CN101559661A - Scratch resistance resin board and use thereof - Google Patents
Scratch resistance resin board and use thereof Download PDFInfo
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- CN101559661A CN101559661A CNA2009101312508A CN200910131250A CN101559661A CN 101559661 A CN101559661 A CN 101559661A CN A2009101312508 A CNA2009101312508 A CN A2009101312508A CN 200910131250 A CN200910131250 A CN 200910131250A CN 101559661 A CN101559661 A CN 101559661A
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Abstract
The invention relate to a scratch resistance resin board and use thereof. A curing envelope is formed on at least one surface of an extruded plate formed by the extrusion molding of the thermoplastic resin and having the in-surface delay value of less than 15 nm. The thermoplastic resin may be methacrylate resin, the thickness of the extruded plate may be 0.2 to 3mm. The curing envelope be formed by the curing paint containing the compound with at least three (methyl) acryloyloxyls in the molecule.
Description
Technical field
The present invention relates to scratch resistant resin board and uses thereof.
Background technology
In recent years, along with popularizing of network, mobile phone, PHS (Personal Handy-phoneSystem) the portable telephone type of etc.ing are as not only having simple sound sound conveying function but also having the carrying type information terminal of display text information, image information function and extensively universal.In addition, except such portable telephone type, the PDA (Personal Digital Assistant) that has function of surfing the Net and e-mail function in function aspects such as address lists concurrently also is used on a large scale.In this manual, such mobile phone, PHS, PDA etc. are collectively referred to as " carrying type information terminal ".That is, said among the present invention " carrying type information terminal " is meant to the people and can carries the size of degree and have the general name of the information terminal of the window that is used for display text information, image information etc.
In these carrying type information terminals; come display text information, image information by liquid crystal, EL modes such as (electroluminescents), in its display window, generally use the plate of transparent resin system as baffle; especially from the aspect of the transparency, preferably use the methacrylic resin plate.In addition; for this baffle; in order to prevent surface tear, the scheme that the employing curable coating is provided with the curing tunicle of marresistance (hard conating) (open with reference to the spy 2002-6764 communique, spy are opened the 2004-143365 communique, the spy opens the 2004-299199 communique) has been proposed.
Summary of the invention
Angle from productivity ratio; extrusion molding make of transparent resin plate by thermoplastic resin that becomes the substrate of carrying type information terminal display window protective panel is favourable; but be provided with on the extrusion board of thermoplastic resin when solidifying tunicle, this marresistance of solidifying tunicle may not be abundant.
Thereby the inventor to be applicable to the extrusion board of thermoplastic resin and to have carried out concentrated research as substrate and have the scratch resistant resin board of the carrying type information terminal display window protective panel of the high curing tunicle of marresistance in order to develop.
The invention provides following means.
[1] a kind of scratch resistant resin board is characterized in that, be form to solidify tunicle in the one side at least of extrusion board to form, described extrusion board be thermoplastic resin is carried out that extrusion molding forms and face in length of delay be below the 15nm.
[2] according to above-mentioned [1] described scratch resistant resin board, wherein, thermoplastic resin is a methacrylic resin.
[3] according to above-mentioned [1] or [2] described scratch resistant resin board, wherein, the thickness of extrusion board is 0.2～3mm.
[4] according to each described scratch resistant resin board in above-mentioned [1]～[3], wherein, solidify tunicle and form by curable coating, described curable coating contains the compound that has 3 (methyl) acryloxies in molecule at least.
[5], wherein, solidify tunicle and form by the curable coating that contains electroconductive particle according to each described scratch resistant resin board in above-mentioned [1]～[4].
[6] according to each described scratch resistant resin board in above-mentioned [1]～[5], wherein, extrusion board is that the molten thermoplastic resin that will extrude from the mouth mould is clamped at least 1 and forms for moulding between two rollers of resilient roller.
[7] according to each described scratch resistant resin board in above-mentioned [1]～[6], wherein, extrusion board is carrying out heat treatment than the temperature of low 3～25 ℃ of the glass transition temperature of the thermoplastic resin that constitutes it.
[8] a kind of display window protective panel of carrying type information terminal is made by each described scratch resistant resin board in above-mentioned [1]～[7].
[9] a kind of display protection plate is made by each described scratch resistant resin board in above-mentioned [1]～[7].
According to the present invention; can easily obtain having the scratch resistant resin board of the high curing tunicle of marresistance; by the display window protective panel of this scratch resistant resin board as display protection plate, especially carrying type information terminal used, can effectively protect this display window.
The specific embodiment
Scratch resistant resin board of the present invention is to be substrate thermoplastic resin is carried out the extrusion board that extrusion molding forms, and its at least one side form and solidify that tunicle forms.In addition, length of delay is below the 15nm in the face of above-mentioned extrusion board.
As thermoplastic resin, can enumerate for example methacrylic resin, mylar, polycarbonate resin, poly-cyclic olefin resin, polystyrene resin, styrene-methacrylic acid copolymer (MS resin), acrylonitritrile-styrene resin (AS resin), polyvinylidene fluoride resin transparent resins such as (PVDF resins).Its kind can suitably be selected, and especially preferably uses methacrylic resin.
Methacrylic resin is the polymer based on methacrylate, can be the homopolymers of methacrylate, can also be the copolymer of the monomer beyond the following methacrylate of above methacrylate of 50 weight % and 50 weight %.Here, as methacrylate, use the Arrcostab of methacrylic acid usually.
The preferred monomers of methacrylic resin is formed, with whole monomers is benchmark, alkyl methacrylate is that 50～100 weight %, alkyl acrylate are that 0～50 weight %, the monomer except that them are 0～49 weight %, and more preferably alkyl methacrylate is that 50～99.9 weight %, alkyl acrylate are that 0.1～50 weight %, the monomer except that them are 0～49 weight %.
Here, as the example of alkyl methacrylate, can enumerate methyl methacrylate, EMA, butyl methacrylate, methacrylic acid 2-Octyl Nitrite etc., the carbon number of its alkyl is generally 1～8, is preferably 1～4.Wherein, preferably use methyl methacrylate.
In addition, as the example of alkyl acrylate, can enumerate methyl acrylate, ethyl acrylate, butyl acrylate, 2-EHA etc., the carbon number of its alkyl is generally 1～8, is preferably 1～4.
In addition, as the monomer beyond alkyl methacrylate and the alkyl acrylate, both can be monofunctional monomer, promptly in molecule, have a compound of 1 polymerism carbon-to-carbon double bond, also can be polyfunctional monomer, promptly in molecule, have the compound of 2 polymerism carbon-to-carbon double bonds at least, preferably use monofunctional monomer.In addition, as the example of this monofunctional monomer, can enumerate the aromatic series alkenyl compound of styrene, AMS, vinyltoluene and so on; The alkenyl cyano compound of acrylonitrile, methacrylonitrile and so on; The unsaturated carboxylic acid of acrylic acid, methacrylic acid and so on; Maleic anhydride, N-substituted maleimide amine etc.
And then, make the homopolymers of methyl methacrylate or methyl methacrylate and methacrylic acid and/or acrylic acid copolymer carry out cyclization, thereby the polymer with glutaric anhydride structure [formula (1)], glutarimide structure [formula (2)] also can be used as methacrylic resin and uses.
In the formula (1), R
1Expression hydrogen atom or methyl, R
2Expression hydrogen atom or methyl.In the formula (2), R
3Expression hydrogen atom or methyl, R
4Expression hydrogen atom or methyl, R
5Expression hydrogen atom or substituting group as this substituent example, can be enumerated the alkyl of methyl, ethyl and so on; The cycloalkyl of cyclohexyl and so on; The aryl of phenyl and so on; The aralkyl of benzyl and so on, its carbon number is generally about 1～20.
In addition, as the example of polyfunctional monomer, can enumerate many esters of unsaturated carboxylic acids of the polyalcohol of GDMA, tetramethylene dimethacrylate, trimethylolpropane triacrylate and so on; The alkenyl ester of the unsaturated carboxylic acid of allyl acrylate, allyl methacrylate, cinnamic acid allyl ester and so on; The polyalkenyl ester of the polyacid of diallyl phthalate, diallyl maleate, TAC, cyamelide triallyl and so on; The aromatic series polyalkenyl compound of divinylbenzene and so on etc.
In addition, above-mentioned alkyl methacrylate, alkyl acrylate and monomer in addition can use as required separately in them more than 2 kinds.
From the stable on heating angle of extrusion board, the glass transition temperature of methacrylic resin is preferably more than 60 ℃, more preferably more than 80 ℃.This glass transition temperature can suitably be set by adjusting monomeric species, its ratio.
Methacrylic resin can prepare the polymerization of monomer whose composition by methods such as suspension polymerisation, emulsion polymerisation, polymerisation in bulks.At this moment, for glass transition temperature or the viscosity that obtains suiting, preferably when polymerization, use chain-transferring agent to extrusion board demonstration mouldability in order to obtain suiting.The amount of chain-transferring agent can suitably be determined according to the kind of monomer, its ratio etc.
Can in thermoplastic resin, cooperate other composition, thereby use as resin combination.As this gradation composition, can enumerate colouring agent, antioxidant, ultra-violet absorber of for example rubber particles, dyestuff or pigment and so on etc.Especially the situation of methacrylic resin, during the compound rubber particle, the resistance to impact of extrusion board, flexibility improve, cracky not, thereby be preferred.
As the rubber particles that in thermoplastic resin, especially methacrylic resin, cooperates, can use for example various rubber particles such as acrylic acid series, butadiene-based, styrene-butadiene system, wherein, from the angle of weatherability, preferably use the acrylic rubber particle.As the acrylic rubber particle, can use the acrylic rubber particle of single layer structure for example, acrylic rubber particle of sandwich construction etc., the acrylic rubber particle of described single layer structure is formed by the elastomeric polymer based on the alkyl acrylate of butyl acrylate and so on, the acrylic rubber particle of described sandwich construction is provided with the skin that is formed by the elastomeric polymer based on the alkyl acrylate of butyl acrylate and so on around the internal layer that is formed by the rigid polymer based on methyl methacrylate.In addition, general copolymerization has a small amount of polyfunctional monomer in the above-mentioned elastomeric polymer.
In addition, the rubber particles that is provided with the outermost sandwich construction that is formed by the rigid polymer based on methyl methacrylate around above-mentioned elastomeric polymer also can effectively use.Can enumerate the rubber particles of for example following two-layer structure, the rubber particles of three-decker etc., the rubber particles of described two-layer structure is around the internal layer that is formed by the elastomeric polymer based on the alkyl acrylate of butyl acrylate and so on, be provided with the skin that forms by rigid polymer based on methyl methacrylate, the rubber particles of described three-decker is around the internal layer that is formed by the rigid polymer based on methyl methacrylate, the intermediate layer that setting is formed by the elastomeric polymer based on the alkyl acrylate of butyl acrylate and so on, and then around it, the skin that is formed by the rigid polymer based on methyl methacrylate is set.The rubber particles of such sandwich construction is disclosed in for example special public clear 55-27576 communique.The rubber particles of preferred especially above-mentioned three-decker, the rubber particles of record is one of preferred composition among the embodiment 3 of special public clear 55-27576 communique.
As the rubber particles that in thermoplastic resin, cooperates,, preferably use the rubber particles of average grain diameter at 0.05～0.4 μ m from the angle of case hardness, resistance to impact, surface smoothing.When the average grain diameter of rubber particles was too small, the case hardness of extrusion board was insufficient, and perhaps extrusion board becomes fragile.On the other hand, when the average grain diameter of rubber particles is excessive, there is the tendency of the surface smoothing of infringement extrusion board.Rubber particles generally can be made by emulsion polymerisation, at this moment, can average grain diameter be controlled to be desirable value by the addition of regulating emulsifying agent, the addition of monomer etc.
During the compound rubber particle, both ratios are preferably, and add up to 100 weight portions with both in thermoplastic resin, and thermoplastic resin is 50～95 weight portions, and rubber particles is 5～50 weight portions.When the amount of rubber particles is very few, the resistance to impact of extrusion board, flexibility are fully improved, in the time of too much, the case hardness of extrusion board, rigidity become insufficient, thereby are not preferred.
By with above-mentioned thermoplastic resin extrusion molding, can obtain extrusion board as the substrate of scratch resistant resin board of the present invention.Specifically, extrusion molding can be undertaken by the extrusion by melting of T modulus method, blow moulding and so on.The surface of the extrusion board that obtains can be level and smooth, also can be provided with fine concavo-convex.In order to give flatness or concaveconvex shape, from obtaining the angle of the good plate of surface texture, preferably thermoplastic resin is melt extruded from for example T type mouth mould, make the one side at least of the plate object that obtains contact the method for carrying out making sheet with roller or band.Especially from the flatness that improves extrusion board or the viewpoint of the accuracy that shape is given, the two sides of the plate object that thermoplastic resin is melt extruded and obtain is contacted and the method for moulding with roller surface or belt surface.At this moment roller of Shi Yonging or band all are preferably metal system.Therefore, as preferred scheme, can enumerate thermoplastic resin melt extruded from T type mouth mould after, the method for carrying out moulding under the state that is held contacting with at least 1 mirror roller, more preferably contacting with 2 mirror rollers.
In addition, extrusion board also can adopt sandwich construction as required.For example, as an example, can enumerate the sandwich construction etc. of the thermoplastic resin beyond the methacrylic resin of sandwich construction, methacrylic resin and polycarbonate resin and so on of the methacrylic resin that the contains rubber particles multiple methacrylic resin different with sandwich construction, the glass transition temperature of the methacrylic resin that does not conform to rubber particles.
When making the extrusion board of such sandwich construction, can use the known multilayer extruder of mechanisms such as the branch manifold mode that for example has the laminated resin that a plurality of extruders and being used for will extrude from them, feed block mode.
The thickness of extrusion board is generally 0.2～3mm, is preferably 0.25～2.5mm.When thickness was too small, as the substrate of display protection plate, intensity or rigidity were insufficient sometimes, and thickness is as the substrate of display protection plate, improper in design sometimes when excessive.In addition, when extrusion board is used as the substrate of display protection plate, can correspondingly use with the surface configuration of this display window with flat shape or shape with curved surface.
Among the present invention, in order to obtain length of delay in the necessary face is extrusion board below the 15nm, as long as mentioned above, to be held between 2 rollers by the molten thermoplastic resin that T type mouth mould is extruded and carry out moulding, the method of then using resilient roller and making molten thermoplastic resin's two sides contact, pass through with roller with face as at least 1 roller, distortion in the time of can reducing moulding reduces the anisotropy of intensity, heat-shrinkable, so is the method for optimizing that obtains the extrusion board that length of delay is little in the face.As resilient roller, the preferred metallic elastic roller that uses, for example, have beaming roller and the cylindrical metal made membrane that disposes and contact in the mode of the outer peripheral face of this beaming roller that is covered and between this beaming roller and metal made membrane, enclosed the roller of the controlled fluid of water, wet goods temperature with the molten thermoplastic resin; Reeled on the surface of the rubber rollers roller of metal tape.In addition, for the method for using 2 high rigid metal rollers, the speed of production when temperature that also can be by adjusting pressure between metallic roll, each metallic roll, extrusion molding etc., length of delay is below the 15nm in the face of the extrusion board that obtains thereby make.
And then, even length of delay is greater than the extrusion board of 15nm in the face, also can make that length of delay is below the 15nm in the face by carry out heat treated in the temperature of regulation.The temperature of this heat treated is preferably hanged down about 3～25 ℃ temperature than the glass transition temperature of the thermoplastic resin that constitutes extrusion board.In addition, the processing time can suitably be selected, and is generally 30 minutes～24 hours.Heating means also can suitably be selected, and for example can enumerate the method that in heated-air circulation oven standing methods, the radiant heat by heaters such as infrared rays heat.Wherein, standing methods preferred use in heated-air circulation oven owing to can handle a large amount of extrusion boards simultaneously.As the method that in heated-air circulation oven, leaves standstill extrusion board, both can leave standstill 1 separately, also can will leave standstill simultaneously after many coincidences.In addition, can also apply loading to the extrusion board that leaves standstill to avoid because of thermogenetic distortion.Loading can suitably be selected, but distributes for fear of produce loading in face, preferably sets loading in the mode that reaches equalization pressure.Loading also can suitably be selected, but is generally 0.001～0.1kg/cm
2About.After the heat treated of stipulated time, it is necessary that extrusion board is cooled to room temperature.Cooling means is not particularly limited, and both can take out extrusion board immediately, cools off after removing loading, takes out extrusion board after the state that also can keep applying loading slowly cools to room temperature.Reduce length of delay in the face, the preferred latter's method.When slowly cooling off, its temperature changing speed is not particularly limited, and is generally 2～30 ℃/Hr.
Be form to solidify tunicle on the one side at least of the extrusion board below the 15nm by length of delay in the face that obtains like this, can obtain having the scratch resistant resin board of the present invention of the high curing tunicle of marresistance.Being used to form the curable coating that solidifies tunicle is main component with the various curing compounds that bring marresistance, is mixed with solvent, electroconductive particle, curing catalysts etc. as required.
At first, curing property compound is described, and can use acrylate, urethane acrylate, epoxy acrylate, carboxy-modified epoxy acrylate, polyester acrylate, copolymerization is to have the curing compound of giving the marresistance effect in acrylate, alicyclic epoxy resin, tetraglycidel ether epoxy resin, vinyl ether compound, the oxetane compound etc.Wherein, as the curing compound that brings high marresistance, can enumerate radical polymerization syzygies such as polyfunctional acrylic ester system, multifunctional polyurethane acrylic ester, multi-functional epoxy's acrylic ester curing property compound; Hot polymerization such as alkoxy silane, alkylalkoxy silane syzygy curing property compound.Electron beam, radioactive ray, ultraviolet homenergic ray solidify these curing property compounds by for example shining, and perhaps solidify by heating.These curing property compounds can be distinguished use separately, also a plurality of compounds can be used in combination.
The compound that preferably in molecule, has 3 (methyl) acryloxies in these curing property compounds at least.Here, so-called (methyl) acryloxy is meant acryloxy or methacryloxy." (methyl) " when in addition, in this manual, being called (methyl) acrylate, (methyl) acrylic acid etc. also is the same meaning.
As the curing compound that in molecule, has 3 (methyl) acryloxies at least, can enumerate for example many (methyl) acrylate of the above polyalcohol of ternary of trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, glycerine three (methyl) acrylate, five glycerine three (methyl) acrylate, pentaerythrite three or four (methyl) acrylate, dipentaerythritol three, four, five or six (methyl) acrylate, tripentaerythritol four, five, six or seven (methyl) acrylate and so on; The number that makes the compound that has 2 NCOs in (methyl) acrylate monomer with hydroxyl and the molecule at least react (methyl) acryloxy that get, in a part with respect to above ratios of mole such as NCO serve as with hydroxyl be more than 3 polyurethane (methyl) acrylate [for example, by the reaction of vulcabond and pentaerythrite three (methyl) acrylate, obtain polyurethane (methyl) acrylate of 3～6 officials energy]; Three (methyl) acrylate of three (2-hydroxyethyl) cyamelide etc.Here show monomer, these monomers can directly use, and also can use becomes for example compound of the form of oligomer such as dimer, tripolymer.In addition, can also and use monomer and oligomer.
At least have in the curing compound of 3 (methyl) acryloxies, commercially available compound is also arranged, therefore also can use such commercially available product.As commercially available product, can enumerate for example " NKHARD M101 " [Xin Zhong village chemical industrial company goods, urethane acrylate system], " NKESTER A-TMM-3L " [Xin Zhong village chemical industrial company goods, pentaerythritol triacrylate], " NK ESTERA-TMMT " [Xin Zhong village chemical industrial company goods, tetramethylol methane tetraacrylate], " NK ESTER A-9530 " [Xin Zhong village chemical industrial company goods, dipentaerythritol five acrylate], " NK ESTER A-DPH " [Xin Zhong village chemical industrial company goods, dipentaerythritol acrylate], " KAYARAD DPCA " [Japanese chemical drug corporate system product, dipentaerythritol acrylate], " NOPCOCURE 200 " series [SAN NOPCO company goods], " UNIDIC " series [big Japanese ink chemical industrial company goods] etc.
At least the compound that has 3 (methyl) acryloxies preferably accounts for more than 50 weight portions with solid constituent 100 weight portions with respect to curable coating and then the mode that accounts for more than 60 weight portions is used.At least the content of curing compound that has 3 (methyl) acryloxies is during less than 50 weight portions, and case hardness may be insufficient.
Except the compound that in molecule, has 3 (methyl) acryloxies at least of above explanation, various mixtures for example shown below can also be used as curing property compound.These compounds can and be used with the compound that has 3 (methyl) acryloxies at least.
By malonic acid/trimethylolethane/(methyl) acrylic acid, malonic acid/trimethylolpropane/(methyl) acrylic acid, malonic acid/glycerine/(methyl) acrylic acid, malonic acid/pentaerythrite/(methyl) acrylic acid, succinic acid/trimethylolethane/(methyl) acrylic acid, succinic acid/trimethylolpropane/(methyl) acrylic acid, succinic acid/glycerine/(methyl) acrylic acid, succinic acid/pentaerythrite/(methyl) acrylic acid, adipic acid/trimethylolethane/(methyl) acrylic acid, adipic acid/trimethylolpropane/(methyl) acrylic acid, adipic acid/glycerine/(methyl) acrylic acid, adipic acid/pentaerythrite/(methyl) acrylic acid, glutaric acid/trimethylolethane/(methyl) acrylic acid, glutaric acid/trimethylolpropane/(methyl) acrylic acid, glutaric acid/glycerine/(methyl) acrylic acid, glutaric acid/pentaerythrite/(methyl) acrylic acid, decanedioic acid/trimethylolethane/(methyl) acrylic acid, decanedioic acid/trimethylolpropane/(methyl) acrylic acid, decanedioic acid/glycerine/(methyl) acrylic acid, decanedioic acid/pentaerythrite/(methyl) acrylic acid, fumaric acid/trimethylolethane/(methyl) acrylic acid, fumaric acid/trimethylolpropane/(methyl) acrylic acid, fumaric acid/glycerine/(methyl) acrylic acid, fumaric acid/pentaerythrite/(methyl) acrylic acid, itaconic acid/trimethylolethane/(methyl) acrylic acid, itaconic acid/trimethylolpropane/(methyl) acrylic acid, itaconic acid/pentaerythrite/(methyl) acrylic acid, maleic anhydride/trimethylolethane/(methyl) acrylic acid, the combination of the compound compositions of maleic anhydride/glycerine/(methyl) acrylic acid and so on and, saturated or unsaturated dibasic acid and (methyl) acrylic acid mixed polyester etc.
When curable coating being solidified, use Photoepolymerizationinitiater initiater with ultraviolet ray.As Photoepolymerizationinitiater initiater, can enumerate for example benzil, benzophenone and derivative thereof, thioxanthene ketone, benzil dimethyl ketal class, Alpha-hydroxy alkylbenzene ketone, hydroxyl ketone, aminoalkyl benzophenone class, acylphosphine oxide class etc.The addition of Photoepolymerizationinitiater initiater is generally the scope of 0.1～5 weight portion with respect to curing property compound 100 weight portions.
How these Photoepolymerizationinitiater initiaters can mix use more than 2 kinds except can distinguishing use separately.In addition, these various Photoepolymerizationinitiater initiaters are commercially available, therefore can use such commercially available product.As commercially available Photoepolymerizationinitiater initiater, for example can enumerate " IRGACURE 651 ", " IRGACURE 184 ", " IRGACURE 500 ", " IRGACURE 1000 ", " IRGACURE 2959 ", " DAROCUR 1173 ", " IRGACURE 907 ", " IRGACURE 369 ", " IRGACURE 1700 ", " IRGACURE 1800 ", " IRGACURE 819 ", " IRGACURE 784 " [above IRGACURE series and DAROCUR series are sold by Ciba company], " KAYACURE ITX ", " KAYACURE DETX-S ", " KAYACURE BP-100 ", " KAYACUREBMS ", " KAYACURE 2-EAQ " [above KAYACURE series is sold by Japanese chemical drug company] etc.
In addition, in the present invention,, can in curable coating, add electroconductive particle in order to give static electricity resistance to solidifying tunicle.As the electroconductive particle that is used for this purpose, can enumerate the tin oxide that for example is doped with antimony, the tin oxide that is doped with phosphorus, antimony oxide, zinc antimonates, titanium oxide, ITO inorganic particulates such as (indium tin oxides).
When cooperating electroconductive particle, its particle diameter can suitably be selected according to the kind of particle, uses the following particle of 0.5 μ m usually, from the static electricity resistance of the curing tunicle that obtains, the viewpoint of the transparency, in the preferred 0.001 μ m of average grain diameter～0.1 μ m, more preferably 0.001 μ m～0.05 μ m.When the average grain diameter of electroconductive particle was excessive, it is big that the mist degree of the scratch resistant resin board that obtains sometimes becomes, and the transparency reduces.In addition, the use amount of electroconductive particle is generally about 2～50 weight portions, about preferred 3～20 weight portions with respect to curing property compound 100 weight portions.It is measured when very few, lacks the effect that static electricity resistance improves.And it is measured when too much, and the transparency of solidifying tunicle is reduced.
This electroconductive particle can wait and make by for example gas-phase decomposition method, plasma evaporation method, alkoxide decomposition method, coprecipitation, hydro-thermal method.In addition, the surface of electroconductive particle can be that surfactant, cation are that surfactant, anion are that surfactant, silicon are that coupling agent, aluminium are that coupling agent etc. carries out surface treatment with for example nonionic.
In the curable coating, use retarder thinner, when especially adding electroconductive particle, must use for its dispersion for purpose such as the viscosity adjusting of coating.When using electroconductive particle and using solvent, for example can be with electroconductive particle and solvent, make electroconductive particle be dispersed in the solvent after, with curing property compound, can also mix to wherein adding electroconductive particle after curing property compound and the solvent.
Solvent so long as can dissolving cured property compound and after coating volatilizable solvent get final product, and when using electroconductive particle, so long as the solvent of its dispersion is got final product as paint ingredient.Can enumerate for example alcohols of DAA, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, 2-methyl cellosolve, cellosolvo, butoxy ethanol, 1-methoxyl group-2-propyl alcohol and so on; The ketone of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), DAA and so on; The arene of toluene, dimethylbenzene and so on; The ester class of ethyl acetate, butyl acetate and so on; Water etc.The use amount of solvent is not particularly limited in the curable coating, can cooperate the proterties etc. of curing property compound to use with suitable amount.
In addition, can add known levelling agent in this curable coating.As levelling agent, can illustration for example silicone oil be levelling agent etc.Can use common silicone oil as silicone oil; specifically, can the illustration dimethicone, phenyl methyl silicone oil, alkyl aralkyl modified silicon oil, fluorosilicon oil, polyether modified silicon oil, fatty acid ester modified silicon oil, methyl hydrogen silicone oil, the silicone oil that contains silanol group, the silicone oil that contains alkoxyl, the silicone oil that contains phenolic group, methacryl modified silicon oil, amino-modified silicone oil, carboxyl acid modified silicone oil, methyl alcohol modified silicon oil, epoxy radicals modified silicon oil, sulfhydryl modified silicone oil, fluorine modified silicon oil, polyether modified silicon oil etc.These levelling agents are existing commercially available, therefore can use commercially available product.As commercially available levelling agent, for example can enumerate " SH200-100cs ", " SH28PA ", " SH29PA ", " SH30PA ", " ST83PA ", " ST80PA ", " ST97PA ", " ST86PA " [above] etc. by the sale of TORAYDOWCORNING SLICONE company.These levelling agents can be used alone, can also be two or more kinds in combination respectively.The use amount of levelling agent can suitably be selected according to the characteristic of curable coating, with respect to curing property compound 100 weight portions, is about 0.01～5 weight portion generally.
Like this, in curing property compound as required mixed conductivity particle, solvent, levelling agent, Photoepolymerizationinitiater initiater etc. and curable coating, forming curing property in the coating of the surface of described extrusion board films, make it then to solidify, thereby can be formed in the scratch resistant resin board that the surface forms the curing tunicle of marresistance.
Coating curable coating on described extrusion board and when forming curing property and filming, can be coated with known coating processes such as method, spraying process and be coated with by for example scraper rubbing method, nick version (microgravure) rubbing method, rolling method, flow coat method, dip coating, spin-coating method, mould.Like this, forming curing property on the surface of described extrusion board films.Then, according to the kind of curable coating, by irradiation ultraviolet radiation, electron beam homenergic ray, perhaps heating, thus make curing property curing of coating, form the curing tunicle of marresistance.
Energy-ray when being cured as the irradiation energy ray can be enumerated for example ultraviolet ray, electron beam, radioactive ray etc., and its intensity, irradiation time etc. can suitably be selected according to the kind of the curable coating that uses.In addition, the heating-up temperature when being cured by heating, heat time heating time etc. can suitably be selected according to the kind of the curable coating that uses, and when being heating and curing, do not deform etc. in order to make extrusion board as substrate, generally preferred temperature below 100 ℃.When curable coating contains solvent, can after coating, make solvent evaporates, make curing property curing of coating then, also can carry out the curing that the volatilization of solvent and curing property are filmed simultaneously.Here, the volatilization of solvent, promptly film dry insufficient the time, the marresistance of the curing tunicle that obtains becomes insufficient easily, in this case, according to the present invention, the extrusion board by adopting afore mentioned rules can easily form the high curing tunicle of marresistance as substrate.
The thickness that solidifies tunicle is preferably about 0.5～50 μ m, more preferably about 1～20 μ m.Solidify the thickness of tunicle when excessive, have the tendency that easily produces be full of cracks, when too small, have the marresistance inadequate tendency that becomes.
For the scratch resistant resin board that obtains, can pass through known method such as rubbing method, sputtering method, vacuum vapour deposition the antireflection processing is implemented on its surface.In addition, the antireflection sheet of making separately of can also fitting on the single face of above-mentioned scratch resistant resin board or two sides is given anti-reflection effect.
The scratch resistant resin board that obtains like this has the high curing tunicle of marresistance; can be used for various uses; wherein; be suitable for display window protective panel as carrying type information terminals such as mobile phones; in addition; can also be as the view finder portion of digital camera, handheld video camera etc., the display window protective panel of portable game machine etc. and home-use or work with the picture baffle of TV etc., not only with carrying type information terminal, also be that the display protection plate of object uses with other portable display device, the type display device of setting.Scratch resistant resin board of the present invention is brought into play particularly advantageous effect as mobile phone, especially adopt the display window protective panel of the display part mobile phone of the structure of folding and overlapping operation button portion when not using comprise display window.
When making display protection plate, processing such as print, punch at first as required, be cut to the size that needs and get final product by scratch resistant resin board of the present invention.Then, be installed on display, can make the high display of marresistance.
Embodiment
Below, embodiment is shown further describes the present invention, but the present invention is not subjected to the restriction of these embodiment.In the example, unless otherwise specified, the % of expression content or use amount and part are weight basis.In addition, length of delay in the face of extrusion board (below, note by abridging be " Re ") uses automatic birefringence meter [KOBRA-CCD/X of prince's tester corporate system] to measure.
[preparation of extrusion board (A1)]
With methacrylic resin pellet [sumitomo chemical company system Sumipex EX, 97 ℃ of glass transition temperatures] use the single shaft extruder [Toshiba Machine Co. Ltd's system] of 65mm φ to carry out melting mixing, Jie is extruded by T type mouth mould, cool off with the mode that the metal system polishing rod of 2 high rigidity contacts fully with the two sides, obtain the extrusion board (A1) of thick 1.0mm.
[preparation of extrusion board (A2)]
Resistance to impact methacrylic resin pellet [the sumitomo chemical company system Sumipex HT-55X of rubber will be added with, 94 ℃ of glass transition temperatures] use the single shaft extruder [Toshiba Machine Co. Ltd's system] of 65mm φ to carry out melting mixing, Jie is extruded by T type mouth mould, cool off with the mode that the metal system polishing rod of 2 high rigidity contacts fully with the two sides, obtain the extrusion board (A2) of thick 0.5mm.
[preparation of extrusion board (A3)]
With methacrylic resin pellet [sumitomo chemical company system Sumipex EX, 97 ℃ of glass transition temperatures] use the single shaft extruder [Toshiba Machine Co. Ltd's system] of 65mm φ to carry out melting mixing, Jie is extruded by T type mouth mould, be held on the metal system polishing rod of 1 high rigidity and 1 between the metallic elastic rod that coiling metal sleeve on the rubber stick forms, cool off with the mode that roll surface contacts fully on two sides with molten resin, obtains the extrusion board (A3) of thick 1.0mm.
[preparation of curable coating (B1)]
With 30 parts of dipentaerythritol acrylates [by " the NK ESTERA-DPH " of Xin Zhong village chemical industrial company sale], 1-methoxyl group-20 parts of 2-propyl alcohol, 50 parts of cellosolvos, 2 parts of Photoepolymerizationinitiater initiaters [by " IRGACURE 184 " of Ciba company sale] and 0.045 part of mixing of silicone oil [by " SH28PA " of TORAY DOWCORNING SLICONE company sale], preparation curable coating (B1).
[preparation of curable coating (B2)]
With 27.7 parts of dipentaerythritol acrylates [" the NK ESTERA-DPH " that sell by Xin Zhong village chemical industrial company], 1.5 parts of Photoepolymerizationinitiater initiaters [IRGACURE 184 of Ciba company], [catalyst changes into the ELCOM-7514 of industrial group to antimony pentaoxide particulate colloidal sol, solid component concentration 20%] 0.045 part of mixing of 12 parts, 29.4 parts of isobutanols, 1-methoxyl group-29.4 parts of 2-propyl alcohol and silicone oil [" SH28PA " that sell by TORAY DOWCORNING SLICONE company], preparation curable coating (B2).
Embodiment 1
(1) heat treated of extrusion board
Extrusion board (A1) is cut to the size of 200mm * 300mm, and leave standstill in 80 ℃ heated-air circulation oven 5 overlapping backs, applies the loading (0.017kg/cm of 10kg in the mode that reaches equalization pressure
2), left standstill 8 hours.Then under the state that has applied loading, be cooled to room temperature with the speed of 10 ℃/Hr.
(2) making of scratch resistant resin board
Extrusion board (A1) after the heat treated that obtains in the dipping above-mentioned (1) in curable coating (B1) (Re5.4nm), speed with 5mm/sec is mentioned, thereby,, form on the surface of extrusion board and to film then drying at room temperature 1 minute at the two sided coatings curable coating.Then, after making solvent evaporates, use the high-pressure sodium lamp of 120W, to this irradiation 0.5J/cm that films 45 ℃ hot-air oven inner dryings 10 minutes
2Ultraviolet ray make it to solidify, obtain scratch resistant resin board.This scratch resistant resin board is carried out following evaluation, show the result in table 1.
[total light transmittance (Tt) and mist degree (H)]
Measure total light transmittance (Tt) according to JIS K7361-1, measure mist degree (H) according to JIS K7136.
[solidifying the thickness of tunicle]
Use the micro-film thickness gauge of high speed [big tomb electronics corporation system, MS-2000] to measure.
[pencil hardness]
Measure according to JIS K5600.
[surface resistivity]
Measure according to ASTM-D257.
Embodiment 2
Except the temperature of heated-air circulation oven is changed into 90 ℃ by 80 ℃,, carry out the heat treated of extrusion board (A1) by the operation same with embodiment 1 (1).Use after this heat treated extrusion board (A1) (Re2.8nm), carry out the operation same with embodiment 1 (2), obtain scratch resistant resin board.This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
Comparative example 1
Extrusion board (A1) is cut to the size of 200mm * 300mm, does not carry out heat treated (Re15.8nm), carry out the operation same, obtain scratch resistant resin board with embodiment 1 (2).This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
Embodiment 3
Except using extrusion board (A2) to replace the extrusion board (A1),, carry out the heat treated of extrusion board (A2) by the operation same with embodiment 1 (1).Use after this heat treated extrusion board (A2) (Re10.1nm), carry out the operation same with embodiment 1 (2), obtain scratch resistant resin board.This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
Embodiment 4
Except using extrusion board (A2) to replace extrusion board (A1) and the temperature of heated-air circulation oven is changed into 90 ℃ by 80 ℃,, carry out the heat treated of extrusion board (A2) by the operation same with embodiment 1 (1).Use after this heat treated extrusion board (A2) (Re2.7nm), carry out the operation same with embodiment 1 (2), obtain scratch resistant resin board.This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
Comparative example 2
Extrusion board (A2) is cut to the size of 200mm * 300mm, does not carry out heat treated (Re19.0nm), carry out the operation same, obtain scratch resistant resin board with embodiment 1 (2).This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
Embodiment 5
Extrusion board (A3) is cut to the size of 200mm * 300mm, does not carry out heat treated (Re6.5nm), carry out the operation same, obtain scratch resistant resin board with embodiment 1 (2).This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
Embodiment 6
By carrying out the heat treated of extrusion board (A1) with the same operation of embodiment 1 (1), use after this heat treated extrusion board (A1) (Re5.3nm), except using curable coating (B2) replacement curable coating (B1), carry out the operation same, obtain scratch resistant resin board with embodiment 1 (2).This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
Comparative example 3
Extrusion board (A1) is cut to the size of 200mm * 300mm, does not carry out heat treated (Re16.4nm), replace the curable coating (B1), carry out the operation same, obtain scratch resistant resin board with embodiment 1 (2) except using curable coating (B2).This scratch resistant resin board is carried out similarly to Example 1 evaluation, show the result in table 1.
[table 1]
| Re (nm) | Thickness (μ m) | Tt (％) | H (％) | Pencil hardness | Surface resistivity (Ω/) | |
| Embodiment 1 | 5.4 | 3.2 | 91.5 | 0.3 | 5H | 10 15≤ |
| Embodiment 2 | 2.8 | 3.4 | 91.5 | 0.3 | 5H | 10 15≤ |
| Comparative example 1 | 15.8 | 3.3 | 91.5 | 0.2 | 4H | 10 15≤ |
| Embodiment 3 | 10.1 | 3.3 | 91.2 | 0.4 | 3H | 10 15≤ |
| Embodiment 4 | 2.7 | 3.2 | 91.2 | 0.5 | 3H | 10 15≤ |
| Comparative example 2 | 19.0 | 3.3 | 91.2 | 0.5 | 2H | 10 15≤ |
| Embodiment 5 | 6.5 | 3.4 | 91.5 | 0.3 | 5H | 10 15≤ |
| Embodiment 6 | 5.3 | 3.6 | 91.3 | 0.5 | 5H | 2×10 11 |
| Comparative example 3 | 16.4 | 3.5 | 91.3 | 0.5 | 4H | 2×10 11 |
Claims (9)
1. a scratch resistant resin board is characterized in that, be form to solidify tunicle in the one side at least of extrusion board to form, described extrusion board be thermoplastic resin is carried out that extrusion molding forms and face in length of delay be below the 15nm.
2. scratch resistant resin board according to claim 1, wherein, thermoplastic resin is a methacrylic resin.
3. scratch resistant resin board according to claim 1, wherein, the thickness of extrusion board is 0.2～3mm.
4. scratch resistant resin board according to claim 1 wherein, solidifies tunicle and is formed by curable coating, and described curable coating contains the compound that has 3 (methyl) acryloxies in molecule at least.
5. scratch resistant resin board according to claim 1 wherein, solidifies tunicle and is formed by the curable coating that contains electroconductive particle.
6. scratch resistant resin board according to claim 1, wherein, extrusion board is that the molten thermoplastic resin that will extrude from the mouth mould is clamped at least 1 and forms for moulding between two rollers of resilient roller.
7. scratch resistant resin board according to claim 1, wherein, extrusion board is carrying out heat treatment than the temperature of low 3～25 ℃ of the glass transition temperature of the thermoplastic resin that constitutes it.
8. the display window protective panel of a carrying type information terminal is made by each described scratch resistant resin board in the claim 1～7.
9. a display protection plate is made by each described scratch resistant resin board in the claim 1～7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008105381 | 2008-04-15 | ||
| JP2008105381 | 2008-04-15 | ||
| JP2008177646 | 2008-07-08 |
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| CN101559661A true CN101559661A (en) | 2009-10-21 |
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| JP (1) | JP5262366B2 (en) |
| CN (1) | CN101559661A (en) |
| TW (1) | TW201004801A (en) |
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| JP5523948B2 (en) * | 2009-07-16 | 2014-06-18 | 日本合成化学工業株式会社 | Resin molded body and protective plate for display |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006341393A (en) * | 2005-06-07 | 2006-12-21 | Fujifilm Holdings Corp | Manufacturing method of cellulose acylate resin film |
| CN101117402A (en) * | 2006-08-04 | 2008-02-06 | 住友化学株式会社 | Scratch resistant resin board and usage thereof |
| CN101157260A (en) * | 2006-06-06 | 2008-04-09 | 富士胶片株式会社 | Thermoplastic resin membrane as well as preparing method thereof, polaroid, optical compensation membrane, reflecting resistance membrane as well as LCD |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4223359B2 (en) * | 2003-09-05 | 2009-02-12 | Ｊｓｒ株式会社 | Method for producing transparent conductive laminate and touch panel |
| JP2007042284A (en) * | 2003-10-27 | 2007-02-15 | Teijin Ltd | Transparent conductive lamination body and transparent touch panel |
| JP5044941B2 (en) * | 2005-02-02 | 2012-10-10 | 三菱瓦斯化学株式会社 | Polyester film, method for producing the same, and use thereof |
| JP2007113109A (en) * | 2005-09-26 | 2007-05-10 | Asahi Kasei Chemicals Corp | Zinc oxide transparent conductive multilayer body by ion-plating process and method for producing the same |
| JP2007113110A (en) * | 2005-09-26 | 2007-05-10 | Asahi Kasei Chemicals Corp | Zinc oxide transparent conductive multilayer body and method for producing the same |
-
2008
- 2008-07-08 JP JP2008177646A patent/JP5262366B2/en active Active
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2009
- 2009-04-10 CN CNA2009101312508A patent/CN101559661A/en active Pending
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006341393A (en) * | 2005-06-07 | 2006-12-21 | Fujifilm Holdings Corp | Manufacturing method of cellulose acylate resin film |
| CN101157260A (en) * | 2006-06-06 | 2008-04-09 | 富士胶片株式会社 | Thermoplastic resin membrane as well as preparing method thereof, polaroid, optical compensation membrane, reflecting resistance membrane as well as LCD |
| CN101117402A (en) * | 2006-08-04 | 2008-02-06 | 住友化学株式会社 | Scratch resistant resin board and usage thereof |
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| JP2009274430A (en) | 2009-11-26 |
| TW201004801A (en) | 2010-02-01 |
| JP5262366B2 (en) | 2013-08-14 |
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Application publication date: 20091021 |