CN1841094A - Anti-glare film - Google Patents
Anti-glare film Download PDFInfo
- Publication number
- CN1841094A CN1841094A CNA2006100683329A CN200610068332A CN1841094A CN 1841094 A CN1841094 A CN 1841094A CN A2006100683329 A CNA2006100683329 A CN A2006100683329A CN 200610068332 A CN200610068332 A CN 200610068332A CN 1841094 A CN1841094 A CN 1841094A
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- Prior art keywords
- refractive index
- index layer
- coating
- mentioned
- low
- Prior art date
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- OTBGVKCQFOAAQH-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl OTBGVKCQFOAAQH-UHFFFAOYSA-N 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- VIFIHLXNOOCGLJ-UHFFFAOYSA-N trichloro(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC[Si](Cl)(Cl)Cl VIFIHLXNOOCGLJ-UHFFFAOYSA-N 0.000 description 1
- SSBOTKQTCWQWMG-UHFFFAOYSA-N trichloro(nonyl)silane Chemical compound CCCCCCCCC[Si](Cl)(Cl)Cl SSBOTKQTCWQWMG-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- FZXOVEZAKDRQJC-UHFFFAOYSA-N triethoxy(nonyl)silane Chemical compound CCCCCCCCC[Si](OCC)(OCC)OCC FZXOVEZAKDRQJC-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- JEPXSTGVAHHRBD-UHFFFAOYSA-N trimethoxy(nonyl)silane Chemical compound CCCCCCCCC[Si](OC)(OC)OC JEPXSTGVAHHRBD-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- ZVPKMEQEIHFILG-UHFFFAOYSA-N tripropoxy(3,3,3-trifluoropropyl)silane Chemical compound CCCO[Si](CCC(F)(F)F)(OCCC)OCCC ZVPKMEQEIHFILG-UHFFFAOYSA-N 0.000 description 1
- ZLDJTZCGPNHTGL-UHFFFAOYSA-N tris(1,1,2,2,2-pentafluoroethoxy)-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZLDJTZCGPNHTGL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
An anti-glare film is superior in low reflectivity and economy and balances conductivity, abrasion resistance, and contamination resistance. The anti-glare film has a transparent substrate, and at least a hard coat layer, a high refractive index layer, and a low refractive index layer provided on the transparent substrate, the high refractive index layer contains a radiation curable resin composition containing electroconductive inorganic ultrafine particles, and has a refractive index after curing of 1.6 to 1.8, the low refractive index layer contains fluorine containing polysiloxane, and has a refractive index after curing of 1.36 to 1.42, and the electroconductive inorganic ultrafine particle is at least one selected from tin oxide, indium tin oxide (ITO), and zinc oxide, and is contained at 75% or more by weight ratio in the high refractive index layer.
Description
Technical field
The present invention relates to the anti-dazzling film of various display surfaces such as a kind of LCD of being located at and PDP, particularly relate to a kind of anti-dazzling film that can pass through the cheap supply of coating.
Background technology
In recent years, the product that is fit to multi-purpose wide variety of sizes from regular handset to the large-scale tv display, has been made, has been sold out in the display screen fast development of LCD and PDP etc.In order to improve the resolution of this class display screen, the surface of these display screens generally all is provided with the layer with antireflection function specially.This class antireflection technology roughly is divided into two kinds, and a kind of is the anti-dazzle technology that prevents that ambient light from mirroring, i.e. Anti-Glare technology (hereinafter referred to as " AG "); Another kind is to utilize the interference of light effect to be used to reduce the antireflection technology of reflectivity itself, i.e. Anti-Reflection technology (hereinafter referred to as " AR ").
At present, main method is: for AG, utilization with sand-blast or embossing etc. directly make substrate surface become the method for hair side, contain in the substrate surface setting filler hard conating method and form the method etc. of the perforated membrane of island structure at substrate surface, form concavo-convex on the anti-dazzling film surface, for AR, wait by sputtering method to form.Yet, the sputter equal vacuum film build method that the latter adopts, the adaptation between cost height and the plastic foil is insufficient, is difficult to carry out the even film forming of large tracts of land in addition, therefore begins a plurality of layers of pressing refractive index to have nothing in common with each other by the wet type coating layer recently.The reflectivity of the AR that makes with sputter is generally below 0.3%, but with its height of its luminance factor of film that the wet type coating is made, mostly is greatly about 1.0%, therefore in order to be different from AR, be called low reflection Low Refletion (hereinafter to be referred as " LR).
LR film with wet type coating making, its basic comprising is successively to be laminated to matrix on to the antiradar reflectivity layer high refractive index layer, can be as required, between matrix and the high refractive index layer, between high refractive index layer and the low-index layer, on the low-index layer, design is layer arbitrarily.Here alleged high refractive index layer, low-index layer are not the absolute refractive index of regulation, but relatively more two-layer refractive index is called height relatively, and when both had concerning of following formula 1, its reflectivity was minimum.
n
2=(n
1)
1/2(formula 1) (n
1Refractive index for high refractive index layer; n
2Refractive index for low-index layer)
High-index material as the LR film that utilizes the wet type coating to make, in order to improve refractive index, the general organic polymer that contains elements such as chlorine or bromine, sulphur that uses perhaps makes the metal oxide ultramicron of highs index of refraction such as titanium dioxide, zirconia, zinc paste be dispersed in the layer.In addition, in low-index layer, generally use the silicon dioxide, magnesium fluoride of the organic polymer of fluorinated or low-refraction etc., or particulate is piled up emptying aperture is set, sneaks into by air and realize low-refraction etc.
, be used for large-scale tv in recent years and be the soaring gesture of first mate, therefore be coated with the demand of the LR film of making also in continuous increase with wet type with the display demand.With regard to the LR film, the general product sold of making, be on transparent membranes such as polyethylene terephthalate (being called " PET " once) triacetyl cellulose (below be called " TAC "), with the hard conating, low-index layer that have the high index of refraction layer function concurrently lamination successively, form double-layer structure, perhaps hard conating, high refractive index layer and low-index layer lamination are successively formed three-decker.For this LR film, generally require except antiradar reflectivity, also to require it to have high-wearing feature, chemical resistance and soil resistance etc., also begin its surface of requirement in recent years and have static electricity resistance.Because these are to come from its dust that not only prevents generation of static electricity to adhere to, also to improve the market demand of the wiping of adhered dust simultaneously, its surface resistance must be made as 10
7～10
11Ω/ scope.Need to prove that Ω/ is the unit of surface resistivity, is a unit area, is also write as Ω/sq sometimes.
For the surface that makes anti-dazzle thin-membrane has static electricity resistance, identical with the situation of above-mentioned LR film, must make arbitrary layer or multilayer in hard conating, high refractive index layer, the low-index layer have static electricity resistance.Making it have the used material of this static electricity resistance for example has: surfactant, electroconductive polymer and electric conductivity inorganic particles etc.Inorganic particles is dispersed in method in filming, is realizing aspect the low resistance effectively, thereby obtained widespread use.
Angle from electrostatic prevention, preferably make the electric conductivity inorganic particles be configured in outside surface, but because the general refractive index height of these materials, when considering its reflection preventing ability, preferably it is included in the internal layer of low-index layer, also gives higher refractive index when giving electric conductivity.
This example is opened on the 2003-294904 communique on the books the spy, it is dispersed in the transparent conductivity ultramicron of the metal oxide in the conductive layer of 2 series of strata (conductive layer/low-index layer) and 3 series of strata (conductive layer/high refractive index layer/low-index layer), uses needle-like or spherical antimony-doped tin oxide, the particulate of aluminium-doped zinc oxide.In addition, open on the 2002-167576 communique the spy, high index of refraction conductive material composition is disclosed, it is made of at dielectric microparticles more than 2.0 (B component) and cementing agent (C component) electrically conductive microparticle (A component), refractive index, it forms composition: when being 100 weight portions with the A component, the B component is 5～100 weight portions, and the C component is 5～100 weight portions; Wherein, electrically conductive microparticle is selected from tin indium oxide, tin oxide, antimony oxide zinc, zinc oxide aluminum.And, open on the 2001-302945 communique the spy, disclose ultraviolet hardening electrically conducting transparent based coating composition, it is that tetragonal system tin oxide particulate and acrylate compounds with the plasma method manufacturing are made in alcohols solvent.
But in addition electrostatic prevention and high index of refraction for anti-dazzling film also have many patented claims, yet at aspects such as low reflectivity, static electricity resistance, wearing quality, chemical resistance and soil resistances, the anti-dazzling film that has various characteristics concurrently still is unrealized.
In addition, as the method for giving many performances such as low reflectivity, static electricity resistance, wearing quality, chemical resistance and soil resistance simultaneously, advancing the exploitation of the film that is laminated to multilayer, but this method needs multiple stratification, i.e. repeatedly operation of coating on base material, cost height.In addition, owing to be difficult to adjust the balance of each interlayer that multiple stratification causes, thereby in practice, only, select, realize the part in these performances according to the purpose of using.
Summary of the invention
In view of above-mentioned condition, the present invention is by being provided with hard conating and another layer on transparent base, perhaps hard conating, high refractive index layer and low-index layer provide a kind of low reflectivity, economy is good and can takes into account the anti-dazzling film of performance electric conductivity, wearing quality, soil resistance function well.
The 1st kind of embodiment of anti-dazzling film of the present invention is characterised in that, lamination hard conating at least successively on translucent matrix, high refractive index layer and low-index layer, high refractive index layer comprises the radiation-curing type resin combination that contains the electric conductivity ultrafine inorganic particle, refractive index after it solidifies is 1.6～1.8, low-index layer contains fluorinated polysiloxane, refractive index after it solidifies is 1.36～1.42, the electric conductivity ultrafine inorganic particle that high refractive index layer contains is by being selected from tin oxide, tin indium oxide (ITO), at least a formation of zinc paste, the weight ratio of electric conductivity ultrafine inorganic particle are more than 75%.
In addition, second kind of embodiment of anti-dazzling film of the present invention is characterised in that, lamination hard conating at least successively on translucent matrix, low-index layer, hard conating comprises the radioactivity hardening resin composition that contains the electric conductivity ultrafine inorganic particle, thickness is 1.0～5.0 μ m, refractive index after it solidifies is 1.6～1.8, low-index layer contains fluorinated polysiloxane, refractive index after it solidifies is 1.36～1.42, the electric conductivity ultrafine inorganic particle that contains in the hard coat is by being selected from tin oxide, tin indium oxide (ITO), at least a formation of zinc paste, the weight ratio of electric conductivity ultrafine inorganic particle are more than 75%.
Need to prove that hard conating of the present invention is meant the coating that shows the above hardness of H in the pencil hardness test (JISK5400), in addition, high index of refraction of the present invention and low-refraction, be meant adjoin each other layer the height of relative index of refraction.
Feature of the present invention also is, in the surface resistance less than 10 of the low-index layer surface measurements of anti-dazzling film of the present invention
11Ω/.
Feature of the present invention is that also the average reflectance of anti-dazzling film of the present invention is below 1%, and total light transmittance reaches more than 90%, and its mist degree is below 2%.
Feature of the present invention is that also after anti-dazzling film of the present invention utilized steel wool to carry out abrasion test, its haze change amount was below 0.5%.
Feature of the present invention is that also the hard conating of anti-dazzling film of the present invention contains the translucent resin particulate, and above-mentioned hard coating surface has micro concavo-convex.
Feature of the present invention is that also the refractive index after its of the hard conating of the 1st embodiment of anti-dazzling film of the present invention solidifies is 1.45～1.55.
Embodiment
Below, to the various inscapes in the anti-dazzling film of the present invention, be divided into the 1st embodiment and the 2nd embodiment is illustrated respectively.
1. the 1st embodiment
The 1st embodiment of anti-dazzling film of the present invention is characterised in that, lamination hard conating at least successively on translucent matrix, in the formation of high refractive index layer and low-index layer, high refractive index layer comprises the radiation-curing type resin combination that contains the electric conductivity ultrafine inorganic particle, refractive index after it solidifies is 1.6～1.8, low-index layer contains fluorinated polysiloxane, refractive index after it solidifies is 1.36～1.42, the electric conductivity ultrafine inorganic particle that high refractive index layer contains is by being selected from tin oxide, tin indium oxide (ITO), at least a formation in the zinc paste, the weight ratio of electric conductivity ultrafine inorganic particle are more than 75%.
By aforesaid formation, the 1st embodiment of anti-dazzling film of the present invention reaches the harmonious good effect of low reflection characteristic, electric conductivity, wearing quality and soil resistance.
Although the translucent matrix that the present invention uses also can use quartz and soda-lime glass etc., preferably use PET, TAC, PEN (PEN), polymethylmethacrylate (PMMA), polycarbonate (PC), polyimide (PI), tygon (PE), polypropylene (PP), polyvinyl alcohol (PVA) (PVA), Polyvinylchloride (PVC), cyclic olefine copolymer (COC), contain various resin films such as norbornene resin, polyethersulfone, cellophane, aromatic polyamide.In addition, under the situation that is used for PDP, LCD, more preferably PET, TAC film.
The transparency of these translucent matrix is high more good more.Its light transmittance (JISK7361-1) can be more than 80%, more preferably more than 90%.In addition,, consider preferred thinly from the angle of lighting, but, preferably use the matrix of 1～700 mu m range, more preferably the scope of 25～250 μ m from productivity and operability as the thickness of transparent base.
In addition, by translucent matrix being carried out surface treatments such as alkali treatment, corona treatment, Cement Composite Treated by Plasma, and coating surface activating agent, silane coupling agent etc. or carry out surface modification treatment such as Si evaporation, can improve the adaptation between translucent matrix and the hard conating.
The resin of hard conating that constitutes the 1st embodiment of anti-dazzling film of the present invention can use by radioactive ray, pine for the resin that the combination of any or they is cured.The composition that radiation-curing type resin uses, monomer, oligomer and prepolymer that acryloyl group, methacryl, acryloxy, methacryloxy etc. are had a polymerism unsaturated link suitably mix and form.Monomer for example has: styrene, methyl acrylate, methyl methacrylate, methoxyl polymethylacrylic acid glycol ester, cyclohexyl methacrylate, methacrylic acid phenoxy group ethyl ester, Ethylene glycol dimethacrylate, dipentaerythritol acrylate, trimethylol-propane trimethacrylate etc.Oligomer, prepolymer for example have: acrylate such as polyester acrylate, urethane acrylate, epoxidation propylene acid esters, polyether acrylate, alkyd acrylate, melamine acrylate, silicon Acrylote, unsaturated polyester (UP), epoxy compounds etc.These materials can use separately also can mix a plurality of uses.Require to have under the flexual situation in cured film, preferred monomers is added fewly, and in order further to reduce cross-linking density, monomer preferably uses the monomer of the esters of acrylic acid of simple function group, difunctional.On the contrary, but require to have thermotolerance in cured film, wearing quality, solvent resistance waited under the situation of cruel permanance, preferably increases amount of monomer, uses the above acrylic ester monomer of trifunctional.
In order to solidify aforesaid radiation-curing type resin, for example can irradiation ultraviolet radiation, electron ray, X ray isoradial, can suitably add polymerization initiator as required.Polymerization initiator just is not particularly limited so long as use is hot or visible light, ultraviolet homenergic ray generation living radical or cationic material.Produce the material of the polymerization initiator of free radical by heat, for example have: 2,2-azo two organic peroxides such as azo-compound, benzoyl peroxide, lauroyl peroxide such as (2, the 4-methyl pentane nitrile).The material that is produced the polymerism initiating agent of living radical by energy-ray for example has: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-sulfidomethyl phenyl) propane-acetophenones such as 1-ketone, the styrax methyl ether, the styrax ethylether, benzoin isobutyl propyl group ether, styrax ethers such as benzoin isobutyl butyl ether, benzophenone, o-benzoyl base benzoic acid methyl esters, the 4-phenyl benzophenone, 4-benzoyl 4 '-methyl-diphenyl sulfite, the 4-benzoyl-N, N-dimethyl-N-[2-(1-oxo-2-propenyl oxygen base) ethyl] benzalkonium bromide (benzenemethanaminium bromide), benzophenones such as (4-benzoyl benzyl) trimethyl ammonium chloride; 2, thioxanthene classes such as 4-diethyl thioxanthene, 1-chloro-4-dichloro thioxanthene, 2,4,6-trimethylbenzoyl diphenyl benzene formyl oxide etc.In addition, producing cationic cationic polymerization initiators for example has: triphenylsulfonium hexafluoro antimonate, three (4-methoxyphenyl) sulfonium hexafluorophosphoric acid ester etc.
These can use separately, also can multiple mixing use.In addition, promoter (sensitizer) also can be with N, N-dimethyl-p-toluidine, 4, and aminated compoundss such as 4 '-diethylamino benzophenone mix use.The content of polymerization initiator is: relative radiation-curing type resin, its scope is 0.1～10 weight %, the scope of preferred 3～7 weight %.Under the too much situation of polymerization initiator, the analyte of unreacted polymerization initiator causes layer intensity to reduce sometimes or makes coloring resin, and opposite under very few situation, resin does not solidify.In addition,, use when the wavelength region may of irradiation energy ray has the filler of absorption, must improve the ratio of polymerization initiator utilizing visible light, ultraviolet light homenergic ray to make in its polymerization initiator that produces living radical.And, also can add stabilizing agents (agent is forbidden in thermal polymerization) such as quinhydrones, 1,4-benzoquinone, tertiary butylated hydroquinone, in this case, preferred resin content relatively is the scope of 0.1～5.0 weight %.
Use the hard conating of above-mentioned radiation-curing type resin preferred below 20% along with solidifying the volumetric shrinkage (calculating) that produces by following method.Volumetric shrinkage is greater than 20% o'clock, transparent base be the situation of film then crimping is remarkable, in addition, when matrix material is hard material type such as glass then the adaptation of its hard conating reduce.
Volumetric shrinkage:
Volumetric shrinkage: D=(S-S '/D * 100 ... (formula 2)
S: the proportion before solidifying
S ': the proportion after the curing
(proportion can be measured by the B method pycnometer method among the JIS K-7112)
In addition, in the hard conating of the 1st embodiment, also radiation-curing type resin adds stabilizing agents (agent is forbidden in thermal polymerization) such as quinhydrones, 1,4-benzoquinone, tertiary butylated hydroquinone relatively.The scope that the preferred relative radioactivity gel-type resin of addition is 0.1～5.0 weight %.
The thermohardening type resin that can use in hard conating for example has: phenolics, furane resin, xylene formal dehyde resin, ketone-formaldehyde resin, urea resin, melamine resin, anline resin, alkyd resin, unsaturated polyester resin, epoxy resin etc.These resins both can use separately, also can select some mixing to use.When if the transparent body is plastic foil, the thermosetting temperature can not be set too highly; Particularly when using PET, TAC, wish that the thermohardening type resin that uses can solidify below 100 ℃.
The transparency of the gel-type resin that uses in the hard conating is high more good more, and (JIS K-736-1) is the same with transparent base for its light transmittance, more than 80%, preferably reaches more than 90%; The refractive index of hard conating preferably in 1.45～1.55 scopes, if exceed this scope, then can not get suitable anti-reflective effect.
Among the present invention, directly or by the method that other layer is provided with hard conating for example having on the one or both sides of the transparent body: it is in above-mentioned resin, mixed fillers and water or organic solvent as required, it is utilized the paint vibrating machine, skin grinder, the pearl grinding machine, bowl mill, agitator mill, roller mill, the high speed turbine dispersion machine, jet grinding machine, the high speed impact grinding machine, ultrasonic dispersing machines etc. disperse, make coating or China ink, it is utilized airblade coating, the scraper plate coating, the scraper coating, contrary roller coat cloth, the transfer roller coating, the intaglio plate coating, kiss-coating, casting is coated with, spraying plating, slotted hole coating (slot orifice coating), the calenderstack coating, the electro-deposition coating, dip coated, coatings such as die head coating, reach letterpress such as flexographic printing, directly intaglio printing, intaglio printings such as indirect gravure, lithographys such as hectographic printing, printing processes such as porous printing such as serigraphy, on the one or both sides of transparent base, single or multiple lift is set, and contain solvent, at this moment, through the heated drying operation, utilize radioactive ray (ultraviolet situation, need Photoepolymerizationinitiater initiater) irradiation etc., coating layer or printed layers are solidified, obtain hard conating thus.Need to prove, radioactive ray are utilizing under the situation of electron ray, use pause from various electron ray accelerators such as Cockcroft-Wal type, model De Graff type, resonance transformation type, insulating core transformer etc., linear pattern, the electron ray with 50～1000KeV energy of emitting rummy type, the high-frequency type etc. etc., under the ultraviolet situation, can use the ultraviolet ray of light generations such as extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, carbon arc, acetylene arc, metal halide lamp etc.
For coating application or the printing application that improves coating, China ink, as required, can suitably use levelling agents such as silicone oil, the grease of Tissuemat E, Brazil wax, higher alcohol, diamides, higher fatty acid etc., hardening agent such as isocyanates, the adjuvants such as ultramicron that 0.1 μ m such as lime carbonate and silicasol, synthetic mica are following.
The thickness of hard conating is in the scope of 1.0～20.0 μ m, the scope of preferred 1.0～5.0 μ m.Hard conating is under than the thin situation of 1.0 μ m, and the wearing quality of hard conating reduces, use under the situation such as ultraviolet curing resin since oxygen hinder make solidify bad.Under the situation thicker, because the cure shrinkage of resin produces crimping sometimes, perhaps on hard conating, produce fine crack, and then the adaptation of itself and transparent base is reduced than 10 μ m.
Among the present invention, the translucent resin microparticulate can be included in the hard conating of above-mentioned explanation, form fine concavo-convexly at hard coating surface, make so-called AG.Translucent resin particulate used herein can use the organic light transmission particle that is made of acryl resin, polystyrene resin, styrene-propene acid copolymer, polyvinyl resin, epoxy resin, organic siliconresin, polyvinylidene fluoride, polyvinyl fluoride resinoid etc.The refractive index of translucent resin particulate is preferred 1.40～1.75, and in refractive index less than 1.40 or greater than 1.75 o'clock, the refringence of itself and translucent matrix or hard conating is excessive, and transmissivity reduces.The scope of preferred 0.3～10 μ m of the particle diameter of light transmission particle, the scope of preferred 1～5 μ m.This is because the situation of particle diameter below 0.3 μ m, and AG reduction, and under the situation more than the 10 μ m occurs reflectively, and the concave-convex surface degree becomes excessive simultaneously, and so the surface whiting is preferably use.
In order further to improve anti-reflective effect, can between hard conating and low-index layer, high refractive index layer be set.The refractive index of high refractive index layer described herein, the refractive index height of hard conating that connects near being meant and low-index layer.
High refractive index layer in anti-dazzling film the 1st embodiment of the present invention need be provided with than the refractive index height of the low-index layer that forms on it, and this refractive index is preferably in 1.60～1.80 scope.When less than 1.60 the time, be difficult to obtain enough low reflecting effect, in addition,, the tendency of system film difficulty is arranged 1.80 when above.
The thickness of high refractive index layer preferably has thickness identical with visible wavelength or the thickness below it, for example gives under the situation to the anti-reflective effect of visible light, and the thickness nd of design high refractive index layer satisfies 500≤4nd (nm)≤750.Here n is the refractive index of high refractive index layer, and d is a layer thickness.High refractive index layer owing to be film, can not obtain enough dura maters as mentioned above among the present invention.Therefore, must between high refractive index layer and transparent base, hard conating be set.
The electric conductivity ultrafine inorganic particle that high refractive index layer contains for example has: tin oxide, phosphorus doping tin oxide, antimony-doped tin oxide (ATO), tin indium oxide (ITO), indium oxide, zinc paste, aluminium-doped zinc oxide, antimony pentaoxide.Preferred especially tin oxide, ITO, zinc paste, these because its refractive index all high be near 2.0, therefore not only play the effect of electric conductivity, also can play the effect of the refractive index that improves the high refractive index layer that contains these materials.
The diameter of these electric conductivity ultrafine inorganic particles is preferably in the scope of 1～300nm, more preferably 5～100nm.This is because the particle diameter of electric conductivity ultrafine inorganic particle during less than 1nm, is difficult to disperse equably, in addition, when surpassing 300nm, the bad phenomenon that the transparency reduces occurs.
The radiation-curing type resin combination that high refractive index layer uses; can use separately have acryloyl group, free-radical polymerised functional group such as methacryl, acryloxy, methacryloxy; and have monomer, oligomer, the prepolymer of cationically polymerizable functional groups such as epoxy radicals, vinyl ether group, oxetanyl, perhaps use it is suitably mixed the composition of forming.Monomer for example has: methyl acrylate, methyl methacrylate, methoxyl polymethylacrylic acid glycol ester, cyclohexyl methacrylate, methacrylic acid phenoxy group ethyl ester, Ethylene glycol dimethacrylate, dipentaerythritol acrylate, trimethylol-propane trimethacrylate etc.Oligomer, prepolymer for example has: polyester acrylate, urethane acrylate, the epoxidation propylene acid esters, polyether acrylate, the alkyd acrylate, the melamine acrylate, acrylate compounds such as silicon Acrylote, unsaturated polyester (UP), butanediol diglycidyl ether, propylene glycol diglycidylether, neopentylglycol diglycidyl ether, epoxy compounds such as bisphenol A diglycidyl ether and various ester ring type epoxy radicals, 3-ethyl-3-hydroxymethyl oxetanes, 1, two { [(3-ethyl-3-oxa-cyclobutyl) methoxyl] methyl } benzene of 4-, oxetane compounds such as two [1-ethyl (3-oxetanyl)] methyl ether.These materials can use separately also can mix a plurality of uses.
Above-mentioned radiation-curing type resin combination can directly solidify by the electron ray irradiation, utilizing the ultraviolet ray irradiation to make under the situation of its curing, needs to add Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater can use separately: radical polymerization initiators such as acetophenones, benzophenone, thioxanthene class, styrax, benzoin methyl ether, cationic polymerization initiators such as aromatic series diazo salt, aromatic series sulfonium salt, aromatic series iodine salt, metallocene compound perhaps suitably are used it.
In above-mentioned radiation-curing type resin combination, can in the scope that does not influence its polymerizing curable, add and use macromolecule resin among the present invention.These macromolecule resins are the soluble thermoplastic resins of organic solvent that use in the hard coating described later, concrete example is if any acryl resin, alkyd resin, vibrin etc., in order to increase the compatibility of itself and electric conductivity ultrafine inorganic particle, preferably have acidic functionalities such as carboxyl and phosphate, sulfonic group in these resins.
In addition, among the present invention,, can utilize the surface of various coupling agent modified conducting ultrafine inorganic particles as required for the electric conductivity ultrafine inorganic particle stably being dispersed in the above-mentioned radiation-curing type resin combination.Such coupling agent for example has: silane coupling agent, metal alkoxides such as aluminium, titanium, zirconium, organic acid and salt thereof such as fatty acid, phosphate cpd etc.
The ratio of shared electric conductivity ultrafine inorganic particle is counted more than 75% with weight ratio in the high refractive index layer, and preferred weight ratio is 75～95% scope, more preferably 80～90% scope.This ratio was difficult to obtain good electrical conductivity less than 75% o'clock, surpassed at 95% o'clock, had the problem that mist degree rises, the wearing quality of while high refractive index layer reduces.
High refractive index layer mainly utilizes the solidfied material of above-mentioned electric conductivity ultrafine inorganic particle and radiation-curing type resin combination to constitute.Its formation method is as follows: the coating coating with electric conductivity ultrafine inorganic particle and radiation-curing type resin combination and organic solvent formation, utilize electron ray or ultraviolet ray irradiation behind the volatilization organic solvent, and make its curing.When organic solvent used herein must be according to dissolving radiation-curing type resin combination, be fit to the electric conductivity ultrafine inorganic particle and disperse to select.The concrete coating characteristics of considering ground such as wetting state, viscosity, rate of drying, can use separately be selected from alcohols, ester class, ketone, ethers, aromatic hydrocarbon in material, or use mixed solvent.
Arrive the surface resistance preferred 10 in high refractive index layer low-index layer stage in the 1st embodiment of anti-dazzling film of the present invention
7～10
9Ω/.If for static electricity resistance then its surface resistance are necessary for below it, if surpass 10
9Ω/, the surface resistance of outermost surface is 10 when then on it low-index layer being set
11More than Ω/, can not bring into play enough static electricity resistances, so not preferred.In addition, the skin hardness of high refractive index layer is meant to be the above hardness of H, the more preferably hardness that 2H is above or 3H is above in the pencil hardness test (JIS K5400-5-4).
The low-index layer that is provided with on the high refractive index layer of anti-dazzling film the 1st embodiment of the present invention is made of fluorinated polysiloxane.This fluorinated polysiloxane is to obtain after containing the mixture solidified of water-disintegrable silane compound and/or its hydrolysate and curing accelerator at least, what this water-disintegrable silane compound used is, at least a in the silane compound shown in following general formula [1]～[3], and the potpourri of at least a formation of the fluorine containing silane compound of general formula [4], [5] expression.
Change 1
R
1 a-SiX
4-a 0≤a≤2 [1]
X
3Si-R
2-SiX
3 [2]
Y-(Si(OR
3)
2O)
n-Y [3]
R
5a-SiX
4-a 1≤a≤2 [4]
X
3Si-R
6-SiX
3 [5]
(X represents Cl, Br, NCO, OR
4In any.Y represents that H or carbon number are 1～20 organic group.R
1, R
2, R
3, R
4The expression carbon number is 1～20 organic group.R
5, R
6Expression contains the organic group of a fluorine atom at least.N represents 1～30 integer.)
The concrete material of water decomposition silane compound for example has silicon atom to have the silane compound of 4 hydrolysising groups, concrete example is if any tetramethoxy-silicane, tetraethoxysilane, four (1-propoxyl group) silane, four (2-propoxyl group) silane, four (1-butoxy) silane, tetrachloro silicane, tetrabromo silane, tetraisocyanate silane, dimethoxysiloxane oligomer, diethoxy siloxane oligomer etc., but is not limited to these materials.In addition, the fluorine containing silane compound for example has: 3,3,3-trifluoro propyl trimethoxy silane, 3,3,3-trifluoro propyl triethoxysilane, 3,3,3-trifluoro propyl tripropoxy silane, 3,3,3-trifluoro propyl trichlorosilane, 3,3,3-trifluoro propyl three isocyanide ester silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluoro hexyl trimethoxy silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluoro hexyl triethoxysilane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluoro hexyl tripropoxy silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluoro hexyl trichlorosilane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluoro hexyl triisocyanate silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor nonyl trimethoxy silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor nonyl triethoxysilane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor nonyl tripropoxy silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor nonyl trichlorosilane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor nonyl triisocyanate silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor decyl trimethoxy silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor decyl triethoxysilane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor decyl tripropoxy silane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor decyltrichlorosilane, 1H, 1H, 2H, 2H-tetrahydrochysene perfluor decyl triisocyanate silane, 1-seven fluorine isopropoxide propyl trimethoxy silanes, 1-seven fluorine isopropoxide propyl triethoxysilanes, 1-seven fluorine isopropoxide propyl tripropoxy silane, 1-seven fluorine isopropoxide propyl trichlorosilanes, 1-seven fluorine isopropoxide propyl triisocyanate silane, 1, two (trimethoxysilyl)-2,2 of 4-, 3,3-tetrafluoro butane, 1, two (trimethoxysilyl)-2,2 of 5-, 3,3,4,4-hexafluoro pentane etc., wherein, from refractive index, reactive, the viewpoint of solvent solubility is considered, is preferably used 1H, 1H, 2H, 2H-tetrahydrochysene perfluor decyl triethoxysilane.
In addition, water-disintegrable silane compound of the present invention also can make to contain to have the cation-modified silane compound that tunicle forms agent and antistatic agent effect outside above-claimed cpd.The concrete material of cation-modified silane compound for example has: octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, 3-(N-ス チ Le methyl-2-aminoethylamino)-propyl trimethoxy silicane hydrochloride, (N-trimethoxy-silylpropyl)-N-methyl-N, the N-diallyl ammonium chloride, (N, N-didecyl-N-methyl-N-(3-trimethoxy-silylpropyl) ammonium chloride, octadecyl dimethyl (3-trimethoxy-silylpropyl) ammonium chloride, myristyl dimethyl (3-trimethoxy-silylpropyl) ammonium chloride, N-trimethoxy-silylpropyl-N, N, N-three-normal-butyl chlorination ammonium, N-trimethoxy-silylpropyl-N, N, the N-trimethyl ammonium chloride, trimethoxy-silylpropyl (polyethyleneimine), dimethoxy-methyl silicyl propyl group modification (polyethyleneimine) etc.
For refractive index and the coating strength of taking into account low-index layer, in above water-disintegrable silane compound,, preferably silane compound (compound of a=0 in the general formula [1]) and the fluorine-containing water-disintegrable silane compound that has 4 hydrolization groups on the silicon atom suitably mixed use in order to improve the coating strength of low-index layer.At this moment mixing ratio is according to the kind of silane compound and difference is preferably used with respect to silane compound 100 weight portions that have 4 hydrolization groups on the silicon atom, and fluorine-containing water-disintegrable silane compound is 1～500 weight portion, more preferably 20～300 weight portions.
The said hydrolyzed silane compound is dissolved in the alcoholic solvent usually, carries out partial hydrolysis and polycondensation in advance, and it by the heating of coating back, is carried out polycondensation again, forms cured film.In order to carry out these hydrolysis, condensation reaction, water-disintegrable relatively silane compound and/or its hydrolysate 100 weight portions add the use curing accelerator in the scope of 1～30 weight portion.This curing accelerator for example has: organic acid such as mineral acid such as nitric acid, hydrochloric acid and oxalic acid, acetate, acidic catalysts such as orthophosphoric acid, benzene sulfonic acid, p-toluenesulfonic acid, perhaps base catalyst such as ammonia.
After these curing promotion compositions also can make itself and silane compound mix, directly be coated with, make film.In silane compound, add water in advance, after being hydrolyzed, add and solidify the promotion composition, coating, system film.In this case, with silane compound-water-solvent mixture or after adding the potpourri preparation of micro-strong acid (hydrochloric acid etc.) formation therein, at room temperature place a few hours to a few days, be diluted to the concentration of coating usefulness, add to solidify and promote composition, coating, system film.In addition, under the situation that does not have water, can use polymerizable silane catalyzer such as oxalic acid, silane compound is made oligomer after, add the curing accelerator composition, coating, system film.In this case, by with silane compound-solvent-carboxylic acid catalyst's potpourri,, after other identical dilution of situation, add to solidify and promote to become to assign to use in the scope heating of room temperature to 100 ℃.
The low-refraction coating that uses during low-index layer is made by following coating preparation, coating, dry, and polymerization, curing process make, preparation coating can be by being dissolved in above-mentioned silane compound arbitrarily in the solvent, be hydrolyzed as required or oligomeric materialization after, promote composition to mix above-mentioned curing and carry out.In this case, in order to obtain the coating thickness of purpose, the concentration of silane compound is formulated in about common 0.1～50 weight %, about preferred 0.5～30 weight %.Solvent must contain can dissolve hydrolysis at least the polar solvent of silane compound.In addition, volatility aspect during from drying considers, uses boiling point at 50～150 ℃ solvent.Such solvent for example has: alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, butanols, glycolss such as ethylene glycol, propylene glycol, hexanediol, glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylene glycol diethyl ether, diethyl carbitol, ketones such as acetone, MEK, methyl isobutyl ketone; Ester classes such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, arenes such as benzene,toluene,xylene, nitrogenous class such as N-Methyl pyrrolidone, dimethyl formamide, halogenated hydrocarbons such as chloroform, methylene chloride, triclene etc., but be not limited to these materials.In addition, above-mentioned solvent can be used alone, but also also mix together.
Use above-mentioned coatings formulated, can utilize coating or printing process one side or the two-sided low-index layer that is provided with at transparent support matrices.Specifically can use following printing process: airblade coating, the scraper plate coating, line scraper (wire doctor) coating, the scraper coating, contrary roller coat cloth (reverse coating), the transfer roller coating, the intaglio plate coating, miniature intaglio plate (microgravure) coating, kiss-coating, casting is coated with, spraying, the slotted hole coating, the calenderstack coating, the electro-deposition coating, dip coated, coating processes such as die head coating, reach letterpress such as flexographic printing, directly intaglio printing, intaglio printings such as hectograph intaglio printing, lithographys such as hectographic printing, printing processes such as porous printings such as serigraphy etc.In addition, the thickness of the low-index layer of the Xing Chenging relation of refractive index and optical wavelength is with due regard to determined the thickness of layer, but is not particularly limited, about preferred 70～120nm as mentioned above.So long as the thickness of this degree, just, therefore the surface resistance of low-index layer can be suppressed at less than 10 because the surface resistance of the hard conating of lower floor can be promoted about one digit number
11Ω/.
The drying of low-refraction coating film and polymerization, curing need make solvent evaporates by heat drying, proceed heating again, and it is cured.Heating-up temperature is more than 40 ℃, preferred 80～120 ℃.The upper limit of heating-up temperature is different and different according to the matrix that uses, and general transparent membrane can not use softening more than 120 ℃.
The preferred less than 10 of the surface resistance of low-index layer
11Ω/, more preferably 10
11Below Ω/.When it is 10
11When Ω/ is above, because can not give full play to static electricity resistance, thereby not preferred.
The relation of the hard conating in the anti-dazzling film of the present invention, high refractive index layer and low-index layer and refractive index is preferably: the refractive index after its curing of hard conating is 1.45～1.55 scope, refractive index after its curing of high refractive index layer is 1.6～18 scope, and, refractive index after its curing of low-index layer is 1.36～1.42 scope, when exceeding this scope, its low reflection function reduces.
Anti-dazzling film of the present invention is by optimizing above material and combination thereof, and can make average reflectance is below 1%, and making total light transmittance is more than 90%, and making mist degree is below 2%.In addition, carry out in the abrasion test, the haze change amount can be suppressed at below 0.5% at the steel wool that utilizes the surface.
2. the 2nd embodiment
The 2nd embodiment of putting dizzy film of the present invention is characterised in that, it is a lamination hard conating at least successively on translucent matrix, constitute behind the low-index layer, hard conating comprises the radiation-curing type resin combination that contains the electric conductivity ultrafine inorganic particle, its thickness is 1.0～5.0 μ m, refractive index after it solidifies is 1.6～1.8, low-index layer contains fluorinated polysiloxane, refractive index after it solidifies is 1.36～1.42, the electric conductivity ultrafine inorganic particle that contains in the hard conating is by being selected from tin oxide, tin indium oxide (ITO), at least a formation in the zinc paste, the weight ratio of electric conductivity ultrafine inorganic particle are more than 75%.
Utilize aforesaid structure, the 2nd embodiment of anti-dazzling film of the present invention has reached the effect of taking into account low reflection characteristic, electric conductivity, wearing quality, soil resistance, can play the effect that reduces cost by reducing painting process simultaneously.
Each inscape of the 2nd embodiment of anti-dazzling film of the present invention, hard conating in above-mentioned the 1st embodiment and high refractive index layer are altered to one deck of the function that has these layers concurrently, just change to the hard conating of the 2nd embodiment, other is identical with each inscape of the 1st embodiment, therefore only the hard conating in the 2nd embodiment is described below.
Hard conating in the 2nd embodiment shows the hardness that H is above in utilizing pencil hardness test (JIS K5400), its can use with the 1st above-mentioned embodiment in the identical structure and material of high refractive index layer.Wherein, difference part following points:
The thickness of the hard conating in the 2nd embodiment is in the scope of 1.0～5.0 μ m, and preferred range is 2.0～4.0 μ m.Hard conating is under than the thin situation of 1.0 μ m, when using ultraviolet curing resin, because the obstruction of oxygen, cause that curing is bad, the wearing quality deterioration of hard conating, under its situation thicker, because the cure shrinkage of resin generation crimping, the adaptation reduction that on hard conating, produces fine crack and transparent base or and then reduction light transmission than 5 μ m.And,, also cause cost to improve thus along with the coating weight of increase necessity of thickness needs to increase.
In addition, the refractive index preferred 1.6～1.8 after the hard conating in the 2nd embodiment solidifies.When refractive index less than 1.6,, can not realize enough antiradar reflectivities even low-index layer is set on the upper strata, in addition, if refractive index ratio 1.8 height, then the refringence of itself and translucent matrix becomes excessive, thereby has the problem of interfering spot to increase after low-index layer is set.
In the 2nd embodiment, can be with the translucent resin microparticulate, be included in the hard conating of above-mentioned explanation, form fine concavo-convexly at hard coating surface, make so-called AG.Transparent resin particle used herein can use the organic light transmission particle that is made of acryl resin, polystyrene resin, styrene-propene acid copolymer, polyvinyl resin, epoxy resin, organic siliconresin, polyvinylidene fluoride, polyvinyl fluoride resinoid etc.The refractive index of translucent resin particulate is preferred 1.40～1.75, and in refractive index less than 1.40 or greater than 1.75 o'clock, the refringence of itself and translucent matrix or hard conating is excessive, and transmissivity reduces.The scope of preferred 0.3～10 μ m of the particle diameter of light transmission particle, the more preferably scope of 1～5 μ m.Because the situation of particle diameter below 0.3 μ m, the AG reduction in addition under the situation more than the 10 μ m, occurs reflectively, and the concave-convex surface degree is excessive simultaneously, and so the surface whiting is preferably use.
Embodiment
Below, the present invention will be further described by embodiment.Need to prove that hereinafter " part " all refers to weight portion.
1. the 1st embodiment
Sample 1
(1) making of hard conating
On the thick PET film of 100 μ m (trade name: A4300 Japan Japan textile company is produced), carry out the coating of following hardcoat coatings with contrary roller coat cloth, through 100 ℃, dry 1 minute, under nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) then, make curing of coating with a 120W/cm light-focusing type high-pressure mercury-vapor lamp.Having made thickness like this is that 2.5 μ m, refractive index are 1.52 hard conating.
The prescription of＜hard coating 〉
38 parts of ultraviolet hardening ammonia ester acrylate oligomers (trade name: UV7600B Japan synthetic chemical industry company solid component concentration 100%)
Light overlaps 2 parts of initiating agents (trade name: イ Le ガ キ ユ ア 1, チ バ ガ イ ギ one company produce)
36 parts of MEKs
24 parts of ring ethyl ketones
(2) making of high refractive index layer
On above-mentioned hard conating, be coated with following high index of refraction coating with contrary roller coat cloth, through 100 ℃, dry 1 minute, under nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) then, make curing of coating with a 120W/cm light-focusing type high-pressure mercury-vapor lamp.Having made thickness like this is that 0.1 μ m, refractive index are 1.64 high refractive index layer.
The prescription of＜high index of refraction coating 〉
Make neopentyl glycol and, generate the vibrin of weight-average molecular weight 65000, acid number 7mgKOH/g, non-volatile component 60%) by the polyprotonic acid reaction that m-phthalic acid and hexane diacid constitute
7 parts
1.8 parts of dipentaerythritol tetraacrylate
Average primary particle diameter is that the content of 0.05 μ m, the relative In of tin is the ito powder of 5 moles of %
34 parts
The weight ratio of normal butyl alcohol/dimethylbenzene is 57.2 parts of 4/6 mixed solvents
The beaded glass of above-mentioned material and 50cc is put into the container of 250cc, paint stirrer and disperseed 5 hours.After the separation, make 0.2 part light overlap initiating agent (trade name: イ Le ガ キ ユ ア 1, チ バ ガ イ ギ-corporate system) dissolving, made high index of refraction coating.
(3) making of low-index layer
On above-mentioned high refractive index layer, with contrary roller coat cloth, be coated with following low-refraction coating, through 100 ℃ of temperature, dry 1 minute, make curing of coating.
The prescription of＜low-refraction coating 〉
7.9 parts of fluorinated polysiloxanes (trade name: LR204-1, daily output chemical industrial company make solid component concentration 6.46%)
12.1 parts of methyl isobutyl ketones
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtain the anti-dazzling film of the present invention of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.57% in order to make low-index layer.
Sample 2
(1) making of hard conating
Will with the hard coat film coating of sample 1 same recipe, be coated on the thick PET film of 100 μ m (trade name: A4300 Japan Japan textile company is produced) with contrary roller coat cloth, through 100 ℃, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.So just having made thickness is that 2.5 μ m, refractive index are 1.52 hard conating.
(2) making of high refractive index layer
To contain zirconic ultraviolet line style gel-type resin (ZrO content is 68.0% in trade name: KZ7391, JSR company manufacturing solid component concentration 42% solid constituent), be coated on the above-mentioned hard conating with contrary roller coat cloth as high index of refraction coating, through 100 ℃, dry 1 minute, then under nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Thick 0.1 μ m, refractive index have so just been made and are 1.64 high refractive index layer.
(3) making of low-index layer
Will with the identical low-refraction coating of sample 1 prescription, on the above-mentioned high refractive index layer of contrary roller coat cloth coating,, make curing of coating through 100 ℃ of temperature, dry 1 minute.
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.62% in order to make low-index layer.
Sample 3
(1) making of hard conating
Will with the identical hard coating of sample 1 prescription, be coated on the thick PET film of 100 μ m (trade name: A4300 Japan textile company is made) with contrary roller coat cloth, through 100 ℃ of temperature, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.So just having made thickness is that 2.5 μ m, refractive index are 1.52 hard conating.
(2) making of low-index layer
Will with the identical low-refraction coating of sample 1 prescription, be coated on the above-mentioned hard conating with contrary roller coat cloth, through 100 ℃ of temperature, dry 1 minute, make curing of coating.
Then, solidify, need under 60 ℃ of conditions, to solidify 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 2.13% in order to make low-index layer.
Sample 4
(1) making of hard conating
Will with the identical hard coating of sample 1 prescription, be coated on the thick PET film of 100 μ m (trade name: A4300 Japan Japan textile company is made) with contrary roller coat cloth, through 100 ℃ of temperature, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.So just having made thickness is that 2.5 μ m, refractive index are 1.52 hard conating.
(2) making of high refractive index layer
Will with the identical high index of refraction coating of sample 1 prescription, be coated on the above-mentioned hard conating with contrary roller coat cloth, through 100 ℃, dry 1 minute, then under nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Thick 0.1 μ m, refractive index have so just been made and are 1.64 high refractive index layer.
(3) making of low-index layer
With following low-refraction coating, be coated on the above-mentioned high refractive index layer with contrary roller coat cloth, through 100 ℃, dry 1 minute, make curing of coating.
The prescription of＜low-refraction coating 〉
Silicasol (particle diameter 15nm, as SiO
2The alcohol dispersion liquid that contains 30% silica ultramicron) 10 part
15 parts of film forming agents (hydrolysate of tetraethoxysilane is pressed silicon dioxide and calculated solid component concentration 6%)
53 parts of ethanol
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.68% in order to make low-index layer.
Sample 5
(1) making of hard conating
Will with the identical hard coating of sample 1 prescription, be coated on the thick PET film of 100 μ m (trade name: this Japan of A4300 textile company is made) with contrary roller coat cloth, through 100 ℃ of temperature, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Having made thickness like this is that 2.5 μ m, refractive index are 1.52 hard conating.
(2) making of high refractive index layer
With following high index of refraction coating, be coated on the above-mentioned hard conating with contrary roller coat cloth, through 100 ℃ of temperature, dry 1 minute, then under nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Thick 0.1 μ m, refractive index have been made like this and are 1.61 high refractive index layer.
The prescription of＜high index of refraction coating 〉
The polyprotonic acid that neopentyl glycol and m-phthalic acid and hexane diacid are formed reacts, and forms the alkyd resin of weight-average molecular weight 65000, acid number 7mgKOH/g, non-volatile component 60%
14 parts
3.6 parts of dipentaerythritol tetraacrylate
The content of average primary particle diameter 0.05 μ m, the relative In of Sn is 28 parts of the ito powders of 5 moles of %
The weight ratio of normal butyl alcohol/dimethylbenzene is 54.4 parts of 4/6 mixed solvents
The beaded glass of above-mentioned raw materials and 50cc is put into the container of 250cc, paint stirrer and disperseed 5 hours.After the dispersion, the light that dissolves 0.2 part overlaps initiating agent (trade name: イ Le ガ キ ユ ア 1, チ バ ガ イ ギ-company makes), has made high index of refraction coating.
(3) making of low-index layer
Will with the identical low-refraction coating of sample 1 prescription, be coated on the above-mentioned high refractive index layer with contrary roller coat cloth, through 100 ℃, drying 1 minute, make curing of coating.
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.95% in order to make low-index layer.
Use the anti-dazzling film of the sample 1～5 that obtains as mentioned above, utilize following method, respectively total light transmittance, mist degree, reflectivity, sheet resistance value, wearing quality and soil resistance are measured and estimated.
The mensuration of total light transmittance and mist degree aspect utilizes mist degree instrument (trade name: NDH2000, Japanese electric look company make) to measure.
Reflectivity uses spectrophotometer (trade name: UV3100, Tianjin, island company make) to measure, and measures 5 ° of normal reflections of wavelength region may 400～700nm scope, proofreaies and correct visible sensitivity according to JIS Z8701, with the Y value representation that obtains.Need to prove, fully with the blacking of non-mensuration face, under this state, measure with black pattern (マ ジ Star Network).
Sheet resistance value uses sheet resistance value high resistance meter (trade name: Ha イ レ ス ア Star プ Mitsubishi Chemical Ind makes) to measure.
The mensuration of wearing quality is the steel wool #0000 with Japanese steel wool system corporate system, is installed on the wear-resistant experimental machine of paperboard (Xiong Gu reason machine industrial group makes), and the low-refraction aspect that makes anti-dazzling film comes and goes 10 times under loading 250g.Measure the variable quantity δ H of its part haze value of following formula 3 calculating then with the mist degree instrument.At this as seen, measured value is big more, and its wearing quality is poor more.
Haze value (formula 3) before haze value-test after the δ H=test
The mensuration of antifouling property is finished by following method, specific practice is: with dropper with salad oil dropping on the low-index layer drop by drop, then with the cloth for wiping or dusting that is adsorbed with sherwood oil (trade name: CLEAN WIPER, SF30C Network ラ レ company make) wiping 20 times repeatedly, then, to the face of wiping optics microphotograph, it is residual to define no salad oil.Do " * " if on low-index layer, as seen be attached with salad oil with regard to note, if see that fully just note is not done " zero ".
Table 1
| Sample | Inorganic particles weight ratio (%) | Total light transmittance (%) | Mist degree (%) | Reflectivity (%) | Sheet resistance value (Ω) | Wearing quality δ H | Soil resistance |
| Sample 1 | 85 | 94.30 | 0.64 | 0.57 | 3.9×10 9 | 0.47 | ○ |
| Sample 2 | 67 | 94.07 | 0.75 | 0.62 | ≥10 14 | 1.50 | ○ |
| Sample 3 | 0 | 93.12 | 0.60 | 2.13 | ≥10 14 | 0.58 | ○ |
| Sample 4 | 85 | 93.75 | 0.68 | 0.76 | 4.6×10 9 | 1.17 | × |
| Sample 5 | 70 | 94.28 | 0.72 | 0.65 | ≥10 14 | 1.22 | ○ |
By table 1 result as can be known, the anti-dazzling film of the sample 1 that the 1st embodiment of the present invention obtains, by in high refractive index layer, using the radiation line style gel-type resin that contains the electric conductivity inorganic particles, contain the fluorine polysiloxane with using in low-index layer, aspects such as the low reflection characteristic, electric conductivity, wearing quality and the soil resistance that obtain are all relatively good; The anti-dazzling film of sample 2 of contrast usefulness, its electric conductivity and wearing no resistance; The anti-dazzling film of the sample 3 of contrast usefulness, low reflectivity and poorly conductive; The anti-dazzling film of the sample 4 of contrast usefulness, wearing quality and soil resistance are poor, are not durable.In addition, the anti-dazzling film of the sample 5 of contrast usefulness, when the electric conductivity inorganic particles in its hard conating contained quantity not sufficient 75%, its poorly conductive was not durable.
2. the 2nd embodiment
Sample 6
(1) making of hard conating
With following hard coating, be coated on the thick PET film of 100 μ m (trade name: this Japan of A4300 textile company is produced) with contrary roller coat cloth, through 100 ℃, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Having made thickness like this is that 2.5 μ m, refractive index are 1.64 hard conating.
The prescription of＜hard coating 〉
The polyprotonic acid that neopentyl glycol and m-phthalic acid and hexane diacid are formed reacts, and forms the alkyd resin of weight-average molecular weight 65000, acid number 7mgKOH/g, non-volatile component 60%
7 parts
1.8 parts of dipentaerythritol tetraacrylate
The content of average primary particle diameter 0.05 μ m, the relative In of Sn is 34 parts of the ito powders of 5 moles of %
The weight ratio of normal butyl alcohol/dimethylbenzene is 57.2 parts of 4/6 mixed solvents
The beaded glass of above-mentioned raw materials and 50cc is put into the container of 250cc, paint stirrer and disperseed 5 hours.After the dispersion, make 0.2 part light overlap initiating agent (trade name: イ Le ガ キ ユ ア-907, チ バ ガ イ ギ-company makes) dissolving, made hard coating.
(2) making of low-index layer
With following low-refraction coating, be coated on the above-mentioned hard conating with contrary roller coat cloth, through 100 ℃, dry 1 minute, make curing of coating.
The prescription of＜low-refraction coating 〉
7.9 parts of fluorinated polysiloxanes (trade name: LR204-1, daily output chemical industrial company make solid constituent 6.46%)
12.1 parts of methyl isobutyl ketones
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtain the anti-dazzling film of the present invention of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.81% in order to make low-index layer.
Sample 7
(1) making of hard conating
With following hard coating, be coated on the thick PET film of 100 μ m (trade name: this Japan of A4300 textile company is produced) with contrary roller coat cloth, through 100 ℃, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Having made thickness like this is that 2.5 μ m, refractive index are 1.61 hard conating.
The prescription of＜hard coating 〉
The polyprotonic acid that neopentyl glycol and m-phthalic acid and hexane diacid are formed reacts, and forms the alkyd resin of weight-average molecular weight 65000, acid number 7mgKOH/g, non-volatile component 60%
8.4 part
2.1 parts of dipentaerythritol tetraacrylate
32.8 parts in the tin oxide of average primary particle diameter 0.05 μ m
The weight ratio of normal butyl alcohol/dimethylbenzene is 56.7 parts of 4/6 mixed solvents
The beaded glass of above-mentioned raw materials and 50cc is put into the container of 250cc, paint stirrer and disperseed 5 hours.After the dispersion, make 0.2 part light overlap initiating agent (trade name: イ Le ガ キ ユ ア-907, チ バ ガ イ ギ-company makes) dissolving, made hard coating.
(2) making of low-index layer
On above-mentioned hard conating,,, make curing of coating through 100 ℃ of temperature, dry 1 minute with the low-refraction coating of contrary roller coat cloth coating with sample 6 same recipe.
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the anti-dazzling film of the present invention of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.79% in order to make low-index layer.
Sample 8
(1) making of hard conating
To contain ultraviolet curing resin (trade name: ESB-3, the manufacturing of big Nippon Paint Co., Ltd. of tin oxide, contain solid component concentration 29.7%, tin oxide content 82% in the solid constituent), as hard coating, be coated on the thick PET film of 100 μ m (trade name: A4300 Japan Japan textile company is produced) with contrary roller coat cloth, through 100 ℃ of temperature, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Having made thickness like this is that 2.5 μ m, refractive index are 1.60 hard conating.
(2) making of low-index layer
On above-mentioned hard conating,,, make curing of coating through 100 ℃, dry 1 minute with the low-refraction coating of contrary roller coat cloth coating with sample 6 same recipe.
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the anti-dazzling film of the present invention of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.82% in order to make low-index layer.
Sample 9
(1) making of hard conating
(trade name: KZ7391, JSR company make will to contain zirconic ultraviolet curing resin, solid component concentration 42%, ZrO content 68.0% in the solid constituent) as hard coating, be coated on the thick PET film of 100 μ m (trade name: this Japan of A4300 textile company is produced) with contrary roller coat cloth, through 100 ℃ of temperature, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.So just having made thickness is that 2.5 μ m, refractive index are 1.69 hard conating.
(2) making of low-index layer
On above-mentioned hard conating,,, make curing of coating through 100 ℃, dry 1 minute with the low-refraction coating of contrary roller coat cloth coating with sample 6 same recipe.
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.85% in order to make low-index layer.
Sample 10
(1) making of hard conating
With following hard coating, be coated on the thick PET film of 100 μ m (trade name: this Japan of A4300 textile company is produced) with contrary roller coat cloth, through 100 ℃, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Having made like this into thickness is that 2.5 μ m, refractive index are 1.52 hard conating.
The prescription of＜hard coating 〉
Ultraviolet hardening ammonia ester acrylate oligomer (trade name: UV7600B, Japanese synthetic chemical industry company, solid component concentration 100%)
38 parts
Light overlaps 2 parts of initiating agents (trade name: イ Le ガ キ ユ ア-184, チ バ ガ イ ギ-company makes)
36 parts of MEKs
24 parts of cyclohexanone
(1) making of low-index layer
On above-mentioned hard conating,,, make curing of coating through 100 ℃, dry 1 minute with the low-refraction coating of contrary roller coat cloth coating with sample 6 same recipe.
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 2.13% in order to make low-index layer.
Sample 11
(1) making of hard conating
Will with the hard coating of sample 6 same recipe, be coated on the thick PET film of 100 μ m (trade name: A4300 Japan Japan textile company is produced) with contrary roller coat cloth, through 100 ℃, dry 1 minute, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Having made thickness like this is that 2.5 μ m, refractive index are 1.64 hard conating.
(2) making of low-index layer
On above-mentioned hard conating, be coated with following low-refraction coating with contrary roller coat cloth, through 100 ℃, dry 1 minute, make curing of coating.
The prescription of＜low-refraction coating 〉
Silicasol (particle diameter 15nm, as SiO
2The alcohol dispersion liquid that contains 30% silica ultramicron) 10 part
15 parts of film forming agents (the water decomposition thing of tetraethoxysilane is in the concentration 6% of silicon dioxide solid constituent)
53 parts of ethanol
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.92% in order to make low-index layer.
Sample 12
(1) making of hard conating
With following hard coating, be coated on the thick PET film of 100 μ m (trade name: this Japan of A4300 textile company is produced) with contrary roller coat cloth, through 100 ℃ of temperature, 1 minute drying, then in nitrogen environment, carry out ultraviolet ray irradiation (irradiation distance 10cm, irradiation time 30 seconds) with a 120W/cm light-focusing type high-pressure mercury-vapor lamp, make curing of coating.Having made thickness like this is that 2.5 μ m, refractive index are 1.61 hard conating.
The prescription of＜hard coating 〉
The polyprotonic acid that neopentyl glycol and m-phthalic acid and hexane diacid are formed reacts, and forms the alkyd resin of weight-average molecular weight 65000, acid number 7mgKOH/g, non-volatile component 60%
14 parts
3.6 parts of dipentaerythritol tetraacrylate
The content of average primary particle diameter 0.05 μ m, the relative In of Sn is the ITO of 5 moles of %
28 parts
The weight ratio of normal butyl alcohol/dimethylbenzene is 54.4 parts of 4/6 mixed solvents
The beaded glass of above-mentioned raw materials and 50cc is put into the container of 250cc, paint stirrer and disperseed 5 hours.After the dispersion, make 0.2 part light overlap initiating agent (trade name: イ Le ガ キ ユ ア-907, チ バ ガ イ ギ-company makes) dissolving, made hard coating.
(2) making of low-index layer
On above-mentioned hard conating,,, make curing of coating through 100 ℃, dry 1 minute with the low-refraction coating of contrary roller coat cloth coating with sample 6 same recipe.
Then, solidify, under 60 ℃ of conditions, solidified 120 hours, obtained the contrast anti-dazzling film of thickness 0.1 μ m, refractive index 1.38, reflectivity 0.95% in order to make low-index layer.
Use the anti-dazzling film of the sample 6～12 that obtains as mentioned above, utilize and the identical method of above-mentioned the 1st embodiment, respectively its total light transmittance, mist degree, reflectivity, sheet resistance value, wearing quality, soil resistance are measured and estimated.
Table 2
| Sample | Inorganic particles weight ratio (%) | Total light transmittance (%) | Mist degree (%) | Reflectivity (%) | Sheet resistance value (Ω) | Wearing quality δ H | Soil resistance |
| Sample 6 | 85 | 92.03 | 0.51 | 0.81 | 7.0×10 6 | 0.03 | ○ |
| Sample 7 | 82 | 91.95 | 0.96 | 0.79 | 4.0×10 9 | 0.08 | ○ |
| Sample 8 | 82 | 91.96 | 0.77 | 0.82 | 2.5×10 9 | 0.14 | ○ |
| Sample 9 | 67 | 93.73 | 0.41 | 0.85 | ≥10 14 | 1.22 | ○ |
| Sample 10 | 0 | 93.12 | 0.60 | 2.13 | ≥10 14 | 0.58 | ○ |
| Sample 11 | 85 | 91.75 | 0.60 | 0.92 | 8.0×10 6 | 1.24 | × |
| Sample 12 | 70 | 91.08 | 0.60 | 0.95 | 1.0×10 12 | 0.80 | ○ |
As can be known from Table 2, in the 2nd embodiment of the present invention, the anti-dazzling film of sample 6～8, in hard conating, use the radiation-curing type resin that contains the electric conductivity inorganic particles, with in low-index layer, use fluorinated polysiloxane, obtained low reflection characteristic, electric conductivity, wearing quality and soil resistance thus; The contrast anti-dazzling film relative therewith, that sample 9 is made, its electric conductivity and wearing quality are wanting in; The contrast anti-dazzling film that sample 10 is made, its low reflectivity and electric conductivity are wanting in; The contrast anti-dazzling film that sample 11 is made, its wearing quality and soil resistance are poor, are not durable.The contrast anti-dazzling film made of sample 12 in addition, the electric conductivity inorganic particles that contains in its hard conating contains under the situation of quantity not sufficient 75%, and its poorly conductive is not durable yet.
Claims (8)
1. an anti-dazzling film is characterized in that, on translucent matrix, and lamination hard conating, high refractive index layer and low-index layer at least successively,
Above-mentioned high refractive index layer comprises the radiation-curing type resin combination that contains the electric conductivity ultrafine inorganic particle, and the refractive index after it solidifies is 1.6～1.8,
Above-mentioned low-index layer comprises fluorinated polysiloxane, and the resin refractive index after it solidifies is 1.36～1.42,
The electric conductivity ultrafine inorganic particle that contains in the above-mentioned high refractive index layer is by at least a formation in tin oxide, tin indium oxide (ITO), the zinc paste,
The weight ratio of above-mentioned electric conductivity ultrafine inorganic particle is more than 75%.
2. an anti-dazzling film is characterized in that, on translucent matrix, and lamination hard conating and low-index layer at least successively,
Above-mentioned hard conating comprises the radiation-curing type resin combination that contains the electric conductivity ultrafine inorganic particle, and thickness is 1.0～5.0 μ m, and the refractive index after it solidifies is 1.6～1.8,
Above-mentioned low-index layer comprises fluorinated polysiloxane, and the refractive index after it solidifies is 1.36～1.42,
The electric conductivity ultrafine inorganic particle that contains in the above-mentioned hard conating is by at least a formation in tin oxide, tin indium oxide (ITO), the zinc paste,
The weight ratio of above-mentioned electric conductivity ultrafine inorganic particle is more than 75%.
3. anti-dazzling film as claimed in claim 1 or 2 is characterized in that, the surface resistance less than 10 that above-mentioned anti-dazzling film is measured on above-mentioned low-refraction laminar surface
11Ω/.
4. anti-dazzling film as claimed in claim 1 or 2 is characterized in that, the average reflectance average out to of above-mentioned anti-dazzling film is below 1%, and total light transmittance is more than 90%, and mist degree is below 2%.
5. anti-dazzling film as claimed in claim 1 or 2 is characterized in that, above-mentioned anti-dazzling film surface is after the steel wool abrasion test, and the variable quantity of its mist degree is below 0.5%.
6. anti-dazzling film as claimed in claim 1 or 2 is characterized in that above-mentioned hard conating contains the translucent resin particulate.
7. anti-dazzling film as claimed in claim 1 or 2 is characterized in that, above-mentioned hard coating surface has trickle concavo-convex.
8. anti-dazzling film as claimed in claim 1 or 2 is characterized in that, the refractive index after above-mentioned hard conating solidifies is 1.45～1.55.
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| JP2005093804 | 2005-03-29 | ||
| JP2005093804 | 2005-03-29 | ||
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| JP2006042128 | 2006-02-20 |
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| CN100582817C CN100582817C (en) | 2010-01-20 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101398491B (en) * | 2007-09-28 | 2012-04-18 | 富士胶片株式会社 | Optical film, polarizing plate, and image display apparatus |
| CN103640305A (en) * | 2013-11-26 | 2014-03-19 | 大连创达技术交易市场有限公司 | Double-coating material |
| US8730441B2 (en) | 2009-12-18 | 2014-05-20 | Toppan Printing Co., Ltd. | Anti-reflection film |
| CN104245158A (en) * | 2012-03-30 | 2014-12-24 | 富士胶片株式会社 | Production method for film with coating |
| CN107142012A (en) * | 2017-06-20 | 2017-09-08 | 合肥市惠科精密模具有限公司 | A kind of TFT LCD displays nano protective film |
| CN109923165A (en) * | 2016-08-31 | 2019-06-21 | 三星Sdi株式会社 | For antireflection film composition, formed by it antireflection film, comprising its polarizer and comprising its optical display |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20160146975A1 (en) | 2014-11-25 | 2016-05-26 | Ppg Industries Ohio, Inc. | Antiglare touch screen displays and other coated articles and methods of forming them |
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2006
- 2006-03-29 CN CN200610068332A patent/CN100582817C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101398491B (en) * | 2007-09-28 | 2012-04-18 | 富士胶片株式会社 | Optical film, polarizing plate, and image display apparatus |
| US8730441B2 (en) | 2009-12-18 | 2014-05-20 | Toppan Printing Co., Ltd. | Anti-reflection film |
| CN102656486B (en) * | 2009-12-18 | 2014-11-12 | 凸版印刷株式会社 | Antireflection film |
| CN104245158A (en) * | 2012-03-30 | 2014-12-24 | 富士胶片株式会社 | Production method for film with coating |
| CN104245158B (en) * | 2012-03-30 | 2016-03-16 | 富士胶片株式会社 | The manufacture method of the film with film |
| CN103640305A (en) * | 2013-11-26 | 2014-03-19 | 大连创达技术交易市场有限公司 | Double-coating material |
| CN109923165A (en) * | 2016-08-31 | 2019-06-21 | 三星Sdi株式会社 | For antireflection film composition, formed by it antireflection film, comprising its polarizer and comprising its optical display |
| CN109923165B (en) * | 2016-08-31 | 2021-02-19 | 三星Sdi株式会社 | Composition for antireflection film, antireflection film formed therefrom, polarizing plate comprising same, and optical display device comprising same |
| CN107142012A (en) * | 2017-06-20 | 2017-09-08 | 合肥市惠科精密模具有限公司 | A kind of TFT LCD displays nano protective film |
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| CN100582817C (en) | 2010-01-20 |
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