CN100488767C - Decorative thin sheet - Google Patents

Decorative thin sheet Download PDF

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Publication number
CN100488767C
CN100488767C CNB2005100598571A CN200510059857A CN100488767C CN 100488767 C CN100488767 C CN 100488767C CN B2005100598571 A CNB2005100598571 A CN B2005100598571A CN 200510059857 A CN200510059857 A CN 200510059857A CN 100488767 C CN100488767 C CN 100488767C
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China
Prior art keywords
decorative laminate
sealer
resin
methyl
decorative
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CN1676319A (en
Inventor
菅玲子
清水正文
增田洋史
金木润
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/131—Interconnections, e.g. wiring lines or terminals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H05K1/189—Printed circuits structurally associated with non-printed electric components characterised by the use of a flexible or folded printed circuit
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/17—Passive-matrix OLED displays
    • H10K59/179—Interconnections, e.g. wiring lines or terminals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10128—Display
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
    • H05K2201/10621—Components characterised by their electrical contacts
    • H05K2201/10681—Tape Carrier Package [TCP]; Flexible sheet connector

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

To effectively provide a decorative sheet having improved wear resistance and abrasion resistance. The decorative sheet to be laminated on an adhered material is characterized in that (1) the sheet has at least a base sheet, a pattern layer, a transparent resin layer and a surface protective layer in this order, and that (2) the surface protective layer is made of a composition containing an ionized radiation-curable type resin (a) and a spherical particle having a specific gravity of 0.3 to 1 g/cm<SP>3</SP>(b).

Description

Decorative laminate
Technical field
The present invention relates to a kind of as building materials such as furniture, door and windows surface decoration material and implement the decorative laminate of effective pattern and be laminated with the decorative panel of this decorative laminate.
Background technology
Decorative laminate is to be the thin slice of purpose with the surface protection of adhesion materials such as wood based panel, decoration etc., uses by this decorative laminate being fitted on the surface that adheres to material.Then, resulting thus decorative panel is used to various building materials, furniture etc.
Decorative laminate like this for example uses the duplexer that substrate sheet, patterned layer, synthetic resin layer etc. are laminated.These decorative laminates are for example special open that flat 11-240113 communique put down in writing like that, in order to protect it the most surperficial, form sealer (so-called OP layer: the chromatography layer) usually.It is known particularly using the ionizing radiation gel-type resin in order to improve antifriction consumption, marresistance etc. at sealer.
But even forming under the situation of sealer with ionization radiation gel-type resin, antifriction consumption, marresistance etc. also also have room for improvement.For example; when the decorative laminate of carrying manufacturing; the sealer of two decorative laminates is carried each other with overlapping, but when when there is fine dust each other in its sealer, because of the deadweight and the dust of decorative laminate is damaged sealer.
Relative therewith, if thicken sealer in order to give higher hardness, the variation such as bendability of decorative laminate then, this also becomes the reason of albinism.
Moreover, also consider to be added on employed particle in the known thin slice, but might damage employed doctor blade device, galley etc. when forming sealer.Under the situation that produces such state of affairs, bring obstacle for the cost degradation of decorative laminate.And, if use employed hard particles in known decorative laminate, then might reduce weatherability.
Summary of the invention
Therefore, main purpose of the present invention is to provide effectively a kind of decorative laminate that improves antifriction consumption and marresistance.
What the inventor attentively studied in view of prior art problems point found that: the duplexer that has specific formation by use can achieve the above object as decorative laminate, thereby has finished the present invention.
That is, the present invention relates to following decorative laminate.
1. decorative laminate, it is to be layered in to adhere on the material and the decorative laminate that uses is characterized in that:
(1) this thin slice has substrate sheet, patterned layer, transparent resin bed and sealer at least successively;
(2) this sealer is by a) ionizing radiation gel-type resin and b) to contain apparent specific gravity be 0.3～1g/cm 3The composition of spherical particle form.
2. as 1 described decorative laminate, it is characterized in that: between transparent resin bed and sealer, form priming coat at least.
3. as 1 or 2 described decorative laminates, it is characterized in that: the average grain diameter of spherical particle is below the 8 μ m.
As 1～3 in each described decorative laminate, it is characterized in that: part or all of spherical particle is silicon dioxide granule.
As 1～4 in each described decorative laminate, it is characterized in that: transparent resin bed is a polyolefin-based resins.
As 1～5 in each described decorative laminate, it is characterized in that: sealer is with 15g/cm 2With the formation of getting off.
7. the manufacture method of a decorative laminate, this decorative laminate has substrate sheet, patterned layer, transparent resin bed and sealer at least successively, it is characterized in that: comprise by a) ionizing radiation gel-type resin and b) to contain apparent specific gravity be 0.3～1g/cm 3The composition of spherical particle form the operation of this sealer.
8. decorative panel is characterized in that: with the sealer of each described decorative laminate in above-mentioned 1～6 as the mode of superficial layer, this sheet lamination is formed adhering on the material.
Below, explain decorative laminate of the present invention.
Decorative laminate of the present invention, be adhere on the material stacked and the decorative laminate that uses is characterized in that:
(1) this thin slice has substrate sheet, patterned layer, transparent resin bed and sealer at least successively;
(2) this sealer is by a) ionizing radiation gel-type resin and b) to contain apparent specific gravity be 0.3～1g/cm 3The composition of spherical particle form.
Below, each layer is described.
Substrate sheet
With regard to substrate sheet, for example can use paper, nonwoven, thermoplastic resin thin slice or their composite etc.
With regard to paper, for example can enumerate tissue paper, brown paper, fine paper, cotton linter paper, barium monoxide paper, template, Japan paper etc.
Moreover, with regard to nonwoven, for example can enumerate the nonwoven of making by fibers such as mylar, acrylic resin, nylon, vinylon, glass.The level ground amount of paper or nonwoven can be 20～100g/m usually 2About.Moreover, for between the fiber of strengthening paper or nonwoven or with the interlaminar strength of other layer, prevent that fluffing, paper or nonwoven from can add (contain resin pickup after manufacturing paper with pulp or when manufacturing paper with pulp in fill out resin) resins such as acrylic resin, SBR styrene butadiene rubbers, melmac, carbamate resins for example.In addition, use the decorative laminate of paper (or nonwoven) to become facing paper in the substrate sheet.
With regard to the thermoplastic resin thin slice, for example can enumerate acrylic resin, mylar, vistanex, Corvic, polystyrene, ABS resin, polycarbonate resin, polyamide etc.More specifically can enumerate following (1)～(4).
(1) polyolefin-based resins such as polyethylene (high density, middle density or low-density), polypropylene (waiting a formalism or a formalism), polybutene, ethylene-propylene copolymer, ethylene-propylene-butylene copolymer, olefin-based thermoplastic-resin-elastomer.
In addition, with regard to above-mentioned olefin-based thermoplastic elastomer (TPE), mix and form as the above-mentioned illustrative hard segment that constitutes by the crystalline vistanex with by the soft chain segment that elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, random polypropylene, SBR styrene butadiene rubbers, hydrogenation SBR styrene butadiene rubbers constitute.About the mixing ratio of hard segment and soft chain segment (soft chain segment/hard 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, the meaning of so-called (methyl) acrylate is meant 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-M-phthalic acid ester copolymer, PEN, polyester based thermoplastic elastomer, non-crystalline polyester.
In addition, with regard to above-mentioned polyester based thermoplastic elastomer, there is hard segment to use high crystalline and dystectic aromatic polyester, soft chain segment to use glass transition temperature for the block polymer of the amorphism polyethers below-70 ℃ etc., this high crystalline and dystectic aromatic polyester for example use polybutylene terephthalate (PBT), this amorphism polyethers uses and gathers 1,4-butanediol etc.Moreover with regard to the noncrystalline polyester, representational have ethylene glycol-1, a 4-cyclohexanedimethanol-terephthaldehyde's acid copolymer.
(4) other resin
For example, can enumerate polycarbonate resin, Corvic, polyamide, polyphenylene sulfide, polyether-ether-ketone etc.
With regard to the layer of substrate sheet constitutes, can above-mentioned paper, nonwoven, thermoplastic resin thin slice etc. stacked be individual layer or two-layer with on use.
The thickness of substrate sheet (being gross thickness under the situation of duplexer) is unqualified, but usually can be for about 25～500 μ m.
Patterned layer
Patterned layer except that the styles that natural material had such as wood grain, joint eye, also can show as literal, mark, figure etc.
During the layout layer, the kind of the formation method of patterned layer, material, pattern etc. is not particularly limited.The formation of patterned layer can be used ink usually, use formation such as known print process such as woodburytype, silk screen print method, hectograph trans-printing method, intaglio plate trans-printing method, ink jet printing method.Pattern for example can adopt wood grain style, bag style, sand holes style, woven design style, tiling style, the style of laying bricks, strand ginned cotton sample, literal, mark, geometry style or their two or more combinations etc.
Forming the employed ink of patterned layer is made of following composition, that is various additives such as the extender pigment that suitably adds as composition arbitrarily, stabilizing agent, plasticizer, catalyst, curing agent, the 1) medium, 2 that constitutes by bonding agent etc.) colouring agents, 3 such as pigment, dyestuff).
With regard to the resin of bonding agent, can from bonding agents such as thermoplastic resin, thermosetting resin, ionizing radiation curable resin, suitably select according to desired physical property, printing adaptability etc.For example, except cellulose-based resins such as nitrocellulose, cellulose acetate, cellulose acetate propionic esters; Beyond poly-(methyl) methyl acrylate, poly-(methyl) butyl acrylate, (methyl) methyl acrylate-(methyl) butyl acrylate-acrylic resins such as (methyl) acrylic acid 2-hydroxyl ethyl ester copolymer, can also use the monomer of carbamate resins, vinyl chloride-vinyl acetate copolymer, mylar, alkyd resins etc. or contain their mixture.
Moreover, with regard to colouring agent, except photoluminescent pigment such as paper tinsel powder such as organic pigments such as inorganic pigments such as titanium white, carbon black, iron oxide black, red oxide, chrome yellow, ultramarine, nigrosine, quinacridine is red, isoindolone is yellow, phthalocyanine blue, coated by titanium dioxide mica, aluminium etc., can also use various dyestuffs.
Transparency resin bed
Transparency resin bed is so long as transparent, just unqualified.Therefore, comprise water white transparency, painted in transparent, translucent etc. any.
With regard to transparent resin bed, for example can preferably use the resin bed that forms by thermoplastic resin.Can enumerate soft, semi-rigid or RPVC, PETG, polybutylene terephthalate (PBT), polyamide, polyethylene, polypropylene, vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, iolon, acrylate, methacrylate etc. particularly.In the present invention, be preferably polyolefin-based resins such as polypropylene especially as transparent resin bed.
Transparency resin bed as required can be painted.At this moment, adding coloured material (pigment or dyestuff) can carry out painted to above-mentioned and so on thermoplastic resin.With regard to painted material, can suitably use known or commercially available pigment or dyestuff.They can select one or more.Moreover the addition of coloured material also can be according to suitably settings such as desired tones.
As required, also can contain filler, delustering agent, blowing agent, fire retardant, lubricant, antistatic additive, antioxidant, ultra-violet absorber, light stabilizer, free radical scavenger, soft composition various additives such as (for example rubber) in the transparent resin bed.
Fire retardant adds in order to give flame resistance.For example can preferably use chlorinated paraffin wax, tricresyl phosphate, chlorinated oil, tetrachloro-phthalic acid acid anhydride, tetrabromo-benzene dicarboxylic acid anhydride, tetrabromobisphenol A, phosphoric acid dibromo propyl ester, tricresyl phosphate (2, the 3-dibromopropyl) ester, antimony oxide, aqueous alumina, barium borate etc.
Antioxidant is in order to suppress or to prevent oxidation Decomposition and add.For example can be preferably alkylbenzene phenols, amine, quinones etc.
Ultra-violet absorber is to absorb that to cause the wavelength of resin (particularly polyolefin-based resins) deterioration be the ultraviolet absorbent in 280～450nm field.For example can enumerate each ultra-violet absorber such as benzophenone series, salicylate system, BTA system, acrylic.
Free radical scavenger is for preventing because of the change that daylight causes is faded, be full of cracks, albefaction, strength deterioration etc. and improve weatherability and add.With regard to free radical scavenger, remove beyond two-(2,2,6,6-tetramethyl-4-piperazine) sebacate, for example can use hindered amine such as the special open disclosed compound of 4-82625 communique is free radical scavenger, piperidines base system free radical scavenger etc.
The formation method of transparency resin bed is unqualified, for example can adopt on the layer of formed thin slice in advance or film, carry out stacked method, by melt extrude the resin combination that can form transparent resin bed and be coated in method on the layer of adjacency, with in the method for the layer lamination of adjacency etc. any.In the present invention, be preferably especially by melt extruding and form transparent resin bed.Especially expect that transparent resin bed applies by melt extruding polyolefin-based resins.Specifically, on patterned layer, form bond layer in advance, melt extrude polypropylene-based thermoplastic elastomer (TPE) and be coated on this bond layer, can suitably form transparent resin bed.The method that melt extrudes for example can be utilized known method such as using the T mould.
The thickness of transparency resin bed can suitably be set according to the purposes of end article, using method etc., but is preferably 50～250 μ m usually, is preferably about 20～200 μ m especially.
For the surface and/or the back side of transparent resin bed,, also can carry out Corona discharge Treatment as required in order to improve the cementability with adjacent layer.The method of Corona discharge Treatment, condition can be utilized known method.
Moreover, on the surface and/or the back side of transparent resin bed, also can form priming coat.With regard to the material that is used to form priming coat, for example except mylar, polyurethane resin, acrylic resin, polycarbonate resin, vinyl chloride/vinyl acetate copolymer, polyvinyl butyral resin, nitrocellulose etc., also can use compounds such as metatitanic acid alkane ester, Ethylenimine.With regard to priming coat, the carbamate that especially preferably uses two-solution curing type is a resin.When using HDI aliphatic acid isocyanates (aliphatic isocyanates) such as (HMDI) as isocyanates, acrylic polyol during respectively as polyalcohol, because of obtain more excellent weatherability, fitting tightly property is preferred.
The formation of priming coat can directly be used them or to use and to utilize known printing process, coating method etc. to form priming coat its dissolving or the state in the solvent of being distributed to.
Bond layer
In decorative laminate of the present invention, be preferably between patterned layer and transparent resin bed and have bond layer.
The bonding agent that uses in bond layer can suitably be selected from known or commercially available bonding agent according to the composition that constitutes patterned layer or transparent resin bed etc.For example except polyolefin-based resins such as polyethylene, polypropylene, can also enumerate polyester based resin, polyurethanes is that resin, epoxy are thermosetting resins such as resin.These resins also can with the state use of emulsion.
Wherein, in the present invention, be resin from can further improving stable on heating viewpoint, being preferably carbamate.Carbamate be resin adhesive can to enumerate with the polyalcohol be host, be the two-solution curing type carbamate resin of crosslinking agent (curing agent) with the isocyanates.
With regard to above-mentioned polyalcohol, has plural hydroxyl in the molecule.For example can enumerate polyethylene glycol, polypropylene glycol, acrylic polyol, PEPA, PPG, polycarbonate polyol etc.
Moreover, with regard to above-mentioned isocyanates, use the multicomponent isocyanate that has plural NCO in the molecule.For example use 2,4-toluene di-isocyanate(TDI), XDI, 4, aliphatic (or alicyclic) isocyanates such as aromatic isocyanate class, HDI, IPDI, HTDI, hydrogenated diphenyl methane diisocyanate such as 4 '-methyl diphenylene diisocyanate.That in addition, can also use above-mentioned various isocyanates adds adult or polymer.For example, can enumerate the tripolymer that adds adult, toluene di-isocyanate(TDI) of toluene di-isocyanate(TDI).
In addition, as required, also can implement known easy bonding processing such as Corona discharge Treatment, plasma treatment, ungrease treatment, surface roughening processing to bonding plane.
With regard to adhering method, can utilize known method according to kind of employed bonding agent etc.For example can adopt polyolefin-based resins such as using polyethylene, polypropylene, utilize and melt extrude (extruding coating process) method and be coated in method on the patterned layer; Apply following such bonding agent and the method for carrying out dry-pressing, this bonding agent is, as required polymerization accelerants such as polymerization initiator, cobalt naphthenate, dimethylaniline such as crosslinking agents such as isocyanates, amine, butanone peroxide, hydrogen peroxide, azepine bis-isobutyronitrile added to polyester based resin, polyurethanes is that resin, epoxy are in the thermosetting resins such as resin.Moreover in the present invention, the bonding agent that use can thermo-compressed can lamination pattern layer and transparent resin bed by thermo-compressed.
In addition, in the present invention, also can implement known easy bonding processing such as Corona discharge Treatment, plasma treatment, ungrease treatment, surface roughening processing as required to bonding plane.
The thickness of adhesive linkage is with the difference of kind of sealer, employed bonding agent etc. and difference, but usually can be for about 0.1～30 μ m.
Sealer
In the present invention, sealer is provided with as superficial layer.Sealer is colored also passable so long as transparent.Moreover, also can be translucent in the scope that can see patterned layer clearly.By forming sealer, can remedy the scar on decorative laminate surface and adhering to easiness and can improving marresistance of dirt.
Sealer is by a) ionizing radiation gel-type resin or b) to contain apparent specific gravity be 0.3～1g/cm 3The composition of spherical particle form.
The ionizing radiation gel-type resin can use known goods or commercially available product.Specifically, can preferably use by the weight average molecular weight that has two free-radical polymerised unsaturated groups in the molecule is the solidfied material that has the mixture that aliphatic carbamate (methyl) acrylate oligomer (B) 20 weight %～70 weight % of 3～15 free-radical polymerised unsaturated group constitute in carbamate (methyl) acrylate oligomer (A) 30 weight %～80 weight % of 1000～4000 and the molecule.
Carbamate (methyl) acrylate oligomer (A) is the what is called two functionality urethane acrylate oligomers that have two free-radical polymerised unsaturated groups in the molecule, is that to have plural weight average molecular weight in vulcabond and the molecule be that 500～2000 polyalcohol and the terminal weight average molecular weight that also has (methyl) acrylate compounds be combined into of free-radical polymerised unsaturated group when having hydroxyl are 1000～4000 oligomer.
When the molecular weight of carbamate (methyl) acrylate oligomer (A) less than 1000 the time, resin bed after the curing can not be given full play to carbamate (methyl) flexibility that acrylate had, and V-type is sheared the processability reduction that bending machining such as processing, attrition process and stamp add man-hour.Moreover, when molecular weight surpasses 4000, might make characteristic reductions such as stain resistance.
Above-mentioned vulcabond is aliphatic, ester ring type or the aromatic isocyanates that has plural NCO in the molecule, for example can enumerate 2,4-toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, 1,6-HDI, IPDI, HTDI, hydrogenated diphenyl methane diisocyanate etc.
With regard to the polyalcohol that weight average molecular weight is 500～2000, there are two ends to have PEPA, PPG and polycarbonate polyol, acrylic polyol of hydroxyl etc.With regard to above-mentioned PEPA, have (1) have addition reaction product, (2) polyacid and the alkylene glycol of the diatomic alcohol compounds of aromatic series or volution skeleton and lactone compound or derivatives thereof or epoxide the condensation product, and (3) by open loop petchem of cyclic ester compound deriving, they can use or mix two or more uses separately.With regard to above-mentioned PPG, polytetramethylene ether diol, polyethylene glycol, polypropylene glycol etc. are arranged.Using the polyacid of adipic acid as above-mentioned (2), is that the various physical propertys of polyester diol with hydroxyl of 500～2000 two ends are good as the weight average molecular weight that obtains with the condensation product of alkylene glycol, so preferred the use.
Moreover, when having hydroxyl, end also has (methyl) acrylate of free-radical polymerised unsaturated group, and be the ester compounds of acrylic or methacrylic acid or their derivative, end has hydroxyl.Specifically, can illustration (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 4-hydroxyl cyclohexyl, (methyl) acrylic acid 5-hydroxyl ring monooctyl ester, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester etc. have (methyl) acrylate compounds that has plural polymerism unsaturated group in (methyl) acrylate compounds of a polymerism unsaturated group or the molecule in addition etc.
Carbamate (methyl) acrylate oligomer (A) is preferably, the weight average molecular weight that will form by alkylene glycol and adipic acid be 500～2000 PEPA as the polyalcohol composition and also with IPDI as the vulcabond composition, with (methyl) hydroxy-ethyl acrylate as the acrylate composition, make their reactions and the weight average molecular weight that obtains is 1000～3000 oligomer.
The employed aliphatic carbamate of gel-type resin layer (methyl) acrylate oligomer (B) is the oligomer that has 3～15 free-radical polymerised unsaturated groups such as (methyl) acryloyl group in the molecule, is aliphatic diisocyanate, multi-functional polyol, also has (methyl) acrylate reactions of free-radical polymerised unsaturated group resulting multifunctional (3～15 officials can) urethane acrylate when end has hydroxyl.
Above-mentioned aliphatic diisocyanate can enumerate 1,6-hexamethylene diisocyanate, IPDI, HTDI, hydrogenated diphenyl methane diisocyanate etc.
Moreover, above-mentioned (methyl) acrylate with hydroxyl and free-radical polymerised unsaturated group can be enumerated (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 4-hydroxyl cyclohexyl, (methyl) acrylic acid 5-hydroxyl ring monooctyl ester, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester etc. and have (methyl) acrylate compounds of a polymerism unsaturated group.
In the composition that is used to form the gel-type resin layer, the use level of carbamate (methyl) acrylate oligomer (A) and aliphatic carbamate (methyl) acrylate oligomer (B) is, the content of carbamate (methyl) acrylate oligomer (A) in the resin composition of composition is 30 weight %～80 weight %, and the content of aliphatic carbamate (methyl) acrylate oligomer (B) is 20 weight %～70 weight %.When carbamate (methyl) acrylate oligomer (A) during less than 30 weight %, the flexibility of gel-type resin layer, extensibility is insufficient and resistance to impact reduces, on the other hand, when carbamate (methyl) acrylate oligomer (A) surpassed 80% weight %, marresistance and stain resistance reduced.In addition, the use level of above-mentioned carbamate (methyl) acrylate oligomer (A) and aliphatic carbamate (methyl) acrylate oligomer (B) represents, forms the weight % with respect to each composition of the total weight of above-mentioned oligomer (A) and oligomer (B) in the coating composition of gel-type resin layer.
It is 0.3～1g/cm that spherical particle uses apparent specific gravity 3, be preferably 0.45～0.85g/cm 3Particle.When apparent specific gravity less than 0.3 the time, because be crisp particle, so antifriction consumption and marresistance reduce sometimes.When apparent specific gravity surpassed 1, most cases was the high rigidity particle, when making decorative laminate, and damage pump, embossing plate, scraper etc. sometimes.
In addition, the apparent specific gravity of the spherical particle in this specification is that utilization is the value of the method mensuration of standard with JIS K 5101.
The average grain diameter of spherical particle is unqualified, can suitably set according to the kind of particle, the kind of ionizing radiation gel-type resin, the thickness of sealer etc.Usually the expectation average grain diameter is below the 8 μ m.When considering productivity, the thickness of the kind of pipe resin, sealer and being preferably about 2.6～6 μ m not.
The oil absorption of spherical particle is preferably below the 100ml/100g, more preferably 0～70ml/100g.That is,, can obtain more excellent marresistance by using more highdensity particle.
The specific area of spherical particle (BET specific area) is preferably 0～50m usually 2About/g.
The pore capacity of spherical particle is preferably below the 1ml/g usually, more preferably about 0.1～0.4ml/g.That is, by using the littler particle of pore capacity, and become the spherical particle of high density and high rigidity, obtain excellent marresistance.
The Mohs' hardness of spherical particle is preferably below 5 usually, and more preferably 3～5.When Mohs' hardness surpasses 5, the productivity, antifriction consumption, marresistance, weatherability etc. of decorative laminate are all reduced.
The spherical particle that the present invention can use, so long as possess the material of physical property as described above, just unqualified, for example except inorganic particulates such as silica, wollastonite, aluminium oxide, can also use resin particles such as acrylic acid.In the present invention, can especially preferably use silicon dioxide granule.
In the present invention, the content of spherical particle is unqualified, but with respect to ionizing radiation gel-type resin 100 weight portions, is preferably 3～10 weight portions, is preferably 5～8 weight portions especially.
Moreover the present invention also can contain wax.When containing wax, sheet surface can have slickness.With regard to wax, for example can use resinaes such as polypropylene, polyethylene are dissolved or dispersed in the organic solvent and the resin system wax that obtains.With regard to organic solvent, for example can from hydrocarbon system, ester system, ketone system or their mixed solvent etc., suitably select according to the kind of employed resin etc.
In the present invention, the content of wax but with respect to ionizing radiation gel-type resin 100 weight portions, is preferably 3～20 weight portions without limits usually, is preferably 5～10 weight portions especially.
Above-mentioned composition can be modulated by these each compositions of even mixing.Utilize the formation method of the formed sealer of said composition, also can utilize known method, for example utilize above-mentioned composition to form and film, under known service condition, shine electron ray and make the crosslinking curing of filming.
With regard to the electronic radial source of ionizing radiation, various electron ray accelerators such as (cockcroft-walton) type, バ Application デ グ ラ Off ト type, resonance transformer type, insulation nuclear transformer type, linear pattern, ダ イ Na ミ ト ロ Application type, high-frequency type pause in use Cockcroft-Wal.Can use and shine the electronic radial source that has 100～1000keV energy, is preferably the electronics of 200～300keV energy.Moreover, with regard to ultraviolet light source, for example can use light sources such as extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, carbon lamp, ultraviolet lamp, metal halide lamp.
Sealer is preferably with 15g/m 2With the formation of getting off.More particularly, when decorative laminate being used for horizontal plane purposes (flooring material etc.), be preferably 10～15g/m 2About, when being used for vertical plane purposes (door material etc.), be preferably 4～7g/m 2
Moreover, in the present invention, be preferably in advance priming coat (particularly utilizing carbamate is the formed priming coat of resin) is arranged on the transparent resin bed as substrate.With regard to priming coat, can use and above-mentioned same material.
Be preferably and utilize embossing processing etc. that sealer (that is, decorative laminate is the most surperficial) is implemented concavo-convex style.More preferably wipe (wiping) to above-mentioned embossing recess enforcement filling ink processes, and is the structure on its surface of resin-coating (being coated with processing outward) and become with two-solution curing type carbamate.
Embossing processing is the processing of carrying out for decorative laminate being given desired texture such as timber plate surface.For example, after making the propylene resin thermoplastic on the heated roller, utilize infrared radiation to be heated to 160～180 ℃ again, with the matrixes for embossing of concavo-convex style that is provided with desired shape pressurize, figuration and cooling are fixing and form.This can use known individual or rotary-type embossing machine.With regard to concavo-convex style, for example can enumerate the wood grain conduit trough, float and make style (the concavo-convex style of annual ring emersion), microgroove, sand holes, pears ginned cotton sample etc., can therefrom suitably select desired style.
What is called wipes processing and is meant that utilizing embossing to process on the set recess scrapes the surface processing of filling ink on one side with scraper on one side.As the examination erasable ink, can use usually with the carbamate resins of two-solution curing type ink as bonding agent.Particularly by wiping processing to the wood grain conduit trough is concavo-convex, the appearance design that shows more approaching actual wood grain can improve commodity value thus.
Adhere to material
The adhesion material that decorative laminate of the present invention adopted is unqualified, can use the thin slice same with known decorative laminate.For example can enumerate wooden material, metal, pottery, plastics, glass etc.Decorative laminate particularly of the present invention is suitable for wooden material.With regard to wooden material, can enumerate the prominent plate made by various raw material such as China fir, cypress, Zelkova, pine, sal, teak, メ ラ ピ-wait, wood single-plate, wood composite board, fiber laminate, medium density fibre board (MDF) (MDF) etc.
Adhering to stacked on the material
Decorative laminate of the present invention is laminated on the various adhesion materials, uses as decorative panel.Laminating method is unqualified, for example can adopt the method utilizing bonding agent that decorative laminate is sticked on to adhere on the material etc.Bonding agent can be according to suitably selections from known bonding agent such as the kinds that adheres to material.For example except polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, iolon etc., can also enumerate butadiene-acrylonitrile rubber, neoprene, natural rubber etc.
The decorative panel of Zhi Zaoing so for example can be preferred for the incrustation plate etc. of cabinet of incrustation plate, furniture or light current, business automation equipment etc. of the door and window such as inner decoration material, window frame, door, railing of buildings such as wall, ceiling, floor.
According to decorative panel of the present invention, owing to utilize the composition that contains specific spherical particle and ionizing radiation gel-type resin to form sealer, so obtain following effect.
(1) can bring into play excellent marresistance, antifriction consumption and stain resistance.Therefore, be difficult to scratch, make dirty etc., the process long period also can be kept good surface appearance.
(2) owing to not damaging employed manufacturing installation in the formation operation of sealer, so can help the long lifetime of manufacturing installation.Consequently, can provide a kind of a large amount of production and the more cheap decorative laminate of price that be fit to.
(3) owing to not needing to thicken sealer, so can bring into play excellent in vending workability (three-dimensional processability).
(4) owing to using specific spherical particle, so can keep good weatherability by adding this spherical particle.
The specific embodiment
Following illustrative embodiments more clearly illustrates feature of the present invention.But the present invention is not limited to embodiment.
Embodiment 1
Prepared polypropylene based resin film (thickness 60 μ m, transmitance 10%) as substrate sheet.After its surface and the back side implemented Corona discharge Treatment, utilize intaglio printing to form wood grain pattern design layer from the teeth outwards.On the other hand, utilizing intaglio printing to form overleaf with propenoic methyl carbamate is that resin is the priming coat of bonding agent.
Then, coating has formed bond layer (thickness is 3 μ m) by the masking liquid that the two-solution curing type carbamate resin constitutes on above-mentioned patterned layer.And, melt extrude and apply the polypropylene-based thermoplastic elastomer (TPE) that constitutes by ethylene-propylene-butylene copolymer with the T mould, formed transparent resin bed (thickness 80 μ m).
Coating is a resin by the two-solution curing type carbamate that acrylate-carbamate block polymer (host) and HDI (curing agent) constitute on transparent resin bed, has formed priming coat (thickness 2 μ m).
Then; intaglio printing applies silicon dioxide granule (commercially available product) 5 weight portions shown in embodiment 1 hurdle that contains table 1 with respect to 65 parts of ionizing radiation curing type polyfunctional carbamate oligomer 35 parts/two sense oligourethanes and the composition of wax 5 weight portions (PE is 110～200 ℃ of wax, fusing points); after formation is filmed; condition irradiation electron ray with 175keV and 5Mrad (50kGy); make the above-mentioned crosslinking curing of filming; thus, form sealer (thickness 5 μ m).
At last; heater area of heating surface protective layer one side with infrared ray noncontact mode; after making substrate sheet and transparent resin bed deliquescing; utilize the embossing processing of hot pressing immediately from the surface of sealer; by the concavo-convex style of figuration wood grain conduit trough style, obtained the decorative laminate of regulation.
Table 1
Figure C200510059857D00161
Embodiment 2
Except the silicon dioxide granule that embodiment 2 hurdles that use table 1 are put down in writing, all the other have obtained the decorative laminate of regulation similarly to Example 1.
Comparative example 1～3
Except the silicon dioxide granule that comparative example 1～3 hurdle that uses table 1 is put down in writing, all the other are (wherein, the addition of the silicon dioxide granule of comparative example 3 is 6 weight portions) similarly to Example 1, has obtained the decorative laminate of regulation.
Test example 1
Investigated the following physical property of the decorative laminate that in embodiment and comparative example, obtains respectively.Each evaluation result is as shown in table 2.
(1) anti-steel wool
Use steel wool (#0), with certain pressure (300g/cm 2) come and go to wipe the sealer of 20 decorative laminates of examination after, estimated surface state (having or not scar).
(2) transportation property (actual usability)
Using emulsion is that bonding agent is fitted in decorative laminate on the MDF (15mm * 120mm * 20mm is thick).With stacked this ornament materials of the downward mode of MDF material, carry this ornament materials with truck and travel to and fro between between Okayama and the Tokyo.After coming and going, calculate the scar number on decorative laminate surface, estimated surface state (having or not scar).
(3) stain resistance
Cotton is placed on the decorative laminate.Then, cotton is dipped in full blue-black liquid.Then, coat decorative laminate with shrouding disc.After 24 hours, behind the clean decorative laminate of neutral detergent, estimated painted, the dustiness on decorative laminate surface.The evaluation method of contaminative is estimated according to JIS K 6902.
Test example 2
Investigated the physical property (frictional property) that in embodiment and comparative example, forms the employed composition of sealer.Evaluation result is as shown in table 2.
Make ink (above-mentioned each composition) circulation (rotating speed: 40m/m) with testing machine (version, scraper are arranged).Then, sampling in per 10 minutes is once used the visualization change color.Specifically, take ink one time in per 10 minutes, confirmed the change color of the coating in the ink tank.When the ink melanism, expression is owing to the friction with composition makes the scraper abrasion." the scraper abrasion are good " expression is difficult to produce abrasion.The time of time representation in the bracket of table 2 from on-test to the abrasion of affirmation scraper.
Table 2
Anti-steel wool Transportation property Stain resistance Frictional property
Embodiment 1 There is not scar There is not scar There is not residual look Scraper abrasion good (more than 2 hours)
Embodiment 2 There is not scar There is not scar There is not residual look Scraper abrasion good (more than 2 hours)
Comparative example 1 There is not scar There is not scar Confirm to have residual look Scraper abrasion bad (below 10 minutes)
Comparative example 2 Confirm to have scar Confirm to have a plurality of scars There is not residual look Scraper abrasion good (more than 2 hours)
Comparative example 3 Confirm to have scar Confirm to have a plurality of scars There is not residual look Scraper abrasion good (more than 2 hours)

Claims (8)

1. decorative laminate, it is to be layered in to adhere on the material and the decorative laminate that uses is characterized in that:
(1) this thin slice has substrate sheet, patterned layer, transparent resin bed and sealer at least successively;
(2) this sealer is by a) ionizing radiation gel-type resin and b) to contain apparent specific gravity be 0.3～1g/cm 3The composition of spherical particle form.
2. decorative laminate as claimed in claim 1 is characterized in that: form priming coat between transparent resin bed and sealer at least.
3. decorative laminate as claimed in claim 1 is characterized in that: the average grain diameter of spherical particle is below the 8 μ m.
4. decorative laminate as claimed in claim 1 is characterized in that: part or all of spherical particle is silicon dioxide granule.
5. decorative laminate as claimed in claim 1 is characterized in that: transparent resin bed is a vistanex.
6. decorative laminate as claimed in claim 1, it is characterized in that: sealer is with 15g/cm 2With the formation of getting off.
7. the manufacture method of a decorative laminate, this decorative laminate has substrate sheet, patterned layer, transparent resin bed and sealer at least successively, it is characterized in that: comprise by a) ionizing radiation gel-type resin and b) to contain apparent specific gravity be 0.3～1g/cm 3The composition of spherical particle form the operation of this sealer.
8. decorative panel is characterized in that: with the sealer of the described decorative laminate of claim 1 as the mode of superficial layer, this sheet lamination is formed adhering on the material.
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KR100792592B1 (en) * 2006-06-13 2008-01-09 주식회사 제승 Exterior panel of furniture or household electric appliances
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