CN101633257A - Scratch resisting resin plate and application thereof - Google Patents
Scratch resisting resin plate and application thereof Download PDFInfo
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- CN101633257A CN101633257A CN200910164759A CN200910164759A CN101633257A CN 101633257 A CN101633257 A CN 101633257A CN 200910164759 A CN200910164759 A CN 200910164759A CN 200910164759 A CN200910164759 A CN 200910164759A CN 101633257 A CN101633257 A CN 101633257A
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- methyl
- acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
The invention provides a scratch resisting resin plate which has excellent impact resistance and is not easy to rupture. A laminated plate of a (methyl)acrylic acid resin layer containing the rubber particles is arranged on at least one side of the polycarbonate resin layer and is as a substrate. A solidified envelop is formed on at least one side of the substrate. The substrate is preferably equipped with the (methyl)acrylic acid resin layer on two sides of the polycarbonate resin layer. The rubber particles are the multilayer acrylic polymer. The solidified envelop is preferably formed of the solidified paint constituted by the compound comprising at least three (methyl)acryloxy groups in the molecule.
Description
Technical field
The present invention relates to dispose the scratch resistant resin board that marresistance is solidified tunicle in the one side at least of resin substrate.In addition, the invention still further relates to the display baffle of making by this scratch resistant resin board, especially relate to the display window protective panel of carrying type information terminal.
Background technology
In patent documentation 1～6, disclose the one side at least as the acrylic resin board of substrate dispose solidify tunicle, be suitable for scratch resistant resin board as the display window protective panel of carrying type information terminal.With this acrylic resin board as the scratch resistant resin board of substrate resistance to impact and insufficient sometimes.In patent documentation 7,8, the resistance to impact height that is laminated with the duplexer of acrylate resin layer at a face of polycarbonate resin is disclosed, disclose the duplexer that will on this acrylate resin layer, further form the curing tunicle and be used for lcd cover.
Patent documentation 1: TOHKEMY 2004-143365 communique
Patent documentation 2: TOHKEMY 2004-299199 communique
Patent documentation 3: TOHKEMY 2007-190794 communique
Patent documentation 4: TOHKEMY 2008-6811 communique
Patent documentation 5: TOHKEMY 2008-36927 communique
Patent documentation 6: TOHKEMY 2008-49697 communique
Patent documentation 7: TOHKEMY 2006-103169 communique
Patent documentation 8: TOHKEMY 2007-237700 communique
Summary of the invention
The objective of the invention is to, even provide resistance to impact excellence and extruding also to be difficult for the scratch resistant resin board that breaks.In addition, other purpose of the present invention is, the display baffle of being made by this scratch resistant resin board, the display window protective panel of carrying type information terminal are provided.
That is, the invention provides a kind of scratch resistant resin board, it is characterized in that, dispose the curing tunicle in the one side at least of substrate, described substrate disposes (methyl) acrylate resin layer that contains rubber particles in the one side at least of polycarbonate resin.In addition, the present invention also provides the display window protective panel of display baffle, the especially carrying type information terminal made by this scratch resistant resin board.
Scratch resistant resin board of the present invention, the resistance to impact excellence, even and extruding also be difficult for breaking, therefore this scratch resistant resin board can be used as the display baffle.By the display window protective panel of this scratch resistant resin board as carrying type information terminal used, can effectively protect the display window of carrying type information terminal.
The specific embodiment
Scratch resistant resin board of the present invention, be the one side at least at polycarbonate resin is disposed (methyl) acrylate resin layer that contains rubber particles plywood as substrate, and dispose the duplexer that solidifies tunicle in the one side at least of this substrate.
So-called polycarbonate resin is the layer that is formed by polycarbonate resin.So-called polycarbonate resin is that joint portion between the monomeric unit is all by the carbonate group ((polymer that O-(C=O)-O-) constitutes.
As polycarbonate resin, for example can enumerate by interface polycondensation, melt transesterification process etc. making polymer that dihydric phenol and carbonylation agent reaction gets, making polymer that the polymerization of carbonic ester prepolymer gets, make polymer that the cyclic carbonate compound polymerization gets etc. by the ring-opening polymerisation method by solid phase ester-interchange method etc.
As dihydric phenol, for example can enumerate 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, also can use in them more than 2 kinds.
Wherein, the preferred use is selected from bisphenol-A, 2, two { (4-hydroxy-3-methyl) 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)-4-methylpentanes of 2-, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane and α, the dihydric phenol more than a kind between α '-two (4-hydroxy phenyl) in the diisopropyl benzene, the preferred especially bisphenol-A that uses separately, perhaps bisphenol-A and 1, two (the 4-hydroxy phenyls)-3,3 of 1-, the 5-trimethyl-cyclohexane, bisphenol-A be selected from 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 the carbonylation agent, for example can enumerate the haloformate (Ha ロ ホ Le メ one ト) of the carbonic ester of the carbonyl halide, diphenyl carbonate and so on of phosgene and so on, bishaloformate (ジ Ha ロ ホ Le メ one ト) of dihydric phenol and so on, also can use in them more than 2 kinds.
So-called acrylate resin layer is the layer that is formed by (methyl) acrylic resin.Here, so-called (methyl) acrylic resin is acrylic resin or methacrylic resin.
So-called (methyl) acrylic resin is polymer or the copolymer that is formed by acrylate or methacrylate.
(methyl) acrylic resin as constituting (methyl) acrylate resin layer generally uses methacrylic resin.Methacrylic resin is to be the resin of main component with the methyl methacrylate units, particularly, preferably contain methyl methacrylate units usually at the polymethyl methacrylate resin more than the 50 weight %, more than the preferred 70 weight %, can be that methyl methacrylate units is the imperplex of 100 weight %, can also be the copolymer of methyl methacrylate and other monomers more than a kind.
As can with the example of other monomers of methyl methacrylate copolymer, can enumerate the methyl acrylic ester beyond the methyl methacrylate of EMA, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2-Octyl Nitrite, 2-hydroxyethyl methacrylate and so on; The esters of acrylic acid of methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-EHA, acrylic acid 2-hydroxy methacrylate and so on.In addition, can also enumerate styrene, substituted phenylethylene class, for example the halogenated styrenes class of chlorostyrene, bromstyrol and so on; The ring-alkylated styrenes class of vinyltoluene, AMS and so on.And then, can also enumerate unsaturated acids, acrylonitrile, methacrylonitrile, maleic anhydride, phenyl maleimide, the cyclohexyl maleimide of methacrylic acid, acrylic acid and so on.
Acrylic resin can mix with rubber particles and use.As the example of rubber particles, graft copolymer that the alkene unsaturated monomer that can enumerate the acrylic acid series multilayer structure polymer, is unsaturated monomer and so on by the rubber-like polymer and 20～95 parts by weight of acrylic of 5～80 weight portions forms etc.The acrylic acid series multilayer structure polymer preferably contain about 20～60 weight % by elastomer form the layer.The acrylic acid series multilayer structure polymer preferably has hard layer as outermost layer, further preferably has hard layer as innermost layer.
So-called acrylic acid series multilayer structure polymer is to have structure that is laminated with the layer that is formed by polymer more than 2 layers and the polylayer forest that is formed by the particle shaped polymer, and being at least 1 layer is the polylayer forest of the polymer that formed by acrylate and/or methacrylate.
So-called rubber-like polymer is acrylate and/or methacrylate and the copolymer that contains the compound of 2 above unsaturated groups.
So-called acrylic acid series unsaturated monomer is acrylate or the methacrylate that has unsaturated bond in molecular end.
So-called alkene unsaturated monomer is that molecular end has unsaturated bond and this unsaturated bond is ethene skeleton (CH=CH
2) monomer.
Formation by elastomer form the layer elastomer, can be glass transition temperature (Tg) less than 25 ℃ acrylic acid series polymeric compounds, particularly, can be the polyfunctional monomer and the copolymer that is selected from more than one monofunctional monomers in lower alkyl acrylate, methacrylic acid lower alkyl esters, acrylic acid low-grade alkoxy alkyl ester, acrylic acid cyano group ethyl ester, acrylamide, acrylic acid hydroxyl low-grade alkyl ester, methacrylic acid hydroxyl lower alkyl esters, acrylic acid and the methacrylic acid of allyl methacrylate and so on.
In the present invention, so-called monofunctional monomer is the monomer that has 1 acryloyl group in molecule, and so-called polyfunctional monomer is the monomer that has the acryloyl group more than 2 in molecule.
So-called hard layer is the polymer that is formed by acrylate and/or methacrylate.
Constitute the polymer of hard layer, preferably Tg is the acrylic acid series polymeric compounds more than 25 ℃, particularly, preferably have carbon number be 1～4 alkyl alkyl methacrylate homopolymers or to have carbon number be 1～4 the alkyl methacrylate of alkyl and the copolymer of copolymer composition.In having the copolymer that carbon number is 1～4 the alkyl methacrylate of alkyl and copolymer composition, the alkyl methacrylate unit that preferably has carbon number and be 1～4 alkyl is a main component.Particularly, have carbon number and be 1～4 the alkyl methacrylate of alkyl and the copolymer of copolymer composition, preferably contain 95 weight % above have an alkyl methacrylate unit that carbon number is 1～4 a alkyl.Having carbon number is that 1～4 the alkyl methacrylate of alkyl and the copolymer of copolymer composition contain under the situation of alkyl methacrylate as main component, as copolymer composition, can use the monofunctional monomer of other alkyl methacrylate, alkyl acrylate, styrene, substituted phenylethylene, acrylonitrile, methacrylonitrile and so on, and then can also add polyfunctional monomer and make cross-linked polymer.
The acrylic acid series multilayer structure polymer is recorded in that for example special public clear 55-27576 communique, spy are opened flat 6-80739 communique, the spy opens in the clear 49-23292 communique.
In the graft copolymer that the alkene unsaturated monomer by the rubber-like polymer of 5～80 weight portions and 20～95 weight portions forms, as rubber-like polymer, can use for example diene series rubber of polybutadiene rubber, acrylonitrile/butadiene copolymer rubber, styrene/butadiene copolymers rubber and so on; The acrylic rubber of butyl polyacrylate, polyacrylic acid propyl ester, polyacrylic acid 2-Octyl Nitrite and so on; Ethylene/propene/non-conjugated diene is a rubber etc.In addition, as the alkene unsaturated monomer that is used for carrying out graft copolymerization, for example can enumerate styrene, acrylonitrile, (methyl) alkyl acrylate etc. with this rubber-like polymer.These graft copolymers for example are documented in, and the spy opens in clear 55-147514 communique, the special public clear 47-9740 communique.
About the content of rubber particles, with respect to acrylic resin 100 weight portions, be generally 3～150 weight portions, preferred 4～50 weight portions, more preferably 5～9 weight portions.The content of rubber particles is many more, compare when not containing rubber particles, the resistance to impact of scratch resistant resin board improves, even consequently the scratch resistant resin board extruding also is difficult for breaking, if but the content of rubber particles is too much, the case hardness of scratch resistant resin board can reduce sometimes.
In addition, can in polycarbonate resin and (methyl) acrylate resin layer, add the additives more than a kind such as light diffusing agent, delustering agent, dyestuff, light stabilizer, ultra-violet absorber, antioxidant, releasing agent, fire retardant, antistatic agent respectively.
Substrate is by adopting co-extrusion modling with polycarbonate resin and stacked manufacturing of (methyl) acrylate resin layer.This co-extrusion modling can followingly be carried out, promptly, use 2 or 3 single shafts or biaxial extruder, with the material of the material of polycarbonate resin and (methyl) acrylate resin layer respectively behind the melting mixing, undertaken stacked by feed conduit mould (Off イ one De Block ロ Star Network ダ イ), branch manifold mould etc., carry out co-extrusion modling thus, the fusion laminated resin plate by polycarbonate resin and (methyl) acrylate resin layer form for example can use roller unit to carry out cooling curing.The substrate of making by co-extrusion modling and is compared by the substrate that has used adhesive, the applying of bonding agent to make, and is being preferred aspect post forming easily.
Substrate is generally sheet or membranaceous, and its thickness is generally 0.3～3mm, preferred 0.3～2mm, more preferably 0.4～1.5mm.In addition, in substrate, the thickness of (methyl) acrylate resin layer is generally 50～120 μ m, preferred 60～110 μ m, more preferably 70～100 μ m.The thickness of (methyl) acrylate resin layer is more little, the resistance to impact of scratch resistant resin board improves, even and scratch resistant resin board exists extruding also to be difficult for the trend of breaking, if but the thickness of (methyl) acrylate resin layer is too small, then the case hardness of scratch resistant resin board can excessively reduce.
Substrate can be the duplexer that only disposes 2 layers of structure of (methyl) acrylate resin layer at the single face of polycarbonate resin, also can be the duplexer that disposes the 3-tier architecture of (methyl) acrylate resin layer on the two sides of polycarbonate resin.From scratch resistant resin board environment resistant, for example be exposed under the high temperature, aspect that high humidity following time is difficult for warpage, preferably dispose the substrate of (methyl) acrylate resin layer on the two sides of polycarbonate resin.In addition, when being 3-tier architecture, the composition of two (methyl) acrylate resin layer can be the same or different, and the thickness of two (methyl) acrylate resin layer can be the same or different.For example, when acrylate resin layer contained rubber particles, (methyl) acrylate resin layer of the opposing party can contain rubber particles and also can not contain at a side (methyl).
So-called cured film is that curing property compound by external energies such as light, heat the film that forms takes place to solidify.
In scratch resistant resin board of the present invention, dispose the curing tunicle of marresistance in the one side at least of substrate.That is, solidify the two sides that tunicle can be configured in substrate, also can only be configured in single face.Therefore, layer example that constitutes as scratch resistant resin board can be listed below:
(1): curing tunicle/(methyl) acrylate resin layer/polycarbonate resin,
(2): curing tunicle/(methyl) acrylate resin layer/polycarbonate resin/curing tunicle,
(3): (methyl) acrylate resin layer/polycarbonate resin/curing tunicle,
(4): curing tunicle/(methyl) acrylate resin layer/polycarbonate resin/(methyl) acrylate resin layer,
(5): solidify tunicle/(methyl) acrylate resin layer/polycarbonate resin/(methyl) acrylate resin layer/curing tunicle.
When only using when the single face of polycarbonate resin disposes the substrate of (methyl) acrylate resin layer, preferably at least on (methyl) acrylate resin layer configuration solidify tunicle, that is, and preferred (1), (2) in above-mentioned (1)～(3).In addition, form when solidifying tunicle on the two sides of substrate, two compositions that solidify tunicle can be the same or different, and two thickness that solidify tunicle can be the same or different.
Be used to form the curable coating that solidifies tunicle, as necessary composition, as required, can contain curing catalysts, electroconductive particle, solvent, levelling agent, stabilization agent, antioxidant, colouring agent etc. with the curing compound that brings marresistance.
So-called curing property compound is meant the compound that solidifies by external energies such as light, heat.
As curing property compound, for example can enumerate acrylate compounds, urethane acrylate compound, epoxy acrylic ester compounds, carboxy-modified epoxy acrylic ester compounds, polyester acrylic ester compounds, copolymerization is acrylate compounds, alicyclic epoxy resin, tetraglycidel ether epoxy resin, vinyl ether compound, oxetane compound.Wherein, from the aspect of the marresistance of solidifying tunicle, preferably use the curing compound that radical polymerization is solidified that passes through of polyfunctional acrylic ester compound, multifunctional polyurethane acrylate compounds, multi-functional epoxy's acrylate compounds and so on; Alkoxy silane, alkylalkoxy silane and so on pass through the curing compound that thermal polymerization is solidified.The compound that these curing property compounds preferably solidify by irradiating electron beam, radioactive ray, ultraviolet homenergic ray, or by heating the compound that solidifies.The formation of solidifying tunicle can be used a kind of curing property compound, also can use a plurality of curing compounds.
So-called acrylate compounds is the compound that has 1 above acryloyl group in molecule.
So-called carboxy-modified epoxy acrylic ester compounds is to have the compound that contains the construction unit that derives from carboxyl (C (=O) O-) in the molecule between acryloyl group and epoxy radicals.
So-called copolymerization is an acrylate compounds, is the compound that has 1 above acryloyl group in molecule.
So-called alicyclic epoxy resin is the ester ring type compound that contains epoxy radicals.
[28] particularly preferred curing compound is the compound that has at least 3 (methyl) acryloxies in molecule.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.
[29], for example can enumerate 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 as the compound that has at least 3 (methyl) acryloxies in the molecule; Make (methyl) acrylate with hydroxyl and the compound that in molecule, has at least 2 isocyanate bases (isocyanato group) [for example react polyurethane (methyl) acrylate that gets, have (methyl) acryloxy more than 3 with respect to ratios more than the mole such as isocyanate base serve as with hydroxyl, by the reaction of vulcabond and pentaerythrite three (methyl) acrylate, obtain polyurethane (methyl) acrylate of 6 officials energy]; Three (methyl) acrylate of three (2-hydroxyethyl) cyamelide.Here show monomer, these monomers can directly use, and also can use for example oligomer such as dimer, trimer.In addition, can also and use monomer and oligomer.Form the curing tunicle, can use the compound that in a kind of molecule, has at least 3 (methyl) acryloxies, also can use the compound that in a plurality of molecules, has at least 3 (methyl) acryloxies.
[30], for example can enumerate " NK HARD M101 " (urethane acrylate system), " NK ESTER A-TMM-3L " (pentaerythritol triacrylate), " NK ESTERA-TMMT " (tetramethylol methane tetraacrylate), " NK ESTER A-9530 " (dipentaerythritol five acrylate) and " NK ESTER A-DPH " (dipentaerythritol acrylate) of Xin Zhong village chemical industrial company as in molecule, having the commercially available product of the compound of at least 3 (methyl) acryloxies; " KAYARAD DPCA " (dipentaerythritol acrylate) of Japan chemical drug company; " NOPCOCURE 200 " series of company of Sheng Nuo spectrum section (SAN NOPCO); " UNIDIC " series of big Japanese ink chemical industrial company.
In addition, using the compound in molecule, have at least 3 (methyl) acryloxies during as curing property compound, can also with other curing property compounds, two (methyl) acrylic acid glycol ester for example, two (methyl) acrylic acid binaryglycol ester, two (methyl) acrylic acid 1,6-hexylene glycol ester, the compound that has 2 (methyl) acryloxies in molecule of two (methyl) acrylic acid DOPCP and so on is also used, about its use amount, the compound that has at least 3 (methyl) acryloxies in molecule with respect to 100 weight portions is generally till 20 weight portions.
When curable coating being solidified with ultraviolet ray, use Photoepolymerizationinitiater initiater as curing catalysts for well.As Photoepolymerizationinitiater initiater; for example can enumerate benzil, benzophenone and derivative thereof, thioxanthene ketone, benzil dimethyl ketal class, Alpha-hydroxy alkylbenzene ketone, hydroxyl ketone, aminoalkyl benzophenone class, acylphosphine oxide class, can also use in them more than 2 kinds.About the use amount of Photoepolymerizationinitiater initiater,, be generally 0.1～5 weight portion with respect to curing property compound 100 weight portions.
As the commercially available product of Photoepolymerizationinitiater initiater, for example can enumerate the IRGACURE series and the DAROCUR series of " IRGACURE 651 ", " IRGACURE 184 ", " IRGACURE 500 ", " IRGACURE 1000 ", " IRGACURE 2959 ", " DAROCUR 1173 ", " IRGACURE 907 ", " IRGACURE 369 ", " IRGACURE 1700 ", " IRGACURE 1800 ", " IRGACURE 819 ", " IRGACURE 784 " and so on of Ciba company; The KAYACURE series of " KAYACUREITX ", " the KAYACURE DETX-S " of Japan chemical drug company, " KAYACURE BP-100 ", " KAYACUREBMS ", " KAYACURE 2-EAQ " and so on.
Contain electroconductive particle in the curable coating by making, can give static electricity resistance solidifying tunicle.As electroconductive particle, preferably use the inorganic particulate of antimony-Xi composite oxides, phosphorous tin oxide, antimony oxide, antimony-zinc composite oxide, titanium oxide, indium-Xi composite oxides (ITO) and so on.
The average grain diameter of electroconductive particle is generally below the 0.5 μ m, from the static electricity resistance of cured film, the aspect of the transparency, and in average grain diameter, more than the preferred 0.001 μ m, and below the preferred 0.1 μ m, more preferably below the 0.05 μ m.The average grain diameter of electroconductive particle is more little, can reduce the mist degree of scratch resistant resin board, can improve the transparency.
[36] about the content of electroconductive particle,, be generally 2～50 weight portions, preferred 3～20 weight portions with respect to curing property compound 100 weight portions.The content of electroconductive particle is many more, compares with the situation that does not contain electroconductive particle, and the static electricity resistance that solidifies tunicle improves, but the content of electroconductive particle is when too much, and the transparency of solidifying tunicle sometimes reduces.
[37] electroconductive particle can be made 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 carries out surface treatment with for example nonionic.
[38] in curable coating, be purpose with viscosity adjusting of coating etc., containing solvent for well, when especially containing electroconductive particle, in order to make its dispersion to contain solvent for well.When preparation contains the curable coating of electroconductive particle and solvent, for example can be with electroconductive particle and solvent, make electroconductive particle be scattered in the solvent after, with the dispersion liquid that obtains and curing property compound; Can also be with curing property compound and solvent, in the mixed liquor that electroconductive particle is scattered in obtain.
[39] solvent so long as can dissolving cured property compound and the solvent that after coating, can easily volatilize get final product, in addition, when using electroconductive particle, so long as the solvent of its dispersion is got final product as paint ingredient.As the example of solvent, can enumerate the alcohols of 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; Toluene, dimethylbenzene and so on aromatic hydrocarbon based; The ester class of ethyl acetate, butyl acetate and so on; Water.The use amount of solvent can cooperate the proterties of curing property compound etc. suitably to adjust.
[40] when curable coating contains levelling agent, as levelling agent, the preferred silicone oil that uses, as its example, can enumerate dimethicone, phenyl methyl silicone oil, alkyl and/or aralkyl modified silicon oil, fluoro silicone oil, polyether modified silicon oil, fatty acid ester modified silicon oil, Methyl Hydrogen Polysiloxane Fluid, the silicone oil that contains silanol group, the silicone oil that contains alkoxyl, the silicone oil that contains phenolic group, methacrylic acid 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.Curable coating can contain the levelling agent more than a kind.About the content of these levelling agents,, be generally 0.01～5 weight portion with respect to curing property compound 100 weight portions.
As the commercially available product of levelling agent, for example can enumerate " SH200-100cs ", " SH28PA ", " SH29PA ", " SH30PA ", " ST83PA ", " ST80PA ", " ST97PA " and " ST86PA " of TORAY DOWCORNINGSLICONE company; " BYK-302 " of Bi Ke chemistry (Japan), " BYK-307 ", " BYK-320 " and " BYK-330 ".
The curable coating that so obtains is coated on the one side at least of aforesaid substrate, makes curing property and film, the curing compound of curing property in filming solidified, make the curing tunicle, thereby obtain scratch resistant resin board of the present invention.
The coating of curable coating can be coated with method, nick version (microgravure) method rubbing method, rolling method, flow coat method, dip coating, spin-coating method, mould by rod and be coated with known coating processes such as method, spraying process and carry out.The curing that curing property is filmed can be undertaken by irradiation energy ray or heating according to the kind of curable coating.
When curing property compound is solidified, as energy-ray, for example can enumerate ultraviolet ray, electron beam, radioactive ray, conditions such as its intensity, irradiation time can suitably be selected according to the kind of curable coating.In addition, when curing property compound was solidified, conditions such as its temperature, time can suitably be selected according to the kind of curable coating, but in order not make base plate deformation, heating-up temperature is general preferred 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.
The thickness that solidifies tunicle is preferably 0.5～50 μ m, more preferably 1～20 μ m.Exist to solidify the trend of the more little then difficult more generation be full of cracks of thickness of tunicle, but when too small, marresistance becomes insufficient sometimes.
For the scratch resistant resin board that obtains, can pass through rubbing method, sputtering method, vacuum vapour deposition etc. the antireflection processing is implemented on its surface.In addition, can also on the single face of scratch resistant resin board or two sides, give anti-reflection effect by applying antireflection sheet.
The scratch resistant resin board that obtains like this, its resistance to impact excellence, even and extruding also be difficult for breaking, therefore can be used for various uses, be particularly suited for using as the display baffle.As the kind of protected display, for example can enumerate CRT monitor, LCD, plasma scope, EL display.In addition, as the purposes of protected display, for example can enumerate the monitor of TV or computer; PersonalHandy-phone System), PDA (personal digital assistant: the display window of carrying type information terminal such as Personal Digital Assistant) mobile phone or PHS (personal mobile communication system:; The view finder portion of digital camera or handheld video camera; The display window of portable game machine.Scratch resistant resin board of the present invention is particularly suited for the display window protective panel as the carrying type information terminal that adopts LCD, EL display etc.; scratch resistant resin board of the present invention is brought into play particularly advantageous effect especially as mobile phone, particularly 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 the display baffle by scratch resistant resin board of the present invention, print at first as required, processing such as perforate, be cut to the size that needs and get final product.Then, as long as the display baffle of making is installed on display, just can effectively protect display.At this moment, for only disposing the scratch resistant resin board that solidifies tunicle, preferably according to being the outside (observer's side) to dispose a side of solidifying tunicle, being that the mode of dorsal part (demonstration side) is provided with a side of configuration curing tunicle not at the single face of substrate.In addition, dispose the scratch resistant resin board that solidifies tunicle for two sides, preferably be the outside, be that the mode of dorsal part is provided with the polycarbonate resin side with (methyl) acrylate resin layer side at substrate (this substrate only disposes (methyl) acrylate resin layer at the single face of polycarbonate resin).
Embodiment
Below, embodiments of the invention are shown, but the present invention is not subjected to the restriction of these embodiment.In the example, unless otherwise specified, % and part are weight basis.
As acrylic resin, use the particle of the thermoplastic polymer (104 ℃ of glass transition temperatures) that obtains by polymerisation in bulk by the monomer that contains methyl methacrylate 97.8% and methyl acrylate 2.2%.It should be noted that this glass transition temperature is according to JIS K 7121:1987, begin temperature by differential scanning calorimetry and the extrapolation glass transition obtained with 10 ℃/minute of firing rates.
As rubber particles, use following rubber particles: the innermost layer rigid polymer that the monomer that contains methyl methacrylate 93.8%, methyl acrylate 6% and allyl methacrylate 0.2% gets by emulsion polymerisation of serving as reasons, the intermediate layer elastomeric polymer that the monomer that contains butyl acrylate 81%, styrene 17% and allyl methacrylate 2% gets by emulsion polymerisation of serving as reasons, the outermost layer rigid polymer that the monomer that contains methyl methacrylate 94% and methyl acrylate 6% gets by emulsion polymerisation of serving as reasons.
Embodiment 1～7, comparative example 1～2
(making of substrate)
Use high-speed mixer that methacrylic resin and rubber particles are mixed with the ratio shown in the table 1, carry out melting mixing,, obtain the particle (embodiment 1～7) of methacrylic resin composition the mixing thing granulation that obtains with biaxial extruder.Then, make methacrylic resin composition (embodiment 1～7) or methacrylic resin (comparative example 1,2) fusion with 65mm φ single shaft extruder [Toshiba Machine Co. Ltd], on the other hand, make polycarbonate resin [Sumitomo Dow corporate system " Calibre 301-10 "] fusion with 45mm φ single shaft extruder [Toshiba Machine Co. Ltd].Then, two fused mass are passed through the feed conduit and stacked, Jie is extruded by the T pattern tool of 265 ℃ of design temperatures.The membranoid substance that obtains is clamped in carry out moulding between the metal system roller of a pair of surface smoothing after, cooling.Like this, the single face that is formed in the polycarbonate resin of thick 430 μ m disposes 2 layers of structure substrate (embodiment 1～4, comparative example 1) of gross thickness 500 μ m of the methacrylic resin layer of thick 70 μ m; Perhaps dispose the 3-tier architecture substrate (embodiment 5～7, comparative example 2) of gross thickness 500 μ m of the methacrylic resin layer of thick 70 μ m on the two sides of the polycarbonate resin of thick 360 μ m.
(preparation of hardening coating)
[catalyst changes into the ELCOM-7514 of industrial group with the colloidal sol of 28 parts of dipentaerythritol acrylates [" the NK ESTER A-DPH " of Xin Zhong village chemical industrial company], 1 part of Photoepolymerizationinitiater initiater [IRGACURE 184 of Ciba company], antimony pentaoxide particulate, solid component concentration 20%] 8 parts, 1-methoxyl group-32 parts of 2-propyl alcohol, 32 parts of isobutanols and 0.045 part of mixing of silicone oil [" SH28PA " of TORAYDOWCORNING SLICONE company], the preparation curable coating.
(manufacturing of scratch resistant resin board)
Substrate is cut to 100mm * 60mm size, forms filming of curable coating on the two sides with dip coating.Then, at room temperature drying is 1 minute, and then makes solvent evaporates in 3 minutes at 45 ℃ hot-air oven inner drying.Using the high-pressure sodium lamp of 120W, is 0.5J/cm to the integrating energy of the dry coating irradiation ultraviolet radiation that obtains
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.
[crushing strength]
Externally in the metal system frame of size 60mm * 100mm, inside dimension 30mm * 50mm, the test film of configuration 55mm * 85mm is (for embodiment 1～4, the comparative example 1 of the substrate that uses 2 layers of structure, making methacrylic resin layer side is that upside (squeeze side), polycarbonate resin side are downside), metal bar with diameter 10mm with spherical front end, with the central authorities of 10mm/ minute speed squeeze test sheet, the ruined intensity of determination test sheet.Test is implemented 3 times, with the mean value of 3 result of the tests as measurement result.
[falling sphere intensity]
In the metal rounding cartridge type frame of external diameter 60mm, internal diameter 50mm, dark 5mm, the test film of configuration 60mm * 60mm.For embodiment 1～4, the comparative example 1 of the substrate that uses 2 layers of structure, making methacrylic resin layer side is that upside (falling sphere side), polycarbonate resin side are downside.The Metal Ball of operating weight 36g diameter 20mm is carried out falling ball impact test according to JIS K 7211-1, calculates 50% impact failure height.With this 50% impact failure height as falling sphere intensity.In addition, for each embodiment and comparative example, 20 samples are carried out falling ball impact test.In falling ball impact test, maximum height is 100cm.
[pencil hardness]
Measure pencil intensity (, measuring the pencil intensity of methacrylic resin layer side) according to JIS K 5600 for embodiment 1～4, the comparative example 1 of the substrate that uses 2 layers of structure.
[durability warpage]
The test film of 70mm * 50mm after placing 3 days under 85 ℃ the environment, is configured to four jiaos of perks on horizontal plane, measures its height, will with the maximum of the difference of the same value of measuring before the test as amount of warpage.
Table 1
| Example | Methacrylic resin (part) | Rubber particles (part) | Substrate | Crushing strength (kgf) | Falling sphere intensity (cm) | Pencil hardness | Durability warpage (mm) |
| Comparative example 1 | ??100 | ??0 | 2 layers | ??19 | ??3 | ??4H | ??1.4 |
| Embodiment 1 | ??96 | ??4 | 2 layers | ??25 | ??51 | ??4H | ??1.4 |
| Embodiment 2 | ??94 | ??6 | 2 layers | ??27 | ??55 | ??4H | ??1.5 |
| Embodiment 3 | ??90 | ??10 | 2 layers | ??33 | ??59 | ??3H | ??1.5 |
| Embodiment 4 | ??80 | ??20 | 2 layers | ??50 | ??60 | ??2H | ??1.5 |
| Comparative example 2 | ??100 | ??0 | 3 layers | ??23 | ??4 | ??4H | ??0.3 |
| Embodiment 5 | ??94 | ??6 | 3 layers | ??29 | ??58 | ??4H | ??0.3 |
| Embodiment 6 | ??90 | ??10 | 3 layers | ??38 | ??62 | ??3H | ??0.4 |
| Embodiment 7 | ??80 | ??20 | 3 layers | ??55 | ??68 | ??2H | ??0.4 |
Claims (6)
1. a scratch resistant resin board is characterized in that,
One side at least at substrate disposes the curing tunicle, and described substrate is the substrate that disposes (methyl) acrylate resin layer that contains rubber particles in the one side at least of polycarbonate resin.
2. scratch resistant resin board according to claim 1 is characterized in that,
Described substrate is the duplexer that disposes (methyl) acrylate resin layer on the two sides of polycarbonate resin.
3. scratch resistant resin board according to claim 1 and 2 is characterized in that,
Described rubber particles is the acrylic acid series multilayer structure polymer.
4. according to each described scratch resistant resin board in the claim 1～3, it is characterized in that,
Solidifying tunicle is the film that is formed by the curable coating that contains the compound that has 3 (methyl) acryloxies in the molecule at least.
5. a display protection plate is characterized in that,
Make by each described scratch resistant resin board in the claim 1～4.
6. the display window protective panel of a carrying type information terminal is characterized in that,
Make by each described scratch resistant resin board in the claim 1～4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2008190649 | 2008-07-24 | ||
| JP2008190649A JP5176749B2 (en) | 2008-07-24 | 2008-07-24 | Scratch-resistant resin plate and its use |
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| JP (1) | JP5176749B2 (en) |
| KR (1) | KR20100011920A (en) |
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| CN102236121A (en) * | 2010-04-27 | 2011-11-09 | 住友化学株式会社 | Lamination plate for protecting liquid crystal display |
| CN102673063A (en) * | 2011-03-18 | 2012-09-19 | 住友化学株式会社 | Laminated plate |
| CN104416999A (en) * | 2013-08-27 | 2015-03-18 | 住友化学株式会社 | Layered plate |
| CN112512808A (en) * | 2018-07-27 | 2021-03-16 | 株式会社可乐丽 | Infrared shielding laminate and method for producing same |
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| JP2012121143A (en) * | 2010-12-06 | 2012-06-28 | Sumitomo Chemical Co Ltd | Laminate, and scratch-resistant resin plate obtained by using the same, protective plate for display and protective plate for touch panel |
| JP6043053B2 (en) * | 2011-07-21 | 2016-12-14 | 住友化学株式会社 | Resin plate, scratch-resistant resin plate using the same, protective plate for display, protective plate for display window of portable information terminal, protective plate for touch panel, and method for producing resin plate |
| JP6530583B2 (en) * | 2013-03-13 | 2019-06-12 | 住友化学株式会社 | Resin laminate and scratch resistant resin laminate using the same |
| KR20160080277A (en) | 2014-12-01 | 2016-07-08 | 엘지엠엠에이 주식회사 | Multi-layer sheet |
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Also Published As
| Publication number | Publication date |
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| TW201010858A (en) | 2010-03-16 |
| JP2010023444A (en) | 2010-02-04 |
| KR20100011920A (en) | 2010-02-03 |
| JP5176749B2 (en) | 2013-04-03 |
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