CN102162863A - Anti-dazzle hard film and polarizer equipped with hard film - Google Patents
Anti-dazzle hard film and polarizer equipped with hard film Download PDFInfo
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- CN102162863A CN102162863A CN2011100437791A CN201110043779A CN102162863A CN 102162863 A CN102162863 A CN 102162863A CN 2011100437791 A CN2011100437791 A CN 2011100437791A CN 201110043779 A CN201110043779 A CN 201110043779A CN 102162863 A CN102162863 A CN 102162863A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
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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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
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Abstract
The invention relates to an anti-dazzle hard film and a polarizer equipped with the hard film capable of avoiding the fading and the contrast descending. The anti-dazzle hard film is high in image definition. The anti-dazzle hard film is characterized in that the surface of a transparent plastic film is equipped with a hard coating formed with hard coating formation material. The hard coating formation material contains (A) active energy induction composition and (B) spherical organic particles. The total haze valve of the hard coating is smaller than 20%. The valve of "the total haze valve-internal haze valve" is within the range of -10 - +1%. The opposite side of the hard coating formation surface is attached with a polarizer so as to form a polarizer.
Description
Technical field
The polaroid that the present invention relates to anti-dazzle hardness film coating and use this hard coat film.More specifically, the present invention relates to a kind of anti-dazzle hardness film coating and relate to the polaroid that uses this anti-dazzle hardness film coating, this hard coat film setting has comprised the hard conating of organic fine particles, wherein be setting by total mist value and " the total mist value-inner mist value " that makes hard conating, can reduce and fade and the reduction of contrast, and have high image definition and suitable anti-dazzle property concurrently.
Background technology
In cathode ray tube (CRT) and LCD (LCD), the plasma display displays such as (PDP), light incides on the picture from the outside, this light reflection, can be difficult to see clearly display image, particularly along with the maximization of display in recent years, addressing the above problem becomes more and more important problem.As means that address this problem, can list and use parts with antiglare hardcoat.And the formation method of this antiglare hardcoat can be divided into following three classes: (1) makes the method for surface roughening by physical method when forming the curing of hard conating; (2) in forming the hard paint of usefulness, hard conating sneaks into the method for filling agent; (3) in the hard paint of hard conating formation usefulness, sneak into immiscible two kinds of compositions, utilize their method that is separated.These methods all are by forming micro concavo-convex on the surface, suppress the direct reflection of outer light, prevent mirroring of outer light such as fluorescent light.In these methods, the method for main flow is the method for sneaking into filling agent in hard paint of (2).Generally use with the inorganic particles of original silica as filling agent as representative.Can list as the reason of using silica granule does not have the curing of hard conating deficiency to cause mar proof low etc.
On the other hand, use organic fine particles as filling agent, for example in patent documentation 1, disclose a kind of mar proof antiglare film, this antiglare film is to form in essence the antiglare layer that resin bead and ionizing radiation curable resin composition by refractive index 1.40～1.60 constitute to form on transparency carrier; In addition, in patent documentation 2, a kind of antiglare film is disclosed, this antiglare film contains the antiglare layer that two or more light transmission particulates forms and constitutes by transparent base film with in translucent resin, the refringence of above-mentioned light transmission particulate and above-mentioned translucent resin is more than 0.03, below 0.20, forms at antiglare layer surface formation concaveconvex shape by above-mentioned two or more light transmission particulate.
Yet based on the purpose that is clear that the image that mirrors from picture, it is disadvantageous that this antiglare hardcoat is set.Antiglare hardcoat is because its surface irregularity has the character of the light scattering that sees through, and the result can produce image definition and descend the problem that sense of vision is low.In addition, owing to be called turning white of fading, black concentration lowers, and has the problem that contrast reduces thus; Otherwise, if, then produce the problem that mirrors that can't prevent fluorescent light and outer light for the sharpness of improving image reduces concave-convex surface with fading.
On the other hand, as anti-dazzle property excellence, prevent the phenomenon of dazzling, and prevent anti-white, anti-dazzle hardness film coating in the demonstration contrast excellence of bright position, a kind of anti-dazzle hardness film coating is disclosed, this hard coat film is on the one side at least of transparent plastic film base material, anti-dazzle hardness film coating with the antiglare hardcoat that contains particulate, it is characterized in that: above-mentioned Antidazzle hard coating laminar surface is a concaveconvex structure, total mist value ht is 40～70% scope, and the relation of the inside mist value hi that the scattering-in of above-mentioned total mist value ht and above-mentioned antiglare hardcoat causes is the relation (with reference to patent documentation 3) of total mist value ht≤inner mist value hi.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 6-18706 communique
No. 3515401 communique of [patent documentation 2] Japan special permission
[patent documentation 3] TOHKEMY 2007-334294 communique
Summary of the invention
Yet, the technology of above-mentioned patent documentation 3 records is defined as " total mist value ht≤inner mist value hi " by the relation with total mist value ht and inner mist value hi, prevent the phenomenon of dazzling, and attempt to prevent to turn white, improve the demonstration contrast of bright position, but be that total mist value that relation with total mist value ht and inner mist value hi is defined in the sense of vision difference is the technology in 40～70% the high scope.
The present invention proposes according to this problem, and its purpose is to provide a kind of anti-dazzle hardness film coating, and this hard coat film can reduce and fades and contrast low, and has high image definition and suitable anti-dazzle property concurrently; And the polaroid that this anti-dazzle hardness film coating of use is provided.
The inventor to achieve these goals, carry out repeatedly conscientious research, thereby find a kind of anti-dazzle hardness film coating, this hard coat film is to have on the surface of transparent plastic film to use the hard conating that contains active energy ray induction type composition and spherical organic fine particles to form the hard conating that material forms, and total mist value of this hard conating is below the particular value, and the value of " total mist value-inner mist value " forms with specific scope, thereby can realize above-mentioned purpose.The present invention is based on this understanding and finishes.
Just, the invention provides:
[1] a kind of anti-dazzle hardness film coating, it is characterized in that: have on the surface of transparent plastic film and use hard conating to form the hard conating that material forms, this hard conating forms material and contains (A) active energy ray induction type composition and (B) spherical organic fine particles, and total mist value of this hard conating is below 20%, and the value of " total mist value-inner mist value " is-10～+ 1% scope;
[2] anti-dazzle hardness film coating of being put down in writing according to above-mentioned [1], wherein the mean grain size of the spherical organic fine particles of (B) composition is 1～10 μ m;
[3] anti-dazzle hardness film coating of being put down in writing according to above-mentioned [1] or [2], wherein 60 ° mirror surface luster is below 150;
[4] according to each anti-dazzle hardness film coating of putting down in writing of above-mentioned [1]～[3], wherein the arithmetic average roughness Ra on the surface of hard conating is 0.02～0.30 μ m;
[5] according to each anti-dazzle hardness film coating of putting down in writing of above-mentioned [1]～[4], wherein the surface resistivity of hard conating is 10
13Below Ω/; And
[6] a kind of polaroid, this polaroid are to form at the face applying polarizer that the hard conating of each anti-dazzle hardness film coating of putting down in writing of above-mentioned [1]～[5] forms the opposition side of face.
In addition, the preferred scheme as anti-dazzle hardness film coating of the present invention can list:
(a) total image definition of 5 kinds of slits is the anti-dazzle hardness film coating more than 300;
(b) (B) content of spherical organic fine particles is the anti-dazzle hardness film coating of 0.1～30 mass parts with respect to the solid matter of 100 mass parts (A) active energy ray induction type composition;
(c) (A) active energy ray induction type composition comprises the anti-dazzle hardness film coating of the compound that contains quaternary ammonium salt base;
(d) difference of the refractive index of the refractive index of the solidfied material of active energy ray induction type composition and spherical organic fine particles is 0.01～0.05 anti-dazzle hardness film coating in absolute value.
According to the present invention, the polaroid that a kind of anti-dazzle hardness film coating is provided and uses this anti-dazzle hardness film coating, this hard coat film is the anti-dazzle hardness film coating that the hard conating formation that comprises spherical organic fine particles is set, be particular value by total mist value and " the total mist value-inner mist value " that makes hard conating, can reduce and fade or the reduction of contrast, and have high image definition and suitable anti-dazzle property concurrently.
Description of drawings
Fig. 1 is the stereographic map of structure of an example of expression polaroid.
Fig. 2 is the diagrammatic cross-section of structure of an example of expression polaroid of the present invention.
Embodiment
In anti-dazzle hardness film coating of the present invention, when formation is arranged on hard conating on the one side at least of transparent plastic film, use hard conating to form material with following composition.
[hard conating formation material]
Hard conating among the present invention forms material and comprises (A) active energy ray induction type composition and (B) spherical organic fine particles.
((A) active energy ray induction type composition)
Form in the material at above-mentioned hard conating, as the active energy ray induction type composition that (A) composition uses, can preferably use the material of (b) silica based fine particles that comprises (a) multi-functional (methyl) acrylic ester monomer and/or (methyl) esters of acrylic acid prepolymer and use as required.
In addition, in the present invention, described active energy ray is meant that electromagnetic wave or charged particle are intrafascicular and has the quantum of energy, just ultraviolet ray and an electron beam etc.
＜(a) multi-functional (methyl) acrylic ester monomer and/or (methyl) esters of acrylic acid prepolymer 〉
In the present invention, as (A) active energy ray induction type composition, use multi-functional (methyl) acrylic ester monomer and/or (methyl) esters of acrylic acid prepolymer (below, be also referred to as the active energy ray-curable compound sometimes).
As above-mentioned multifunctional (methyl) acrylic ester monomer, for example can list 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, two cyclopentane base two (methyl) acrylate, two cyclopentene two (methyl) acrylate of caprolactone modification, the di(2-ethylhexyl)phosphate of oxirane modification (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol three (methyl) acrylate of propionic acid modification, pentaerythrite three (methyl) acrylate, the trimethylolpropane tris of epoxy pronane modification (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, dipentaerythritol five (methyl) acrylate of propionic acid modification, dipentaerythritol six (methyl) acrylate, multi-functional (methyl) acrylate such as dipentaerythritol six (methyl) acrylate of caprolactone modification.These monomers can use a kind of, also can make up two or more uses.
On the other hand, as above-mentioned (methyl) esters of acrylic acid prepolymer, can list for example polyester acrylate class, epoxy acrylate class, urethanes esters of acrylic acid, polyalcohol acrylate class etc.Wherein, as polyester acrylate class prepolymer, for example can have the hydroxyl of the polyester oligomer of hydroxyl at two ends, with (methyl) acroleic acid esterification by what polybasic carboxylic acid and polyol condensating were obtained; The hydroxyl of end that perhaps will the oligomer that the addition alkylene oxide obtains in polybasic carboxylic acid obtains with (methyl) acroleic acid esterification.
Epoxy acrylate class prepolymer for example can be by making more low-molecular-weight bisphenol-type epoxy resin or phenolic resin varnish type epoxy resin oxirane ring and the reaction of (methyl) acrylic acid, esterification and obtaining.Urethanes esters of acrylic acid prepolymer for example can obtain with (methyl) acroleic acid esterification by the urethane oligomer that the reaction of polyester polyol or polyester polyol and polyisocyanate is obtained.In addition, polyalcohol acrylate class prepolymer can obtain by hydroxyl and (methyl) acroleic acid esterification with polyether glycol.These prepolymers can use a kind of, also can make up two or more uses, perhaps, can also use together with above-mentioned multi-functional (methyl) acrylic ester monomer.
＜(b) silica based fine particles 〉
In the present invention, can use the gel silica microparticle as (b) silica based fine particles that uses according to hope and/or have the silica microparticle of surface functional group.
The mean grain size of gel silica microparticle is about 1～400nm; In addition, as silica microparticle, for example can list and have the group that comprises (methyl) acryloxy as the silica microparticle of surface functional group (below, be called reactive silica particulate) with surface functional group.
Above-mentioned reactive silica particulate for example can be by with the silanol group on the silica microparticle surface about mean grain size 0.005～1 μ m with comprise and have and can obtain with the organic compound reaction of the polymerism unsaturated group of the functional group of this silanol group reaction.As the polymerism unsaturated group, can list for example free-radical polymerised (methyl) acryloxy etc.
As comprise have can with the organic compound of the polymerism unsaturated group of the functional group of above-mentioned silanol group reaction, preferably use for example acrylic acid, acryloyl chloride, acrylic acid 2-isocyanate group ethyl ester, acrylic acid glyceride, acrylic acid 2,3-imino group propyl diester, acrylic acid 2-hydroxy methacrylate, acryloxy propyl trimethoxy silicane etc. and and the methacrylic acid derivative of these acrylic acid derivative correspondences.These acrylic acid derivatives or methacrylic acid derivative may be used singly or in combination of two or more use.
The silica microparticle that combines the organic compound that comprises the polymerism unsaturated group that obtains like this is subjected to crosslinked, the curing of irradiation of active energy ray as the active energy ray-curable compound.
This reactivity silica particulate has the effect of the mar proof that improves the hard coat film that obtains.
As the active energy ray induction type composition (A) that is included in the compound that forms in conjunction with organic compound in this silica microparticle with polymerism unsaturated group, commodity " オ プ ス タ one Z7530 ", " オ プ ス タ one Z7524 " by name that for example JSR (Co., Ltd.) manufacturing is arranged of listing, " オ プ ス タ one TU4086 " etc.
In the present invention, the content that is somebody's turn to do the silica based fine particles of (b) composition is in the solid constituent of the active energy ray induction type composition of (A) composition, normally about 5～90 quality %, is preferably about 10～70 quality %.
In addition, the mean grain size of the silica granule in the silica based fine particles of this (b) composition can be passed through laser diffraction-scattering method.This method be by contact in the liquid that has disperseed particle during laser diffraction, scattered intensity change and measure mean grain size.
((B) spherical organic fine particles)
Hard conating in the present invention forms in the material, spherical organic fine particles as the use of (B) composition, (for example for example can list silicone particulate, melamine based fine particles, acrylic compounds particulate, can list polymethylmethacrylate particulate (below, be also referred to as the PMMA based fine particles sometimes) etc.), acrylic acid-styrene copolymer particulate, polycarbonate based fine particles, polyethylene kind particulate, polystyrene based fine particles, benzoguanamine resinoid particulate etc.
In the present invention, though use organic fine particles, from the viewpoint of the quality stability of anti-dazzle performance, for the light-scattering state homogenising that makes spherical particle is used.The mean grain size of this sphere organic fine particles is preferably 1～10 μ m; If mean grain size less than 1 μ m then may produce and fade etc., if surpass 10 μ m, then anti-dazzle property may be not enough.From this point of view, mean grain size is preferably 2～8 μ m especially.
In the present invention, the spherical organic fine particles that is somebody's turn to do (B) composition can be used alone, and also can make up two or more uses; In addition, its combined amount with respect to the solid constituent of 100 mass parts as the active energy ray induction type composition of above-mentioned (A) composition, is preferably 0.1～30 mass parts, more preferably 1～20 mass parts from the viewpoint of anti-dazzle performance.
In addition, in order to make total mist value described later is below 20%, the value of " total mist value-inner mist value " is-10～+ 1% scope, and the refractive index of the solidfied material of above-mentioned active energy ray induction type composition and the refractive index of spherical organic fine particles poor is preferably 0.01～0.05 in absolute value.Thus, can be when having enough anti-dazzle performances, ground such as do not fade obtains seeing through the high anti-dazzle hardness film coating of sharpness.
In anti-dazzle hardness film coating of the present invention, when requiring hard conating that antistatic performance is arranged, preferably in above-mentioned (A) active energy ray induction type composition, add the compound that contains quaternary ammonium salt base.Contain the compound of quaternary ammonium salt base as this, can contain (1) by applying active energy ray, can with the active energy ray-curable compound of active energy ray-curable compound copolymerization in the said composition, promptly contain the monomer of quaternary ammonium salt base; Perhaps (2) contain the polymkeric substance of quaternary ammonium salt base.
As the monomer that contains quaternary ammonium salt base of above-mentioned (1), can list for example compound shown in the general formula (1) etc.
In the formula, R represents hydrogen atom or methyl.
In the present invention, this monomer that contains quaternary ammonium salt base can use a kind of, also can make up two or more uses.
By in the active energy ray induction type composition of (A) composition, containing the monomer that this contains quaternary ammonium salt base, can be by applying active energy ray, make the active energy ray-curable compound and the above-mentioned monomer copolymerization that contains quaternary ammonium salt base that exist in the said composition, in the cured resin that obtains, import quaternary ammonium salt base.
On the other hand, as the polymkeric substance that contains quaternary ammonium salt base of above-mentioned (2), can list preference as at the high molecular polymer that has the quaternary ammonium salt base shown in the general formula (2) in the molecule.
In the formula, R
1And R
2Represent that respectively identical or differently carbon number is 1～10 alkyl, R
3The expression carbon number is that 1～10 alkyl or carbon number are 7～10 aralkyl, X
N-The negative ion of expression n valency, n represents 1～4 integer.
In above-mentioned general formula (2), as R
1And R
2Shown alkyl and R
3In alkyl, preferred carbon number is that 1～6 alkyl, particularly carbon number are 1～4 alkyl; In addition, as R
3In aralkyl, preferred benzyl.As carbon number is 1～4 alkyl, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group.
On the other hand, X
N-Can be any situation of inorganic anion, organic anion,, can list F as its example
-, Cl
-, Br
-, I
-Halide anion, NO
3 -, ClO
4 -, BF
4 -, CO
3 2-, SO
4 2-Deng inorganic anion, CH
3OSO
3 -, C
2H
5OSO
3 -, and the organic anion that forms by organic acid residues such as acetate, malonic acid, succinic acid, maleic acid, fumaric acid, p-toluenesulfonic acid, trifluoroacetic acids.
As this polymkeric substance that contains quaternary ammonium salt base, can list for example following illustrative compound, just polyvinyl benzylic type [(a)], poly-(methyl) acrylic ester type [(b)], styrene-(methyl) acrylate copolymer type [(c)], styrene-maleimide copolymer type [(d)], methacrylate-metering system imide copolymer type [(e)] etc.In addition, in (c), (d) and copolymer type (e), can be any situation of atactic copolymer type and segmented copolymer type.
In the present invention, this polymkeric substance that contains quaternary ammonium salt base can use a kind of, also can make up two or more uses.
There is no particular limitation to the content of the quaternary ammonium salt base in the hard conating, can suitably select so that the surface resistivity of hard conating is desirable value.
Can infer by forming in the material and contain above-mentioned monomer or polymkeric substance (compound that contains quaternary ammonium salt base) with quaternary ammonium salt base at hard conating, this monomer or polymkeric substance play with the cationic surfactant and similarly act on, this hard conating is formed material be applied to transparent plastic surface, when forming wet coating, infer and improve the dispersiveness of spherical organic fine particles in this wet coating, thus, the anti-dazzle hardness film coating that obtains shows good anti-dazzle property, simultaneously the image definition height.
(Photoepolymerizationinitiater initiater)
Form in the material at hard conating of the present invention, can contain Photoepolymerizationinitiater initiater according to hope.As this Photoepolymerizationinitiater initiater, can list for example styrax, the styrax methyl ether, the styrax ethylether, benzoin isobutyl propyl group ether, the styrax n-butyl ether, benzoin isobutyl butyl ether, acetophenone, dimethylamino acetyl benzene, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, the 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino-third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, benzophenone of dichloro, 2-methylanthraquinone, the 2-EAQ, 2-tert-butyl group anthraquinone, the 2-amino anthraquinones, 2-methyl thioxanthones, 2-ethyl thioxanthones, the 2-chloro thioxanthone, 2,4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, benzyl dimethyl ketal, the acetophenone dimethyl ketal, ESCAROL 507 ester etc.
They can use a kind of, also can make up two or more uses; In addition, its combined amount is selected in the scope of 0.2～10 mass parts usually with respect to the whole active energy ray-curable compounds of 100 mass parts.
(hard conating forms the preparation of material)
The hard conating that uses among the present invention forms material as required in appropriate solvent, add the active energy ray induction type composition of above-mentioned (A) composition, the organic fine particles of (B) composition and Photoepolymerizationinitiater initiater and the various adding ingredient that uses according to hope with the ratio of regulation respectively, for example antioxidant, ultraviolet light absorber, silane coupling agent, light stabilizer, levelling agent, defrother etc., make its dissolving or dispersion, be prepared.
As the solvent that uses this moment, can list for example aliphatic hydrocarbon such as hexane, heptane, aromatic hydrocarbons such as toluene, dimethylbenzene, halogenated hydrocarbons such as methylene chloride, ethylene dichloride, alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, propylene glycol monomethyl ether, ketone such as acetone, MEK, 2 pentanone, isophorone, cyclohexanone, esters such as ethyl acetate, butyl acetate, and cellosolve kind solvent such as cellosolve etc.
As long as the hard conating as such preparation forms concentration of material, viscosity can be coated with regard to there is no particular limitation, can according to circumstances suitably select.
[transparent plastic film]
In anti-dazzle hardness film coating of the present invention, the hard conating that forms as above-mentioned preparation on the one side at least of transparent plastic film forms material, forms hard conating.
There is no particular limitation to above-mentioned transparent plastic film, can be from suitably selecting to use with the base material of hard coat film and the known plastic sheeting as present optics.As this plastic sheeting; can list for example polyethylene terephthalate; polybutylene terephthalate; mylars such as Polyethylene Naphthalate; polyethylene film; polypropylene film; viscose paper; the diacetyl cellulose film; the tri acetyl cellulose film (below, be also referred to as " TAC film " sometimes); acetyl group cellulose butylate film; polyvinyl chloride film; the Vingon film; polyvinyl alcohol film; the ethylene-vinyl acetate copolymer film; plasticon; polycarbonate film; poly-methyl pentene film; polysulphone film; poly (ether ether ketone) film; the polyethersulfone film; the polyetherimide film; Kapton; fluorine resin film; polyamide film; the acryl resin film; the norbornane based resin film; plastic sheetings such as cyclic olefin resins film.
The film of these plastic sheeting preferably clears.
There is no particular limitation for the thickness of these plastic sheetings, can according to circumstances suitably select 15～300 μ m normally, the scope of preferred 30～200 μ m.In addition, this plastic sheeting by oxidizing process or concavo-convexization method etc., carries out surface treatment according to hope based on the purpose of the adaptation of raising and antiglare hardcoat on one or both sides.As above-mentioned oxidizing process, can list for example Corona discharge Treatment, plasma treatment, chromic acid processing (wet method), flame treatment, hot blast processing, ozone ultraviolet ray treatment with irradiation etc.In addition, as concavo-convexization method, can list for example sand-blast, solvent treatment method etc.These surface treatment methods are suitably selected according to the kind of plastic sheeting, and in general, the Corona discharge Treatment method is preferred the use from aspects such as effect and operability.In addition, bottom can also be set.
[formation of hard conating]
On the one side at least of above-mentioned transparent plastic film, use existing known method, for example excellent rubbing method, scraper rubbing method, rolling method, scraper plate rubbing method, slit die rubbing method, intaglio plate rubbing method etc., be coated with above-mentioned hard conating and form material, formation is filmed, after the drying, to its irradiation active energy ray, make this curing of coating, form hard conating.
As active energy ray, can list for example ultraviolet ray or electron beam etc.Above-mentioned ultraviolet ray obtains by high-pressure mercury-vapor lamp, electrodeless lamp, metal halide lamp, xenon lamp etc., and exposure is 100～500mJ/cm normally
2, on the other hand, electron beam obtains by electron-beam accelerator etc., and exposure is 150～350kV normally.In this active energy ray, specially suitable is ultraviolet ray.In addition, when using electron beam, can not add Photoepolymerizationinitiater initiater, obtain cured film.
The thickness of the hard conating of Xing Chenging normally about 3～15 μ m, is preferably 3～10 μ m from the particle diameter of spherical organic fine particles with prevent viewpoint such as warpage like this.
[anti-dazzle hardness film coating]
The anti-dazzle hardness film coating of the present invention that obtains like this has following optical property.
(mist value)
Total mist value of hard conating is below 20%, and " total mist value-inner mist value " (just, outside mist value) value is-10～+ 1%, is preferably-5～+ 1%.The value of total mist value and " total mist value-inner mist value " is as long as in above-mentioned scope, then can reduce to fade and the reduction of contrast, has high image definition and suitable anti-dazzle property simultaneously concurrently.
In addition, the mist value is measured according to JIS K 7136, and inner mist value and total mist value are the values of measuring according to following method.
The mensuration of＜inner mist value and total mist value 〉
According to JIS K 7136, measure the mist value and the independent mist value of this transparent plastic film of anti-dazzle hardness film coating.
To deduct the value of the independent mist value of above-mentioned transparent plastic film from the mist value of above-mentioned anti-dazzle hardness film coating, as total mist value.
Then, the transparent adhesive tape bonding die that the bonding coat of thickness 20 μ m will be set on the transparent membrane of thickness 50 μ m is fitted in the hard conating side of anti-dazzle hardness film coating, calculates as inner mist value and uses sample.The mist value of this transparent adhesive tape bonding die and inner mist value are calculated with the mist value of sample and are measured according to JIS K 7136.
And, mist value internally calculated deduct the mist value of above-mentioned transparent adhesive tape bonding die and the value that the independent mist value of transparent plastic film obtains, as the inside mist value of the hard conating of anti-dazzle hardness film coating with the mist value of sample.
In addition, the mist value of above-mentioned transparent adhesive tape bonding die can directly not influence inner mist value and total mist value owing to deduct in the aforementioned calculation process, so there is no particular limitation, from improving the viewpoint of measuring precision, preferably uses mist value less than 15%.In addition, based on same viewpoint, total light penetration of above-mentioned transparent adhesive tape bonding die is preferably more than 85%.
(60 ° of mirror surface lusters)
Use glossmeter, 60 ° of mirror surface lusters measuring according to JIS K 7105 normally below 150, are preferably 80～150, and more preferably 100～150.
In addition, the surface average roughness Ra of the hard conating of anti-dazzle hardness film coating of the present invention normally about 0.02～0.30 μ m, is preferably 0.04～0.20 μ m when carrying out the mensuration of JIS B 0601-1994.
In addition, make the surface resistivity of hard conating be preferably 10
13Below Ω/, more preferably 10
12Below Ω/, can give antistatic performance.
(other functional layer)
In anti-dazzle hardness film coating of the present invention, as required,, anti-reflection layer can be set, for example type siloxane overlay film, fluorine class overlay film etc. in the superiors based on giving purposes such as antireflection.What at this moment, the thickness of this anti-reflection layer was suitable is about 0.05～1 μ m.By this anti-reflection layer is set, can eliminate mirroring of the picture that produces by reflections such as sunshine, fluorescent lights; In addition,, can improve total light penetration, improve the transparency by suppressing the reflectivity on surface.In addition, change the kind of anti-reflection layer, can improve static electricity resistance.
(adhesive phase)
In anti-dazzle hardness film coating of the present invention, with the face of the hard conating opposition side of plastic sheeting on, be formed for fitting to liquid crystal display etc. by the adhesive phase on the adherend.Preferably use as the bonding agent that constitutes this adhesive phase to be fit to optical applications, for example acrylic adhesives, polyurethane binding, silicone based bonding agent.The thickness of this adhesive phase is 5～100 μ m normally, are preferably the scope of 10～60 μ m.
In addition, on this adhesive phase, as required stripping film can be set, can list on various plastic sheetings such as for example polyethylene terephthalate, polypropylene etc., the stripping film that removers such as coating organic siliconresin form etc. as this stripping film.There is no particular limitation for the thickness of this stripping film, normally about 20～150 μ m.
This anti-dazzle hardness film coating that has formed adhesive phase is suitable as displays such as CRT, LCD, PDP, gives the parts of anti-dazzle performance or abrasion resistance properties etc., particularly is suitable as the polaroid applying purposes among LCD etc.
[polaroid]
The present invention also provides the anti-dazzle hardness film coating with the invention described above to fit to the polaroid that forms on the polarizer.
Liquid crystal cell among the LCD generally is following structure: two transparent electrode substrates that will form oriented layer, with its oriented layer is the inboard, form the configuration of specified gap ground by partition, with sealing around it, in this gap, clamp liquid crystal material, outer surface at above-mentioned two transparent electrode substrates passes through adhesive phase respectively simultaneously, the configuration polaroid.
Fig. 1 is the stereographic map of structure of an example of the above-mentioned polaroid of expression.As shown in the drawing; this polaroid 10 generally is on the two sides of polyvinyl alcohol polarizer 1; applying tri acetyl cellulose (TAC) film 2 and 2 '; form the base material of 3-tier architecture; and; on its one side, be formed for fitting to the adhesive phase 3 of optics such as liquid crystal cell, then, applying stripping film 4 on this adhesive phase 3.In addition, on this polaroid and faces these adhesive phase 3 opposition sides, surface protection film 5 is set usually.
In the TAC film 2,2 ' of polaroid of the present invention on the two sides that is arranged on polarizer 1, the hard conating of the invention described above is set on a TAC film.When adhesive phase 3, stripping film 4 and surface protection film 5 were set on polaroid, particularly the TAC film 2 ' side in surface protection film 5 sides was provided with hard conating of the present invention.
As the method for making polaroid of the present invention, for example can be undertaken by operation shown below.
In addition, Fig. 2 is the diagrammatic cross-section of structure of an example of expression polaroid of the present invention.
At first, use the transparent plastic film of the so non-optical anisotropic film 12 ' of TAC film, on its one side, form hard conating 13 of the present invention, form anti-dazzle hardness film coating 14 as base material.Then, use adhesive layer 15,15 ', the stacked TAC film 12 that does not form hard conating 13 on the one side of polarizer 11 is at the stacked above-mentioned anti-dazzle hardness film coating 14 of opposing face.When transparent plastic film used the TAC film, the adaptation when using adhesive stacked in order to improve can also be carried out above-mentioned surface treatment saponification processing in addition etc.
Thus, obtain the polaroid 20 of anti-dazzle performance and abrasion resistance properties excellence.Polaroid 20 on the face that hard conating 13 is set, is provided with the above-mentioned surface protection film that can peel off 5 shown in Figure 1 also as required, or is provided for fitting to adhesive phase 16 or stripping film 17 on the opticses such as liquid crystal cell at its opposing face.
It is that the light quantity of representative is regulated uses such as purposes, polarization interference application apparatus purposes, optical defect detecting device purposes that polaroid of the present invention can be used as with the liquid crystal cell purposes among the LCD.
[embodiment]
Then, the present invention will be described in more detail by embodiment, but the present invention is not subjected to any qualification of these examples.
In addition, the refractive index of the solidfied material of the mean grain size of spherical organic fine particles and refractive index, active energy ray induction type composition and the performance of hard coat film are tried to achieve according to following method.
＜spherical organic fine particles 〉
(1) refractive index
On microslide, carry the spherical organic fine particles of determination object, after dripping the refractive index titer on the particulate, cover cover glass, make sample.This sample is based on the B method of JIS K 7142, by microscopic examination, will not see the refractive index of refractive index titer of Chu's particulate profile most as the refractive index of this particulate.
＜active energy ray induction type composition 〉
(2) refractive index of solidfied material
In each preparation example, make the smears that forms by active energy ray induction type composition (A), Photoepolymerizationinitiater initiater and diluting solvent.Itself and embodiment similarly are applied on the TAC film [the Off イ of Fuji Le system (Co., Ltd.) is made, trade name " TAC80TD80ULH "], solidify by the ultraviolet ray irradiation, as the detecting refractive index hard coat film of this solidfied material.With its A method based on JIS K 7142, use the ア Star ベ refractometer of (Co., Ltd.) ア タ go manufacturing, try to achieve the refractive index of hard conating, with its refractive index as the solidfied material of active energy ray induction type composition.
＜hard coat film 〉
(3) total light penetration
The atomizing instrument " NDH-2000 " that uses Japanese electric look industry (Co., Ltd.) to make according to JIS K 7361-1, is measured total light penetration to the anti-dazzle hardness film coating of embodiment and comparative example manufacturing.
(4) the inside mist value of hard conating, total mist value and " total mist value-inner mist value "
The haze meter " NDH-2000 " that uses Japanese electric look industry (Co., Ltd.) to make according to JIS K 7136, is measured anti-dazzle hardness film coating that embodiment and comparative example make and as the independent mist value of the transparent plastic film of the constituent material of this film.
The mist value of the mist value deduction transparent plastic film of the anti-dazzle hardness film coating that obtains from said determination, thus calculate total mist value of the hard conating of anti-dazzle hardness film coating.
Then, [Japanese カ one バ イ ト company makes at 100 mass parts acrylic adhesives, trade name " PE-121 "] middle 2 mass parts isocyanate crosslinkings [Japan イ Application キ company makes, trade name " BHS-8515 "] and the 100 mass parts toluene of adding, make binder solution.
Then, coat binding agent solution in the polyethylene terephthalate thin film as transparent membrane [Japan's textile company is made, trade name " A4300 "] of thickness 50 μ m is so that the thickness of dried bonding coat is 20 μ m, drying is 3 minutes under 100 ℃, makes transparent pressure-sensitive adhesive sheet.
The transparent pressure-sensitive adhesive sheet of making is fitted to the hard conating side of anti-dazzle hardness film coating, calculate as inner mist value and use sample.This transparent pressure-sensitive adhesive sheet and inner mist value are calculated with the various mist values of sample and above-mentioned similarly according to JIS K 7136 mensuration.
And the mist value is calculated the mist value with sample internally, and the mist value of deduction transparent pressure-sensitive adhesive sheet and the mist value of transparent plastic film are calculated the inside mist value of the hard conating of anti-dazzle hardness film coating.
At last, by deducting inner mist value, calculate " total mist value-inner mist value " of the hard conating of anti-dazzle hardness film coating from above-mentioned total mist value.
(5) evaluation of anti-dazzle property
On acryl resin blackboard [manufacturing of レ イ ヨ Application company of Mitsubishi],,, estimate anti-dazzle property according to following judgment standard with the sample visualization under fluorescent light that forms by acrylic adhesives applying hard coat film.
Zero: fully prevent mirroring of fluorescent light, and do not fade.
*: prevent the deficiency that mirrors of fluorescent light, prevent fully that perhaps fluorescent light from mirroring, but fade obviously, sense of vision is poor.
(6) 60 ° of mirror surface lusters
The glossmeter " VG2000 " that uses Japanese electric look industry (Co., Ltd.) to make is measured according to JIS K 7105.
(7) image definition
The imaging analyzer " ICM-10P " that uses ス ガ testing machine (Co., Ltd.) to make is measured according to JIS K 7374.The aggregate values note of 5 kinds of slits (slit is wide: 0.125mm, 0.25mm, 0.5mm, 1mm and 2mm) is made image definition.
(8) thickness of hard conating
[ニ コ Application company makes by level pressure thickness meter respectively for TAC (tri acetyl cellulose) film of the transparent plastic film that uses in the anti-dazzle hardness film coating of embodiment and comparative example manufacturing, the manufacturing as this anti-dazzle hardness film coating and PET (polyethylene terephthalate) film; trade name " MH-15M "] mensuration thickness; by getting its difference, calculate the thickness of hard conating.
Preparation example 1 hard conating smears 1
[Japan changes into (Co., Ltd.) and makes will to contain the hard paint of antistatic agent (compound that contains quaternary ammonium salt base) as 50 mass parts of (A) active energy ray induction type composition, trade name " L80313 ", solid component concentration 70 quality %, propylene glycol monomethyl ether 30 quality %] and the hard paint that does not contain antistatic agent of 35 mass parts [industry (Co., Ltd.) manufacturing of refining big day, trade name " セ イ カ PVC one system EXF-01L (NS) ", solid component concentration 100 quality %, the active energy ray-curable compound 95 quality % that contain reactive monomer and polyfunctional acrylic ester, Photoepolymerizationinitiater initiater 5 quality %], polystyrene-poly methyl methacrylate (PSt-PMMA) particulate [Plot aquation finished product industry (Co., Ltd.) as 4 mass parts of (B) spherical organic fine particles is made, mean grain size 2.5 μ m, refractive index 1.555], 90 mass parts toluene as diluting solvent evenly mix, and make the hard conating smears 1 that solid constituent is about 41 quality %.In addition, the refractive index of the solidfied material of active energy ray induction type composition is 1.525.
Preparation example 2 hard conatings smears 2
[combine and grind chemistry (Co., Ltd.) manufacturing as polymethylmethacrylate (PMMA) particulate of (B) spherical organic fine particles except adding 4 mass parts, mean grain size 3 μ m, refractive index 1.49], beyond the propylene glycol monomethyl ether of 90 mass parts as diluting solvent, with preparation example 1 similarly, the hard conating of preparation solid constituent about 41 quality % is with smears 2.
Preparation example 3 hard conatings smears 3
Make as the PMMA particulate [Plot aquation finished product industry (Co., Ltd.) of (B) spherical organic fine particles except adding 4 mass parts, mean grain size 5 μ m, refractive index 1.49] in addition and preparation example 1 similarly, the hard conating of preparation solid constituent about 41 quality % is with smears 3.
Preparation example 4 hard conatings smears 4
[combine and grind chemistry (Co., Ltd.) manufacturing as polystyrene (PSt) particulate of (B) spherical organic fine particles except adding 4 mass parts, mean grain size 1.3 μ m, refractive index 1.59], beyond the 36 mass parts MEKs and 54 mass parts propylene glycol monomethyl ether as diluting solvent, with preparation example 1 similarly, the hard conating of preparation solid constituent about 41 quality % is with smears 4.
Preparation example 5 hard conatings smears 5
Make as the PSt-PMMA particulate [Plot aquation finished product industry (Co., Ltd.) of (B) spherical organic fine particles except adding 4 mass parts, mean grain size 2 μ m, refractive index 1.555] in addition and preparation example 2 similarly, the hard conating of preparation solid constituent about 41 quality % is with smears 5.
Preparation example 6 hard conatings smears 6
[Japan changes into (Co., Ltd.) and makes as the hard paint that contains antistatic agent (compound that contains quaternary ammonium salt base) of (A) active energy ray induction type composition with 100 mass parts, trade name " L80313 ", solid component concentration 70 quality %, propylene glycol monomethyl ether 30 quality %], 35 mass parts MEKs and 35 mass parts propylene glycol monomethyl ether as diluting solvent are evenly mixed, the hard conating smears 6 of the about 41 quality % of preparation solid constituent.
Embodiment 1
By the smears 1 that Meyer rod coating preparation example 1 obtains, is about 5 μ ms so that solidify thickness on the surface of tri acetyl cellulose (TAC) film [the Off イ of Fuji Le system (Co., Ltd.) manufacturing] of thickness 80 μ m.In 70 ℃ baking oven, after dry 1 minute,, shine 300mJ/cm by high-pressure mercury-vapor lamp
2Ultraviolet ray, make anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Except the smears 2 that obtains by Meyer rod coating preparation example 2, be beyond about 5 μ m so that solidify thickness, carry out the operation same with embodiment 1, make anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Except the smears 3 that obtains by Meyer rod coating preparation example 3, be beyond about 5 μ m so that solidify thickness, carry out the operation same with embodiment 1, make anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Except surface polyethylene terephthalate (PET) film of thickness 188 μ m (Japan spins (Co., Ltd.) and makes), be coated with the smears 3 that preparation example 3 obtains by the Meyer rod, so that solidify thickness is beyond about 5 μ m, carries out the operation same with embodiment 1, makes anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Comparative example 1
Except the smears 4 that obtains by Meyer rod coating preparation example 4, be beyond about 4 μ m so that solidify thickness, carry out the operation same with embodiment 1, make anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Comparative example 2
Except the smears 4 that obtains by Meyer rod coating preparation example 4, be beyond about 4 μ m so that solidify thickness, carry out the operation same with embodiment 4, make anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Comparative example 3
Except the smears 5 that obtains by Meyer rod coating preparation example 5, be beyond about 5 μ m so that solidify thickness, carry out the operation same with embodiment 1, make anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Comparative example 4
Except the smears 6 that obtains by Meyer rod coating preparation example 6, be beyond about 5 μ m so that solidify thickness, carry out the operation same with embodiment 1, make anti-dazzle hardness film coating.
The performance of this hard coat film is represented in table 1.
Table 1-1
[notes]
PSt-PMMA: polystyrene-poly methyl methacrylate particulate
PMMA: polymethylmethacrylate particulate
PSt: ps particle
PGM: propylene glycol monomethyl ether
MEK: MEK
TAC: triacetyl fiber membrane
PET: polyethylene terephthalate
Table 1-2
Industrial applicibility
Anti-dazzle hardness film coating of the present invention has the hard conating that comprises spherical organic fine particles, be setting by total mist value and " the total mist value-inner mist value " that makes this hard conating, can reduce fade and contrast low, and have high image definition and suitable anti-glare concurrently, so be suitable as the parts of the displays such as CRT, LCD, PDP being given anti-dazzle performance and abrasion resistance properties etc., be particularly suitable as the applying purposes of the polarizer among LCD etc.
Claims (6)
1. anti-dazzle hardness film coating, it is characterized in that: have on the surface of transparent plastic film and use hard conating to form the hard conating that material forms, this hard conating forms material and contains (A) active energy ray induction type composition and (B) spherical organic fine particles, and total mist value of this hard conating is below 20%, and the value of " total mist value-inner mist value " is-10～+ 1% scope.
2. the anti-dazzle hardness film coating of putting down in writing according to claim 1, wherein the mean grain size of the spherical organic fine particles of (B) composition is 1～10 μ m.
3. according to claim 1 or 2 anti-dazzle hardness film coatings of being put down in writing, wherein 60 ° mirror surface luster is below 150.
4. according to claim 1 or 2 anti-dazzle hardness film coatings of being put down in writing, wherein the arithmetic average roughness Ra on the surface of hard conating is 0.02～0.30 μ m.
5. according to claim 1 or 2 each anti-dazzle hardness film coatings of putting down in writing, wherein the surface resistivity of hard conating is 10
13Below Ω/.
6. polaroid, this polaroid are that the face applying polarizer that the hard conating of the anti-dazzle hardness film coating put down in writing in claim 1～5 forms the opposition side of face forms.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010038795A JP5690491B2 (en) | 2010-02-24 | 2010-02-24 | Anti-glare hard coat film and polarizing plate using the same |
| JP2010-038795 | 2010-02-24 |
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| CN102162863A true CN102162863A (en) | 2011-08-24 |
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| CN201110043779.1A Active CN102162863B (en) | 2010-02-24 | 2011-02-22 | Anti-dazzle hardness film coating and use the polaroid of this hard coat film |
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| Country | Link |
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| JP (1) | JP5690491B2 (en) |
| KR (1) | KR101772232B1 (en) |
| CN (1) | CN102162863B (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107003462A (en) * | 2014-12-15 | 2017-08-01 | 3M创新有限公司 | Product and its manufacture method with hard conating |
| CN107960080A (en) * | 2015-04-07 | 2018-04-24 | 日产化学工业株式会社 | Anti-glare coating solidification compound |
| CN111948744A (en) * | 2015-11-20 | 2020-11-17 | Ａｇｃ株式会社 | Curved substrate with film, method for manufacturing same, and image display device |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5960995B2 (en) * | 2012-01-26 | 2016-08-02 | リンテック株式会社 | Newton ring prevention sheet |
| WO2015145618A1 (en) | 2014-03-26 | 2015-10-01 | リンテック株式会社 | Anti-glare hard coat film |
| KR102670776B1 (en) * | 2016-04-20 | 2024-05-31 | 삼성전자주식회사 | Polarizer and display apparatus comprising the same |
| JP2020024240A (en) * | 2018-08-06 | 2020-02-13 | 日東電工株式会社 | Method for manufacturing polarizer |
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| JP4595925B2 (en) | 2006-11-06 | 2010-12-08 | 凸版印刷株式会社 | Antiglare antistatic hard coat resin composition, hard coat film and hard coat film-formed article |
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| JP5058253B2 (en) * | 2007-05-29 | 2012-10-24 | リンテック株式会社 | Antiglare light transmissive hard coat film |
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- 2011-02-14 KR KR1020110012630A patent/KR101772232B1/en active IP Right Grant
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| JP2003131009A (en) * | 2001-10-23 | 2003-05-08 | Nitto Denko Corp | Antireflection film, optical element and image display device |
| JP2009037046A (en) * | 2007-08-02 | 2009-02-19 | Nof Corp | Antiglare film for liquid crystal display and liquid crystal display including the same |
| CN101412837A (en) * | 2007-10-18 | 2009-04-22 | Tdk株式会社 | Active energy ray-curable resin composition and laminate thereof |
| TW200946995A (en) * | 2008-03-28 | 2009-11-16 | Lintec Corp | Antiglare hard coat film and polarizer plate using the film |
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| CN107003462A (en) * | 2014-12-15 | 2017-08-01 | 3M创新有限公司 | Product and its manufacture method with hard conating |
| CN107960080A (en) * | 2015-04-07 | 2018-04-24 | 日产化学工业株式会社 | Anti-glare coating solidification compound |
| CN107960080B (en) * | 2015-04-07 | 2020-11-24 | 日产化学工业株式会社 | Curable composition for antiglare coating |
| CN111948744A (en) * | 2015-11-20 | 2020-11-17 | Ａｇｃ株式会社 | Curved substrate with film, method for manufacturing same, and image display device |
| CN111948744B (en) * | 2015-11-20 | 2023-05-09 | Ａｇｃ株式会社 | Film-attached curved substrate, method for producing the same, and image display device |
Also Published As
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| KR20110097636A (en) | 2011-08-31 |
| TW201140158A (en) | 2011-11-16 |
| JP5690491B2 (en) | 2015-03-25 |
| KR101772232B1 (en) | 2017-08-28 |
| CN102162863B (en) | 2015-11-25 |
| JP2011175081A (en) | 2011-09-08 |
| TWI519826B (en) | 2016-02-01 |
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