening, the impact of generation reduction adhesive force etc.
The thickness of priming coat is according to purposes etc. and different, usually about preferred 1～10 μ m.
Sealer
In the present invention, sealer is set to superficial layer.That sealer is defined as is transparent, also can be colored.Also can be translucent in the scope that patterned layer can be recognized.Sealer remedies the easy scratch degree on cosmetic sheet surface, improves marresistance.
In cosmetic sheet of the present invention, sealer is by containing a) ionizing radiation polyreactive oligomers and b) composition of reactive organic silicon acrylic ester forms.
(ionizing radiation polyreactive oligomers)
The ionizing radiation polyreactive oligomers can use operable oligomer in known ionizing radiation gel-type resin.Concrete, can enumerate polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyalcohol acrylate etc.
In the present invention, as the ionizing radiation polyreactive oligomers, preferably contain (A) has polyurethane (methyl) acrylate oligomer of 2 free-radical polymerised unsaturated groups and (B) have 3～15 free-radical polymerised unsaturated groups in 1 molecule in 1 molecule aliphatic polyurethane (methyl) acrylate oligomer.
Above-mentioned polyurethane (methyl) acrylate oligomer (A) is the oligomer (so-called 2 functional polyurethanes acrylate oligomers) that has 2 free-radical polymerised unsaturated groups in 1 molecule.For example, these can enumerate a) vulcabond, b) in 1 molecule, have polyalcohol (preferable weight-average molecular weight is 500～2000), a c of 2 above hydroxyls) have endways hydroxyl, and (methyl) acrylate compounds with free-radical polymerised unsaturated group in conjunction with and the oligomer that forms.The weight average molecular weight of this oligomer preferably 1000～4000.Above-mentioned molecular weight might can not be given full play to the flexibility that polyurethane (methyl) acrylate has in the resin bed after curing less than 1000 o'clock.In addition, the processability when the bending machining of V cutting processing, polishing etc. and embossing descends.Greater than 4000 o'clock, also possible so that the decline of the characteristics such as stain resistance at above-mentioned molecular weight.
In the above-mentioned vulcabond, a) be aliphatic, ester ring type or the aromatic isocyanates that in 1 molecule, has 2 above NCOs, for example, can enumerate 2,4-benzal vulcabond, 4,4 '-'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, IPDI, hydrogenation benzal vulcabond, hydrogenation '-diphenylmethane diisocyanate etc.
As above-mentioned polyalcohol b), PEPA, PPG, polycarbonate polyol, acrylic polyol of having hydroxyl at two ends etc. are arranged.As above-mentioned PEPA, there be (i) to have the diatomic alcohol compounds of aromatic series and volution skeleton, with the lactone compound or derivatives thereof or with the condensation product of addition reaction product, (ii) many basic acids and the alkylene glycol of epoxide and the open loop petchem of (iii) deriving from the cyclic ester compound, these can separately or mix use more than 2 kinds.For example, as many basic acids of above-mentioned (ii), use adipic acid, can obtain the condensation product with alkylene glycol, have the polyester diol (particularly weight average molecular weight 500～2000) of hydroxyl at two ends, can preferably use because various physical property is good.As above-mentioned PPG, polytetramethylene ether diol, polyethylene glycol, polypropylene glycol etc. are arranged.
Above-mentioned (methyl) acrylate c), be the ester compounds of acrylic or methacrylic acid or these derivative, hydroxyl is arranged endways.Concrete, illustration has: (methyl) acrylate compounds 2-ethoxy (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxyl butyl (methyl) acrylate, 4-hydroxy-cyclohexyl (methyl) acrylate, 5-hydroxyl ring octyl group (methyl) acrylate, 2-hydroxyl-3-phenyl hydroxypropyl acrylate etc., that have 1 polymerism unsaturated group or other (methyl) acrylate compounds that has 2 above polymerism unsaturated groups in 1 molecule.
In the present invention, polyurethane (methyl) acrylate oligomer (A), preferably: polyol component is the PEPA of the weight average molecular weight 500～2000 that formed by alkylene glycol and adipic acid, and, the vulcabond composition is that IPDI, acrylate composition are ethoxy (methyl) acrylate, be 1000～3000 oligomer by making the reaction of these compositions, obtaining weight average molecular weight.
Above-mentioned aliphatic polyurethane (methyl) acrylate oligomer (B) is the oligomer that has the free-radical polymerised unsaturated group of 3～15 (methyl) acryloyl groups etc. in 1 molecule.For making the following compositions reaction, multifunctional (3～15 officials energy) urethane acrylate that obtains: a) aliphatic diisocyanate, b) multi-functional polyol, c) have endways hydroxyl, and have (methyl) acrylate of free-radical polymerised unsaturated group.
As above-mentioned aliphatic diisocyanate a), for example, can enumerate 1,6-hexamethylene diisocyanate, IPDI, hydrogenation benzal vulcabond, hydrogenation '-diphenylmethane diisocyanate etc.
Above-mentioned multi-functional polyol b), take above-mentioned polyalcohol as basic framework, can use the polyalcohol with a plurality of functional groups.
As above-mentioned (methyl) acrylate c), can enumerate 2-ethoxy (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxyl butyl (methyl) acrylate, 4-hydroxy-cyclohexyl (methyl) acrylate, 5-hydroxyl ring octyl group (methyl) acrylate, 2-hydroxyl-3-phenyl hydroxypropyl acrylate etc. and have (methyl) acrylate compounds of 1 polymerism unsaturated group.
As ionizing radiation polyreactive oligomers of the present invention, as the ionizing radiation polyreactive oligomers, preferably use following (A) and mixture (B): polyurethane (methyl) acrylate oligomer 40～80 % by weight that (A) in 1 molecule, have 2 free-radical polymerised unsaturated groups; (B) in 1 molecule, have aliphatic polyurethane (methyl) acrylate oligomer 60～20 % by weight of 3～15 free-radical polymerised unsaturated groups.
Above-mentioned (A) less than 40 % by weight, the pliability of gel-type resin layer, ductility might wait and become insufficient, and resistance to impact might descend.And, at above-mentioned (A) during greater than 70 % by weight, might so that marresistance and resistance to impact descend.In addition, the use level of above-mentioned polyurethane (methyl) acrylate oligomer (A) and aliphatic polyurethane (methyl) acrylate oligomer (B) is illustrated in the % by weight of each composition of total weight in the coating composition that forms the gel-type resin layer, relatively above-mentioned oligomer (A) and oligomer (B).
(reactive organic silicon acrylic ester)
As reactive organic silicon acrylic ester, there is no particular limitation, but the material of preferred and above-mentioned electric wire radioactive ray polyreactive oligomers reaction.Above-mentioned organic silicon acrylic ester is to have the material that is called the dimethyl silica alkyl structure.In the kind of considering the functional group, when particularly considering that EB solidifies (electron beam irradiation), preferable methyl acrylic, acrylic, sulfydryl.
In addition, in the present invention, above-mentioned organic silicon acrylic ester can exist with the former state state solidifying in the mixture of polyreactive oligomers with electric wire, also can to a certain degree with above-mentioned oligomer copolymerization, the present invention also comprises such form.
The content of reactive organic silicon acrylic ester can suitably determine according to the kind of ionizing radiation polyreactive oligomers etc., is below 5 % by weight usually in said mixture, is preferably 0.1～3.0 % by weight, more preferably the scope of 0.5～2.0 % by weight.
(spherical particle)
Be used to form the composition of sealer, more preferably contain spherical particle.
As spherical particle, use apparent specific gravity 0.3～1g/cm 3Particle, preferably use 0.65～0.85g/cm 3Particle.By containing the spherical particle in this scope, sealer can access sufficient marresistance.
Wherein, in this manual the apparent specific gravity of spherical particle is the value of measuring according to the method for JIS K5101.
The average grain diameter of spherical particle is unqualified, and usually preferred average grain diameter is below the 5 μ m.
The oil absorption of spherical particle is preferably below the 50ml/100g.That is, by using more highdensity spherical particle, can easier raising marresistance.
The specific area of spherical particle (BET specific area), usually preferred 0～50m 2About/g.
The pore capacity of spherical particle is usually preferably below the 0.5ml/g, more preferably about 0.1～0.4ml/g.That is, by using more highdensity particle, can easier raising marresistance.
As spherical particle, so long as the material that possesses above-mentioned physical property just without limits, for example, beyond the inorganic particle of silica, wollastonite, aluminium oxide etc., also can use the resin particle of acrylate etc.In the present invention, the suitable silica dioxide granule that uses, preferably setting part or all spherical particle is silica dioxide granule.
The content of spherical particle has no particular limits, can suitably determine according to the kind of ionizing radiation polyreactive oligomers etc., but preferably usually in said mixture be about 1～10 % by weight, 3～5 weight portion % particularly preferably.
(other additive)
Cosmetic sheet of the present invention can contain arbitrarily additive in sealer.For example, can contain and be useful on the known delustering agent that improves the surface dulling sense of cosmetic sheet.
As delustering agent, for example, can enumerate the inorganic particle of silica, silicones (powder, particle (beads)) etc.; The organic material powder of crosslinked alkyl, cross-linked styrene, benzene guanamine resin, urea-formaldehyde resin, phenolic resins, polyethylene, nylon etc., particle etc.Wherein, can be particularly suitable for using silica.In addition, preferably use untreated silica.Reason is because of the organic process silica of process Treating Cuttings with Paraffin Wax and has material and the usefulness of scolding fluidity, might ooze out from the sheet surface.
As delustering agent, preferred oil absorption 100ml/100g is above, and (particularly 200～400ml/100g) particle, pore capacity are that (particularly 1～1.7ml/g) particle, apparent specific gravity are 0.08～0.4g/cm more than the 0.6ml/g 3Particle.By using the smaller particle of such density, can give the cosmetic sheet delustring sense that wish on the surface.
The particle diameter of delustering agent is also unqualified, can be according to suitably decisions such as purposes.Usually about preferable particle size 0.1～30 μ m, the scope of particle diameter 3～6 μ m particularly preferably.
The content of delustering agent is also unqualified, and relative 100 weight portion said mixtures, are particularly preferably 5～15 weight portions at preferred 3～20 weight portions.
Above-mentioned composition can be prepared by mixing equably these various compositions.Obtain forming method and also can carrying out according to known method of sealer by said composition, for example, form by the filming of combinations thereof deposits yields, with known service condition irradiation electron ray, can make the crosslinking curing of filming.
Electronic radial source as ionizing radiation, use the various electron ray accelerators of Cockcroft-Walton type, Fan Dege pressgang (Van de Graaff) type, resonance transformer type, insulating core transformer type, linear pattern, Dynamitron type, high-frequency type etc., can use and shine the electron ray accelerator that has 100～1000keV energy, preferably has the electronics of 200～300keV energy.In addition, as ultraviolet source, for example, can use the light source of ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc lamp, black light lamp, metal halide lamp etc.
In sealer (being the most surperficial of cosmetic sheet), preferably apply ridge design by embossing processing etc.More preferably apply the friction of filling printing ink at above-mentioned embossing recess and fill processing, it is that resin (priming coat), ionizing radiation polyreactive oligomers apply the structure of (external coating processing) that this surface is made for the bi-component curable polyurethane.
Embossing processing is processed for the texture (texture) of giving the hope such as plank surface in cosmetic sheet.For example, after on the heating roller cosmetic sheet surface (olefin resin) being carried out thermoplastic, be heated to 160～180 ℃ with infrared-radiation heater again, pressurize and figuration with the graining board of the ridge design that is set as desirable shape, cooling is fixing and form.Embossing processing can be used known blade and revolving embossing machine.As ridge design, for example, can enumerate the wood grain conduit trough, float figure (ridge design of the annual ring of emersion), hachure (hairline), sand streak, pears line etc., can from these, suitably select desirable decorative pattern.
Processing is filled in so-called friction, refers in embossing processing, describes the processing that Surface Edge is filled printing ink at the recess of setting with spatula edge.Fill printing ink as friction, usually can use with the acrylate polyurethane copolymerization resin of the bi-component curing type printing ink as adhesive.Processing is filled in friction, and by concavo-convex friction of wood grain conduit trough filled processing, therefore the design that can show the wood grain of more approaching reality can improve commodity value especially.
By enclosure material
Be applied to cosmetic sheet by enclosure material without limits, can use the material same with known cosmetic sheet.For example, can enumerate wood materials, metal, pottery, plastics, glass etc.The cosmetic sheet of the present invention wood materials that can suit to use.As wood materials, for example, can enumerate the fancy veneer (prominent plate) made from the various logs of China fir, Japan cypress, beech, pine, lauan, teak, yellow sal (メ ラ ピ one) etc., wood single-plate, timber plywood, sawdust-board, medium density fibre board (MDF) (MDF) etc.
By the lamination of enclosure material
By superimposed layer cosmetic sheet such as enclosure materials, become decorative panel various.Laminating method is unqualified, for example, can cosmetic sheet be fitted in by on the enclosure material and lamination by adhesive.Adhesive can be according to being selected from known adhesive by the kind of enclosure material etc.For example, beyond polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer etc., also have butadiene-propylene nitrile rubber, chloroprene rubber, natural rubber etc.
Decorative panel goes for such as the interior material at the building on wall, top, floor etc., the surface decorating plate of the bins such as the surface decorating plate of the building services of window frame, fan, railing etc., furniture or light current, OA machine etc.
Embodiment
At the following embodiment that enumerates, further offer some clarification on feature of the present invention, just the present invention is not subjected to the restriction of scope of embodiments.
Embodiment 1～3
As substrate sheets, prepare polypropylene based resin film (thickness 60 μ m, transmitance 10%).After this surface and the back side apply Corona discharge Treatment, form the grain pattern layer on the surface by intaglio printing.On the other hand, overleaf, utilize intaglio printing to form priming coat.
Then, the coating fluid in that above-mentioned patterned layer coating is made of bi-component curable polyurethane resin forms adhesive phase (thickness 3 μ m).With the T mould the polypropylene-based thermoplastic elastomer (TPE) that ethylene-propylene-butylene copolymer consists of is melt extruded, applies again, form transparent resin bed (thickness 80 μ m).
The bi-component curable polyurethane that is comprised of acrylic acid-polyurethane block polymer (host) and hexamethylene diisocyanate (curing agent) in transparent resin bed coating is resin, forms priming coat (thickness 2 μ m).
Then, use the composition that contains at composition shown in the table 1, form sealer.
Table 1
Figure G2009101295911D00161
Each composition in the table 1 uses respectively following substances.
Oligomer (A): polyurethane (methyl) acrylate oligomer that in 1 molecule, has 2 free-radical polymerised unsaturated groups
Oligomer (B): aliphatic polyurethane (methyl) acrylate oligomer that in 1 molecule, has 3～15 free-radical polymerised unsaturated groups
Silica: product (apparent specific gravity 0.1～0.4)+average grain diameter 4 μ m (apparent specific gravity 0.45～0.85) are untreated for average grain diameter 5 μ m, surface
Be not stained with composition (reactive organic silicon acrylic ester): two terminal-reactive organic silicon acrylic esters
By form at each composition shown in the table 1 film after, with the condition of 175keV and 5Mrad (50kGy) irradiation electron ray, make the above-mentioned crosslinking curing of filming, form sealer (thickness 5 μ m).
At last; heat with the contactless heater effects on surface of infrared ray protective layer side, after substrate sheets and transparent resin bed softening, the embossing that directly carries out being produced by hot pressing from the surface protection aspect is processed; by giving the ridge design of wood grain conduit trough decorative pattern, the cosmetic sheet that obtains stipulating.
Comparative example 1～3
Except by forming sealer in forming shown in the table 1, operate similarly to Example 1, make cosmetic sheet.
Test example 1
Following physical property to the cosmetic sheet that obtains in embodiment and comparative example is investigated respectively.This result of expression in table 1.
(1) is not stained with performance (initial stage)
Use thick magic ink (magic ink) (oil-based ink that interior field foreign firm produces), confirm when the sealer of cosmetic sheet is write, not to be stained with characteristic.With oily dirt free China ink, to be the printing ink state evaluation that becomes drop be " * " for " zero ", the good state evaluation that soaks that printing ink is not stained with.
(2) be not stained with performance (color and luster after the wiping)
Utilize the person's handwriting that the rag wiping writes in above-mentioned (1) after, observe this residual color.With the state evaluation wiped fully for " zero ", will wipe that the state evaluation of the same state of state is " * " before not removal ink, maintenance and the wiping.The results are shown in table 1.
(3) be not stained with performance (erasing rubber)
Repeatedly behind 10 cosmetic sheet sealers of wiping surface, this surface is implemented the test of above-mentioned (2) with erasing rubber.The state evaluation of wiping fully is " zero ", will wipes not removal ink, and maintenance is " * " with the state evaluation of the front state equal state of wiping.The results are shown in table 1.
(4) be not stained with performance (after the S-UV test)
As promoting atmospheric exposure test, take JIS-B-7350 as benchmark, cosmetic sheet is implemented test.Use sunlight carbon arc lamp formula atmospheric exposure test machine, with 63 ℃ of blackboard temperatures, exposure 25.5mW/cm 2(365nm), irradiation 120 minutes, rain time was under 18 minutes the condition, implemented to add up to 200 hours.After test, this surface is implemented the test of above-mentioned (2).The state evaluation of wiping fully is " zero ", will wipes not removal ink, and maintenance is " * " with the state evaluation of the front state equal state of wiping.The results are shown in table 1.
By above result as can be known, cosmetic sheet of the present invention has excellent performance (stain resistance) and the durability of not being stained with.
Embodiment 4
Prepare polypropylene based resin film (thickness 60 μ m, transmitance 10%) as substrate sheets.After this surface and the back side apply Corona discharge Treatment, utilize intaglio printing to form the grain pattern layer on the surface.On the other hand, utilize intaglio printing, form overleaf priming coat.
Then, the coating fluid that is consisted of by bi-component curable polyurethane resin in the coating of above-mentioned patterned layer, form adhesive phase (thickness 3 μ m).With the T mould the polypropylene-based thermoplastic elastomer (TPE) that ethylene-propylene-butylene copolymer consists of is melt extruded, applies again, form transparent resin bed (thickness 80 μ m).
Form priming coat at transparent resin bed.Priming coat is by to the bi-component curable polyurethane being the material that coating contains 25 % by weight antistatic additive (quaternary amine) and 30 % by weight antistatic additive (barium sulfate) on the resin, form priming coat (thickness 2 μ m), wherein, the bi-component curable polyurethane is that resin has: acrylic acid-polyurethane block polymer (host) and hexamethylene diisocyanate (curing agent).
Then, use the composition that contains composition shown in the table 2, form sealer.
Table 2
Oligomer (A) Oligomer (B) Organosilicon Spherical particle
Embodiment 4 65 35 1 5
Comparative example 4 65 35 1 -
Comparative example 5 65 35 - 5
Comparative example 6 65 35 1 5
Comparative example 7 65 35 - -
(in the table 2, numeric representation " % by weight ".The numeric representation of oligomer (A) and oligomer (B) is take the part by weight of both total weight each oligomer during as 100 % by weight.Containing in the numeric representation coating composition of organosilicon and spherical particle is proportional.)
Each composition in the table 2 uses respectively following material.
Oligomer (A): polyurethane (methyl) acrylate oligomer that in 1 molecule, has 2 free-radical polymerised unsaturated groups
Oligomer (B): aliphatic polyurethane (methyl) acrylate oligomer that in 1 molecule, has 3～15 free-radical polymerised unsaturated groups
Siloxanes (reactive organic silicon acrylic ester): two terminal-reactive organic silicon acrylic esters
Spherical particle: apparent specific gravity 0.65～0.85g/cm 3, oil absorption 45ml/100g, BET specific area 0m 2/ g, average grain diameter 3.6 μ m, pore capacity 0.1ml/g
By form at each composition shown in the table 2 film after, with the condition of 175keV and 5Mrad (50kGy) irradiation electron ray, make the above-mentioned crosslinking curing of filming, form sealer (thickness 5 μ m).
At last; heat with the contactless heater effects on surface of infrared ray protective layer side, after substrate sheets and transparent resin bed softening, the embossing that directly carries out being produced by hot pressing from the surface protection aspect is processed; give the convex-concave pattern of wood grain conduit trough figure, the cosmetic sheet that obtains stipulating.
Comparative example 4～7
Utilize the composition shown in the table 2 to form sealer, and do not use antistatic additive and antistatic auxiliary agent in comparative example 6 and 7, in addition, cosmetic sheet is made in similarly to Example 4 operation.
Test example 2
Investigate respectively the following physical property of the cosmetic sheet that in embodiment 4 and comparative example 4～7, obtains.The results are shown in table 3.
(1) antifouling properties (not being stained with test)
Use thick magic ink (black, Lan Hehong, oiliness, the oiliness marking ink that interior field foreign firm produces), confirm when the sealer of cosmetic sheet is write, not to be stained with characteristic.To not be stained with marking ink (being that marking ink becomes drop) state evaluation is not that the state evaluation that soaks of not being stained with is bad (*) for good (zero), with printing ink.
(2) antistatic characteristic (cigarette ash test)
With rag 20 wipings are carried out on the cosmetic sheet surface, made cigarette ash near charged test portion, the situation that visual observations cigarette ash adheres to.With the average evaluation of non-cohesive cigarette ash be (zero), the average evaluation that will adhere to is (*).
(3) anti-scratch characteristic (steel wire lump (steel wool test)
With steel wire lump 20 wipings (load 300g/cm is carried out on the cosmetic sheet surface repeatedly 2), visual observations has or not scar.To not have being evaluated as of scar good (zero), be evaluated as (*) of scar will be arranged.
Table 3
Be not stained with test The cigarette ash test The steel wire lump test
Embodiment 4 ○ ○ ○
Comparative example 4 ○ ○ ×
Comparative example 5 × ○ ○
Comparative example 6 ○ × ○
Comparative example 7 × × ×

Claims (8)

1. a cosmetic sheet being used by the enclosure material superimposed layer, is characterized in that,
(1) this sheet has substrate sheets, patterned layer, transparent resin bed, priming coat and sealer at least successively,
(2) this priming coat contains antistatic additive,
(3) this sealer is by containing a) ionizing radiation polyreactive oligomers, b) reactive organic silicon acrylic ester and c) apparent specific gravity is 0.3～1g/cm 3The composition of spherical particle form.
2. cosmetic sheet as claimed in claim 1 is characterized in that, the pore capacity of described spherical particle is below the 0.5ml/g.
3. cosmetic sheet as claimed in claim 1 or 2 is characterized in that, described sealer contains delustering agent.
4. cosmetic sheet as claimed in claim 1 or 2 is characterized in that, part or all of described spherical particle is silica dioxide granule.
5. cosmetic sheet as claimed in claim 1 or 2 is characterized in that, described sealer has utilize embossing to be processed to form concavo-convex.
6. cosmetic sheet as claimed in claim 1 or 2 is characterized in that,
Described ionizing radiation polyreactive oligomers comprises: polyurethane (methyl) acrylate oligomer 40～80 % by weight that (A) have 2 free-radical polymerised unsaturated groups in 1 molecule; (B) in 1 molecule, have aliphatic polyurethane (methyl) acrylate oligomer 60～20 % by weight of 3～15 free-radical polymerised unsaturated groups.
7. cosmetic sheet as claimed in claim 1 or 2 is characterized in that, at least one in described transparent resin bed and the substrate sheets is polyolefin-based resins.
8. decorative panel, is being formed by this cosmetic sheet of enclosure material superimposed layer for superficial layer with the sealer of each described cosmetic sheet in the claim 1～7.
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Families Citing this family (35)

* Cited by examiner, † Cited by third party
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KR102580100B1 (en) 2015-09-04 2023-09-20 도판 인사츠 가부시키가이샤 makeup sheet
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PL3549764T3 (en) * 2016-11-29 2022-04-04 Toppan Printing Co., Ltd. Cosmetic sheet and method for producing cosmetic sheet
GB2560307B (en) * 2017-03-02 2022-02-16 Anglian Windows Ltd Laminated structure
JP6732681B2 (en) * 2017-03-09 2020-07-29 大日本印刷株式会社 Floor decorative sheet
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JP7272115B2 (en) * 2019-05-30 2023-05-12 凸版印刷株式会社 makeup sheet
KR20220151681A (en) * 2020-03-11 2022-11-15 다이니폰 인사츠 가부시키가이샤 makeup sheet and makeup board
CN111645391A (en) * 2020-06-03 2020-09-11 苏州库盈新材料有限公司 Automobile decoration membrane with self-repairing function on surface and preparation process

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2248634Y (en) * 1995-11-16 1997-03-05 黑龙江威科实业有限公司 Pattern transfering printing film

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3396303B2 (en) * 1994-09-22 2003-04-14 住友化学工業株式会社 Masterbatch for polyolefin film and composition for polyolefin film
JPH10250023A (en) * 1997-03-13 1998-09-22 Dainippon Printing Co Ltd Decorative sheet, woody decorative material, and metallic decorative material
JP3388437B2 (en) * 2000-02-18 2003-03-24 大日本印刷株式会社 Decorative sheet
JP4440409B2 (en) * 2000-02-22 2010-03-24 大日本印刷株式会社 Decorative sheet and method for producing the same
JP4327330B2 (en) * 2000-04-14 2009-09-09 共同印刷株式会社 Antistatic decorative sheet
JP2002059518A (en) * 2000-08-21 2002-02-26 Toyo Kohan Co Ltd Resin film for laminating decorative plate excellent in antistatic property and decorative plate laminated with the film
JP4352605B2 (en) * 2000-11-20 2009-10-28 東洋インキ製造株式会社 Antistatic agent
JP2003025509A (en) * 2001-07-17 2003-01-29 Waaron:Kk Light pervious synthetic resin sheet
JP4090731B2 (en) * 2001-12-10 2008-05-28 大日本印刷株式会社 Decorative paper

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2248634Y (en) * 1995-11-16 1997-03-05 黑龙江威科实业有限公司 Pattern transfering printing film

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JP特开10-250023A 1998.09.22
JP特开2001-225420A 2001.08.21
JP特开2003-170539A 2003.06.17
JP特开2003-25509A 2003.01.29

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CN101519018A (en) 2009-09-02

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