CN101321622A - Multilayer film, method for producing same, optical sheet using multilayer film, and display - Google Patents
Multilayer film, method for producing same, optical sheet using multilayer film, and display Download PDFInfo
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- CN101321622A CN101321622A CNA2006800457951A CN200680045795A CN101321622A CN 101321622 A CN101321622 A CN 101321622A CN A2006800457951 A CNA2006800457951 A CN A2006800457951A CN 200680045795 A CN200680045795 A CN 200680045795A CN 101321622 A CN101321622 A CN 101321622A
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Abstract
A supporting body (11) composed of a polyester is biaxially stretched. A multilayer film (10) is produced by forming a coating layer (12) on the biaxially stretched supporting body (11). The coating layer (12) is composed of organic or inorganic fine particles, a binder and a carbodiimide compound. The fine particles have an average particle diameter of not less than 0.3 [mu]m and not more than 12 [mu]m. Since the fine particles are securely captured by the carbodiimide compound, separation of the fine particles can be suppressed during the production steps or the following processing steps. The average particle diameter of the fine particles is set at 0.3-12 [mu]m, and the haze value of the multilayer sheet (10) is set at not more than 3%.
Description
Technical field
[0001] the present invention relates to a kind of bonding multilayer film and production method thereof.The invention still further relates to by film formed optical sheet of described multilayer and display unit.
Background technology
[0002] because the excellent transparency, dimensional stability, chemical resistance and low hygroscopicity, polyester film, particularly as the basilar memebrane of optical sheet, these films are as the basilar memebrane of the prismatic lens, antireflection sheet, light diffusing patch and the hard conating sheet that for example are used for LCD and the basilar memebrane that is used for IR absorbing sheet, electromagnetic shielding sheet, toning sheet, antireflection sheet, antiglare sheet and the hard conating sheet of plasma scope usually for the polyester film of biaxial orientation.
[0003] basilar memebrane need high transparency and with the high-adhesiveness (easily adhesiveness) of the layer (hereinafter referred to as the upper strata) that on basilar memebrane, comprises layers of prisms.Yet, because basilar memebrane made by different compositions with the upper strata, so be difficult to enough bonding strengths basilar memebrane and upper strata is bonding.Owing to this reason, basilar memebrane (multilayer film) disposes the coating that is called easy adhesion layer usually on the support that is formed by polyester (being called polyester support).For example, list of references 1 has proposed on the surface of polyester film to settle easy adhesion layer to improve and to contain as the prism lens of the acrylic resin of key component and the adhesion of hard conating.List of references 2 has proposed a kind of polyester film that disposes easy adhesion layer on polyester support, and described easy adhesion layer is formed by the mixture of polyester and carbamate.Carbamate shows the height adhesiveness with the upper strata.
[0004] because from the teeth outwards in addition small cut also be considered to the optical defect of multilayer film, so need almost not have cut or be not subjected to the multilayer film of cut damage.In order to prevent cut, be known with the method that improves lubricity by adding easy adhesion layer as the organic or inorganic particulate of delustering agent.For example, in list of references 3, fine particles of silica is added in the easy adhesion layer.
[list of references 1] Japanese Patent Laid-Open Publication 6-340049
[list of references 2] Japanese Patent Laid-Open Publication 2000-229395
[list of references 3] Japanese Patent Laid-Open Publication 2000-296595
Summary of the invention
Problem to be solved by this invention
[0005] because multilayer film must be transparent, so can not increase to the addition of the particulate that improves lubricity and add.In order to keep the transparency, increase the size of particulate, reduce addition simultaneously.Yet when using the particulate of large-size, these particles may drop in production stage or ensuing treatment step, thereby cause new problem.The particulate that drops may be deposited on the surface of conveying roller and film, and produces cut on film, and this is a serious problem.
[0006] in addition, in the method for routine, when display unit big when the thickness on the upper strata of optical sheet or that have this optical sheet was in high-temperature atmosphere or the high humility atmosphere for a long time, the bonding strength at interface between support and the coating and the interface between coating and upper strata reduced.As a result of, peel off mutually on basilar memebrane and upper strata.Owing to this reason, need prevent the multilayer film of adhering reduction.
[0007] an object of the present invention is to provide a kind of multilayer film and production method thereof, described multilayer film prevents dropping of particulate, keeps the transparency and the lubricity of multilayer film simultaneously.
[0008] another object of the present invention provides a kind of multilayer film and production method thereof, described multilayer film has easy adhesion layer, described easy adhesion layer has big thickness or is in high temperature and during high humility, shows the enough adhesivenesses with support and upper strata on the upper strata.Another purpose of the present invention is to use described multilayer film to provide to have the optical sheet and the display unit of excellent optical property.
The means of dealing with problems
[0009] in order to realize above-mentioned and other purpose, multilayer film of the present invention is included at least one lip-deep coating of support, the compound that described coating contains organic or inorganic particulate, adhesive and have the carbodiimide structure in molecule.
[0010] preferred support is by biaxial stretch-formed formation, and is made up of polyester.The adhesive of preferred coatings is the polymer with carboxyl.Preferred this compound comprises a plurality of carbodiimide structures.Preferably with respect to the quality of adhesive, the quality with compound of carbodiimide structure is 1 to 200 quality %.The average grain diameter of preferred particulate is more than or equal to 0.3 μ m and smaller or equal to 12 μ m.The haze value of preferred multilayer film is not more than 3%.
[0011] multilayer film according to another embodiment of the invention comprises the support that is formed by polyester, the ground floor that directly forms and the direct second layer that forms on ground floor at least one surface of support.The second layer contains acrylic resin or polyurethane resin and cross-linking compounds.
[0012] preferred cross-linking compounds is carbodiimide-based compound or epoxy-based compound.Preferred ground floor contains carbodiimide-based compound.Preferred ground floor contains mylar.Preferably after support is biaxial stretch-formed, form the ground floor and the second layer by coating.The thickness of preferred ground floor is more than or equal to 30nm with smaller or equal to 150nm.
[0013] by being placed on the multilayer film of the present invention, at least one of layers of prisms, anti-reflecting layer, optical diffusion layer and antiglare layer form optical sheet.Display unit is to use described optical sheet structure.
[0014] production method of multilayer film comprises the following steps: the biaxial stretch-formed support that is formed by polymer; On at least one surface that coating fluid is coated to described support.Described coating fluid contains organic or inorganic particulate, adhesive and can be formed in the crosslinking agent of the compound that has the carbodiimide structure in the molecule.
[0015] production according to the multilayer film of another embodiment of the invention comprises the following steps: the biaxial stretch-formed support that is formed by polyester; Go up to form ground floor at least one surface that first coating fluid is coated to support; Contain second coating fluid of acrylic resin or polyurethane resin and crosslinking agent to form the second layer with coating.
Effect of the present invention
[0016] according to the present invention, the compound that the organic or inorganic particulate is had a carbodiimide structure is caught reliably and is not dropped.Therefore, prevented lip-deep cut by the multilayer film that particulate caused that drops.In addition, because have the acquisition performance that the compound of carbodiimide structure improves particulate, so, also prevent dropping of particulate even use greater particle size as being not less than 0.3 μ m and being not more than the particulate of 12 μ m.As a result of, prevent transparent decline, guaranteed lubricity simultaneously.Therefore, provide the optical sheet that does not have cut and have the excellent transparency.
[0017],, also provides easy the to be adhering multilayer film that does not descend in high-temperature atmosphere or high humility atmosphere with respect to support and upper strata even the upper strata has big thickness or multilayer film is placed for a long time according to another embodiment of the invention.
[0018] and, by with multilayer film of the present invention with such as the layer combination of layers of prisms and anti-reflecting layer, provide the optical sheet and the display unit of excellent in optical properties.
The accompanying drawing summary
[0019] [Fig. 1] shows the cross-sectional view according to the necessary part of multilayer film of the present invention.
[Fig. 2] is according to the cross-sectional view of the necessary part of the multilayer film of another embodiment of the invention.
Reference marker is described
[0020]
10 multilayer films
11 supports
12 coatings
20 multilayer films
21 supports
22 ground floors
23 second layers
24 coatings
Implement optimum implementation of the present invention
The present invention is described in detail in detail [0021].Following embodiment has been described advantageous applications of the present invention, and does not limit the scope of the invention.
[0022] as shown in FIG. 1, multilayer film 10 of the present invention has coating 12, and described coating 12 is to go up by at least one surface that coating fluid is coated in the transparent support of being made by polymer 11 to form.Coating 12 contains as organic or inorganic particulate, the adhesive of delustering agent and can be formed in the crosslinking agent of the compound that has the carbodiimide structure in the molecule.
[0023] by in the layers of prisms, anti-reflecting layer, optical diffusion layer and the antiglare layer that on the coating 12 of multilayer film 10, form LCD for example at least one, the preparation optical sheet.Use this optical sheet to prepare LCD.Except that LCD, multilayer film 10 also is used for the display unit such as plasma scope, OLED display and CRT monitor.And multilayer film 10 can be used as IR absorbing sheet, electromagnetic wave shielding sheet and the toning sheet of hard conating, plasma scope.
[0024] [support]
The preferred polyester that uses is as transparent support 11 of the present invention.Among polyester, can use PETG, PEN, polybutylene terephthalate (PBT), PBN etc.Consider cost and mechanical strength, preferred especially PETG.Yet, be used for polyester of the present invention and be not subjected to concrete restriction.
[0025] preferably polyester of the present invention is stretched, particularly biaxial stretch-formed to improve mechanical strength.Stretch rate is not subjected to concrete restriction.Yet, preferred 1.5 times to 7 times stretch rate.More preferably 2 times to 5 times stretch rate.Particularly, preferred biaxial stretch-formed 2 to 5 times polyester on vertical and horizontal.When stretch rate during, can not get enough mechanical strengths less than 1.5 times.On the contrary, when stretch rate surpasses 7 times, be difficult to obtain homogeneous thickness.
[0026] thickness of support 11 preferably (comprises 30 μ m and 400 μ m) between 30 μ m and 400 μ m, and more preferably (comprises 35 μ m and 350 μ m) between 35 μ m and 350 μ m.When thickness during less than 30 μ m, support 11 has been lost its intensity, and becomes and be difficult to handle.On the contrary, if thickness becomes too big and surpasses 400 μ m, then the miniaturization of display unit becomes difficult, and this thickness is disadvantageous aspect cost.
[0027] [delustering agent]
The organic particulate or the fine inorganic particle that are contained in the coating 12 as delustering agent are not subjected to concrete restriction.For example, can use polymer fine particles, as polystyrene, poly-(methyl methacrylate), organic siliconresin and benzoguanamine resin and fine inorganic particle, as silica, calcium carbonate, magnesia and magnesium carbonate.Among these, consider and improve lubricity and reduce cost preferred polystyrene, poly-(methyl methacrylate) and silica.
[0028] average grain diameter of preferred delustering agent (comprises 0.3 μ m and 12 μ m) between 0.3 μ m and 12 μ m.More preferably average grain diameter (comprises 0.5 μ m and 9 μ m) between 0.5 μ m and 9 μ m.When average grain diameter during less than 0.3 μ m, it is not enough that the raising effect of lubricity becomes, and when average grain diameter during above 12 μ m, the display quality of display unit may reduce.
[0029] preferably reduces the amount of delustering agent, and increase the amount of delustering agent along with the reduction of average grain diameter along with the increase of average grain diameter.The amount of delustering agent is preferably at 0.1mg/m
2And 30mg/m
2Between (comprise 0.1mg/m
2And 30mg/m
2).More preferably the amount of delustering agent is at 0.5mg/m
2And 20mg/m
2Between (comprise 0.5mg/m
2And 20mg/m
2).When the amount of delustering agent less than 0.1mg/m
2The time, the raising effect of lubricity may be not enough.When the amount of delustering agent surpasses 30mg/m
2The time, the transparency may descend, thereby causes the decline of the display quality of display unit.In the present invention, particle diameter is the diameter of a circle that has with the image area identical of the particulate of taking by SEM.Average grain diameter is the average diameter of optional 50 particulates.
[0030] [adhesive]
The adhesive that is used for coating 12 is not subjected to concrete restriction.Can use acrylic polymer, polyether polyols with reduced unsaturation and polyester polymers.Among them, particularly preferably in the polymer that has carboxyl in the molecule.Particularly, have the polyurethane-based polyalcohol of carboxyl and the good adhesiveness that polyester-based polyalcohol showed and contained the support 11 of polyester.
[0031] a kind of polymer or two or more mixture of polymers can be used as adhesive.Preferred use for example has the mixture of the polyurethane-based polyalcohol of carboxyl and the polyester-based polyalcohol with carboxyl as adhesive.Molecular weight as the polymer of adhesive is unrestricted.Can use the polymer that is used as adhesive usually.
[0032] [crosslinking agent]
The crosslinking agent that forms " compound (following can be called carbodiimide-based compound) that has the carbodiimide structure in molecule " is not subjected to concrete restriction, as long as they can be formed in the compound that has carbodiimide in the molecule, promptly carbodiimide-based cross-linker gets final product.Particularly, preferably in molecule, contain a plurality of carbodiimides.
[0033] usually by the synthetic poly-carbodiimide of the condensation reaction of organic diisocyanate.The organic group that synthesizes the middle organic diisocyanate that uses that has the compound of a plurality of carbodiimide structures in molecule is not subjected to concrete restriction.For example, can use one or their mixture of aromatic group and aliphatic group.Consider reactivity, especially preferably use aliphatic group.Organic isocyanate, organic diisocyanate, organic triisocyanate etc.
[0034] example of available organic isocyanate is organic isocyanate, aliphatic isocyanate and their mixture.More specifically, can use 4,4 '-methyl diphenylene diisocyanate, 4,4-diphenyl dimethylmethane vulcabond, 1,4 '-phenylene diisocyanate, 2, the 4-toluene di-isocyanate(TDI), 2, the 6-toluene di-isocyanate(TDI), hexamethylene diisocyanate, cyclohexane diisocyanate, XDI, 2,2, the 4-trimethyl hexamethylene diisocyanate, 4,4 '-double-hexyl methane vulcabond, 1,3-phenylene diisocyanate etc., and an organic isocyanates, as isophorone diisocyanate, phenyl isocyanate, NSC 87419, butyl isocyanate and naphthyl isocyanate.And, can use commercially available product such as Carbodilite V-02-L2 (name of product, by Nisshinbo Industries, Inc. produces) as being applicable to carbodiimide-based compound of the present invention.
[0035] in the present invention, preferably with respect to adhesive to be scope adding carbodiimide-based cross-linker of 1 to 200 quality %.Preferred scope is 5 to 100 quality %.When addition during, can not fully prevent dropping of particulate less than 1 quality %.When addition surpassed 200 quality %, the coating surface state may deterioration.
[0036] [coating]
[0037] surfactant can be anion, nonionic or the cationic surfactant of knowing.In for example " surfactant handbook " (, publishing 1960 by Sangyo-Tosho), surfactant has been described by editors such as Ichiro Nishi.
[0038] lubricant can be for example wax, low-molecular-weight polyolefin, organosilicon, CnH
2n+1SO
3Na (natural number of n=in 5 to 15 scope) etc.
[0039], conducting polymer such as polyaniline and polypyrrole are arranged as antistatic additive; The ionic conduction polymer that in strand, has carboxyl and sulfonate group; Conductive particulate etc.Among them, particularly, consider the electrical conductivity and the transparency, the fin oxide condutire particulate of preferably in Japanese Patent Laid-Open Publication 61-020033, describing.
[0040] preferably, the thickness of coating 12 preferably (comprises 0.02 μ m and 5 μ m) between 0.02 μ m and 5 μ m.Preferred especially above-mentioned thickness (comprises 0.5 μ m and 2 μ m) between 0.5 μ m and 2 μ m.If the thickness of coating 12 is less than 0.02 μ m, then the adhesiveness between coating 12 and the layer above the coating 12 becomes not enough.If coating thickness surpasses 5 μ m, then mist degree may increase.Coating 12 can be by individual layer two-layer or more multi-layered formation.Coating 12 by two-layer or more multi-layered situation about forming under, the gross thickness of whole coating 12 preferably (comprises 0.02 μ m and 5 μ m) between 0.02 μ m and 5 μ m, and particularly preferably in (comprising 0.5 μ m and 2 μ m) between 0.5 μ m and the 2 μ m.
[0041] in the present invention, the painting method of coating is not subjected to concrete restriction.Can use the method for knowing, apply and the coating of slip coating machine as doctor knife coater.Aqueous solvent, as water, toluene, methyl alcohol, isopropyl alcohol, methyl ethyl ketone or their mixture, perhaps organic solvent can be used as coating solvent.
[0042] can on axial or biaxially oriented, after the stretching support 11 coating be coated on the support 11.Yet,, preferably after biaxial stretch-formed, apply coating in order behind cross directional stretch, to recover the marginal portion of support 11.Not only can be on a surface of support 11, and can on the opposed surface of support 11, form coating surface.
[0043] [mist degree]
The haze value of multilayer film 10 of the present invention must be equal to or less than 3%.This haze value preferably is equal to or less than 2%, and more preferably is equal to or less than 1%.Obtain haze value by using haze meter to measure the light that enters multilayer film from its back of the body surface.If haze value surpasses 3%, then transparent deterioration, thus cause decline in conjunction with the display quality of the display unit of multilayer film 10.Be set at suitable value by addition, haze value is remained in the above-mentioned scope average grain diameter and particulate.
[0044] [display unit]
Can use multilayer film of the present invention as the blooming that is used for LCD, plasma scope, OLED display and CRT monitor.In following document for example, describe these display unit in detail: " display advanced techniques " (edit by Chizuka Tani, publish 1998 by Kyoritsu Publication Inc); " EL, PDP and LCD display (by TORAY RESEARCH CENTER, INC. publishes, 2001); By " colour liquid crystal display device " that Shunsuke Kobayashi edits, by Sangyo Tosho Publishing Co., Ltd. publishes, and 1990) etc.
[0045] has multilayer film prepared in accordance with the present invention and at least one the optical sheet that has in layers of prisms, anti-reflecting layer, optical diffusion layer, antiglare layer and the hard conating shows excellent optical property.The instantiation of optical sheet is the prismatic lens that is used for LCD; The antireflection sheet; Light diffusing patch; The hard conating sheet; Plasma scope IR absorbing sheet; Electromagnetic wave shielding sheet; The toning sheet; Deng.Except that above-mentioned list of references,, the 74th page, these sheets were described in 8 days Augusts in 2002 also at for example " Electric Journal ".
[0046] then, second embodiment of the present invention is described.Omit and the common description of first embodiment.Have support 21 and the coating 24 that is formed by polyester at the multilayer film shown in Fig. 2 20, described coating 24 is formed by the ground floor 22 and the second layer 23 of numbering from the layer of more close support 21.Coating 24 is placed at least one surface of support 21, and described surface is not subjected to concrete restriction.
[0047] polyesters that is used for support 21 is similar to the polyester of the support 11 that is used for first embodiment.Support 21 has and the similar thickness of the thickness of support 11.
[0048] ground floor 22 is the layers that directly form on support 21.It is necessary that ground floor 22 contains adhesive.And preferred ground floor 22 contains carbodiimide-based cross-linker (can form the crosslinking agent of the compound with carbodiimide structure).
[0049] details that add the carbodiimide-based cross-linker in the ground floor 22 will be described after a while.The addition of carbodiimide-based cross-linker preferably the quality of the adhesive (first adhesive) of ground floor 22 1% and 100% between (comprising 1% and 100%), and more preferably between 5% and 50%, (comprise 5% and 50%).If addition less than 1%, then when containing particulate in ground floor 22, can not fully prevent dropping of particulate.On the other hand, if addition surpasses 100%, then the coating surface state of ground floor 12 may deterioration.
[0050] first adhesive is not subjected to concrete restriction.Yet, preferred (a) acrylic resin, (b) polyurethane resin, (c) mylar, (d) rubber-polymer such as Ji resin.
[0051] (a) acrylic resin is the polymer that contains acrylic acid, methacrylic acid and their derivative, and more especially by containing acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, butyl acrylate, 2-EHA, acrylamide, acrylonitrile, hydroxy acrylate etc. as the polymer of key component and the polymer that can form with the combined polymerization of the monomer (for example styrene, divinylbenzene etc.) of above-mentioned key component combined polymerization.
[0052] (b) polyurethane resin is the generic term that has the polymer of amino-formate bond in main chain, and usually the reaction by polyisocyanates and polyalcohol prepares.Polyisocyanates is a Toluene-2,4-diisocyanate, 4-vulcabond, methyl diphenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, IPDI etc.Polyalcohol is ethylene glycol, propane diols, glycerine, hexanetriol etc.In addition, can also use polyether polyols with reduced unsaturation as isocyanates of the present invention, described polyether polyols with reduced unsaturation prepares by the reaction of polyisocyanates and polyalcohol, and its molecular weight increases by using chain elongation to handle.Having described polyisocyanates, polyalcohol and chain elongation in for example " polyurethane resin handbook " (edited by Keiji IWATA, and published 1987 by Nikkan Kogyo Shimbun Ltd.) handles.
[0053] (c) mylar is the generic term that has the polymer of ester bond in main chain, and usually the reaction by polybasic carboxylic acid and polyalcohol prepares.Polybasic carboxylic acid is for example fumaric acid, itaconic acid, adipic acid, decanedioic acid, terephthalic acid (TPA), M-phthalic acid etc.Polyalcohol be for example above-mentioned those.In for example " polyester handbook " (edit by Eiichiro Takiyama, publish 1988 by Nikkan Kogyo Shinbunsha), mylar and material thereof have been described.
[0054] (d) rubber-Ji resin is a dienes synthetic rubber among synthetic rubber.The dienes synthetic rubber is for example polybutadiene, SB, styrene-butadiene-acrylonitrile copolymer, styrene-butadiene-divinyl benzene copolymer, hycar, polychloroprene etc.In for example " synthetic rubber handbook " (by editors such as Shu Kanbara, by AsakuraPublishing Co., Ltd publishes, 1967), rubber-Ji resin has been described.
[0055] in the present invention, especially preferably use mylar as first adhesive to improve the adhesiveness with the support 21 that forms by polyester.
[0056] can use the above-mentioned polymer that is dissolved in organic solvent or the water-borne dispersions as first adhesive.Yet, consider little load to environment, preferably use the water-base emulsion coating of the adhesive of water-borne dispersions form.Water-borne dispersions is not subjected to concrete restriction, and can use commercially available polymer as water-borne dispersions.For example be preferred for commercially available polymer of the present invention and be SUPERFLEX 830,460,870,420,420NS (name of product: by Dai-ichi KogyoSeiyaku Co., the polyurethane that Ltd produces); VONDIC 1370NS, 1320NS, HYDRANAPX-101H, AP-40 (F) (name of product :) by the polyurethane of Dainippon Ink And Chemicals Inc. production; JURYMER ET325, ET410, SEK301 (name of product: by Nihon JunyakuCo., the acrylic compounds that Ltd. produces); VONCOAT AN117, AN226 (name of product :) by the acrylic compounds of Dainippon Ink And Chemicals Inc. production; RACKSTAR DS616, DS807 (name of product :) by the SBR styrene butadiene rubbers of Dainippon Ink And Chemicals Inc. production; Nipol LX110, LX206, LX426, LX433 (name of product :) by the SBR styrene butadiene rubbers of ZeonCorporation production; NIPOL LX513, LX1551, LX550, LX1571 (name of product :) by the acrylonitrile-butadiene rubber of Zeon Corporation production; FINETEX ES650, ES2200 (name of product :) by the polyester of Dainippon Ink And Chemicals Inc. production; And VYLONAL MD1400, MD1480 (name of product: by Toyobo Co., the polyester that Ltd. produces).
[0057] where necessary, first adhesive can comprise a kind of polymer or the polymer of two or more.Although the molecular weight of polymer is not subjected to concrete restriction, preferred weight average molecular weight is 3000 to 1000000.Weight average molecular weight is lower than 3000 polymer and enough intensity is provided may not for ground floor 22.On the other hand, weight average molecular weight increases the viscosity of coating fluid above 1000000 polymer, thereby causes striped on ground floor 22.
[0058] a kind of particulate as key component that preferably will contain in tin oxide (tin ash), zirconium dioxide or the titanium oxide (titanium dioxide) adds in the ground floor 22 with the control refractive index.Tin ash is preferably for example to have by formula SnO
2The tin ash (IV) of the composition of expression.The particulate that is doped with this tin oxide of antimony etc. conducts electricity, so their reduce the surface resistivity of multilayer film, and prevent from the teeth outwards dust and the deposition of impurity.The example of the tin oxide that antimony mixes is to be applicable to commercially available FS-10D of the present invention, SN-38F, SN-88F, SN-100F, TDL-S and TDL-1 (by Ishihara SangyoKaisha, Ltd. produces).
[0059] zirconium dioxide has by formula ZrO
2The composition of expression.The example of this zirconium dioxide is NZS-20A and NZS-30A (by Nissan Chemical Industries, Ltd. produces), and they are applicable to the present invention.Composition is by formula TiO
2The titanium dioxide (IV) of expression is preferably used as titanium oxide.According to crystal structure, titanium oxide is divided into rutile-type (at high temperature having the tetragonal system crystal structure), Detitanium-ore-type (having the tetragonal system crystal structure at low temperatures) etc.Yet the type of titanium oxide is not subjected to concrete restriction.Can also use surface-treated titanium dioxide.Be applicable to that titanium dioxide of the present invention is for example IT-S, IT-O and IT-W (by Idemitsu Kosan Co., Ltd. produces).
[0060] average grain diameter of preferred above-mentioned particulate (comprises 15nm and 200nm) between 15nm and 200nm.By this particulate is added in the ground floor 22, control the refractive index of ground floor 22 easily.When the average grain diameter of particulate during greater than 200nm, light may collide on particulate, and these particulates become obstacle.On the other hand, when average diameter during less than 15nm, particulate may be assembled and become excessive.
[0061] according to application, except that above-mentioned substance, can also be with in various additives such as delustering agent and the surfactant adding ground floor 22.Be preferred for ground floor 22 of the present invention with those similar delustering agents of the coating 12 that is used for first embodiment.
[0062] is preferred for ground floor 22 with those similar surfactants that are used for the coating 12 of first embodiment.With respect to membrane area, the addition of surfactant is preferably at 0.1mg/m
2And 30mg/m
2Between (comprise 0.1mg/m
2And 30mg/m
2), and more preferably 0.2mg/m
2To 10mg/m
2If the addition of surfactant is less than 0.1mg/m
2, then may produce repellency.On the other hand, if addition surpasses 30mg/m
2, the surface state of ground floor 22 may deterioration.
[0063] antistatic additive can also be added in the ground floor 22.Preferably with those similar antistatic additive of the coating 12 that is used for first embodiment.The addition of determining antistatic additive makes the surface resistivity of ground floor 12 1 * 10
5Ω and 1 * 10
13(comprise 1 * 10 between the Ω
5Ω and 1 * 10
13Ω), described surface resistivity is in 30%RH atmosphere, 25 ℃ of measurements down.If surface resistivity is less than 1 * 10
5Ω, then the addition of antistatic additive increases, thereby may cause the transparent deterioration of multilayer film.If surface resistivity surpasses 1 * 10
13Ω, then antistatic property becomes not enough, and dust may be deposited on the surface of multilayer film.
[0064] make the thickness of ground floor 22 between 30nm and 150nm, (comprise 30nm and 150nm) with the easy adhesiveness of realization with support 21.More preferably make the thickness of ground floor 22 between 65nm and 110nm, (comprise 65nm and 110nm).If the coating thickness of ground floor 22 is less than 30nm, then the adhesiveness between support 21 and ground floor 22 may become not enough.On the other hand, if the thickness of ground floor 22 surpasses 150nm, then the surface state of ground floor 22 may deterioration.
[0065] the following second layer 23 of describing.Compare with ground floor 22, the second layer 23 is positioned in from the farther position of the support that formed by polyester 21.The preferred second layer 23 is outermost layers of multilayer film 20.The second layer 23 contains the compound that is formed by second adhesive, i.e. acrylic resin or polyurethane resin and crosslinking agent.Described in the explanation in ground floor 22, can also add a kind of particulate as key component of containing in tin oxide (tin ash), zirconium dioxide or the titanium oxide (titanium dioxide) with the control refractive index, where necessary delustering agent, lubricant, surfactant and antistatic additive etc. be added in the second layer 23.
[0066] in molecule, has the polymer of carboxyl especially preferably as the acrylic resin or the polyurethane resin that are used for second adhesive.Those the similar acrylic resin and the polyurethane resins that can use and in the explanation of ground floor 22, describe.Because various resins have been described in detail in detail, in the explanation of ground floor 22 so the descriptions thereof are omitted.
[0067] can use the above-mentioned polymer that is dissolved in organic solvent or the water-borne dispersions as second adhesive.Yet, consider little load to environment, preferably use the water-base emulsion coating of adhesive of the form of water-borne dispersions.Above-mentioned commercially available polymer also can be used as second adhesive.
[0068] can use a kind of polymer or two or more mixture of polymers as second adhesive where necessary.Be not subjected to concrete restriction although be used as the molecular weight of the polymer of second adhesive, preferred weight average molecular weight is 3000 to 1000000.Weight average molecular weight is lower than 3000 polymer may not provide enough intensity to coating.On the other hand, weight average molecular weight increases the viscosity of coating fluid above 1000000 polymer, thereby causes striped on coating.
[0069] crosslinking agent that is used for the second layer 23 of the present invention is not subjected to concrete restriction.Yet preferred use can form the crosslinking agent of carbodiimide-based compound or epoxy compounds.The preferred use and the similar carbodiimide-based compound of carbodiimide-based compound that is used for the coating 12 of first embodiment.
[0070] the epoxy radicals crosslinking agent is not subjected to concrete restriction, as long as this compound has two or more epoxy radicals in molecule.The example of epoxy radicals crosslinking agent be for example DENACOL (name of product: produce by Nagase ChemteX Corporation, EX614B, EX521, EX512, EX301, EX313, EX314, EX810, EX811) etc.
[0071] with respect to the quality of second adhesive, the addition that is used for the crosslinking agent of the second layer 23 preferably (comprises 1% and 100%) between 1% and 100%, and more preferably (comprises 5% and 50%) between 5% and 50%.If addition is less than 1%, then the adhesiveness between the second layer 23 and upper strata may become not enough.On the other hand, if addition surpasses 100%, then the surface state of the second layer 23 may deterioration.
[0072] where necessary, various additives such as delustering agent, lubricant, surfactant and antistatic additive can be added in the second layer 23.Lubricant and delustering agent give lubricity for the second layer 23.In the particulate performance friction reduction effect of the delustering agent on coating surface, lubricant is by giving lubricity performance friction reduction effect to coating.The kind and the addition that are used for the various additives of the second layer 23 are similar to those that are used for ground floor 22.The details of various additives are similar to those that are used for ground floor, so the descriptions thereof are omitted.
[0073] under situation about lubricant being added as additive in the second layer 23, the kind of lubricant is not subjected to concrete restriction.Preferred lubricant is for example synthetic wax or native paraffin, and organo-silicon compound are by formula R-O-SO
3(R represents to replace or unsubstituted alkyl (C the compound that M represents
nH
2n+1-; N is the natural number in 3 to 20 scope), M represents the monovalence metallic atom) etc.
[0074] instantiation of lubricant is a wax, as Cellosol 524,428,732-B, 920, B-495, Hydrin P-7, D-757, Z-7-30, E-366, F-115, D-336, D-337, PolylonA, 393, H-481, Hi-micron G-110F, 930, G-270 (name of product: CHUKYO YUSHI.CO., LTD), Chemipearl W100, W200, W300, W400, W500, W950 (name of product: Mitsui Chemicals, Inc.) etc., organosilicon such as KF-412,413,414,393,859,8002,6001,6002,857,410,910,851, X-22-162A, X-22-161A, X-22-162C, X-22-160AS, X-22-164B, X-22-164C, X-22-170B, X-22-800, X-22-819, X-22-820, and X-22-821 etc. (name of product: Shin-Etsu Chemical Co., Ltd.) and by formula C
16H
33-O-SO
3Na, C
18H
37-O-SO
3The compound that Na represents etc.With respect to the area of film, the amount of lubricant is preferably at 0.1mg/m
2And 50mg/m
2Between (comprise 0.1mg/m
2And 50mg/m
2), and more preferably at 1mg/m
2To 20mg/m
2Between (comprise 1mg/m
2To 20mg/m
2).If addition is less than 0.1mg/m
2, then the lubricity of the second layer 23 becomes not enough.On the other hand, if addition surpasses 50mg/m
2, then the surface state of the second layer 23 may deterioration.
[0075] thickness of the second layer 23 is not subjected to concrete restriction.Yet this thickness preferably (comprises 10nm and 5000nm) between 10nm and 5000nm, and more preferably (comprises 20nm and 1500nm) between 20nm and 1500nm to realize being easy to the adhere to transparency of maintenance excellence simultaneously.If the thickness of the second layer 23 is less than 10nm, then the adhesiveness with the upper strata may become not enough.On the other hand, if thickness surpasses 5000nm, then surface state may deterioration.
[0076] preferably by applying ground floor 22 and the second layer 23 formation coatings 24.Dope applying method is not subjected to concrete restriction, and can use the coating of knowing, as doctor knife coater coating, the coating of slip coating machine etc.In order to form the ground floor 22 and the second layer 23, can use identical or different method.Can apply simultaneously and the dry ground floor 22 and the second layer 23.Can also after coating and dry ground floor 22, apply and the dry second layer 23.
[0077] can when applying the ground floor 22 and the second layer 23, use solvent.Aqueous solvent such as water, toluene, methyl alcohol, isopropyl alcohol, methyl ethyl ketone and their mixture, and organic coating solvent can be used as solvent.Among these, consider cost and production easily, preferably make the method for water as coating solvent.Identical coating solvent or different coating solvents can be used for the ground floor 22 and the second layer 23.
[0078] after support 21 is stretched on axial or biaxially oriented, coating can be coated on the support 11, described coating is coated and form ground floor 22 and the second layer 23.Yet,, preferably after biaxial stretch-formed, coating is coated on the ground floor 22 and the second layer 23 in order after cross directional stretch, to recover the marginal portion of substrate.Can on any surface of support 21 or two surfaces, form coating 24.
[0079] multilayer film 10 as using first embodiment, the multilayer film 20 that can use such preparation is as the blooming that is used for LCD, plasma scope, OLED display and CRT monitor.At least one the optical sheet that has multilayer film 20 and have layers of prisms, anti-reflecting layer, optical diffusion layer, antiglare layer and a hard conating shows excellent optical property.
[0080] [embodiment]
Below, description is according to the embodiment of the production method of the optical component of first embodiment of the present invention.Can change the kind, composition, prescription of the material of in the following example, describing etc. in due course, as long as they do not depart from spirit of the present invention.Therefore, scope of the present invention is not subjected to the restriction of the following example.
[0081] [support]
By using Ge is 0.66 PETG (hereinafter referred to as PET) as the synthetic inherent viscosity of the polycondensation of catalyst.The PET drying become until its water content is not more than 50ppm, and heter temperature is set to fusion in 280 to 300 ℃ the extruder therein afterwards.The PET of fusion is discharged on the chill roll, partly applies electrostatic charge to chill roll from mould, thus the support that preparation is formed by amorphous PET.When carrying, support is stretched on throughput direction 3.1 times, and on its width, stretch 3.9 times, thereby preparation thickness is the support 11 of 200 μ m.
[0082] [easily adhesion layer]
With above-mentioned thickness is the transporting velocity conveying of the support 11 of 200 μ m with 70m/min, and at 727J/m
2Condition under carry out Corona discharge Treatment.Coating fluid is coated with method by rod is coated on the support 11, and 180 ℃ of dryings 1 minute.Coated weight is 7.1cm
3/ m
2Thereby preparation multilayer film 10.
[0083] [mist degree measurement]
Use haze meter (NDH-1001P, by Nippon Denshoku Industries Co., Ltd. produces), based on measuring mist degree in the method described in the mist degree of JIS-K-6714-1977.
[0084] [dropping of particulate]
Use abrasion test machine (by Shinto Chemical Co., Ltd. produces), estimate the wearability of multilayer film 10.More specifically, make black scrip (produce by Fuji Photo Film Co., Ltd., SKBT390BIGO) contact coating surface, and the area of every 30mm * 25mm be forced the load of 3kg.In this case, carry out friction test, wherein said distance with the 10cm on the speed friction coatings surface of 100cm/min.After friction test, check that visually particulate drops and is deposited on the amount of the white powder on the black paper, and with following Three Estate evaluation.
A: do not find the deposition of white powder, or minimal deposition.
B: white powder slightly deposits.
C: deposited a large amount of white powders.
[0085] [embodiment 1]
Use the coating fluid A of following composition.
The composition of coating fluid A
Polyester adhesive (Finetex ES-650,29% solid content is by Dainippon Ink ﹠amp; Chemicals, Inc. produces) 44.9 mass parts
Carbodiimide-based cross-linker (Carbodilite V-02-L2,40% solid content, 385 carbodiimide equivalent, by Nisshinbo Industries, Inc. produces) 6.4 mass parts
The dispersion liquid of fine particles of silica (SEAHOSTER KE-W30,20% solid content, the average grain diameter of 0.3 μ m, by Nippon Shokubai Co., Ltd. produces) 2.5 mass parts
Surfactant (SANDET BL, 44% solid content are produced anionic by Sanyo chemical industry Co., Ltd) 1.4 mass parts
Surfactant (Naloacty HN-100 is produced nonionic by Sanyo chemical industry Co., Ltd)
0.73 mass parts
Distilled water 944.1 mass parts
[0086] [embodiment 2]
Use the coating fluid B of following composition.
The composition of coating fluid
(Finetex ES-650, solid content are 29% to polyester adhesive, by Dainippon Ink ﹠amp; Chemicals, Inc. produces) 44.9 mass parts
Carbodiimide-based cross-linker (Carbodilite V-02-L2,40% solid content, 385 carbodiimide equivalent, by Nisshinbo Industries, Inc. produces) 6.4 mass parts
The dispersion liquid of polystyrene particulate (Nipol UFN1008,20% solid content are produced by ZeonCorporation) 0.3 mass parts
Surfactant (SANDET BL, 44% solid content are produced anionic by Sanyo chemical industry Co., Ltd) 1.4 mass parts
Surfactant (Naloacty HN-100 is produced nonionic by Sanyo chemical industry Co., Ltd) 0.73 mass parts
Distilled water 946.3 mass parts
[0087] [embodiment 3]
Use the coating fluid C of following composition.
The composition of coating fluid C
Polyacrylic resin adhesive (NIHON JUNYAKU Co., Ltd.JURYMER-ET-410,30% solid content) 43.4 mass parts
Crosslinking agent (Carbodilite V-02-L2,40% solid content, 385 carbodiimide equivalent, by Nisshinbo Industries, Inc. produces) 6.4 mass parts
The dispersion liquid of polystyrene particulate (average grain diameter of 2.0 μ m is produced by Zeon Corporation for Nipol UFN1008,20% solid content) 0.3 mass parts
Surfactant (SANDET BL, 44% solid content are produced anionic by Sanyo chemical industry Co., Ltd) 1.4 mass parts
Surfactant (Naloacty HN-100 is produced nonionic by Sanyo chemical industry Co., Ltd) 0.73 mass parts
Distilled water 947.8 mass parts
[0088] [embodiment 4]
Use the coating fluid D of following composition.
The composition of coating fluid D
Polyurethane adhesive (solid content of SUPERFLEX 830,25%, Dai-ichi Kogyo SeiyakuCo., Ltd.) 52.1 mass parts
Crosslinking agent (Carbodilite V-02-L2,40% solid content, 385 carbodiimide equivalent, by Nisshinbo Industries, Inc. produces) 6.4 mass parts
The dispersion liquid of polystyrene particulate (average grain diameter is 2.0 μ m for Nipol UFN1008,20% solid content, is produced by Zeon Corporation) 0.3 mass parts
Surfactant (SANDET BL, 44% solid content are produced anionic by Sanyo chemical industry Co., Ltd) 1.4 mass parts
Surfactant (Naloacty HN-100 is produced nonionic by Sanyo chemical industry Co., Ltd) 0.73 mass parts
Distilled water 939.1 mass parts
[0089] [embodiment 5]
Use is by the following coating fluid E that forms.
The composition of coating fluid E
Polyester adhesive (Finetex ES-650,29% solid content is by Dainippon Ink ﹠amp; Chemicals, Inc. produces) 31.4 mass parts
Polyurethane adhesive (solid content of SUPERFLEX 830,25%, Dai-ichi Kogyo SeiyakuCo., Ltd.) 15.6 mass parts
Carbodiimide-based cross-linker (Carbodilite V-02-L2,40% solid content, 385 carbodiimide equivalent, by Nisshinbo Industries, Inc. produces) 6.4 mass parts
The dispersion liquid of polystyrene particulate (average grain diameter of 2.0 μ m is produced by Zeon Corporation for Nipol UFN1008,20% solid content) 0.3 mass parts
Surfactant (SANDET BL, 44% solid content are produced anionic by Sanyo chemical industry Co., Ltd) 1.4 mass parts
Surfactant (Naloacty HN-100 is produced nonionic by Sanyo chemical industry Co., Ltd) 0.73 mass parts
Distilled water 944.2 mass parts
[0090] [embodiment 6]
The coating fluid A of embodiment 1 and following coating fluid F are coated to respectively on the support 11 as the ground floor and the second layer, thereby have prepared multilayer film.After forming ground floor, under the situation of support 11 of not reeling, use rod to be coated with method and be coated on the support 11 second layer and drying.Coated weight is 7.1cm
3/ m
2, and with the second layer 170 ℃ of dryings 1 minute.
The composition of coating fluid F
Polyacrylic resin adhesive (JURYMER-ET-410, by NIHON JUNYAKU Co., Ltd. produces, 30% solid content) 57.3 mass parts
Epoxy radicals crosslinking agent (DENACOL EX-521 is produced by Nagase ChemteX Corporation) 1.2 mass parts
Surfactant (SANDET BL, 44% solid content are produced anionic by Sanyo chemical industry Co., Ltd) 0.6 mass parts
Distilled water 940.9 mass parts
[0091] [comparative example 1]
With coating under the condition identical with embodiment 1 coated with the preparation multilayer film, difference is the carbodiimide-based cross-linker that is used for the coating fluid A of embodiment 1 is changed into following melamine-based cross-linker, and the amount of following change distilled water.
Melamine-based cross-linker (Bekkamin M-3,80% solid content is by Dainippon Ink ﹠amp; Chemicals, Inc. produces) 3.2 mass parts
Distilled water 947.3 mass parts
[0092] [comparative example 2]
With coating under the condition identical with embodiment 1 coated with the preparation multilayer film, difference is the carbodiimide-based cross-linker that is used for the coating fluid A of embodiment 1 is changed into following melamine-based cross-linker, and the amount of following change distilled water.
Epoxy radicals crosslinking agent (DENACOL EX-521 is produced by Nagase ChemteX Corporation) 2.6 mass parts
Distilled water 947.9 mass parts
[0093] [comparative example 3]
With coating under the condition identical with embodiment 1 coated with the preparation multilayer film, difference is the carbodiimide-based cross-linker that is used for the coating fluid A of embodiment 1 is changed into following isocyanates-based cross-linker, and the amount of following change distilled water.
Isocyanates-based cross-linker (by Dai-ichi KogyoSeiyaku Co., Ltd. produces for Elastron BN-11,35% solid content) 7.3 mass parts
Distilled water 943.2 mass parts
[0094] the foregoing description and comparative example the results are shown in the table 1.In each embodiment 1 to 6, although haze value according to the particulate that uses and difference, all haze values all are not more than 3%.The evaluation of polishing machine is A.There is not white powder or very a spot of white powder deposition.In comparative example 1 to 3, although haze value all is not more than 3%, the evaluation of its polishing machine is B in comparative example 1 and 2, and is C in comparative example 3.Found the deposition of white powder, this is considered to defective for the viewpoint of practicality.
[0095] [table 1]
In last table 1, E1 to E6 represents embodiment 1 to 6, and CE1 to CE3 represents comparative example 1 to 3.Reagent refers to crosslinking agent.A
*The expression wearability.
[0096] followingly will multilayer film and production method thereof according to second embodiment of the present invention be described by reference example.Can change kind at the material shown in the following example, composition, prescription etc. where necessary, as long as they do not depart from spirit of the present invention.Therefore, scope of the present invention is not subjected to the restriction of the following example.In the following example, under the similar situation of production method of production method and embodiment 7, in embodiment 7, describe details, and in the embodiment except that embodiment 7, omit.
[0097] [embodiment 7]
In the following step, form the support of multilayer film.At first, as the synthetic inherent viscosity of the polycondensation of catalyst 0.66 PETG by using Ge.The PET drying become until its water content is not more than 50ppm, and heter temperature is set to fusion in 280 to 300 ℃ the extruder therein afterwards.The PET of fusion is discharged into the chill roll ester, partly applies electrostatic charge to chill roll from mould, thus the support that preparation is formed by amorphous PET.When carrying, support is stretched on throughput direction 3.3 times, and on its width, stretch 3.8 times, thereby preparation thickness is the support 11 of 100 μ m.
[0098] with thickness of the transporting velocity conveying of the support 11 of 100 μ m with 105m/min, and at 730J/m
2Condition under carry out Corona discharge Treatment.Be coated with method by rod and will be used to form the ground floor coating fluid of ground floor with 4.4cm
3/ m
2Coated weight be coated on two surfaces of support 11, and 180 ℃ of dryings 1 minute.Thereby formation ground floor.Afterwards, be coated with method by rod and will be used to form the second layer coating fluid of the second layer with 4.4cm
3/ m
2Coated weight be coated on two surfaces of ground floor, and 170 ℃ of dryings 1 minute.Thereby preparation is the cated multilayer film of configuration on each surface of support, and described coating is made up of the ground floor and the second layer.
[0099] [ground floor coating fluid]
Above-mentioned ground floor coating fluid contains 49.7 mass parts, and (Finetex ES-650 is by Dainippon Ink ﹠amp as the polyester adhesive of first adhesive; Chemicals, Inc. produce, 29% solid content), 28.2 mass parts is as carbodiimide-based cross-linker (Carbodilite V-02-L2 of crosslinking agent, by Nisshinbo Industries, Inc. produce, 10% solid content, 385 carbodiimide equivalent), 11.4 mass parts surfactant A (SANDET BL, produce by Sanyo chemical industry Co., Ltd, 10% solid content, anionic), 26.8 mass parts surfactant B (Naloacty HN-100, produce by Sanyo chemical industry Co., Ltd, 5% solid content, nonionic), 2.4 mass parts is as the fine particles of silica dispersion liquid (water-borne dispersions of OX-50 of delustering agent A, by NIPPON AEROSILCO., LTD. produce, 10% solid content), 4.6 mass parts is as the cataloid fine particle dispersion liquid (SNOWTEX-XL of delustering agent B, produce by Nissan Chemical Industries Ltd., 10% solid content) and 104.5 mass parts as the tin oxide dispersion liquid A of particulate (the tin oxide SN-38F that antimony mixes, 17% solid content, the average grain diameter of 30nm).Distilled water is added in the said mixture so that the total amount of ground floor coating fluid becomes 1000 mass parts.
[0100] [second layer coating fluid]
Above-mentioned second layer coating fluid contains the acrylic resin adhesive (MMA of 62.7 mass parts as second adhesive
59-St
9-2EHA
26-HEMA
5-AA
1Latex, 28% solid content), the above-mentioned delustering agent A of 2.7 mass parts, 4.6 mass parts delustering agent B, 9.6 mass parts surfactant A, 26.8 mass parts surfactant B, (Cellosol 524 for 7.6 mass parts lubricants, the dispersion of babassu vegetable wax, by Chukyo-yushi Co, Ltd. produce, 3% solid content), 101.0 mass parts tin oxide dispersion liquid A and carbodiimide-based cross-linker (Carbodilite V-02-L2, by Nisshinbo Industries, Inc. produce, 10% solid content, 385 carbodiimide equivalent).Distilled water is added in the said mixture so that the total amount of second layer coating fluid becomes 1000 mass parts.With respect to the quality of second adhesive, the amount of carbodiimide-based cross-linker is 6%.
[0101] for the coating thickness of the ground floor of measuring multilayer film, only the ground floor coating fluid is coated on the surface of support, and it is dry to form sample, and use transmission electron microscope (JEM2010, by JEOL Co., Ltd. produces) measure the coating layer thickness of the ground floor of samples with 200000 times enlargement ratios.
[0102] upper strata of the multilayer film by being listed in two kinds of method evaluations preparations under the condition down and the adhesiveness between the second layer: (following can being called estimates 1) before the moisture absorption and after moisture absorption (following can being called estimates 2).Also embodiment 7 and embodiment afterwards and comparative example are carried out following evaluation.
[0103] [adhesiveness (moisture absorption before) of evaluation 1. between the upper strata and the second layer]
Be described in the production method of estimating the sample A that uses in 1.At first, use doctor knife coater following coating fluid to be coated to the surface of the second layer of the multilayer film of preparation, promptly on the surface of being estimated, and, make that coating layer thickness becomes 3 μ m after drying 100 ℃ of dryings 3 minutes.Then, being exposed to the coating fluid that applies from light quantity is 2000mJ/cm
2The light of ultra high pressure mercury discharge lamp in, and solidify to form the upper strata.Thereby form sample A.Use the single-blade razor blade, on vertical and horizontal, respectively cut 6 times, on the surface on the upper strata of sample A, produce the grid pattern of 25 squares.Then, (No.405, by Nichiban Co., Ltd. produces, the width of 24mm) is placed on the grid pattern with adhesive tape, and rubs adhesive tape so that adhesive tape and grid pattern is bonding fully with eraser.Afterwards, be that upwards peel off the top at right angle with adhesive tape with respect to the sample A of horizontal positioned.Adhere on the adhesive tape and, estimate the adhesiveness between the upper strata and the second layer by calculating from the square quantity that multilayer film is peeled off.By following grade evaluation adhesiveness.Interval between the above-mentioned cutting on the vertical and horizontal is respectively 3mm.For the square peeled off of part, with the peeling off the area addition and be scaled the square number of each square, the square that makes part peel off also is contained in the counting of the square of peeling off.
Grade A: do not peel off
Grade B: the quantity of the square of peeling off is less than 1
Grade C: the quantity of the square of peeling off is more than or equal to 1 and less than 3
Grade D: the quantity of the square of peeling off is more than or equal to 3 and less than 20
Grade E: the quantity of the square of peeling off is more than or equal to 20
[0104] by mixing 225g Seikabeam EXF01 (B) (by Dainichiseika Color andChemicals Mfg.Co., Ltd. production), 75g methyl ethyl ketone, 6.8g 2, two (the trichloromethyl)-6-[4-(N, N-di ethoxy carbonyl methyl) of 4--3-bromophenyl]-s-triazine prepares above-mentioned coating fluid.
[0105] [adhesiveness (moisture absorption after) of evaluation 2. between the upper strata and the second layer]
At first, as estimating preparation sample A in 1.Then, sample A was placed 16 hours in 80 ℃/90%RH atmosphere.Then, sample A is regulated 3 hours in 23 ℃/60%RH atmosphere.Thereby preparation sample B.As the upper strata of assess sample B and the adhesiveness between the second layer 23 in evaluation 1.
[0106] in embodiment 7, adhesiveness is cited as " A " in evaluation 1.Adhesiveness is cited as " B " in 2 estimating.
[0107] [embodiment 8]
In embodiment 8, as form multilayer film in embodiment 7, difference is the addition of the crosslinking agent of the formation carbodiimide compound of second layer coating fluid is changed into respect to 12% of second adhesive quality.Evaluation is in the adhesiveness at the interface between the upper strata and the second layer 23 before the moisture absorption and after moisture absorption.Estimating in 1, adhesiveness is cited as " A ".Estimating in 2, adhesiveness is cited as " B ".
[0108] [embodiment 9]
In embodiment 9, as forming multilayer film in embodiment 7, difference is the addition of the crosslinking agent of second layer coating fluid is changed into 18 quality % with respect to second adhesive quality.As in embodiment 7, estimating adhesiveness, and in evaluation 1 and 2, all be chosen as " A " at the interface between the upper strata and the second layer before the moisture absorption and moisture absorption after.
[0109] [embodiment 10]
In embodiment 10, as form multilayer film in embodiment 7, difference is according to following formulation second layer coating fluid.As in embodiment 7, estimating adhesiveness at the interface between the upper strata and the second layer before the moisture absorption and after moisture absorption.Estimating in 1, adhesiveness is cited as " A ".Estimating in 2, adhesiveness is cited as " C ".
[0110] prescription of the second layer coating fluid that uses in embodiment 10 is as follows: (SUPERFLEX 860 for 43.9 mass parts polyurethane resin adhesives, 40% solid content, Dai-ichi Kogyo SeiyakuCo., Ltd.), 9.6 mass parts surfactant A, 26.8 mass parts surfactant B, 2.7 mass parts delustering agent A, 4.6 mass parts delustering agent B, 7.6 (Cellosol 524 for the mass parts lubricant, the dispersion of babassu vegetable wax, by Chukyo-yushi Co, Ltd. produce, 3% solid content), 101.0 mass parts tin oxide dispersion liquid A and epoxy radicals crosslinking agent (DENACOL EX-521, produce by Nagase ChemteXCorporation, 100% solid content, 183 epoxide equivalent) mixture, and add in the said mixture so that total amount becomes the distilled water of 1000 mass parts.With respect to the quality of second adhesive, the addition of epoxy radicals crosslinking agent is 6 quality %.
[0111] [embodiment 11]
In embodiment 11, as forming multilayer film in embodiment 7, difference is that the addition of the epoxy radicals crosslinking agent of the second layer coating fluid that will use changes into 12 quality % with respect to second adhesive quality in embodiment 10.As in embodiment 7, estimating adhesiveness at the interface between the upper strata and the second layer 23 before the moisture absorption and after moisture absorption.Estimating in 1, adhesiveness is cited as " A ".Estimating in 2, adhesiveness is cited as " B ".
[0112] in embodiment 12, as forming multilayer film 20 in embodiment 7, difference is that the addition of the epoxy radicals crosslinking agent of the second layer coating fluid that will use changes into 18 quality % with respect to second adhesive quality in embodiment 10.As in embodiment 7, estimating adhesiveness at the interface between the upper strata and the second layer 23 before the moisture absorption and after moisture absorption.Estimating in 1 and 2, adhesiveness all is cited as " A ".
[0113] [comparative example 4]
In comparative example 4, as forming multilayer film 20 in embodiment 7, difference is to get rid of crosslinking agent from the second layer coating fluid according to the formulation of embodiment 7.As in embodiment 7, estimating adhesiveness at the interface between the upper strata and the second layer 23 before the moisture absorption and after moisture absorption.Estimating in 1, adhesiveness is cited as " A ", and is estimating in 2, and adhesiveness is cited as " D ".
[0114] [comparative example 5]
In comparative example 5, as forming multilayer film in embodiment 7, difference is to get rid of crosslinking agent from the second layer coating fluid according to the formulation of embodiment 10.As in embodiment 7, estimating adhesiveness at the interface between the upper strata and the second layer before the moisture absorption and after moisture absorption.Estimating in 1, adhesiveness is cited as " A ", and is estimating in 2, and adhesiveness is cited as " D ".
[0115] coating layer thickness of the ground floor in embodiment 7 to 12 and comparative example 4 and 5 and evaluation result thereof are shown in table 2 and 3.In table 2 and 3, estimate 1 and be illustrated in the moisture absorption adhesiveness between the upper strata and the second layer before, be illustrated in the moisture absorption adhesiveness between the upper strata and the second layer afterwards and estimate 2." ES 650 " expression polyester adhesive (Finetex ES650 is produced 29% solid content by DainipponInkAnd Chemicals Inc.) in table 2 and 3, and acrylic compounds 1 expression acrylic resin adhesive (MMA
59-St
9-2EHA
26-HEMA
5-AA
1Latex, 28% solid content).SF860 represents polyurethane resin adhesive (SUPERFLEX 860, and by Dai-ichi Kogyo SeiyakuCo., Ltd. produces, 40% solid content).
[0116] [table 2]
CE7 to CE12 represents comparative example 7 to 12.
[0117] [table 3]
CE4 represents that comparative example 4 and CE5 represent comparative example 5.
[0118] as shown in the table 2, although evaluation result changes according to the addition and the kind of second adhesive that contains in the second layer and crosslinking agent, as commercially produced product, the evaluation result of embodiment 7 to 12 is excellent.On the other hand, as shown in the table 3, some evaluation results are excellent in comparative example 4 and 5, but as commercially produced product, all the other are not gratifying.
[0119], forms optical diffusion layer on each multilayer film by preparation in embodiment 7 to 12, the preparation light diffusing patch based on the embodiment among the Japanese Patent Laid-Open Publication 2001-324609 1.For the viewpoint of practicality, prepared light diffusing patch is excellent aspect optical property, and no problem aspect the adhesiveness between multilayer film and optical diffusion layer.
[0120] based on the embodiment among the Japanese Patent Laid-Open Publication 2001-114831 1, being coated with method by rod is that the light-cured resin compound of 25 μ m is coated on each multilayer film of preparation among the embodiment 7 to 12 with thickness, then, the mould that will have micro-prism-like pattern (has 90 ° prism angle and the prism pitch of 50 μ m, produce by Fuji Photo Film Co., Ltd.) be attached on the multilayer film, and multilayer film was placed 3 minutes in 80 ℃ baking oven.Afterwards, from coated side radiation 1.0J/cm from the UV radiation appliance
2The UV ray.It is 250mW/cm that the UV radiation appliance has radiation intensity
2Metal halide lamp as light source.Then, the mould that will have micro-prism-like pattern separates from multilayer film, thus the preparation prismatic lens.For the viewpoint of practicality, no problem aspect the adhesiveness between multilayer film and layers of prisms, and the prismatic lens of preparation has excellent optical property.
[0121] based on the embodiment among the Japanese Patent Laid-Open Publication 2001-323087, being coated with method by rod is that the active coating fluid that can ray-curable layer (hard conating) of being used to form of 8 μ m is coated on each multilayer film of preparation among the embodiment 7 to 12 with coating layer thickness.Then, use the coating fluid of ultraviolet irradiation cured coated to form hard conating.Adhesiveness between multilayer film and hard conating is excellent, has therefore prepared the hard conating sheet with excellent optical property.
[0122],, forms the antireflection sheet by hard conating, silver colloid layer and anti-reflecting layer are coated on this order on each multilayer film that forms among the embodiment 7 to 12 based on the embodiment among the Japanese Patent Laid-Open Publication 2002-098803 1.Adhesiveness between multilayer film and hard conating is excellent.Prepared antireflection sheet with excellent optical property.The coating layer thickness of hard conating is 12 μ m.The coating weight of silver colloid layer is 70mg/m
2The coating layer thickness of anti-reflecting layer is 85nm.
[0123] [industrial usability]
Multilayer film of the present invention is applicable to optical sheet, such as prismatic lens, antireflection sheet, light diffusing patch, anti-Dizzy and hard conating sheet, and display unit are such as liquid crystal display, plasma scope, organic EL display and CRT monitor.
Claims (18)
1. multilayer film, described multilayer film is included at least one lip-deep coating of support, the compound that described coating contains organic or inorganic particulate, adhesive and have the carbodiimide structure in molecule.
2. the described multilayer film of claim 1, wherein said support is by biaxial stretch-formed formation.
3. the described multilayer film of claim 1, wherein said support is formed by polyester.
4. the described multilayer film of claim 1, wherein said adhesive is the polymer with carboxyl.
5. the described multilayer film of claim 1, wherein said compound has a plurality of carbodiimide structures.
6. the described multilayer film of claim 5, the quality that wherein has the described compound of described carbodiimide structure is 1 to 200% with respect to the quality of described adhesive.
7. the described multilayer film of claim 1, the average grain diameter of wherein said particulate is more than or equal to 0.3 μ m and smaller or equal to 12 μ m.
8. the described multilayer film of claim 1, the haze value of wherein said multilayer film is not more than 3%.
9. multilayer, it comprises:
The support that forms by polyester;
Ground floor, described ground floor directly are formed at least one surface of described support; With
The second layer, the described second layer directly is formed on the described ground floor, and contains acrylic resin or polyurethane resin and cross-linking compounds.
10. the multilayer film of claim 9, wherein said cross-linking compounds is carbodiimide-based compound or epoxy-based compound.
11. the multilayer film of claim 9, wherein said ground floor contains carbodiimide-based compound.
12. the multilayer film of claim 9, wherein said ground floor contains mylar.
13. the multilayer film of claim 9 wherein after described support is biaxial stretch-formed, forms described ground floor by coating.
14. the multilayer film of claim 9, the thickness of wherein said ground floor is more than or equal to 30nm and smaller or equal to 150nm.
15. an optical sheet, it comprises:
At least one described multilayer film in the claim 1 to 14; With
At least one of layers of prisms, anti-reflecting layer, optical diffusion layer, antiglare layer and hard conating.
16. a display unit, it comprises at least one described multilayer film in the claim 1 to 14.
17. the production method of a multilayer film, described method comprises the following steps:
The biaxial stretch-formed support that forms by polymer;
Coating fluid is coated at least one surface of described support, described coating fluid contains organic or inorganic particulate, adhesive and can be formed in the crosslinking agent of the compound that has the carbodiimide structure in the molecule.
18. the production method of a multilayer film, described method comprises the following steps:
The biaxial stretch-formed support that forms by polyester;
Go up to form ground floor at least one surface that first coating fluid is coated to described support;
Second coating fluid is coated on the described ground floor to form the second layer, and described second coating fluid contains acrylic resin or polyurethane resin and crosslinking agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP354907/2005 | 2005-12-08 | ||
| JP2005354907A JP2007152886A (en) | 2005-12-08 | 2005-12-08 | Laminated sheet and its manufacturing method |
| JP026211/2006 | 2006-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101321622A true CN101321622A (en) | 2008-12-10 |
Family
ID=38237826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800457951A Pending CN101321622A (en) | 2005-12-08 | 2006-12-07 | Multilayer film, method for producing same, optical sheet using multilayer film, and display |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2007152886A (en) |
| CN (1) | CN101321622A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961940A (en) * | 2009-06-04 | 2011-02-02 | 株式会社Jiro企业策划 | Optical sheet for direct type liquid crystal display device and backlight unit |
| CN102207572A (en) * | 2010-03-31 | 2011-10-05 | 株式会社日本触媒 | Optical film and the manufacturing method thereof, optical component and image display device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102130700B1 (en) | 2013-05-30 | 2020-07-07 | 삼성디스플레이 주식회사 | Window for display device and display device including the window |
| JP6477989B1 (en) * | 2017-08-24 | 2019-03-06 | 東洋紡株式会社 | Release film for manufacturing ceramic green sheets |
| WO2022176914A1 (en) * | 2021-02-18 | 2022-08-25 | 富士フイルム株式会社 | Liquid crystal polymer film, polymer film, and multilayer body |
-
2005
- 2005-12-08 JP JP2005354907A patent/JP2007152886A/en active Pending
-
2006
- 2006-12-07 CN CNA2006800457951A patent/CN101321622A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961940A (en) * | 2009-06-04 | 2011-02-02 | 株式会社Jiro企业策划 | Optical sheet for direct type liquid crystal display device and backlight unit |
| CN101961940B (en) * | 2009-06-04 | 2013-12-25 | 株式会社Jiro企业策划 | Optical sheet for direct type liquid crystal display device and backlight unit |
| CN102207572A (en) * | 2010-03-31 | 2011-10-05 | 株式会社日本触媒 | Optical film and the manufacturing method thereof, optical component and image display device |
| CN102207572B (en) * | 2010-03-31 | 2017-03-01 | 株式会社日本触媒 | Blooming and its manufacture method, opticses and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007152886A (en) | 2007-06-21 |
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