CN101544085A - Scratch-resistant resin plate and display window protecting plate of portable information terminal using the same - Google Patents
Scratch-resistant resin plate and display window protecting plate of portable information terminal using the same Download PDFInfo
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- CN101544085A CN101544085A CNA2009101293687A CN200910129368A CN101544085A CN 101544085 A CN101544085 A CN 101544085A CN A2009101293687 A CNA2009101293687 A CN A2009101293687A CN 200910129368 A CN200910129368 A CN 200910129368A CN 101544085 A CN101544085 A CN 101544085A
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- resistant resin
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Abstract
The present invention relates to a scratch-resistant resin plate and a display window protecting plate of a portable information terminal using the same. The scratch-resistant resin plate according to the invention is obtained by forming a solidified film with a static friction coefficient less than 0.4 relatively to the resin substrate on one surface of the resin substrate and furthermore forming a solidified film with a static friction coefficient larger than 0.4 relatively to the resin substrate on the other surface of the resin substrate. The display window protecting plate of the portable information terminal according to the invention is manufactured by the scratch-resistant resin plate.
Description
Technical field
The present invention relates to be suitable for as the scratch resistant resin board of the display window protective panel of carrying type information terminal and the display window protective panel that uses its carrying type information terminal.
Background technology
Recently, 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, PDA (Personal Digital Assistant) that has function of surfing the Net and e-mail function in function aspects such as address lists concurrently etc. also is used on a large scale.
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 (for example, open 2002-6764 communique, spy are opened the 2004-143365 communique, the spy opens the 2004-299199 communique) of transparent resin system with reference to the spy as baffle.In addition, for this baffle, in order to prevent surface tear, proposed the employing curable coating the have marresistance scheme of curing tunicle of (hard conating) has been set.
On the other hand, along with the slimming of carrying type information terminal, correspondingly, to the also raising of slimming requirement of display window protective panel.
But,, easily contact with liquid crystal face (i.e. the polarizer of the Liquid crystal component of conduct inside) if with the display window protective panel slimming then be prone to bending.If display window protective panel contacts with polarizer, can produce the light interference pattern that is called as Newton's ring, and it can not disappear, thereby have the problem of the image quality reduction of image.
Summary of the invention
Problem of the present invention is, the one side that is provided at resin substrate is formed with the scratch resistant resin board of curing tunicle of the image quality reduction that can suppress image and the display window protective panel that uses its carrying type information terminal.
The inventor etc. have carried out further investigation repeatedly for solving above-mentioned problem, found that the solution that comprises following formation, thereby have finished the present invention.
(1) a kind of scratch resistant resin board, be formed with respect to the confficient of static friction of described resin substrate less than 0.4 curing tunicle in the one side of resin substrate, and be formed with confficient of static friction with respect to described resin substrate at the curing tunicle more than 0.4 at another side.
(2) above-mentioned (1) described scratch resistant resin board, wherein, described confficient of static friction has 10 at the curing tunicle more than 0.4
9～10
14The surface resistivity of Ω/.
(3) above-mentioned (1) or (2) described scratch resistant resin board, wherein, the thickness of described resin substrate is 0.3～1.5mm.
(4) each described scratch resistant resin board in above-mentioned (1)～(3), wherein, described resin substrate is the acrylic resin plate.
(5) each described scratch resistant resin board in above-mentioned (1)～(3), wherein, described resin substrate is the plywood that forms at the folded methacrylic resin layer in the upper strata of one side at least of polycarbonate resin.
(6) each described scratch resistant resin board in above-mentioned (1)～(5), wherein, described resin substrate contains rubber particles.
(7) 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)～(6).
(8) display window protective panel of above-mentioned (7) described carrying type information terminal, wherein, will be formed with described confficient of static friction less than the face of 0.4 curing tunicle towards the setting of liquid crystal face side.
It should be noted that, described " carrying type information terminal " in this specification, be meant to the people can carry the size of degree and have the information terminal general name of the window (display) that is used for display text information, image information etc., can enumerate for example above-mentioned in illustrative mobile phone, PHS, PDA etc.
According to the present invention, form with respect to the confficient of static friction of described resin substrate less than 0.4 curing tunicle in the one side of resin substrate, therefore even should solidify tunicle contacts with the polarizer of Liquid crystal component and produces Newton's ring, because this curing tunicle leaves polarizer by sliding on polarizer, so Newton's ring easily disappears.Therefore,,, it is disappeared, can suppress the effect that image quality reduces even have the Newton's ring of generation according to the present invention.And, owing to be formed with the curing tunicle of regulation at another side, so, can effectively protect this display window by the display window protective panel of this scratch resistant resin board as carrying type information terminal used.
Especially shown in above-mentioned (2), confficient of static friction has 10 at the curing tunicle more than 0.4
9～10
14During the surface resistivity of Ω/, can suppress dust, dust adheres to this curing tunicle.
When the present invention was applied to flexible scratch resistant resin board shown in above-mentioned (3), serviceability of the present invention further improved.
Shown in above-mentioned (8), will be formed with confficient of static friction less than the face of 0.4 curing tunicle when liquid crystal face side is provided with; be to show excellent characteristic aspect the desired transparency of display window protective panel, case hardness of the carrying type information terminal of representative with the mobile phone; and the Newton's ring that produces is overleaf disappeared; the display window of carrying type information terminal can be protected, its reliability can be improved.
Description of drawings
Fig. 1 is a schematic illustration of measuring the method for confficient of static friction among the expression embodiment.
Symbol description
1 base
10 assess sample
11,21 resin substrates
12,13 solidify tunicle
20 counterweights
The specific embodiment
Scratch resistant resin board of the present invention is to be formed with specific curing tunicle to form on the two sides of resin substrate.As the resin that constitutes described resin substrate, for example can enumerate acrylic resin, polycarbonate resin, polystyrene resin, SAN, cellulose triacetate resins etc. such as methacrylic resin.The transparency of methacrylic resin is high and rigidity is also high, therefore is particularly suitable for as the resin that constitutes substrate.
Described methacrylic resin is the polymer based on methacrylate, for example 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 %.During for copolymer, the ratio that methacrylate accounts for whole monomers is preferably more than the 70 weight %, more preferably more than the 90 weight %.
As described methacrylate, preferably use alkyl methacrylate, especially preferably use methyl methacrylate.In addition, as the monomer beyond the methacrylate, can enumerate for example acrylate such as methyl acrylate, ethyl acrylate; Aromatic series such as styrene, methyl styrene alkenyl compound; Unsaturated carboxylic acid such as acrylic acid, methacrylic acid; Alkenyl such as acrylonitrile, methacrylonitrile cyano compound etc.
As described polycarbonate resin, for example can enumerate by interface polycondensation, melt transesterification process etc. making polycarbonate resin that dihydric phenol and carbonylation agent reaction get, making polycarbonate resin that the polymerization of carbonic ester prepolymer gets, make polycarbonate resin that the cyclic carbonate compound polymerization gets etc. by the ring-opening polymerisation method by solid phase ester-interchange method etc.
As described dihydric phenol, can enumerate for example hydroquinones, resorcinol, 4,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) methane, two { (4-hydroxyls-3, the 5-dimethyl) phenyl } methane, 1, two (4-hydroxy phenyl) ethane of 1-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 2, two (4-hydroxy phenyl) propane (common name bisphenol-A) of 2-, 2, two { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, two { (the 4-hydroxyls-3 of 2-, the 5-dimethyl) phenyl } propane, 2, two { (the 4-hydroxyls-3 of 2-, the 5-dibromo) phenyl } propane, 2, two { (3-isopropyl-4-hydroxyl) phenyl } propane of 2-, 2, two { (4-hydroxyl-3-phenyl) phenyl } propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-the hydroxy phenyl)-3-methybutanes of 2-, 2, two (the 4-hydroxy phenyls)-3 of 2-, the 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-2-methybutanes of 4-, 2, two (4-hydroxy phenyl) pentanes of 2-, 2, two (4-the hydroxy phenyl)-4-methylpentanes of 2-, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, 1, two (4-the hydroxy phenyl)-4-isopropyl cyclohexanes of 1-, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two { (4-hydroxy-3-methyl) phenyl } fluorenes of 9-, α, the adjacent diisopropyl benzene of α '-two (4-hydroxy phenyl), α, diisopropyl benzene between α '-two (4-hydroxy phenyl), α, α '-two (4-hydroxy phenyl) is to diisopropyl benzene, 1, two (the 4-hydroxy phenyls)-5 of 3-, the 7-dimethyladamantane, 4,4 '-dihydroxydiphenylsulisomer, 4,4 '-dihydroxy diphenyl sulfoxide, 4,4 '-dihydroxy diphenylsulfide, 4,4 '-dihydroxy diphenylketone, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxy diphenyl etc., can use as required in them more than 2 kinds.
Wherein, the preferred use is selected from bisphenol-A, 2, two { (4-hydroxy-3-methyl) phenyl } propane, 2 of 2-, two (4-hydroxy phenyl) butane, 2 of 2-, two (4-the hydroxy phenyl)-3-methybutanes, 2 of 2-, two (the 4-hydroxy phenyls)-3 of 2-, 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-4-methylpentanes, 1 of 2-, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane and α, the dihydric phenol between α '-two (4-hydroxy phenyl) in the diisopropyl benzene independent a kind of or more than 2 kinds.The preferred especially bisphenol-A that uses separately, perhaps bisphenol-A be selected from 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane, 2, two { (4-hydroxy-3-methyl) phenyl } propane and the α of 2-, the also usefulness of more than one dihydric phenols between α '-two (4-hydroxy phenyl) in the diisopropyl benzene.
As described carbonylation agent, for example can enumerate, two haloform esters of carbonic esters such as carbonyl halides such as phosgene, diphenyl carbonate, dihydric phenol (haloform ester such as ジ Ha ロ ホ Le メ-ト) (Ha ロ ホ Le メ-ト) etc., can use as required in them more than 2 kinds.
Resin substrate is not limited to individual layer, and the resin substrate that difference can be formed is stacked and form sandwich construction.Can improve the rigidity of resin substrate thus.Can be preferably about 2～4 layers for more than 2 layers as stacked number.
When resin substrate was made sandwich construction, preferably at least 1 layer was the methacrylic resin layer.If enumerate concrete example, can enumerate the sandwich construction etc. of sandwich construction, methacrylic resin layer and phenylethylene resin series layer of sandwich construction, methacrylic resin layer and the polycarbonate resin of the methacrylic resin layer that contains the aftermentioned rubber particles methacrylic resin layer different with sandwich construction, the glass transition temperature of the methacrylic resin layer that does not contain rubber particles.
In addition, when resin substrate was made sandwich construction, from the marresistance aspect, preferred top layer was the methacrylic resin layer.For its thickness, when two top layers are the methacrylic resin layer,, can be preferably more than the 10 μ m for more than the 3 μ m usually, more preferably more than the 30 μ m as the thickness on each top layer.By making above-mentioned thickness, can obtain sufficient surface hardness as the thickness of the methacrylic resin layer on top layer.
In methacrylic resin layer, in the scope that does not reduce case hardness, can contain rubber particles as the top layer.As the content of rubber particles, be 1 weight %～50 weight % usually in methacrylic resin, below the preferred 30 weight %, more preferably below the 20 weight %.
As the resin substrate of sandwich construction, the plywood that forms at the folded methacrylic resin layer in the upper strata of one side at least of polycarbonate resin since mechanical strength height, excellent scratch resistance therefore especially preferably use.In this plywood, the thickness of polycarbonate resin can be more than 50% of gross thickness.In addition, thickness for the methacrylic resin layer, when the two sides of polycarbonate resin is laminated with the methacrylic resin layer, as the thickness of each methacrylic resin layer, with above-mentioned same, be generally more than the 3 μ m, be preferably more than the 10 μ m, more preferably more than the 30 μ m, and be generally below the 120 μ m, be preferably below the 110 μ m, more preferably below the 100 μ m.In addition, during stacked methacrylic resin layer, the composition of two methacrylic resin layers, thickness can be mutually the same, also can be different on the two sides of polycarbonate resin.
From giving the viewpoint of resistance to impact, preferably contain rubber particles in the resin substrate.Kind as rubber particles, can use for example rubber such as acrylic acid series, butadiene-based, styrene-butadiene system, wherein, from all physical properties balance aspects such as the case hardness of the resin substrate that obtains, weatherability, resistance to impact, the rubber particles of preferred acrylic acid series.As the acrylic rubber particle, can use for example acrylic rubber particle of single layer structure, known acrylic rubber particles such as the acrylic rubber particle of sandwich construction, the acrylic rubber particle of described single layer structure is that the elastomeric polymer of main component forms by the alkyl acrylate with butyl acrylate and so on, the acrylic rubber particle of described sandwich construction is around the internal layer that is formed by the rigid polymer that with the methyl methacrylate is main component, and being provided with by the alkyl acrylate with butyl acrylate and so on is the skin that the elastomeric polymer of main component forms.General minor amounts of copolymerized has the polyfunctional monomer of bridging property in the elastomeric polymer.
In addition, the rubber particles that is provided with the outermost structure that is formed by the rigid polymer that with the methyl methacrylate is main component around elastomeric polymer also can effectively use.For example, can enumerate the rubber particles of following three-decker etc., promptly, around the internal layer that forms by the rigid polymer that with the methyl methacrylate is main component, setting is the intermediate layer that the elastomeric polymer of main component forms by the alkyl acrylate with butyl acrylate and so on, and then around it, the outermost layer that is formed by the rigid polymer that with the methyl methacrylate is main component 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.
The average grain diameter of rubber particles can suitably be selected according to this particle, wherein, especially preferably uses the rubber particles of its average grain diameter at 0.1～0.4 mu m range.The average grain diameter of rubber particles can obtain the resin substrate of resistance to impact height, case hardness excellence, surface smoothing when this scope.When the average grain diameter of rubber particles was too small, case hardness was insufficient, and perhaps resin substrate becomes fragile.On the other hand, when its average grain diameter is excessive, there is the tendency of the surface smoothing of infringement resin substrate.Such rubber particles generally can be made by emulsion polymerisation.The average grain diameter of rubber particles can be when regulating emulsion polymerisation the addition of addition, monomer of emulsifying agent wait and be controlled to be desirable value.
Rubber particles is dispersed in the acrylic resin and when making resin substrate, both ratios are the scope of 5～50 weight portions in that to make acrylic resin be 50～95 weight portions, make rubber particles preferably.When the amount of rubber particles is very few, the tendency that exists resulting resin substrate to become fragile, thereby be not preferred.And it is measured when too much, the tendency that exists hear resistance, rigidity to reduce, thereby be not preferred.
Resin substrate can be that the surface as common plate (sheet), film is the substrate on plane, can also be that the surface as convex lens, concavees lens etc. is the substrate of curved surface.
Resin substrate can carry out painted as required with colouring agent, pigment etc., as additive, can contain for example antioxidant, ultra-violet absorber etc.As the thickness of resin substrate, can be 0.1～3.0mm usually, be preferably 0.2～2.0mm, more preferably 0.3～1.5mm.Therefore the resin substrate of thickness is flexible like this, and when being used for scratch resistant resin board of the present invention, serviceability of the present invention further improves.
Resin substrate can be made by extrusion molding.Specifically, extrusion molding can be undertaken by extrusion by meltings such as T modulus method, blow mouldings.The surface of the resin substrate that obtains can be level and smooth.In order to give flatness, from obtaining the aspect of the good resin substrate of surface texture, preferably material resin is melt extruded from for example T type mouth mould, the one side at least that makes the plate object that obtains is the roller of minute surface with the surface or is with the method for carrying out making sheet that contacts.At this moment, as roller, can adopt metallic roll that for example rigidity is high, rubber-like rubber rollers, rubber-like metallic roll etc., these rollers can suitably be selected or be used in combination.In addition, when making the resin substrate of sandwich construction, can use the known multilayer extruder of the mechanisms such as branch manifold mode, feed block mode of the laminated resin that for example has a plurality of extruders and be used for to extrude from them.
In the present invention, form specific curing tunicle on the two sides of described resin substrate and make scratch resistant resin board.At this moment, the formation of the curing tunicle of one side is used can to form with respect to the confficient of static friction of described resin substrate and is carried out less than the curable coating of 0.4 curing tunicle [below, sometimes this curable coating is called coating (A)].The formation of the curing tunicle of another side is used can form with respect to the confficient of static friction of described resin substrate and is carried out at the curable coating of the curing tunicle more than 0.4 [below, sometimes this curable coating is called coating (B)].Like this, by using different coating (A), (B) to form the curing tunicle respectively, even can obtain contacting the also evanescent scratch resistant resin board of Newton's ring with the polarizer of Liquid crystal component at the tow sides of resin substrate.
As curing compound contained among coating (A), (B), the preferred compound that uses, preferred especially multifunctional (methyl) acrylate compounds that uses with the character of solidifying by irradiating electron beam, ultraviolet isoreactivity energy-ray.Here, so-called multifunctional (methyl) acrylate compounds is meant the compound that has at least 2 (methyl) acryloxies in molecule, wherein, preferably uses 3 officials can above, promptly have the compound of at least 3 (methyl) acryloxies in molecule.It should be noted that in this manual so-called (methyl) acryloxy is meant acryloxy or methacryloxy, " (methyl) " when in addition, being called (methyl) acrylate, (methyl) acrylic acid etc. also is the same meaning.
As described multifunctional (methyl) acrylate compounds, can enumerate for example two (methyl) acrylic acid glycol ester, diethylene glycol two (methyl) acrylate, two (methyl) acrylic acid 1,6-hexylene glycol ester, two (methyl) acrylic acid DOPCP, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, five glycerine three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, glycerine three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three [(methyl) acryloxy ethyl] isocyanuric acid ester, tripentaerythritol eight (methyl) acrylate etc.
In addition, can also use phosphonitrile system (methyl) acrylate compounds that in the phosphonitrile ring of phosphazene compound, has imported (methyl) acryloxy; In molecule, has polyurethane (methyl) acrylate compounds that the polyisocyanates of at least 2 NCOs gets with the many alcoholic compound reactions that have 1 (methyl) acryloxy and hydroxyl in molecule at least; In molecule, has polyester (methyl) acrylate compounds that the compound of at least 2 acid halide group gets with the many alcoholic compound reactions that have 1 (methyl) acryloxy and hydroxyl in molecule at least; The oligomer of the dimer of above-mentioned each compound, trimer and so on etc.These multifunctional (methyl) acrylate compounds can be distinguished and use separately or mix more than 2 kinds and to use.
Here, described confficient of static friction is measure to solidify the value that try to achieve with respect to the confficient of static friction of described resin substrate on the tunicle surface.As the assay method of described confficient of static friction, as described later, can measure according to JIS P8147.
In order to obtain target effect of the present invention, the confficient of static friction that makes the curing tunicle that forms on the one side of resin substrate is less than 0.4, and is preferred below 0.3, and more preferably 0.1～0.3.To form such curing tunicle by coating (A), can enumerate to this coating (A) thus in add organic system or inorganic system particulate give the method for micro concavo-convex to solidifying the tunicle surface, add the method etc. that can give the sliding additive of slickness to the surface.Illustrative these methods also only are not limited to use any one method, also can be used in combination.
As described organic system particulate, can for example make the monomer mixture polymerization that contains (methyl) alkyl acrylate system, fragrant family monomer etc. and get.As (methyl) alkyl acrylate is monomer, except methyl methacrylate, can also enumerate can with monofunctional monomer, the polyfunctional monomer of methyl methacrylate copolymer, for example can be that 100 quality % are methyl methacrylate, can also be that 50 quality % are above, preferred 80 quality % above, more preferably 90 quality % are above be methyl methacrylate, and 50 quality % are following, preferred 20 quality % are following, more preferably 10 quality % are following be can with the monomer of methyl methacrylate copolymer.
As described can with the monofunctional monomer of methyl methacrylate copolymer, can enumerate for example acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-EHA, dodecylacrylate, benzyl acrylate, cyclohexyl acrylate, Hydroxyethyl Acrylate, acrylic acid hydroxy propyl ester, acrylic acid hydroxyl butyl ester; Methacrylates such as EMA, propyl methacrylate, butyl methacrylate, methacrylic acid 2-Octyl Nitrite, lauryl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, methacrylic acid hydroxyl ethyl ester, methacrylic acid hydroxyl propyl ester, methacrylic acid hydroxyl butyl ester; Nitrogenous acryloyl such as acrylamide, acrylonitrile is a monomer; Nitrogenous methacryl such as Methacrylamide, methacrylonitrile is a monomer; Glycidyl acrylate, GMA etc. contain the epoxy radicals monomer; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid; Unsaturated acid anhydride such as maleic anhydride, itaconic anhydride etc.
As described can with the polyfunctional monomer of methyl methacrylate copolymer, can enumerate for example ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethyleneglycol diacrylate, polypropyleneglycol diacrylate, diacrylate 1,3-butanediol ester, diacrylate 1, the acrylate of polyalcohols such as 6-hexylene glycol ester, diacrylic acid pentyl diol ester, trimethylolpropane triacrylate, tetramethylol methane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate; GDMA, diethylene glycol dimethylacrylate, triethylene glycol dimethylacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, dimethacrylate 1,3-butanediol ester, dimethacrylate 1, the methacrylate of polyalcohols such as 6-hexylene glycol ester, dimethacrylate DOPCP, trimethylol-propane trimethacrylate, tetramethylol methane trimethyl acrylic ester, tetramethylol methane trimethyl acrylic ester, tetramethylol methane tetramethyl acrylate; Allyl methacrylate, diallyl phthalate etc.
As described fragrant family monomer, can enumerate for example polyfunctional monomers such as monofunctional monomers such as styrene, α-styrene, vinyl xylene, ethyl vinyl benzene, divinylbenzene etc.These monofunctional monomers and polyfunctional monomer can use separately respectively or will be used in combination more than 2 kinds.
Obtain the organic system particulate, can be by above-mentioned monomer mixture polymerization is obtained, in order to obtain required particle diameter, most preferably emulsion polymerization.
As described inorganic be particulate, can enumerate for example metal oxides such as silica, aluminium oxide, titanium oxide, zirconia, they can use a kind or will be more than 2 kinds mix and use.Illustrated these inorganic be that particulate can use with the form of colloidal sol.Described organic system particulate and inorganic be that particulate can mix use.
The volume average particle size of described particulate is preferably 0.05～1 μ m, more preferably 0.08～0.5 μ m.Volume average particle size just must be added a large amount of particulates in order to make confficient of static friction less than 0.4 during less than 0.05 μ m, and during greater than 1 μ m, the transparency reduces.Described volume average particle size is to use dynamic light scattering formula particle size distribution analyzer to measure and the value that obtains as described later.
The addition of described particulate is generally 0.5～50 weight portion with respect to curing property compound 100 weight portions, is preferably 1～20 weight portion.When this addition is very few, can't make confficient of static friction less than 0.4, when addition was too much, the transparency reduced.
As the described additive of giving slickness, can enumerate silicone oil etc.As this silicone oil; can use common silicone oil; specifically, can enumerate dimethicone, phenyl methyl silicone oil, alkyl aralkyl modified silicon oil, fluoro silicone oil, polyether modified silicon oil, fatty acid ester modified silicon oil, the silicone oil that contains alkoxyl, the silicone oil that contains silanol group, 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 silicone oil can be used alone, can also be two or more kinds in combination respectively.
The use amount of silicone oil is 0.1～2 weight portion with respect to curing property compound 100 weight portions, is preferably 0.1～1.0 weight portion.This use amount can't make confficient of static friction less than 0.4 after a little while, and use amount is when too much, and the transparency of solidifying tunicle reduces.
On the other hand, the confficient of static friction of the curing tunicle that forms at the another side of resin substrate is more than 0.4, be preferably 0.4～1.5, form such curing tunicle, for example can in this coating (B), add particulate, the sliding additive of above-mentioned explanation by coating (B).
The curing tunicle that forms with coating (B) must have the necessary marresistance of display window protective panel of carrying type information terminal.Specifically, satisfy the marresistance of use steel wool described later, and pencil hardness is more than the 2H, get final product more than the preferred 3H.Described pencil hardness is the value of measuring according to JIS K5600.For described curing tunicle being given the marresistance of regulation, amount of composition that for example can be by adjusting the described solidification compound that cooperates in the coating (B), amount, electrically conductive microparticle described later etc. and carrying out arbitrarily.
Can also give antistatic performance and make dust, dust be difficult to adhere to the curing tunicle that forms with coating (B).Specifically, the confficient of static friction that forms with coating (B) can have 10 at the curing tunicle more than 0.4
9～10
14The surface resistivity of Ω/.Described surface resistivity is the value that records according to ASTM D-257 as described later.
In order to give antistatic performance, can enumerate the method for interpolation electrically conductive microparticle in coating (B) etc. to described curing tunicle.As described electrically conductive microparticle, can enumerate each particulate such as metal oxide, the indium/tin composite oxides (ITO) of antimony oxide (antimony pentaoxide) and so on for example, the tin oxide (ATO) that is doped with antimony, the tin oxide (PTO) that is doped with phosphorus, antimony/zinc composite oxide.Illustrative these electrically conductive microparticles can use with solation.
Preferred its volume average particle size of electrically conductive microparticle is 0.001～1 μ m.The too small electrically conductive microparticle of described particle diameter is difficult to industrialness production, and when using the excessive electrically conductive microparticle of described particle diameter, the transparency of solidifying tunicle reduces, thereby not preferred.In addition, the use amount of electrically conductive microparticle is preferably 1～100 weight portion with respect to curing property compound 100 weight portions in the coating (B).When this use amount is very few, damage easily when the scratch resistant resin board that obtains is extruded, and can't obtain sufficient anti-static effect, in the time of too much, the marresistance of solidifying tunicle descends or film forming decline, thereby not preferred.
In order to adjust viscosity, to solidify the thickness of tunicle etc., can contain solvent among coating (A), (B).As this solvent, can enumerate for example alcohols of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol (isopropyl alcohol), 1-butanols, 2-butanols (sec-butyl alcohol), 2-methyl isophthalic acid-propyl alcohol (isobutanol), 2-methyl-2-propyl alcohol (tert-butyl alcohol) and so on; The alkoxyl alcohols of cellosolvo, butoxy ethanol, 3-methoxyl group-1-propyl alcohol, 1-methoxyl group-2-propyl alcohol, 1-ethyoxyl-2-propyl alcohol and so on; The ketols of DAA and so on; The ketone of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and so on; The arene of toluene, dimethylbenzene and so on; The ester class of ethyl acetate, butyl acetate and so on etc.These solvents can use separately respectively or will be used in combination more than 2 kinds.The use amount of solvent can be solidified the thickness etc. of tunicle and suitably adjusts according to the material of substrate, shape, coating process, target, is about 20～10000 weight portions with respect to curing property compound 100 weight portions usually.
In addition, as required, can also contain additives such as levelling agent such as stabilization agent, antioxidant, colouring agent, fluorine system, acrylic acid series among coating (A), (B).
After coating (A), (B) of above explanation be coated on the single face of resin substrate respectively, carry out drying as required, make the curing of coating of formation then, thereby can obtain scratch resistant resin board of the present invention.In addition, the coating curing of two coating is arbitrarily in proper order, also can carry out simultaneously.
The coating of coating (A), (B) can apply mask at single face as required, for example adopts nick version (microgravure) rubbing method, rolling method, dip coating, spin-coating method, mould to be coated with methods such as method, curtain coating transfer printing, flow coat method, spraying process and carries out.
The curing of filming can be carried out well by irradiation activate energy ray.As activate energy ray, can enumerate for example electron beam, ultraviolet ray, visible light etc., can suitably select according to the kind of curing property compound.When using ultraviolet ray, visible light, use Photoepolymerizationinitiater initiater usually as activate energy ray.
As described Photoepolymerizationinitiater initiater; can enumerate for example acetophenone; the acetophenone benzil ketals; anthraquinone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; carbazole; xanthene ketone; the 4-chlorobenzophenone; 4; 4 '-diaminobenzophenone; 1; 1-dimethoxy deoxybezoin, desoxybenzoin; 3; 3 '-dimethyl-4-methoxy benzophenone; thioxanthones; 2; 2-dimethoxy-2-phenyl acetophenone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone; triphenylamine; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; Fluorenone; fluorenes; benzaldehyde; the benzoin ethylether; the benzoin isopropyl ether; benzophenone; michaelis ketone; the 3-methyl acetophenone; 3; 3 '; 4,4 '-tetra-tert peroxidating carbonyl benzophenone (BTTB); 2-(dimethylamino)-1-[4-(morpholino) phenyl]-2-(phenyl methyl)-1-butanone; 4-benzoyl-4 '-dimethyl diphenyl sulfide; benzil etc.
Photoepolymerizationinitiater initiater can with dye-sensitized dose be used in combination.As dye-sensitized dose, can enumerate for example xanthene, thioxanthene, cumarin, coumarin ketone etc.As the combination of Photoepolymerizationinitiater initiater and dye-sensitized dose, can enumerate combination of for example combination, BTTB and the coumarin ketone of combination, BTTB and the cumarin of combination, BTTB and the thioxanthene of BTTB and xanthene etc.
Above-mentioned Photoepolymerizationinitiater initiater is commercially available, therefore can use such commercially available product.As commercially available Photoepolymerizationinitiater initiater, can enumerate " IRGACURE651 " that for example sell by Ciba company respectively, " IRGACURE 184 ", " IRGACURE 500 ", " IRGACURE 1000 ", " IRGACURE 2959 ", " DAROCUR 1173 ", " IRGACURE 907 ", " IRGACURE 369 ", " IRGACURE 1700 ", " IRGACURE 1800 ", " IRGACURE 819 " and " IRGACURE 784 ", " the KAYACURE ITX " that sells by Japanese chemical drug company respectively, " KAYACURE DETX-S ", " KAYACURE BP-100 ", " KAYACURE BMS " and " KAYACURE2-EAQ " etc.
When using Photoepolymerizationinitiater initiater, its use amount is generally more than 0.1 weight portion with respect to curing property compound 100 weight portions.When this use amount is very few, compare the tendency that exists curing rate not increase when not using Photoepolymerizationinitiater initiater.In addition, the upper limit of the use amount of Photoepolymerizationinitiater initiater is generally about 10 weight portions with respect to curing property compound 100 weight portions.
In addition, the intensity of activate energy ray, irradiation time can suitably be adjusted according to the kind of curing property compound, its coating thickness etc.Activate energy ray can shine in inert gas environment, as this inert gas, can use nitrogen, argon gas etc.
The thickness of the curing tunicle that forms is preferably 1～10 μ m respectively, more preferably 2～8 μ m.When this thickness was too small, marresistance was insufficient sometimes, and when excessive, the transparency descends, and is exposed to hot and humid following time, and is easily chipping.Solidifying in the amount, curable coating of the unit are of the curable coating that the thickness of tunicle can be by being adjusted at the coating of resin substrate surface contained solid component concentration regulates arbitrarily.
Even having in one side, scratch resistant resin board of the present invention contacts the also evanescent curing tunicle of Newton's ring with the polarizer of Liquid crystal component; therefore and have the high curing tunicle of marresistance at another side, can be suitable for using as the display window protective panel that with mobile phone etc. is the carrying type information terminal of representative.In addition, can also use as various parts such as the view finder portion of digital camera, handheld video camera etc., the display window protective panel of portable game machine.
When making the display window protective panel of carrying type information terminal, processing such as print, punch at first as required, be cut to the size that needs by scratch resistant resin board of the present invention.Then, the scratch resistant resin board that cuts off is installed on the display window of carrying type information terminal.At this moment, when the face that will be provided with the curing tunicle that is formed by coating (A) is arranged on the display window of carrying type information terminal as inboard (being liquid crystal face side), can effectively protect this display window.
Embodiment
Below, embodiments of the invention are shown, but the present invention is not subjected to the restriction of these embodiment.It should be noted that among the following embodiment that unless otherwise specified, the % of expression content or use amount and part are weight basis.In addition, the assay method of each rerum natura, evaluation method are as follows.
(particle size determination)
The volume average particle size of the particle in the curable coating of preparation (below, be sometimes referred to as particle diameter) use dynamic light scattering formula particle size distribution analyzer [the hole field makes " LB-500 " of institute's corporate system] to measure.
(solidifying the thickness of tunicle)
The thickness of the curing tunicle of the scratch resistant resin board that obtains uses determining film thickness device [" F-20 " of Filmetrics corporate system] to measure.
(confficient of static friction)
The confficient of static friction of the curing tunicle of the scratch resistant resin board that obtains is measured according to JIS P8147.Specifically, as shown in Figure 1, the assess sample 10 of A4 size is set on the base 1 that inclined angle alpha is made as 15 degree.Assess sample 10 is that the two sides at resin substrate 11 that obtains in aftermentioned embodiment and the comparative example is formed with the sample that solidifies tunicle 12,13, and the curing tunicle (in the drawings for solidifying tunicle 12) of estimating the confficient of static friction side is arranged on the base 1 up.
On the other hand, prepare with pressure sensitive adhesive double coated at heavy 500g, contact area 100 * 60mm
2Counterweight 20 on attached the shock-resistant acrylic resin " TECHNOLLOY S001A " of the resin substrate 21[sumitomo chemical company system of unidimensional thick 0.5mm] sample.Then, counterweight 20 is positioned on the assess sample 10, estimates counterweight 20 and whether on assess sample 10, slide with resin substrate 21 and the mode that curing tunicle 12 joins.When not sliding, inclined angle alpha is made as than 15 degree greatly, obtains the angle that skids off, i.e. slide angle θ (degree).Then, with the slide angle θ substitution formula of obtaining: calculate confficient of static friction among confficient of static friction=tan θ.In addition, the slide angle θ between the shock-resistant acrylic resin is 62 degree, and confficient of static friction is 1.88.
(polarizer squeeze test)
Jie is by adhesive 2 polarizers of form applying with right-angled intersection on acrylic panel, and mounting has 100 * 150mm thereon
2The acrylic sheet of thick 0.5mm in hole.Become the mode mounting assess sample of polarizer side thereon with curing tunicle to be evaluated,, make it to produce Newton's ring with the finger extruding assess sample corresponding with the hole central portion.Then, confirm whether the Newton's ring that produces disappeared with interior at 10 seconds.It should be noted that judgment standard uses following benchmark.
Zero: Newton's ring disappears.
*: Newton's ring is residual.
(transparency)
Estimate the transparency of resulting scratch resistant resin board by total light transmittance (Tt) and mist degree (H).Total light transmittance (Tt) is measured according to JIS K7136 according to JIS K7361-1, mist degree (H).
(marresistance)
With the surface of the curing tunicle of the scratch resistant resin board that obtains with steel wool #0000[NIHONSTEEL WOOL corporate system] apply 500g/cm
2Reciprocal 10 times of loading, visualization has or not scar evaluation.
(pencil hardness)
The pencil hardness of the scratch resistant resin board that obtains is measured according to JIS K5600.
(surface resistivity)
According to ASTM D-257, measure the surface resistivity of the curing tunicle of the face that does not carry out the polarizer squeeze test.
(squeeze test)
In the metal system frame of profile 60 * 100mm, internal diameter 30 * 50mm, dispose the test film of 55 * 85mm, with the metal bar of diameter 10mm, with the central authorities of 10mm/ minute speed squeeze test sheet, the ruined intensity of determination test sheet with ball tip.Test is implemented 3 times, with its mean value as measurement result.It should be noted that the curing tunicle with the face that do not carry out the polarizer squeeze test is disposed test film by the mode that metal bar pushes.In addition, the scratch resistant resin board that obtains among the embodiment 2,5,6,8～13 described later is also carried out this squeeze test.
Following being prepared of curable coating A1～A8 of using in embodiment and the comparative example.It should be noted that the material that uses in the preparation of curable coating A1～A8 is as follows.
Dipentaerythritol acrylate: " the NK ESTER A-9530 " of Xin Zhong village chemical industrial company system
Tetramethylol methane tetraacrylate: " the NK ESTER A-TMMT " of Xin Zhong village chemical industrial company system
Photoepolymerizationinitiater initiater: " IRGACURE184 " of Ciba corporate system
Crosslinked polymethylmethacrylaparticles particles: ponding changes into the organic system particulate " TECHPOLYMER XX284K " of product industrial group system
Silicone oil: " BYK307 " of BYK-Chemie Japan corporate system
Silicon dioxide gel: it is particulate that catalyst changes into the inorganic of industrial group's system, solid component concentration 20%
(preparation of curable coating A1)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 3.75 parts of crosslinked polymethylmethacrylaparticles particles, 1-methoxyl group-33.8 parts of 2-propyl alcohol, 36 parts of isobutanols and 0.25 part of mixing of silicone oil, preparation curable coating A1.Measure the particle diameter of particulate in the resulting coating, the result is 0.09 μ m.
(preparation of curable coating A2)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 3.75 parts of crosslinked polymethylmethacrylaparticles particles, 1-methoxyl group-33.9 parts of 2-propyl alcohol, 36 parts of isobutanols and 0.125 part of mixing of silicone oil, preparation curable coating A2.Measure the particle diameter of particulate in the resulting coating, the result is 0.09 μ m.
(preparation of curable coating A3)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 3.75 parts of crosslinked polymethylmethacrylaparticles particles, 1-methoxyl group-34 parts of 2-propyl alcohol, 36 parts of isobutanols and 0.0125 part of mixing of silicone oil, preparation curable coating A3.Measure the particle diameter of particulate in the resulting coating, the result is 0.09 μ m.
(preparation of curable coating A4)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 3.75 parts of crosslinked polymethylmethacrylaparticles particles, 1-methoxyl group-34 parts of 2-propyl alcohol and 36 parts of mixing of isobutanol, preparation curable coating A4.Measure the particle diameter of particulate in the resulting coating, the result is 0.09 μ m.
(preparation of curable coating A5)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 1-methoxyl group-37.7 parts of 2-propyl alcohol, 36 parts of isobutanols and 0.0125 part of mixing of silicone oil, preparation curable coating A5.
(preparation of curable coating A6)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 2.5 parts of crosslinked polymethylmethacrylaparticles particles, 1-methoxyl group-35.1 parts of 2-propyl alcohol, 36 parts of isobutanols and 0.125 part of mixing of silicone oil, preparation curable coating A6.Measure the particle diameter of particulate in the resulting coating, the result is 0.09 μ m.
(preparation of curable coating A7)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 1.25 parts of crosslinked polymethylmethacrylaparticles particles, 1-methoxyl group-36.4 parts of 2-propyl alcohol and 36 parts of isobutanols and 0.125 part of mixing of silicone oil, preparation curable coating A7.Measure the particle diameter of particulate in the resulting coating, the result is 0.09 μ m.
(preparation of curable coating A8)
With 12.5 parts of dipentaerythritol acrylates, 12.5 parts of tetramethylol methane tetraacrylates, 1.25 parts of Photoepolymerizationinitiater initiaters, 12.5 parts of silicon dioxide gels, 1-methoxyl group-25.1 parts of 2-propyl alcohol, 36 parts of isobutanols and 0.25 part of mixing of silicone oil, preparation curable coating A8.The coating that obtains after 5 minutes, is measured the particle diameter of particulate with the 6000rpm stirring with homogenizer, and the result is 0.29 μ m.
Following being prepared of curable coating B of using in embodiment and the comparative example.
(preparation of curable coating B)
With 20 parts of dipentaerythritol acrylates [" the NK ESTER A-DPH " of Xin Zhong village chemical industrial company], 1 part of Photoepolymerizationinitiater initiater [" IRGACURE184 " of Ciba company], [catalyst changes into industrial group " ELCOM V-4514 " to antimony pentaoxide particulate colloidal sol, solid component concentration 20%] 8 parts, 1-methoxyl group-35.5 parts of 2-propyl alcohol, 35.5 parts of isobutanols and 0.01 part of mixing of silicone oil [" BYK307 " of BYK-Chemie Japan corporate system], preparation curable coating B.The coating that obtains after 5 minutes, is measured the particle diameter of particulate with the 6000rpm stirring with homogenizer, and the result is 0.04 μ m.
Plywood 1,2 following making of using in embodiment and the comparative example.
(making of plywood 1)
Use the single shaft extruder melting mixing polycarbonate resin [SumitomoDow corporate system " Calibre 301-10 "] of 40mm φ.In addition, use the single shaft extruder melting mixing methacrylic resin [sumitomo chemical company system " Sumipex MH "] of 20mm φ.Then, both by 2 stratification of feed piece, are extruded by T type mouth mould then, between two metal rigidity polishing rolls, form the gradient and moulding, cooling are carried out in clamping, obtain the plywood 1 that constitutes by double-layer structure of thick 0.5mm.At this moment, the thickness of each layer is methacrylic resin layer/polycarbonate resin=0.07mm/0.43mm.
(making of plywood 2)
At first, the particle of preparation methacrylic resin composition.Specifically,, make part by weight reach 94/6, use the biaxial extruder melting mixing, obtain the particle of methacrylic resin composition with super mixed machine mixed methyl acrylic resin [" the Sumipex MH " of sumitomo chemical company system] and acrylic rubber particle.
As described acrylic rubber particle, use following particle: innermost layer is served as reasons and is contained methyl methacrylate 93.8%, the monomer polymerization of methyl acrylate 6% and allyl methacrylate 0.2% and rigid polymer, serve as reasons and contain butyl acrylate 81% in the intermediate layer, the monomer polymerization of styrene 17% and allyl methacrylate 2% and elastomeric polymer, outermost layer serve as reasons the monomer polymerization that contains methyl methacrylate 94% and methyl acrylate 6% and rigid polymer, innermost layer/intermediate layer/outermost part by weight is 35/45/20, the average grain diameter of the elastomeric polymer layer in intermediate layer is 220nm, is the rubber particles that adopts the spherical three-decker that emulsion polymerization obtains.
Then, use the single shaft extruder melting mixing polycarbonate resin [SumitomoDow corporate system " Calibre 301-10 "] of 40mm φ.In addition, use the particle of the above-mentioned methacrylic resin composition that obtains of single shaft extruder melting mixing of 20mm φ.Is mode 3 stratification of methacrylic resin with both with two top layers by the feed piece, extrude by T type mouth mould then, between two metal rigidity polishing rolls, form the gradient and clamping and carry out moulding, cooling, obtain the plywood 2 that constitutes by three-decker of thick 0.5mm.At this moment, the thickness of each layer is methacrylic resin layer/polycarbonate resin/methacrylic resin layer=0.07mm/0.36mm/0.07mm.
Embodiment 1
Use the metering bar coater of No.16, the one side coating curable coating A1 at the resin substrate [the shock-resistant acrylic resin of sumitomo chemical company system " TECHNOLLOY S001A ", lamina] of thick 0.5mm makes thickness reach 6 μ m.Then,, and then, make solvent evaporates, use the high voltage mercury lamp radiation 0.5J/cm of 120W then 45 ℃ hot-air oven inner drying 6 minutes drying at room temperature 1 minute
2Ultraviolet ray make it to solidify.
Then, use the metering bar coater of No.20,, make thickness reach 3 μ m at another side coating curable coating B.Then,, and then, make solvent evaporates, use the high voltage mercury lamp radiation 0.5J/cm of 120W then 50 ℃ hot-air oven inner drying 3 minutes drying at room temperature 1 minute
2Ultraviolet ray make it to solidify, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A1.It is the results are shown in table 1.It should be noted that in the hurdle of " particulate " in the table 1, the volume average particle size and the addition thereof of particulate contained in the curable coating of the curing tunicle that is used to form liquid crystal face side is shown.Described addition is the value with respect to curing property compound 100 weight portions.In addition, " outside " in the table 1 is meant the face with liquid crystal face side opposition side, promptly is coated with the face of curable coating B.
Embodiment 2
Use curable coating A2 to replace curable coating A1, carry out similarly to Example 1 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A2.It is the results are shown in table 1.
Embodiment 3
Use curable coating A3 to replace curable coating A1, carry out similarly to Example 1 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A3.It is the results are shown in table 1.
Embodiment 4
Use curable coating A4 to replace curable coating A1, carry out similarly to Example 1 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A4.It is the results are shown in table 1.
Embodiment 5
Use curable coating A6 to replace curable coating A1, carry out similarly to Example 1 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A6.It is the results are shown in table 1.
Embodiment 6
Use curable coating A7 to replace curable coating A1, carry out similarly to Example 1 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A7.It is the results are shown in table 1.
Embodiment 7
Use curable coating A8 to replace curable coating A1, carry out similarly to Example 1 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A8.It is the results are shown in table 1.
Comparative example 1
Use curable coating A5 to replace curable coating A1, carry out similarly to Example 1 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A5.It is the results are shown in table 1.
Comparative example 2
Use the metering bar coater of No.20, the two sided coatings curable coating B at the resin substrate [the shock-resistant acrylic resin of sumitomo chemical company system " TECHNOLLOY S001A "] of thick 0.5mm makes thickness reach 3 μ m.Then,, and then, make solvent evaporates, use the high voltage mercury lamp radiation 0.5J/cm of 120W then 50 ℃ hot-air oven inner drying 3 minutes drying at room temperature 1 minute
2Ultraviolet ray make it to solidify.Obtain scratch resistant resin board.For the scratch resistant resin board that obtains, estimate in the mode that the first face that is coated with is a liquid crystal face side.It is the results are shown in table 1.
Comparative example 3
As scratch resistant resin board, use has been carried out with the hard conating of forming hard conating plate [" SUMIELECFT200R " of sumitomo chemical company system] that handle, commercially available the two sides of the resin substrate [the shock-resistant acrylic resin of sumitomo chemical company system " TECHNOLLOY S001A "] of thick 0.5mm.With the one side of this hard conating plate is that the mode of liquid crystal face side is estimated.It is the results are shown in table 1.
Embodiment 8
Use the metering bar coater of No.16, the face coating curable coating A2 in the polycarbonate resin side of plywood 1 makes thickness reach 4 μ m.Then,, and then, make solvent evaporates, use the high voltage mercury lamp radiation 0.5J/cm of 120W then 45 ℃ hot-air oven inner drying 6 minutes drying at room temperature 1 minute
2Ultraviolet ray make it to solidify.
Then, use the metering bar coater of No.20, the face coating curable coating B in methacrylic resin layer side makes thickness reach 3 μ m.Then,, and then, make solvent evaporates, use the high voltage mercury lamp radiation 0.5J/cm of 120W then 50 ℃ hot-air oven inner drying 3 minutes drying at room temperature 1 minute
2Ultraviolet ray make it to solidify, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A2.It is the results are shown in table 1.
Embodiment 9
Use curable coating A6 to replace curable coating A2, carry out similarly to Example 8 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A6.It is the results are shown in table 1.
Embodiment 10
Use curable coating A7 to replace curable coating A2, carry out similarly to Example 8 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A7.It is the results are shown in table 1.
Comparative example 4
Use curable coating A5 to replace curable coating A2, carry out similarly to Example 8 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A5.It is the results are shown in table 1.
Embodiment 11
Use the metering bar coater of No.16, the one side coating curable coating A2 at plywood 2 makes thickness reach 4 μ m.Then,, and then, make solvent evaporates, use the high voltage mercury lamp radiation 0.5J/cm of 120W then 45 ℃ hot-air oven inner drying 6 minutes drying at room temperature 1 minute
2Ultraviolet ray make it to solidify.
Then, use the metering bar coater of No.20,, make thickness reach 3 μ m at another side coating curable coating B.Then,, and then, make solvent evaporates, use the high voltage mercury lamp radiation 0.5J/cm of 120W then 50 ℃ hot-air oven inner drying 3 minutes drying at room temperature 1 minute
2Ultraviolet ray make it to solidify, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A2.It is the results are shown in table 1.
Embodiment 12
Use curable coating A6 to replace curable coating A2, carry out similarly to Example 11 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A6.It is the results are shown in table 1.
Embodiment 13
Use curable coating A7 to replace curable coating A2, carry out similarly to Example 11 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A7.It is the results are shown in table 1.
Comparative example 5
Use curable coating A5 to replace curable coating A2, carry out similarly to Example 11 in addition, obtain scratch resistant resin board.For the scratch resistant resin board that obtains, be that the mode of liquid crystal face side is estimated with the face that is coated with curable coating A5.It is the results are shown in table 1.
Table 1
Show as can be known by table 1, be formed with respect to the confficient of static friction of described resin substrate in the one side (liquid crystal face side) of resin substrate and be formed with respect to the confficient of static friction of described resin substrate scratch resistant resin board at the embodiment 1～13 of the curing tunicle more than 0.4 less than 0.4 curing tunicle and at another side (outside), the result of polarizer extruding is all good, even the curing tunicle contacts with polarizer and produces Newton's ring, Newton's ring is disappeared and the decline of inhibition image quality.In addition, also the transparency is also excellent as can be known.
Particularly use to have the embodiment 8～13 of the plywood 1,2 of sandwich construction, in squeeze test, demonstrate good result as resin substrate.By this result as can be known, when resin substrate uses the plywood of regulation, can obtain the not scratch resistant resin board of cracky.
On the other hand, use and not add the curable coating A5 of particulate and form the comparative example 1,4 of curing tunicle of liquid crystal face side and 5 scratch resistant resin board and be the comparative example 3 of commercially available hard conating plate, the confficient of static friction of the curing tunicle of liquid crystal face side is all more than 0.4, and it is poor as a result that polarizer pushes.
Form the scratch resistant resin board of comparative example 2 of the curing tunicle of liquid crystal face side for using curable coating B, the confficient of static friction of the curing tunicle of liquid crystal face side is also more than 0.4, polarizer extruding poor as a result.
In addition, in each scratch resistant resin board of embodiment 1～13 and comparative example 1～5, the evaluation result of the marresistance of the curing tunicle outside being positioned at does not all have scar on curing tunicle surface, is good.In addition, the measurement result of the pencil hardness of each scratch resistant resin board is 3H in the liquid crystal face side and the outside.The measurement result of the surface resistivity of the curing tunicle outside being positioned in each scratch resistant resin board, embodiment 1～13, comparative example 1,2,4 and 5 are 6 * 10
11Ω/, comparative example 3 is 3 * 10
11Ω/.
According to the present invention, owing to form with respect to the confficient of static friction of described resin substrate less than 0.4 curing tunicle in the one side of resin substrate, therefore even should solidify tunicle contacts with the polarizer of Liquid crystal component and produces Newton's ring, because this curing tunicle leaves polarizer by sliding on polarizer, so Newton's ring easily disappears.Therefore,,, it is disappeared, can suppress the effect that image quality reduces even have the Newton's ring of generation according to the present invention.And, owing to be formed with the curing tunicle of regulation at another side, so, can effectively protect this display window by the display window protective panel of this scratch resistant resin board as carrying type information terminal used.
Claims (8)
1. scratch resistant resin board is that the confficient of static friction that the one side at resin substrate is formed with respect to described resin substrate forms at the curing tunicle more than 0.4 less than 0.4 curing tunicle and the confficient of static friction that is formed with respect to described resin substrate at another side.
2. scratch resistant resin board according to claim 1, wherein, described confficient of static friction has 10 at the curing tunicle more than 0.4
9～10
14The surface resistivity of Ω/mouth.
3. scratch resistant resin board according to claim 1, wherein, the thickness of described resin substrate is 0.3～1.5mm.
4. scratch resistant resin board according to claim 1, wherein, described resin substrate is the acrylic resin plate.
5. scratch resistant resin board according to claim 1, wherein, described resin substrate is the plywood that forms at the folded methacrylic resin layer in the upper strata of one side at least of polycarbonate resin.
6. scratch resistant resin board according to claim 1, wherein, described resin substrate contains rubber particles.
7. the display window protective panel of a carrying type information terminal is made by each described scratch resistant resin board in the claim 1～6.
8. the display window protective panel of carrying type information terminal according to claim 7, wherein, will be formed with described confficient of static friction less than the face of 0.4 curing tunicle towards the setting of liquid crystal face side.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008084428 | 2008-03-27 | ||
| JP2008084428 | 2008-03-27 | ||
| JP2008325899 | 2008-12-22 |
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| CN101544085A true CN101544085A (en) | 2009-09-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009101293687A Pending CN101544085A (en) | 2008-03-27 | 2009-03-24 | Scratch-resistant resin plate and display window protecting plate of portable information terminal using the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2009255522A (en) |
| CN (1) | CN101544085A (en) |
| TW (1) | TW201002768A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5149916B2 (en) * | 2010-01-20 | 2013-02-20 | 住友化学株式会社 | Optical matte film |
| JP5707191B2 (en) * | 2011-03-18 | 2015-04-22 | 住友化学株式会社 | Laminated board |
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2008
- 2008-12-22 JP JP2008325899A patent/JP2009255522A/en active Pending
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2009
- 2009-03-24 CN CNA2009101293687A patent/CN101544085A/en active Pending
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| JP2009255522A (en) | 2009-11-05 |
| TW201002768A (en) | 2010-01-16 |
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