CN102746791A - Resin combination, optical film and liquid crystal display apparatus - Google Patents
Resin combination, optical film and liquid crystal display apparatus Download PDFInfo
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- CN102746791A CN102746791A CN2012101149264A CN201210114926A CN102746791A CN 102746791 A CN102746791 A CN 102746791A CN 2012101149264 A CN2012101149264 A CN 2012101149264A CN 201210114926 A CN201210114926 A CN 201210114926A CN 102746791 A CN102746791 A CN 102746791A
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Abstract
The present invention relates to a resin combination, an optical film and a liquid display apparatus both using the resin combination, wherein the resin combination contains a mixture and transparent particles, the mixture contains a transparent resin or a resin component forming the resin and a solvent, the surface tension of the mixture under a temperature of 25 Deg C is 18 mN/m-35 mN/m, and the lower limiting value of the methyl alcohol concentration of a methyl alcohol aqueous solution in which the transparent particles can suspend under the temperature of 25 DEG C is higher than 1.0 wt.% and lower than 15.0 wt.%.
Description
Technical field
The present invention relates to resin combination useful, that contain the light transmission particulate in the blooming purposes.And the invention still further relates to blooming that possesses the resin layer (antiglare layer etc.) that forms by this resin combination and the liquid crystal indicator of using it.
Background technology
In image display devices such as liquid crystal indicator,, can see bloomings such as side surface configuration antiglare film sometimes at it in order to prevent mirroring of extraneous light.This antiglare film is coated on the base material film, forms the resin layer that has based on the concave-convex surface of light transmission particulate through the resin combination (coating fluid) that for example will contain light transmission particulate (pearl) and makes (for example, TOHKEMY 2010-079099 communique).
Summary of the invention
Be coated on through the resin combination that blending dispersion is had the light transmission particulate in the blooming in the past that forms resin layer on the base material film; Because light transmission particulate dispersed bad in resin combination, therefore in the blooming that obtains, produce sometimes turbidity uneven or in resin layer generation bubble and damage exterior quality.Such turbidity is uneven, bubble produces the goods yield that makes blooming and reduces.
The objective of the invention is to, the resin combination that contains the light transmission particulate that turbidity is uneven and bubble is sneaked into that produces in the blooming that can suppress effectively to get coating base material film is provided.In addition, another object of the present invention is to, provide and use above-mentioned resin combination to form, suppressed turbidity inequality and the blooming of bubble generation and the liquid crystal indicator that possesses it.
The present invention contains following proposal.
[1] a kind of resin combination; Comprise mixture and light transmission particulate; Said mixture contains translucent resin or forms the resinous principle and the solvent of translucent resin; The surface tension of said mixture in the time of 25 ℃ is 18mN/m～35mN/m, and said light transmission particulate has its lower value of methanol concentration of methanol aqueous solution of can suspending, and this lower value is more than the 1.0 weight % in the time of 25 ℃ and is lower than 15.0 weight %.
[2] according to [1] described resin combination, wherein, said light transmission particulate is by being selected from PS, gathering any polymer formation in (methyl) propenoate and polystyrene-poly (methyl) Yodo Sol GH 28.
[3] according to claim [1] or [2] described resin combination, wherein, with respect to the said translucent resin of 100 weight parts or form the resinous principle of translucent resin, the content of said light transmission particulate is that 25 weight parts are above and be lower than 50 weight parts.
[4] according to each described resin combination in claim [1]～[3], wherein, the weight average particle diameter of said light transmission particulate is 5 μ m～10 μ m.
[5] a kind of blooming has base material film and the antiglare layer that is layered on the said base material film and is formed by each described resin combination in claim [1]～[4].
[6] a kind of liquid crystal indicator possesses back lighting device, light deflection mechanism, the 1st polaroid, liquid crystal cells, the 2nd polaroid and [5] described blooming successively.
[7] according to [6] described liquid crystal indicator; Wherein, Said smooth deflection mechanism with said the 1st polaroid facing surfaces on possess 2 and contain the prismatical prism film of a plurality of wire; A slice prism film disposes with the mode that the prismatical crest line direction of its wire is roughly parallel to the axis of homology of said the 1st polaroid, and another sheet prism film disposes with the mode that the prismatical crest line direction of its wire is roughly parallel to the axis of homology of said the 2nd polaroid.
[8], wherein, between said back lighting device and said smooth deflection mechanism, further possesses the light diffusion mechanism according to claim [6] or [7] described liquid crystal indicator.
Therefore according to the present invention, the good dispersibility of light transmission particulate in resin combination can provide the blooming that has suppressed the bubble generation in the turbidity resin layer uneven and that is formed by resin combination.The turbidity excellent in uniformity of blooming of the present invention and exterior quality are also excellent.
Description of drawings
Fig. 1 is that pattern ground expression is used to measure the figure of device system of lower value of methanol concentration of methanol aqueous solution of light transmission particulate of can suspending.
Fig. 2 be expression use device system shown in Figure 1 and the chart of relation of methanol concentration and laser-transmitting rate.
Fig. 3 is the summary sectional view of a preference of expression blooming of the present invention.
Fig. 4 is the summary sectional view of other preference of expression blooming of the present invention.
Fig. 5 is the summary sectional view of other preference of expression blooming of the present invention.
Fig. 6 is the summary sectional view of a preference of expression anti-dazzle polarizer of the present invention.
Fig. 7 is the summary sectional view of other preference of expression anti-dazzle polarizer of the present invention.
Fig. 8 is the approximate three-dimensional map that is used to explain the axial relation of transmission of prismatical crest line direction of wire that prism film has and polaroid.
Fig. 9 is the summary sectional view of other preference of expression liquid crystal indicator of the present invention.
Figure 10 is the sketch chart of liquid crystal indicator of the present invention, and Figure 10 (a) is the front view of liquid crystal indicator of the present invention, and Figure 10 (b) is the figure that the plane 4b to Figure 10 (a) observes from its vertical line direction.
Embodiment
< resin combination >
Resin combination of the present invention is the resin combination that contains the light transmission particulate that is suitable for forming the resin layer (resin coated layer) that various bloomings can possess; Particularly; Comprise mixture and light transmission particulate, said mixture contains translucent resin at least or forms its resinous principle and solvent.Resin combination of the present invention can further contain other compositions such as Photoepolymerizationinitiater initiater, flow agent, dispersion agent, antistatic agent, stain control agent.The excellent dispersion of the light transmission particulate of resin combination of the present invention; Has excellent in uniformity through the blooming turbidity that it is coated on the resin layer that forms on the base material; And the generation of bubble has obtained effective inhibition in the resin layer, thereby exterior quality is excellent.
(1) resin
As translucent resin that resin combination contained or form its resinous principle, for example can enumerate translucent resin such as thermoplastic resin, as the resinous principle that forms translucent resin, ultraviolet curing resin, electronic beam solidified resin isoreactivity energy-line solidifying type resin, thermohardening type resin, metal alkoxide etc.Wherein, from demonstrating high firmness through the coating and the curing of resin combination, forming as being located at the lip-deep blooming of liquid crystal indicator and given the resin layer aspect consideration of high scuff resistance, preferred active energy ray-curable resin.
As thermoplastic resin, can enumerate derivatived celluloses such as cellulose acetate, soluble cotton, acetyl tributyl Mierocrystalline cellulose, TKK 021, methylcellulose gum; Vinyl resins such as vinyl-acetic ester and multipolymer thereof, vinylchlorid and multipolymer thereof, vinylidene chloride and multipolymer thereof; Acetal such as PVF, polyvinyl butyral acetal is a resin; (methyl) acrylic resins such as vinyl resin and multipolymer thereof, methacrylic resin and multipolymer thereof; Polystyrene resin; Polyamide-based resin; Polyester based resin; Polycarbonate-based resin etc.
The active energy ray-curable resin can be the resin that contains multifunctional (methyl) acryliccompound.So-called multifunctional (methyl) acryliccompound is the compound that in molecule, has at least 2 (methyl) acryloxies.
Enumerate the concrete example of multifunctional (methyl) acryliccompound, for example have polyvalent alcohol and (methyl) acrylic acid carboxylate, urethane (methyl) acryliccompound, polyester (methyl) acryliccompound, epoxy (methyl) acryliccompound etc. to contain the multifunctional polymerization property compound etc. of (methyl) acryl more than 2.
As polyvalent alcohol; For example can enumerate terepthaloyl moietie, Diethylene Glycol, triethylene glycol, TEG, polyoxyethylene glycol, Ucar 35, dipropylene glycol, tripropylene glycol, four Ucar 35, W 166, Ucar 35, butyleneglycol, pentanediol, pinakon, NSC 6366,2-ethyl-1; 3-pinakon, 2; 2 '-thiodiethanol, 1, the divalent alcohol of 4-cyclohexanediol dimethanol and so on; The alcohol that the ternary of TriMethylolPropane(TMP), glycerine, tetramethylolmethane, two glycerine, Dipentaerythritol, two (trihydroxy-propane) and so on is above.
As polyvalent alcohol and (methyl) acrylic acid carboxylate; Can enumerate ethylene glycol bisthioglycolate (methyl) propenoate, Diethylene Glycol two (methyl) propenoate, two (methyl) vinylformic acid 1 particularly; 6-pinakon ester, two (methyl) vinylformic acid DOPCP, trimethylolpropane tris (methyl) propenoate, trimethylolethane trimethacrylate (methyl) propenoate, tetramethylol methane three (methyl) propenoate, two (methyl) vinylformic acid 1,6-pinakon ester, tetramethylol methane four (methyl) propenoate, five glycerine three (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, glycerine three (methyl) propenoate, Dipentaerythritol three (methyl) propenoate, Dipentaerythritol four (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, Dipentaerythritol six (methyl) propenoate.
As urethane (methyl) acryliccompound, can enumerate isocyanic ester that in 1 molecule, has a plurality of NCOs and urethane reactant with (methyl) acrylic acid derivative of hydroxyl.As the organic isocyanate that in 1 molecule, has a plurality of NCOs; Can enumerate hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethanediisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate etc. have 2 NCOs in 1 molecule organic isocyanate; That the organic isocyanate that will in 1 molecule, have 2 NCOs carries out is isocyanurate-modified, addition modification or biuret modified and the organic isocyanate that in 1 molecule, has 3 NCOs etc.As (methyl) acrylate derivative, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy propyl ester, tetramethylolmethane three (methyl) propenoate with hydroxyl.
As the preferred compound of polyester (methyl) acryliccompound be the polyester that contains hydroxyl react with (methyl) vinylformic acid and polyester (methyl) propenoate.The preferred polyester that contains hydroxyl that uses is the polyester that contains hydroxyl that the esterification through polyvalent alcohol and carboxylic acid, the compound with a plurality of carboxyls and/or its acid anhydrides gets.As polyvalent alcohol, can illustration and the same polyvalent alcohol of above-claimed cpd.In addition, except that polyvalent alcohol, also can use phenols such as dihydroxyphenyl propane.As carboxylic acid, can enumerate formic acid, acetate, butyl carboxylic acid, phenylformic acid etc.As the compound with a plurality of carboxyls and/or its acid anhydrides, can enumerate toxilic acid, phthalic acid, fumaric acid, methylene-succinic acid, hexanodioic acid, terephthalic acid, maleic anhydride, Tetra hydro Phthalic anhydride, trimellitic acid, cyclohexane cyclohexanedimethanodibasic acid anhydride etc.
Among multifunctional (methyl) acryliccompound as above; Consider ester cpds such as preferred two (methyl) vinylformic acid pinakon ester, two (methyl) vinylformic acid DOPCP, Diethylene Glycol two (methyl) propenoate, tripropylene glycol two (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, Dipentaerythritol six (methyl) propenoate from the easy property aspect that the intensity of cured article (overlay film) improves, obtains; The affixture of hexamethylene diisocyanate and (methyl) vinylformic acid 2-hydroxy methacrylate; The affixture of isophorone diisocyanate and (methyl) vinylformic acid 2-hydroxy methacrylate; The affixture of tolylene diisocyanate and (methyl) vinylformic acid 2-hydroxy methacrylate; The affixture of addition modification isophorone diisocyanate and (methyl) vinylformic acid 2-hydroxy methacrylate; And the affixture of biuret modified isophorone diisocyanate and (methyl) vinylformic acid 2-hydroxy methacrylate.The active energy ray-curable resin preferably further contains urethane (methyl) acryliccompound.Multifunctional (methyl) acryliccompound can be respectively individually or with more than 2 kinds and be used for using.
For the active energy ray-curable resin,, also can contain simple function (methyl) acryliccompound except that containing above-mentioned multifunctional (methyl) the acryliccompound.As simple function (methyl) acryliccompound, for example can enumerate (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) Bing Xisuandingzhi, (methyl) NSC 20949, (methyl) tert-butyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy propyl ester, (methyl) glycidyl acrylate, acryloyl morpholine, N-Methyl pyrrolidone, (methyl) tetrahydrofurfuryl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) IBOA, ethanoyl (methyl) propenoate, (methyl) benzyl acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 3-methoxyl group butyl ester, ethyl carbitol (methyl) propenoate, (methyl) vinylformic acid phenoxy ester, oxyethane modification (methyl) propylene phenoxy acid, propylene oxide (methyl) propenoate, nonylphenol (methyl) propenoate, oxyethane modification (methyl) propenoate, epoxy pronane modification nonylphenol (methyl) propenoate, methoxyl group Diethylene Glycol (methyl) propenoate, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester, (methyl) vinylformic acid dimethylamino ethyl ester, methoxyl group triethylene glycol (methyl) propenoate.Simple function (methyl) acryliccompound can be respectively individually or with more than 2 kinds and be used for using.
The active energy ray-curable resin can contain polyreactive oligomers.Through containing polyreactive oligomers, can adjust the hardness of resin layer.Polyreactive oligomers can be for example above-mentioned multifunctional (methyl) acryliccompound, be polyvalent alcohol and the oligopolymer of the dipolymer of (methyl) acrylic acid ester cpds, urethane (methyl) acryliccompound, polyester (methyl) acryliccompound or epoxy (methyl) acryliccompound etc., trimer etc. and so on.
In addition, as other polyreactive oligomers, can enumerate urethane (methyl) origoester acrylate that gets through POLYMETHYLENE POLYPHENYLISOCYANATE that in molecule, has at least 2 NCOs and reaction with polyvalent alcohol of at least 1 (methyl) acryloxy.As POLYMETHYLENE POLYPHENYLISOCYANATE, can enumerate the polymkeric substance of hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, xylylene diisocyanate etc.As polyvalent alcohol with at least 1 (methyl) acryloxy; Be (methyl) propenoate that contains hydroxyl that gets through polyvalent alcohol and (methyl) acrylic acid esterification; As polyvalent alcohol, for example can enumerate 1,3 butylene glycol, 1; 4-butyleneglycol, 1,6-pinakon, Diethylene Glycol, triethylene glycol, NSC 6366, polyoxyethylene glycol, W 166, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, Dipentaerythritol etc.The part alcohol hydroxyl group that this polyvalent alcohol with at least 1 (methyl) acryloxy is a polyvalent alcohol and (methyl) vinylformic acid carry out esterification, simultaneously in molecule residual alcohol hydroxyl group and alcohol.
And then, as the example of other polyreactive oligomers, can enumerate polyester (methyl) origoester acrylate that compound and/or its acid anhydrides and the reaction with polyvalent alcohol of at least 1 (methyl) acryloxy through having a plurality of carboxyls get.As the compound with a plurality of carboxyls and/or its acid anhydrides, can illustration with polyester (methyl) propenoate of above-mentioned multifunctional (methyl) acryliccompound in compound with a plurality of carboxyls and/or the identical compound of its acid anhydrides put down in writing.In addition, as polyvalent alcohol with at least 1 (methyl) acryloxy, can illustration with above-mentioned urethane (methyl) origoester acrylate in the identical polyvalent alcohol of polyvalent alcohol put down in writing with at least 1 (methyl) acryloxy.
Except above polyreactive oligomers; Further as the example of urethane (methyl) origoester acrylate, can enumerate make isocyanates and the polyester that contains hydroxyl, the hydroxyl that contains the polyethers of hydroxyl or contain (methyl) propenoate of hydroxyl react and compound.The preferred polyester that contains hydroxyl that uses is the polyester that contains hydroxyl that the esterification through polyvalent alcohol and carboxylic acid, the compound with a plurality of carboxyls and/or its acid anhydrides gets.As polyvalent alcohol, compound and/or its acid anhydrides, can distinguish carboxylic acid, compound and/or the identical compound of its acid anhydrides put down in writing in polyester (methyl) acryliccompound of illustration and multifunctional (methyl) acryliccompound with a plurality of carboxyls with a plurality of carboxyls.The preferred polyethers that contains hydroxyl that uses is through a kind or alkylene oxide more than 2 kinds and/or 6-caprolactone and polyvalent alcohol are carried out the polyethers that contains hydroxyl that addition gets.Polyvalent alcohol can be identical with the polyvalent alcohol that can be used in the above-mentioned polyester that contains hydroxyl.As (methyl) propenoate that contains hydroxyl of preferred use, can illustration with urethane (methyl) origoester acrylate of polyreactive oligomers in the identical compound of (methyl) propenoate that contains hydroxyl put down in writing.As isocyanates, preferably in molecule, has the compound of 1 above NCO, binary isocyanate compounds such as preferred especially tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.
Above-mentioned polyreactive oligomers compound can be respectively individually or with more than 2 kinds and be used for using.
As the thermohardening type resin; Can enumerate the thermohardening type urethane resin that forms by acryl polyvalent alcohol and isocyanate prepolymer; In addition, can enumerate resol, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin.
As metal alkoxide, can use the silicon alkoxide based material is parent compound etc. as the silicon oxide of raw material.Particularly, for tetramethoxy-silicane, tetraethoxysilane etc., also can form inorganic system or organic and inorganic compound syzygy parent compound (translucent resin) through hydrolysis, dehydrating condensation.
(2) Photoepolymerizationinitiater initiater
Use ultraviolet curing resin when forming the resinous principle of translucent resin, resin combination preferably contains Photoepolymerizationinitiater initiater (radical polymerization initiator).
As Photoepolymerizationinitiater initiater, for example can use methyl phenyl ketone is that Photoepolymerizationinitiater initiater, bitter almond oil camphor are that Photoepolymerizationinitiater initiater, benzophenone series Photoepolymerizationinitiater initiater, thioxanthone are that Photoepolymerizationinitiater initiater, triazine are that Photoepolymerizationinitiater initiater,
diazole are Photoepolymerizationinitiater initiater etc.In addition, as Photoepolymerizationinitiater initiater, for example also can use 2; 4,6-Three methyl Benzene formyl diphenyl phosphine oxide, 2,2 '-two (Chloro-O-Phenyl)-4; 4 ', 5,5 '-tetraphenyl-1; 2 '-bisglyoxaline, 10-butyl-2-chloro-acridine ketone, 2-ethyl-anthraquinone, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.The consumption of Photoepolymerizationinitiater initiater is generally 0.5～20 weight part for the resinous principle that 100 parts by weight resin compsns are contained, be preferably 1～5 weight part.
(3) solvent
The solvent that resin combination contained is preferably organic solvent.As organic solvent, can use aliphatic hydrocarbons such as hexane, hexanaphthene, octane; Aromatic hydrocarbons such as toluene, YLENE; Alcohols such as ethanol, 1-propyl alcohol, Virahol, 1-butanols, hexalin; Ketones such as methyl ethyl ketone, MIBK, pimelinketone; Ester classes such as ETHYLE ACETATE, butylacetate, isobutyl acetate; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether; Esterification such as ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate glycol ethers; Cellosolve classes such as 2-methyl cellosolve, cellosolvo, butoxy ethanol; Trivalin SF classes such as 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, 2-(2-butoxy oxyethyl group) ethanol etc.
Solvent can only use a kind individually, also can mix several kinds as required and use.After the resin combination coating, must make above-mentioned organic solvent evaporation.Therefore, the boiling point of solvent is preferably 60 ℃～160 ℃ scope.In addition, the saturated vapor pressure 20 ℃ the time is preferably the scope of 0.1kPa～20kPa.
At this; Contain the translucent resin that constitutes resin combination or form its resinous principle and the said mixture of solvent; Promptly; (when containing other compositions such as Photoepolymerizationinitiater initiater, flow agent, dispersion agent, antistatic agent, stain control agent at resin combination, said mixture also contains this other composition with the compsn of resin combination same composition except not containing the light transmission particulate.) surface tension in the time of 25 ℃ is 18mN/m～35mN/m.If surface tension is lower than 18mN/m, then resin combination becomes too high to the wettability of base material film, thereby the smoothness of painting layer surface excessively raises, and the anti-pollution function of generally giving to resin layer reduces.On the other hand, if surface tension surpasses 35mN/m, then resin combination became low to the wettability of base material film, and the smoothness of painting layer surface worsens.The surface tension of said mixture is preferably 20mN/m～30mN/m.
The surface tension of said mixture can be adjusted through translucent resin or the kind, solvent types or their mixture ratio that form its resinous principle.Also can come the adjustment sheet surface tension through adding additives such as flow agent.Can be that compound about 25～45mN/m is as translucent resin or form its resinous principle for example through selecting surface tension among the above-claimed cpd; Select surface tension among the above-mentioned solvent be solvent about 20～40mN/m as solvent, the ratio of adjusting them mixes and obtains to have required capillary mixture.
The capillary numerical value of said mixture is to adopt sessile drop method (pendant drop method) and the numerical value of mensuration.
(4) light transmission particulate
For the light transmission particulate that resin combination contained; The lower value (below, be also referred to as suspension methanol concentration lower value) of methanol concentration of methanol aqueous solution of (dispersion) of can suspending is more than the 1.0 weight % in the time of 25 ℃ and is lower than in the scope of 15.0 weight %, preferred 3.0 weight %～13.0 weight %.As Wu Jing he, coating chemistry, Vol.32; No.6; 1997,218-223 puts down in writing, and the surface tension of the methanol solution during suspension methanol concentration lower value (methanol concentration that the light transmission particulate begins to suspend) and the surface tension of light transmission particulate are much at one; Suspension methanol concentration lower value is lower than 1.0 weight % (in brief; Also suspend even the light transmission particulate is lower than in the methanol aqueous solution of 1.0 weight % at methanol concentration) time, the capillary difference of the surface tension of light transmission particulate and said mixture becomes greatly, therefore; It is uneven or in resin layer, produce bubble and damage exterior quality that light transmission particulate dispersed bad in said mixture, the blooming that obtains produce turbidity.
On the other hand; Suspension methanol concentration lower value is that 15.0 weight % are above (in brief; Through making methanol concentration is more than the 15.0 weight %; The light transmission particulate begins to be suspended in the methanol aqueous solution) time light transmission particulate surface tension low excessively, light transmission particulate dispersed bad in said mixture likewise, it is uneven or in resin layer, produce bubble and damage exterior quality that the blooming that obtains produces turbidity.
Through to use suspension methanol concentration lower value be more than the 1.0 weight % 25 ℃ the time and be lower than the light transmission particulate of 15.0 weight %; The capillary difference of the surface tension of light transmission particulate and said mixture becomes enough little; Therefore; The light transmission particulate is dispersed in the said mixture well, and the excellent in uniformity and the bubble in the resin layer that can obtain turbidity thus produce repressed effectively blooming.
Suspension methanol concentration lower value (methanol concentration that the light transmission particulate begins to suspend) adopts device system as shown in Figure 1 to measure.Device system shown in Figure 1 possesses: the container 10 (for example the middle portion external diameter is 55mm, highly is the 100mL beaker of 73mm) that is used to take in pure water 80; The stirrer of in container 10, taking in 50; Be used to make the whisking appliance (magnetic stirring apparatus) 40 of stirrer 50 rotations; Be used for from the light source 20 of the side-irradiation He-Ne laser of container 10; On the extended line of institute's irradiating laser and the detector 30 of the side relative configuration with the side of the container that shines laser 10; And the pump 60 that is used in container 10, dripping methyl alcohol 90.
Suspension methanol concentration lower value adopts device system as shown in Figure 1 to measure as follows.At first, the pure water 80 (25 ℃) that in container 10, adds 100mL.Then, make the light transmission particulate 70 of 100mg float over the pure water surface, use whisking appliance 40 and 50 pairs of pure water 80 of stirrer to stir (speed of rotation of stirrer 50 is 200rpm).Afterwards, continue and to stir.Then, with dripping methyl alcohol 90 (25 ℃) in the pure water 80 of speed under stirring of pump 60 with 3mL/min.With 90 whiles of dropping methyl alcohol or before it; Begin the irradiation of He-Ne laser from the side of container 10 with light source 20; Simultaneously across container 10, through being positioned at the light intensity that detects the laser that transmission comes in light source 20 relative position Detection devices 30, the transsmissivity of laser is monitored.
If proceed the dropping of above-mentioned methyl alcohol, then as shown in Figure 2, when the methanol concentration of the methanol aqueous solution in container 10 reached a certain particular value, light transmission particulate 70 began to suspend, and result viewing reduces to the transsmissivity of laser sharp.The methanol concentration that the transsmissivity that the so-called methanol concentration lower value that suspends in the present invention is a laser begins to reduce sharp; More specifically; With reference to Fig. 2, be expression adopt device system shown in Figure 1 and the diagram curve of methanol concentration and the relation of the transsmissivity of laser in, transsmissivity begins the methanol concentration A at intersection point place of the tangent line of the tangent line of rapid minimizing curved portion before and the curved portion that transsmissivity reduces sharp.
Light transmission particulate as suspension methanol concentration lower value with afore mentioned rules; Also can use commercially available article; When using the commercially available article of the suspension methanol concentration lower value do not have regulation, also can adjust suspension methanol concentration lower value through utilizing pure water etc. to wash.Usually, light transmission particulate (by the light transmission particulate of polymer formation) is made through letex polymerization or suspension polymerization, is the tensio-active agent of representative with the emulsifying agent at remained on surface.With washing light transmission particulates such as pure water the residual quantity of tensio-active agent is reduced, suspension methanol concentration lower value is uprised.In this case, through the adjustment wash conditions, can adjust suspension methanol concentration lower value.On the contrary, contain tensio-active agent, suspension methanol concentration lower value is reduced through making in the light transmission particulate.In this case, the amount of the tensio-active agent that contains through adjustment can be adjusted suspension methanol concentration lower value.
The light transmission particulate can be organic fine particles or the inorganic particles with light transmission.Inorganic particles that for example can enumerate by vinylbenzene, gather organic fine particles that (methyl) propenoate (comprising Rohm tech inc, polyacrylic ester and methacrylate ester monomer and the monomeric multipolymer of acrylic ester), polystyrene-poly (methyl) Yodo Sol GH 28, melamine resin, Vilaterm, organic silicone resin etc. form, forms by lime carbonate, silicon-dioxide, aluminum oxide, barium carbonate, permanent white, titanium oxide, glass etc. etc.In addition, also can use ball, the glass hollow pearl of organic polymer.Wherein, the particulate that demonstrates the suspension methanol concentration lower value of regulation from easy acquisition considers, preferably by PS, gather any polymer formation in (methyl) propenoate or polystyrene-poly (methyl) Yodo Sol GH 28.
In addition,, can only use a kind individually, also can use the particulate more than 2 kinds as the light transmission particulate.For the shape of light transmission particulate, spherical, flats, tabular, needle-like, indefinite shape etc. all can, but preferred spherical or approximate spherical.
The weight average particle diameter of light transmission particulate is preferably 5 μ m～10 μ m, and in addition, the content of light transmission particulate is with respect to the translucent resin of 100 weight parts or form for its resinous principle in the resin combination, and it is above and be lower than 50 weight parts to be preferably 25 weight parts.Weight average particle diameter through making the light transmission particulate and content are in above-mentioned scope; Can be suppressed at the reduction of display qualities such as extensive field angle flicker when forming antiglare layer on the base material film in that resin combination is coated on, and can obtain high positive contrast gradient and transmission image boldness.The weight average particle diameter of light transmission particulate is 6 μ m～9 μ m more preferably, and the content of light transmission particulate is with respect to the translucent resin of 100 weight parts or form for its resinous principle, more preferably 25 weight parts～40 weight parts.
In addition, the weight average particle diameter of light transmission particulate adopts and measures based on the Ku Erte calculating instrument (BECKMAN COULTER manufactured) of Coulter principle (pore electrical resistance method).When using the different light transmission particulate more than 2 kinds of weight average particle diameter as the light transmission particulate, above-mentioned weight average particle diameter is the weight average particle diameter that has the light transmission particulate of maximum weight average particle diameter among the light transmission particulate.
The specific refractory power of the light transmission particulate preferably specific refractory power than the translucent resin that constitutes resin layer is big, and its difference is preferably 0.04～0.1 scope.Refringence through making light transmission particulate and translucent resin is in above-mentioned scope; When resin layer is antiglare layer; To being incident on the light of antiglare layer; Not only can present the surface scattering that causes by the concavo-convex of antiglare layer surface, and can present the scattering-in that causes by this refringence, thereby suppress the generation of flicker.And, if above-mentioned refringence is below 0.1, then there is the trend that suppresses the blooming albefaction, thus preferred.
<blooming >
Blooming of the present invention has base material film, and (typical case is an antiglare layer, but also can be the layer with optical function in addition with being layered in the resin layer that forms on the base material film, by above-mentioned resin combination.)。Fig. 3 is the summary sectional view of a preference of expression blooming of the present invention.The described blooming 100 of Fig. 3 possesses base material film 101 and is layered in the antiglare layer 102 on the base material film 101.Antiglare layer 102 is that light transmission particulate 104 is dispersed in the translucent resin 103 and forms with the layer of translucent resin 103 as base material.Also dry being cured afterwards, as required forms antiglare layer 102 on the base material film 101 through above-mentioned resin combination is coated on.In the blooming 100 of Fig. 3,, form fine concavo-convex through the light transmission particulate of dispersing and mixing on the surface of antiglare layer 102.
Blooming of the present invention is to adopt the resin combination of the excellent dispersion of light transmission particulate to form resin layer (antiglare layer 102), therefore, the excellent in uniformity of turbidity, thereby and the bubble in the resin layer produce that to be suppressed exterior quality excellent.
In addition, blooming of the present invention can have other layer (comprising adhesive layer) between base material film and resin layer (antiglare layer 102).
(1) base material film
(2) antiglare layer
The bed thickness T of antiglare layer 102 is preferably 10 μ m～20 μ m, more preferably 12 μ m～18 μ m.Thus, can wait the reduction of display quality in wide viewing angle inhibition flicker, and can obtain high positive contrast gradient and transmission image boldness.In addition, as the bed thickness T of antiglare layer 102, be meant antiglare layer 102 from the face of base material film 101 opposite sides maximum ga(u)ge (with reference to Fig. 3) to the face of opposition side.
(3) method of manufacture of blooming
The described blooming 100 of Fig. 3 of the present invention can adopt the method that comprises following operation to make well.
(A) on base material film 101, be coated with the operation that the above-mentioned resin combination that contains light transmission particulate 104 forms coating layer, and
(B) through making coating layer be fixed on the operation that forms antiglare layer 102 on the base material film 101.
The coating of resin combination on base material film 101 for example can be adopted intaglio plate coating method, nick version coating method, rod to be coated with method, spread coating, airblade coating method, kiss-coating method, mould Tu Fa and wait and carry out.
As purpose, can implement various surface treatments with the tackiness of the coating of modified resin compsn or improvement and antiglare layer 102 on the surface of base material film 101 (antiglare layer 102 side surfaces).As surface treatment, can enumerate Corona discharge Treatment, photoglow processing, acid surfaces processing, alkali surface treatment, uviolizing processing etc.In addition, can with for example on base material film 101, form other layer such as prime coat, the mode of coating resin compsn is carried out on other layer.
In addition; When after blooming is used as, stating the protective membrane of light polarizing film; For the base material film 101 and the tackiness of light polarizing film are improved, preferably in advance hydrophilization is carried out through various surface treatments (s.t. or alkaline purification etc.) in the surface (with the surface of antiglare layer 102 opposition sides) of base material film 101.
Then, in above-mentioned operation (B), coating layer is fixed on forms antiglare layer 102 on the base material film 101, thereby obtain blooming.Particularly; When resin combination contains active energy ray-curable resin, thermohardening type resin or metal alkoxide; Carried out dry (remove and desolvate) afterwards, coating layer has been solidified through irradiation (when using the active energy ray-curable resin) or the heating (when using thermohardening type resin or metal alkoxide) of coating layer being carried out active energy ray.As active energy ray; Can from ultraviolet ray, electron beam, near-ultraviolet ray, visible rays, near infrared ray, infrared rays, X ray etc., suitably select according to the kind of the resinous principle that resin combination contained; But preferred ultraviolet ray, electron beam among these; Consider preferred especially ultraviolet ray by easy and simple to handle and acquisition high-energy aspect.
As ultraviolet light source, can use for example low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp etc.And, also can use ArF PRK, KrF PRK, Excimer lamp or synchrotron radiating light etc.Among these, preferably use ultrahigh pressure mercury lamp, high voltage mercury lamp, low pressure mercury lamp, xenon arc lamp, metal halide lamp.
In addition; As electron beam, can enumerate having 50～1000keV, preferably having an electron beam of 100～300keV energy of from various electron-beam accelerators such as Cockcroft Walton type, Van de Graff type, resonance transformation type, insulating core transformation type, linear pattern, Dynamitron type, high frequency type, emitting.
On the other hand, when containing translucent resin such as thermoplastic resin at resin combination, can be through carrying out drying (remove and desolvate), perhaps carried out after the drying, made the softening or fusion of coating layer, coating layer is cooled off made blooming afterwards.
So that enumerate as example when for example using ultraviolet curing resin; Through comprising that operation that the base material film that is wound into the roller shape 101 is seen off continuously, the resin combination that will contain light transmission particulate 104 and ultraviolet curing resin are coated with and make its exsiccant operation, coating layer are solidified form the operation of antiglare layer 102 and with the method for the operation of the blooming spooling of gained, can make blooming continuously.
In blooming of the present invention, the concave-convex surface that antiglare layer 102 has can be through carrying out transfer printing, or processing through sandblast and to form to the surface of mold (for example grain roller).The summary sectional view of the blooming that adopts said method and process is shown in Fig. 4.So that enumerate as example when for example using ultraviolet curing resin; Use has the mold of the transfer printing structure of the concaveconvex shape that needs on the surface; Be close on this surface under the state on surface of coating layer mold; To the coating layer irradiation ultraviolet radiation, can process blooming as shown in Figure 4 from base material film 101 sides thus.
(4) other embodiment of blooming
Blooming of the present invention can have the translucent resin layer that is formed by translucent resin of (with the face of base material film 101 opposition sides) on antiglare layer of being layered in 102.As translucent resin layer 105 shown in Figure 5, this translucent resin layer can have the concave-convex surface through the surface of mold (for example grain roller) being carried out transfer printing, perhaps forming through sandblast processing.In the blooming that possesses said translucent resin layer, the surface of antiglare layer 102 can be an even surface.For this even surface, can be employed in and be close to and under the lip-deep state of coating layer coating layer solidified method waited to form having this minute surface of the mold of minute surface for example.
In addition, blooming of the present invention can further possess the anti-reflection layer of (with the face of base material film 101 opposition sides) on antiglare layer of being layered in 102.Anti-reflection layer can be formed directly on the antiglare layer 102, also can prepare in addition to adopt tackiness agent or adhesive layer to be stacked on the antiglare layer 102 at the antireflection film that has formed anti-reflection layer on the transparent film, with it.Anti-reflection layer is the layer that is provided with for reflectivity is ad infinitum reduced, and through forming anti-reflection layer, can more effectively prevent mirroring display frame.As anti-reflection layer, can enumerate the low-index layer that constitutes by the material lower than the specific refractory power of antiglare layer 102; By stepped construction of the material higher high refractive index layer that constitutes and the low-index layer that constitutes by the material lower etc. than the specific refractory power of this high refractive index layer than the specific refractory power of antiglare layer 102.Adopt tackiness agent or adhesive layer to be stacked in 102 last times of antiglare layer antireflection film, can use commercially available antireflection film.
< anti-dazzle polarizer >
The blooming of the invention described above can form anti-dazzle polarizer through making up with polaroid.Anti-dazzle polarizer is the multifunctional membrane with polarisation function and anti-dazzle function.Anti-dazzle polarizer of the present invention possesses the polaroid that has light polarizing film at least and is situated between with the base material film side mode relative with this polaroid and is layered in the blooming of the invention described above on this polaroid by binder layer or adhesive layer.Polaroid can be known in the past structure, for example generally is the polaroid that has protective membrane on the one side or the two sides of light polarizing film.In addition, polaroid can be light polarizing film himself.
Fig. 6 is the summary sectional view of a preference of expression anti-dazzle polarizer of the present invention.Anti-dazzle polarizer 400 shown in Figure 6 possesses light polarizing film 401, stick on light polarizing film 401 one side protective membrane 402 and stick on the blooming 100 of another side.Blooming 100 is pasted with the light polarizing film 401 relative modes of its base material film 101 sides and polaroid.Blooming 100 and protective membrane 402 are situated between and are sticked on the light polarizing film 401 by the not shown adhesive layer that goes out.Like this, light polarizing film and blooming be situated between the structure of pasting by adhesive layer, to be about to structure that blooming uses as the protective membrane of light polarizing film be favourable to the filmization of anti-dazzle polarizer.
As light polarizing film 401, for example can enumerate that dichroic dye or iodine are adsorbed on by polyvinyl alcohol is that resin, Yodo Sol VC 400 are that resin, Ethylene/vinyl acetate (EVA) are on the film that forms such as resin, polyamide-based resin, polyester based resin and make its orientation and the film that forms; By the carrying out of the dichroism dehydration resultant (polyvinylene) that contains polyvinyl alcohol in the polyvinyl alcohol of on molecule, having carried out orientation the film that polyvinyl alcohol/the polyvinylene base co-polymer forms etc. of molecular chain of orientation.Especially preferably will make dichroic dye or iodine be adsorbed on the polyvinyl alcohol resin film and make its orientation and the film that forms as light polarizing film 401.Do not limit for the thickness of light polarizing film 401 is special, but in general consider from the viewpoint of the thin-walled property of polaroid etc., be preferably below the 100 μ m, the scope of 10～50 μ m more preferably further is preferably the scope of 25～35 μ m.
Stick on the film that the protective membrane 402 on the light polarizing film 401 is preferably formed by the polymkeric substance of excellences such as low-birefringence property, the transparency, physical strength, thermostability and covering property of moisture.As this film, for example can enumerate acetate fiber prime system resins such as (triacetyl celluloses) with TAC; (methyl) acrylic resin; The fluorine resin of tetrafluoroethylene/hexafluoropropylene based copolymer and so on; Polycarbonate-based resin; Polyester based resins such as polyethylene terephthalate; Polyimide is a resin; Polysulfones is a resin; Polyethersulfone is a resin; Polystyrene resin; Polyvinyl alcohol is a resin; The polyvinyl chloride resin; Resin formings such as polyolefin-based resins or polyamide-based resin are processed into the membranaceous film that forms.Among these, consider that preferred the use with alkali etc. carried out tri acetyl cellulose membrane, norbornylene based thermoplastic resin molding that saponification is handled to the surface from aspects such as polarized light property, weather resistance.Because the humidity resistance of norbornylene based thermoplastic resin molding is high, thereby the weather resistance of polaroid is raise significantly, and because water absorbability is few, thereby dimensional stability is high, thus preferred especially.
Forming process to film can adopt casting method, rolling process, extrusion molding known method in the past.To the not restriction of the thickness of protective membrane 402, but consider, be preferably below the 500 μ m that the scope of 5～300 μ m more preferably further is preferably the scope of 5～150 μ m from the viewpoints such as filmization of polaroid.
For the anti-dazzle polarizer of above this spline structure of picture, the typical case when being applied to liquid crystal indicator, is that the mode of light emitting side (can see side) is situated between and is sticked on the glass substrate of liquid crystal cells by adhesive layer etc. with blooming 100.
< liquid crystal indicator >
Below, liquid crystal indicator of the present invention is described.Liquid crystal indicator of the present invention possesses the blooming or the anti-dazzle polarizer of the invention described above.One preferred embodiment in, liquid crystal indicator of the present invention possesses the blooming of back lighting device, light deflection mechanism, the 1st polaroid (backlight side polaroid), liquid crystal cells, the 2nd polaroid (can see the side polaroid) and the invention described above successively.Fig. 7 is the summary sectional view of the preference of expression liquid crystal indicator of the present invention.Liquid crystal indicator 500 shown in Figure 7 is liquid crystal indicators of the TN mode of normal white mode, disposes back lighting device 502, light diffusing sheet 503,2 prism film 504a as the light deflection mechanism, 504b, the 1st polaroid 505 successively, liquid crystal layer 512 is located at liquid crystal cells 501 that forms between a pair of transparency carrier 511a, the 511b and the glare-proof polarizing sheet that is formed by the 2nd polaroid 506 and blooming 507 of the present invention.The glare-proof polarizing sheet disposes with its light polarizing film side and liquid crystal cells 501 relative modes.
The vertical line of the light emergence face of light diffusing sheet 503 and Z axle almost parallel shown in Figure 7.In addition, when light diffusing sheet 503 not being set, make the vertical line and the Z axle almost parallel of the light emergence face (peristome) of back lighting device 502.In addition, the vertical line of the light entrance face of prism film 504a, 504b also with Z axle almost parallel.
As shown in Figure 8, the 1st polaroid 505 and the 2nd polaroid 506 are that the mode of the relation of quadrature Niccol disposes with their axis of homology (being respectively Y direction, directions X).In addition, the light entrance face side (back lighting device 502 sides) of 2 prism film 504a, 504b is respectively a tabular surface, forms a plurality of wire prism 541a, 541b abreast in light emergence face (with the 1st polaroid 505 facing surfaces) side.Then; Prism film 504a disposes with the axial mode of transmission that in fact direction of the crest line 542a of its wire prism 541a is parallel to the 1st polaroid 505, and prism film 504b disposes with the axial mode of transmission that in fact direction of the crest line 542b of its wire prism 541b is parallel to the 2nd polaroid 506 that constitutes anti-dazzle polarizer.But; The axial mode of transmission that also can in fact be parallel to the 1st polaroid 505 with the direction of the crest line 542b of the wire prism 541b of prism film 504b disposes, and the axial mode of transmission that in fact is parallel to the 2nd polaroid 506 that constitutes anti-dazzle polarizer with the direction of the crest line 542a of the wire prism 541a of prism film 504a disposes.In addition, when making liquid crystal indicator, can be provided with the parallel mode of axis of homology direction of the 2nd polaroid 506 with the axis of homology direction of the 1st polaroid 505 for normal black pattern.
With reference to Fig. 7, in the liquid crystal indicator 500 of this structure, after spreading through light diffusing sheet 503, the light that comes out from back lighting device 502 radiation incides prism film 504a.With the orthogonal vertical cross-section of axis of homology direction (ZX face) of the 1st polaroid 505 in, the light of the lower surface oblique incidence of prism film 504a is changed route becomes frontal and penetrate.Then, in prism film 504b, with the orthogonal vertical cross-section of axis of homology direction (ZY face) of the 2nd polaroid 506 in, the light of the lower surface oblique incidence of prism film 504b is changed route same as described abovely becomes frontal and penetrate.Therefore, the light that has passed through 2 prism film 504a, 504b in arbitrary vertical cross-section all optically focused in frontal (Z direction), thereby the brightness of frontal improves.
Then; Shown in Figure 10 (a) and Figure 10 (b); In the parallel and parallel plane 4b of the direction that becomes 45 degree roughly with axis of homology 6a with frontal (Z direction) with respect to the axis of homology 5a of the 1st polaroid 505 and the 2nd polaroid 506, with respect to frontal (Z direction) tilt very big direction, the angle beta that for example forms with frontal (Z direction) be the brightness reduction on+35 °～+ 60 ° ,-35 °～-60 ° the direction of scope.Thus, in the liquid crystal indicator 500 of gained, apart from the axis of homology of the polaroid light leak on 45 ° of directions roughly! ?floating I) reduce.So-called " light leak " meaning is some phenomenon of turning white that when black the demonstration, becomes.
Once more with reference to Fig. 7, the light that directive property has been given in the frontal aspect becomes rectilinearly polarized light through the 1st polaroid 505 from circularly polarized light and is injected into the liquid crystal cells 501.The light that is injected into liquid crystal cells 501 is through by the orientation individual element ground control polarization plane of the liquid crystal layer 512 of electric field controls and from liquid crystal cells 501 ejaculations.Then, the light that penetrates from liquid crystal cells 501 injects to the display surface side through the 2nd polaroid 506 with blooming 507.
So, in liquid crystal indicator 500,, be injected into the directive property height of the light frontal direction of liquid crystal cells 501 thus through possessing 2 prism film 504a, 504b.Thus, the brightness of frontal improves, and " light leak " on 45 ° of directions of the axis of homology of polaroid reduces.In addition,, therefore, can not cause the reduction of positive contrast gradient, be difficult for causing that in extensive field angle flicker waits the bad of display quality, and then can obtain high transmission image boldness owing to use blooming 507 of the present invention.
Below, the member of formation that constitutes liquid crystal indicator of the present invention is at length described.
(liquid crystal cells)
(back lighting device)
(light diffusion mechanism)
Liquid crystal indicator of the present invention can possess the light diffusing sheet 503 of the conduct light diffusion mechanism that between back lighting device 502 and light deflection mechanism, disposes.Light diffusing sheet 503 is film or sheets that the dispersing and mixing diffusant forms in base material.As its base material, can use polycarbonate-based resin, methacrylic resin etc. to gather (methyl) propenoate, TEB 3K and cinnamic multipolymer; Vinyl cyanide and cinnamic multipolymer, methylacrylic acid and cinnamic multipolymer, polystyrene resin; The polyvinyl chloride resin, polyolefin-based resins such as Vestolen PP 7052, polymethylpentene, cyclic polyolefine hydrocarbon system resin; Polyester based resin such as polyethylene terephthalate, PEN; Polyamide-based resin, the polyene propyl ester is a resin, polyimide is a resin etc.In addition, the light diffusion mechanism can be and use the mechanism of light diffusing sheet and optical diffusion film.
In addition, as the diffusant of blending dispersion, use by the particle that forms with the substrate material kinds of materials in base material.Enumerate the example of diffusant, for by PS, gather organic fine particles that (methyl) propenoate, polystyrene-poly (methyl) Yodo Sol GH 28, melamine resin, Vilaterm, organic silicone resin etc. form and the inorganic particles that forms by lime carbonate, silicon-dioxide, aluminum oxide, barium carbonate, permanent white, titanium oxide, glass etc. etc.The kind of the diffusant that uses can be a kind or more than 2 kinds.The ball, glass hollow pearl that in addition, also can use organic polymer are as diffusant.The weight average particle diameter of diffusant is preferably the scope of 0.5～30 μ m.In addition, the shape of diffusant can be spherical, flats, tabular, needle-like etc., but preferred spherical or approximate spherical.
Prism film (light deflection mechanism)
The light of prism film 504a, 504b is injected face side (back lighting device 502 sides) for tabular surface, has formed polygon that a plurality of cross sections are taper, has been preferably leg-of- mutton wire prism 541a, 541b at the face (with the 1st polaroid 505 facing surfaces) of light emitting side.Material as prism film 504a, 504b; For example can enumerate polycarbonate-based resin, ABS is that resin, methacrylic resin etc. gather (methyl) propenoate; Copolymer of methyl methacrylatestyrene, polystyrene resin, acrylonitritrile-styrene resin; Polyolefin-based resins such as Vilaterm, Vestolen PP 7052, perhaps ultraviolet curing resin, electronic beam solidified resin isoreactivity energy-line solidifying type resin etc.Prism film can adopt known method such as special-shaped extrusion molding, extrusion forming method, injection moulding, roller transfer method, laser ablation method, mechanical cutting method, mechanical grinding method, photopolymer Process to make.These methods can be distinguished independent use, perhaps the method more than 2 kinds are made up.The thickness of prism film 504a, 504b is generally 0.1～15mm, is preferably 0.5～10mm.
With cross-sectional shape in wire prism 541a, the crest line 542a of 541b, the orthogonal vertical cross-section of 542b be trilateral for example.In this case, the vertex angle theta (with reference to Fig. 8) on the summit of formation crest line is preferably 90～110 ° scope among this vertex of a triangle.In addition, each limit of this trilateral is equilateral, scalene all can, but want optically focused when frontal (normal direction of the display surface of liquid crystal indicator), be preferably the isosceles triangle that the both sides of light emitting side equate.The cross-sectional shape of wire prism 541a, 541b also can combine to set from the characteristic of the ejaculation light of area source, also can be the shape beyond the trilateral with curve etc.
Above-mentioned prism film 504a, 504b preferably have following structure: a plurality of wire prism 541a, the 541b that for example have the trilobal(cross)section dispose with the mode that the base relative with leg-of-mutton vertex angle theta adjoins each other successively, and a plurality of wire prism 541a, the crest line 542a of 541b, 542b arrange with the mode that almost is parallel to each other.In this case, as long as light gathering weakens indistinctively, then its each summit of the trilateral of wire prism 541a, 541b cross-sectional shape just can be curve shape.Distance between each crest line is generally the scope of 10～500 μ m, is preferably the scope of 30～200 μ m.Observe from the light emergence face side, the prismatical crest line 542a of wire, 542b can be linearities, also can be the ripple curve-likes.Observe from the light emergence face side, the direction of the crest line when crest line is the ripple curve-like is meant the direction of the straight line that the employing method of least squares is tried to achieve.
In addition, light diffusing sheet 503 can carry out moulding integratedly with prism film 504a, 504b, engages after also can making independently respectively.In addition, can between light diffusing sheet 503 and prism film 504a, 504b, gas cloud be set.
(polaroid)
The 2nd polaroid 506 that constitutes anti-dazzle polarizer can use above-mentioned polaroid.In addition, as the 1st polaroid 505, can use known in the past polaroid.
(phase retardation film)
Liquid crystal indicator of the present invention can possess polarizer 508 as illustrated in fig. 9.In Fig. 9, polarizer 508 is configured between the 1st polaroid 505 and the liquid crystal cells 501.Polarizer 508 does not produce any optical effect almost nil with the direction phase differential of the Surface Vertical of liquid crystal cells 501 from the right on, from oblique observation the time, present phase differential, thus the phase differential that compensation produces in liquid crystal cells 501.Thus, obtain wider visual angle, obtain more excellent display quality and Color reproduction property.Polarizer 508 can be configured in any one or both between the 1st polaroid 505 and the liquid crystal cells 501 and between the 2nd polaroid 506 and the liquid crystal cells 501.
As polarizer 508; For example can enumerate polycarbonate-based resin, annular ethylene series resin moulding film forming, further this film carried out the biaxial stretch-formed plate that forms, liquid crystal liquid crystal property monomer is coated on the film and through photopolymerization reaction its molecular arrangement is carried out plate that immobilization forms etc.Optical compensation is carried out in the arrangement of 508 pairs of liquid crystal of polarizer, therefore, uses the polarizer of the refractive index characteristic opposite with liquid crystal arrangement.Particularly; Can in the liquid crystal cells of TN pattern, use for example " WV FILM " (manufacturing of FUJI FILM Co., Ltd.) well; In the liquid crystal display of STN pattern, use for example " LC FILM " (Shin Nihon Oil Co., Ltd's manufacturing) well; In the liquid crystal display of IPS pattern, use for example biaxiality phase retardation film well; In the liquid crystal display of VA pattern, use polarizer, the biaxiality phase retardation film that has for example made up A plate and C plate well, in the liquid crystal display of π unit mode, use for example " OCB uses WV FILM " (manufacturing of FUJI FILM Co., Ltd.) etc. well.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not limited to these embodiment.The measuring method of various rerum naturas is following.
(a) do not contain the surface tension of ultraviolet-curing resin composition in the time of 25 ℃ of light transmission particulate
Make " Contact Angle System OCA30L " with Eko Instruments Trading, (pendant drop method) measures through sessile drop method.
(b) the suspension methanol concentration lower value of light transmission particulate in the time of 25 ℃
With the powder wettability test machine " WET-101P " that the RHESCA of Co., Ltd. with apparatus structure shown in Figure 1 makes, try to achieve suspension methanol concentration lower value according to above-mentioned steps.
(c) standard deviation of the weight average particle diameter of light transmission particulate, size-grade distribution and coefficient of variation
Employing is measured based on the Ku Erte calculating instrument (BECKMAN COULTER manufactured) of Coulter principle (pore electrical resistance method).
(d) bed thickness of antiglare layer
Use contact film thickness gauge (NIKON manufactured " DIGIMICRO MH-15 " (main body) and " ZC-101 " (calculating instrument)) to measure maximum bed thickness to the blooming of gained, deduct the thickness 80 μ m of base material film, try to achieve the bed thickness of antiglare layer thus by this value.
(e) turbidity of blooming
With JIS K 7105 is benchmark, uses turbidity computingmachine (SUGA trier manufactured " HGM-2DP ") that the turbidity of any 5 points of blooming is measured, with the turbidity of its MV as blooming.In addition, in order to prevent to survey periodic film warpage, improve and measure circulation ratio,, use base material film side to stick on the goods that form on the glass substrate through transparent adhesives on the optics with blooming as test sample.
< embodiment 1 >
(1) antiglare layer forms the preparation with resin combination
With 60 weight part pentaerythritol triacrylates and 40 weight part multifunctional urethane propenoate (1; The resultant of reaction of hexamethylene-diisocyanate and pentaerythritol triacrylate) mix with propylene glycol monomethyl ether, having obtained solid component concentration is the ultraviolet-curing resin composition of 60 weight %.In addition, from said composition, remove propylene glycol monomethyl ether and carry out ultraviolet curing after the specific refractory power of cured article be 1.53.
Then, the crosslinked polystyrene that in the solids component of the above-mentioned ultraviolet-curing resin composition of 100 weight parts, adds as the light transmission particulate is that (Sekisui Plastics Co., Ltd. makes particle " XX367K ", weight average particle diameter: 7.0 μ m; The standard deviation of size-grade distribution: 0.55 μ m; Coefficient becomes: 7.9%, and specific refractory power: 1.59) 25 weight parts and belong to " the LUSILIN TPO " of Photoepolymerizationinitiater initiater (BASF AG makes, chemical name: 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide) 5 weight parts are that the mode of 60 weight % is diluted with propylene glycol monomethyl ether with the solids component ratio, form and use resin combination thereby process antiglare layer.
Crosslinked polystyrene is that the suspension methanol concentration lower value of particle " XX367 " in the time of 25 ℃ is 12.3 weight %.In addition, except not containing the light transmission particulate, be that the surface tension of compsn 25 ℃ time of same composition is 28.2mN/m with this resin combination.
(2) embossing is with the making of mould
Preparation is that the goods of Ba Lade copper facing (copper バ ラ one De メ ッ キ) have been implemented on the surface of the iron roll (based on the STKM13A of JIS) of 200mm to diameter.Ba Lade copper facing is formed by copper plate/thin silvered film/copper coating layer, and the coating integral thickness is about 200 μ m.This copper coatings is carried out mirror ultrafinish, and further using sparging unit ((strain) only making manufacturing) is that 0.05MPa (gauge pressure, below identical), particulate consumption are 16g/cm at spraying pressure
2(every 1cm
2The consumption of roller surface-area, below identical) condition under this abrasive surface is sprayed zirconium oxide bead TZ-B125 as first particulate (TOSOH (strain) makes, median size: 125 μ m), form concavo-convex on the surface.Is that 0.1MPa, particulate consumption are 4g/cm with sparging unit ((strain) only making manufacturing) at spraying pressure
2Condition under (TOSOH (strain) makes, median size: 20 μ m), concave-convex surface is carried out inching to spraying zirconium oxide bead TZ-SX-17 as second particulate on this male and fomale(M&F).To the concavo-convex copper facing iron roll of being with of gained, utilize cupric chloride liquid to carry out etch processes (etch quantity: 3 μ m).Afterwards, carry out chromium plating processing (chromium plating thickness: 4 μ m), thereby process mould.The Vickers hardness of the chromium plating face of gained mould is 1000.Vickers hardness adopts UW sclerometer " MIC10 " (Krautkramer manufactured), be that benchmark is measured with JIS Z 2244.
(3) making of blooming
Above-mentioned antiglare layer formed use resin combination to be coated on the triacetyl cellulose that thickness is 80 μ m (TAC) film (base material film), in being set at 80 ℃ moisture eliminator, make its dry 1 minute.Use rubber rollers dried base material film to be pressed on the male and fomale(M&F) of the mould of processing in above-mentioned (2) as the mode of die side with the resin combination layer and make its driving fit.Under this state, count 300mJ/cm with h ray conversion light quantity by the irradiation of base material film side
2Intensity be 20mW/cm
2From the light of high voltage mercury lamp and the resin combination layer is solidified, thereby obtain by the blooming that has concavo-convex antiglare layer and base material structure film formed, shown in Figure 4 on the surface.The bed thickness of antiglare layer is 14.0 μ m.
< embodiment 2～3, comparative example 1～2 >
The weight and/or the addition of light transmission particulate are changed as shown in table 1ly, in addition, likewise carry out, use resin combination, likewise carry out with embodiment 1, thereby process blooming thereby process antiglare layer formation with embodiment 1.The light transmission particulate that uses is following in detail.
(1) SX713L-2: crosslinked polystyrene be particle " SX713L-2 " (Soken Chemical & Engineering Co., Ltd. makes, weight average particle diameter: 7.0 μ m, the standard deviation of size-grade distribution: 1.50 μ m, variation factor: 21.4%, specific refractory power: 1.59).With after state " SX713L " with pure water washing and particle, the suspension methanol concentration lower value in the time of 25 ℃ is 8.5 weight %.
(2) XX366K: crosslinked polystyrene be particle " XX366K " (Sekisui Plastics Co., Ltd. makes, weight average particle diameter: 8.1 μ m, the standard deviation of size-grade distribution: 0.56 μ m, variation factor: 6.9%, specific refractory power: 1.59).Suspension methanol concentration lower value in the time of 25 ℃ is 11.7 weight %.
(3) SX713L: crosslinked polystyrene be particle " SX713L " (Soken Chemical & Engineering Co., Ltd. makes, weight average particle diameter: 7.0 μ m, the standard deviation of size-grade distribution: 1.50 μ m, variation factor: 21.4%, specific refractory power: 1.59).Suspension methanol concentration lower value in the time of 25 ℃ is 0 weight % (, in pure water, disperse).
(4) SX713L-3: crosslinked polystyrene be particle " SX713L-3 " (Soken Chemical & Engineering Co., Ltd. makes, weight average particle diameter: 7.0 μ m, the standard deviation of size-grade distribution: 1.50 μ m, variation factor: 21.4%, specific refractory power: 1.59).Be the particle that above-mentioned " SX713L " got with washing with acetone, the suspension methanol concentration lower value in the time of 25 ℃ is 23.6 weight %.
In the table 1, the addition of light transmission particulate is the weight part with respect to the ultraviolet-curing resin composition solids component of 100 weight parts.
(evaluation that turbidity is uneven and bubble is sneaked into)
To any 1m in the gained blooming
2Scope, through having or not bubble to sneak in visual valuation turbidity uneven (inequality of the muddy degree of film) and the antiglare layer.With not seeing the uneven situation of sneaking into of turbidity as zero with bubble, with confirmed situation that the uneven perhaps bubble of turbidity is sneaked into any one as *.In addition, the turbidity value according to the said determination method with blooming is shown in table 1 in the lump.
Table 1
As shown in table 1ly know; The suspension methanol concentration lower value of utilizing the resin combination that does not contain the light transmission particulate to have interior surface tension of specialized range and light transmission particulate is in the resin combination in the specialized range, can suppress the turbidity inequality and the bubble of blooming effectively and sneak into.On the other hand, not in the comparative example 1 and 2 of the resin combination in specialized range, it is uneven then to have produced turbidity in the suspension methanol concentration lower value of having used the light transmission particulate.
Claims (8)
1. a resin combination comprises mixture and light transmission particulate, and said mixture contains translucent resin or forms the resinous principle and the solvent of translucent resin,
The surface tension of said mixture in the time of 25 ℃ is 18mN/m～35mN/m,
Said light transmission particulate has its lower value of methanol concentration of methanol aqueous solution of can suspending, and this lower value is more than the 1.0 weight % in the time of 25 ℃ and is lower than 15.0 weight %.
2. resin combination according to claim 1, wherein, said light transmission particulate is by being selected from PS, gathering any polymer formation in (methyl) propenoate and polystyrene-poly (methyl) Yodo Sol GH 28.
3. resin combination according to claim 1, wherein, with respect to the said translucent resin of 100 weight parts or form the resinous principle of translucent resin, the content of said light transmission particulate is that 25 weight parts are above and be lower than 50 weight parts.
4. resin combination according to claim 1, wherein, the weight average particle diameter of said light transmission particulate is 5 μ m～10 μ m.
5. blooming has base material film and the antiglare layer that is layered on the said base material film and is formed by the described resin combination of claim 1.
6. a liquid crystal indicator possesses back lighting device, light deflection mechanism, the 1st polaroid, liquid crystal cells, the 2nd polaroid and the described blooming of claim 5 successively.
7. liquid crystal indicator according to claim 6, wherein, said smooth deflection mechanism contains the prismatical prism film of a plurality of wire possessing 2 with said the 1st polaroid facing surfaces.
A slice prism film disposes with the mode that the prismatical crest line direction of its wire is roughly parallel to the axis of homology of said the 1st polaroid, and another sheet prism film disposes with the mode that the prismatical crest line direction of its wire is roughly parallel to the axis of homology of said the 2nd polaroid.
8. liquid crystal indicator according to claim 6 wherein, further possesses the light diffusion mechanism between said back lighting device and said smooth deflection mechanism.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-093134 | 2011-04-19 | ||
| JP2011093134A JP2012224735A (en) | 2011-04-19 | 2011-04-19 | Resin composition, optical film, and liquid crystal display device |
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| Publication Number | Publication Date |
|---|---|
| CN102746791A true CN102746791A (en) | 2012-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101149264A Pending CN102746791A (en) | 2011-04-19 | 2012-04-18 | Resin combination, optical film and liquid crystal display apparatus |
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| Country | Link |
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| JP (1) | JP2012224735A (en) |
| CN (1) | CN102746791A (en) |
| TW (1) | TW201247759A (en) |
Cited By (7)
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| CN104479516A (en) * | 2014-12-19 | 2015-04-01 | 苏州菲博特智能科技有限公司 | Video monitoring equipment |
| CN104479498A (en) * | 2014-12-19 | 2015-04-01 | 苏州菲博特智能科技有限公司 | Monitoring equipment |
| CN105593248A (en) * | 2013-09-30 | 2016-05-18 | 积水化成品工业株式会社 | Polymer particles, process for producing same, and use thereof |
| CN105985719A (en) * | 2015-02-09 | 2016-10-05 | 文豪 | Waterproof explosion-proof LED lamp tube coating and preparation method thereof |
| CN106353904A (en) * | 2015-07-17 | 2017-01-25 | 乐金显示有限公司 | Display device |
| CN106716236A (en) * | 2014-09-30 | 2017-05-24 | 富士胶片株式会社 | Backlight unit, liquid crystal display device and wavelength conversion member |
| CN112424290A (en) * | 2018-06-20 | 2021-02-26 | 松下知识产权经营株式会社 | Colloidal structure, colloidal multiple structure, and method for producing colloidal structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101493445B1 (en) | 2013-08-09 | 2015-02-16 | 충남대학교산학협력단 | Prism sheet comprising prism layer having self-adhesive property |
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| CN105593248A (en) * | 2013-09-30 | 2016-05-18 | 积水化成品工业株式会社 | Polymer particles, process for producing same, and use thereof |
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| CN105985719A (en) * | 2015-02-09 | 2016-10-05 | 文豪 | Waterproof explosion-proof LED lamp tube coating and preparation method thereof |
| CN106353904A (en) * | 2015-07-17 | 2017-01-25 | 乐金显示有限公司 | Display device |
| CN112424290A (en) * | 2018-06-20 | 2021-02-26 | 松下知识产权经营株式会社 | Colloidal structure, colloidal multiple structure, and method for producing colloidal structure |
| CN112424290B (en) * | 2018-06-20 | 2023-08-22 | 松下知识产权经营株式会社 | Colloid structure, colloid multiple structure, and method for producing colloid structure |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201247759A (en) | 2012-12-01 |
| JP2012224735A (en) | 2012-11-15 |
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