WO2012124323A1 - 防眩性フィルム、防眩性フィルムの製造方法、防眩性反射防止フィルム、偏光板、及び画像表示装置 - Google Patents
防眩性フィルム、防眩性フィルムの製造方法、防眩性反射防止フィルム、偏光板、及び画像表示装置 Download PDFInfo
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- WO2012124323A1 WO2012124323A1 PCT/JP2012/001780 JP2012001780W WO2012124323A1 WO 2012124323 A1 WO2012124323 A1 WO 2012124323A1 JP 2012001780 W JP2012001780 W JP 2012001780W WO 2012124323 A1 WO2012124323 A1 WO 2012124323A1
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- antiglare
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0221—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133602—Direct backlight
- G02F1/133606—Direct backlight including a specially adapted diffusing, scattering or light controlling members
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact
Definitions
- the present invention relates to an antiglare film, a method for producing an antiglare film, an antiglare antireflection film, a polarizing plate, an image display device, and a liquid crystal display device having a touch panel.
- Anti-glare treatment includes surface roughening by chemical etching or the like, surface unevenness by a transfer method using a mold, etc., and surface unevenness by dispersing fine particles in the resin layer. Some have been granted.
- Patent Document 1 the total haze is 1 to 30%, the internal haze is 0 to 1%, and the average reflectance at 5 ° incidence in the wavelength range of 450 to 650 nm is 0.001 to 2.5%.
- An antiglare film is disclosed.
- the invention described in Patent Document 1 is a technique in which a polymer component (cellulose acetate propionate) that is incompatible with a cured resin is contained, and surface irregularities are formed by spinodal decomposition when the coating film is dried.
- Patent Document 2 has one or more antiglare hard coat layers on a transparent film, the internal haze of the antiglare hard coat layer is 0.5% or less, and the surface haze / internal haze is 2.0 or more.
- An anti-glare hard coat film is disclosed.
- the invention described in Patent Document 2 utilizes phase separation by spinodal decomposition of two types of incompatible resins (resin A; for example, dipentaerythritol hexaacrylate and resin B; for example, a methacrylate copolymer). This is a technique for forming surface irregularities.
- solubility parameter as described in Patent Documents 1 and 2 is different, and an anti-glare film that forms surface irregularities using regular phase separation by mixing incompatible resins and spinodal decomposition.
- Phase separation is difficult to control, and slight changes in the raw material lot, polymer composition, etc. cause large changes in the size of the phase separation structure, resulting in uneven surface irregularities, making it difficult to form stable surface irregularities.
- When used for image display there is a problem in that the visibility is lowered.
- the object of the present invention is that a stable surface irregularity is formed, there is no generation of micro-opacity and micro-cracking of the anti-glare film after the durability test, and visibility (reflection prevention performance) when used in an image display device. And providing an antiglare film excellent in sharpness. Also provided are a method for producing the antiglare film, an antiglare antireflection film using the antiglare film, a polarizing plate having excellent visibility, an image display device, and a liquid crystal display device having a touch panel. It is in.
- one aspect of the present invention is an antiglare film having an antiglare layer containing an active ray curable resin on a base film, wherein the antiglare layer is formed into fine particles and the active ray curable resin.
- the antiglare layer substantially does not contain an incompatible resin, the arithmetic average roughness Ra of the antiglare layer is 300 to 1500 nm, and the haze caused by internal scattering of the antiglare layer is 0 to 1.0. % Is provided.
- the present invention stable surface irregularities are formed, there is no occurrence of micro-opacity and micro-cracking of the anti-glare film after the durability test, and when used in an image display device, the visibility (reflection prevention performance) And sharpness) can be provided. Also provided are a method for producing the antiglare film, an antiglare antireflection film using the antiglare film, a polarizing plate having excellent visibility, an image display device, and a liquid crystal display device having a touch panel. Can do.
- FIG. 1 is an explanatory diagram of protrusions.
- FIG. 2 is a schematic view showing irregular protrusions of the antiglare layer of the antiglare film according to one embodiment of the present invention.
- symbol 1 shows a glare-proof layer and the code
- FIG. 3 is an observation view of an optical interference surface roughness meter on the surface of the antiglare layer of the antiglare film.
- FIG. 4 shows a cross-sectional view of the polarizing plate prepared in the example.
- FIG. 5 shows a cross-sectional view of the liquid crystal panel produced in the example.
- FIG. 6 is a schematic view of a liquid crystal cell of a liquid crystal display device.
- FIG. 7 is a diagram illustrating a configuration example of an antireflection film with an electric film.
- FIG. 8 is a schematic diagram illustrating an example of a configuration of a resistive film type touch panel liquid crystal display device.
- the antiglare film of the present invention is an antiglare film having an antiglare layer containing an active ray curable resin on a base film, and the antiglare layer is formed into fine particles and the active ray curable resin.
- the antiglare layer substantially does not contain an incompatible resin, the arithmetic average roughness Ra of the antiglare layer is 300 to 1500 nm, and the haze caused by internal scattering of the antiglare layer is 0 to 1.0. With this configuration, stable surface irregularities are formed, there is no occurrence of micro-opacity or micro-cracking in the anti-glare film after the durability test, and the visibility (reflection) is used in an image display device. It is possible to provide an anti-glare film having excellent anti-bending performance and sharpness).
- the present inventor conducted intensive studies on the above-mentioned problems. As a result, the occurrence of micro-opacity and micro-cracking in the anti-glare film after the durability test was observed after the durability test (flexibility of the film). ) And further, it has been found that the transmission image quality greatly affects.
- the arithmetic average roughness Ra and the internal haze of the antiglare layer are controlled within a specific range, and the antiglare layer is protected under a condition that does not substantially contain a resin that is incompatible with the fine particles and the active ray curable resin.
- the antiglare film of the present invention for an image display device, it is possible to obtain excellent sharpness as well as excellent visibility.
- the antiglare film referred to in the present invention is an image reflected on the surface of the film substrate or a layer that blurs the outline of external light (that is, an antiglare layer) on the surface of the film substrate, so that the liquid crystal display, organic It is a film that prevents external light or reflected images from being reflected when an image display device such as an EL display or a plasma display is used.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the “surface haze value” and the “internal haze value” are also simply expressed as “surface haze” and “internal haze”, respectively.
- the antiglare film of the present embodiment is an antiglare film having an antiglare layer containing an active ray curable resin on a base film, and the antiglare layer is formed into fine particles and the active ray curable resin.
- the resin does not substantially contain an incompatible resin
- the arithmetic average roughness Ra of the antiglare layer is 300 to 1500 nm
- haze due to internal scattering of the antiglare layer is 0 to 1.0. %.
- incompatible means that each of the resins constituting the molten mixture has a single peak when the melting temperature Tm or the glass transition point Tg of the molten mixture of two or more resins is measured and observed. Means what is observed. Further, it means that each phase is substantially observed in transmission electron microscope observation.
- compatible means that one or less peaks of the molten mixture are observed when the melting temperature Tm or the glass transition point Tg of the molten mixture of the same or two or more resins is measured and observed.
- the Tg and Tm of the resin are temperatures at which the baseline based on the Tg and Tm of DSC measurement starts to deviate.
- substantially does not contain varies depending on the type and properties of fine particles and incompatible resin, but the content in the antiglare layer excludes the extract component from the base film. , 0.01 mass% or less, more preferably not contained at all.
- the resin that is incompatible with the actinic radiation curable resin is a resin obtained by polymerizing or copolymerizing (meth) acrylic or acrylic monomers. And polyester resins, and thermoplastic acrylic resins and cellulose ester resins used in the base film described later.
- Examples of the fine particles include fine particles such as inorganic fine particles and organic fine particles, and specific examples of the inorganic fine particles include silicon oxide, magnesium oxide, and calcium carbonate.
- Examples of the organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, polystyrene resin powder, and melamine resin powder.
- the antiglare layer has an arithmetic average roughness Ra (JIS B0601: 1994) of 300 to 1500 nm.
- the arithmetic average roughness Ra is more preferably 350 to 1300 nm, and particularly preferably 500 to 1300 nm.
- the arithmetic and average roughness Ra of 350 to 1300 nm shows the object effect of the present invention better, and the arithmetic average roughness Ra of 500 to 1300 nm shows a scratched pencil in a hardness test by a pencil hardness evaluation method (details of the test method will be described later). Since the slipperiness in the anti-glare layer is increased and scratches are less likely to occur, even a thin film is preferable because high hardness (4H or more) can be obtained.
- the height of the protrusion shape is preferably 20 nm to 6 ⁇ m.
- the width of the protrusion shape is 50 nm to 300 ⁇ m, preferably 50 nm to 100 ⁇ m.
- the height and width of the protrusion shape can be obtained from cross-sectional observation. For easier understanding, an explanatory diagram for measuring the height of the protrusion shape is shown in FIG. As shown in FIG. 1, the center line a is drawn on the cross-sectional observation image, and the distance between the two intersections of the lines b and c and the center line a forming the mountain ridge is defined as the protrusion size width t and did.
- the 10-point average roughness Rz of the antiglare layer of the antiglare film of this embodiment is 10 times or less the centerline average roughness Ra, and the average mountain valley distance Sm is preferably 5 to 150 ⁇ m, more preferably 20 to 100 ⁇ m. It is preferable that the standard deviation of the height of the convex part from the deepest part of the concavo-convex part is 0.5 ⁇ m or less, the standard deviation of the average mountain-valley distance Sm with respect to the center line is 20 ⁇ m or less, and the area of the inclination angle 0 to 5 degrees is 10% or more.
- the kurtosis (Rku) of the antiglare layer is preferably 3 or less.
- the skewness (Rsk) preferably has an absolute value of 1 or less.
- the arithmetic average roughness Ra, Sm, Rz is a value measured by an optical interference surface roughness meter (for example, RST / PLUS, manufactured by WYKO, New View 5030 manufactured by Zygo) according to JIS B0601: 1994. is there.
- the antiglare film of this embodiment is characterized in that the haze caused by internal scattering of the antiglare layer (hereinafter also referred to as internal haze) is 0 to 1.0%.
- internal haze the haze caused by internal scattering of the antiglare layer
- the internal haze within the above range is controlled, and the arithmetic average roughness Ra of the protrusion shape is controlled within the above range, and the antiglare layer is incompatible with the fine particles and the actinic radiation curable resin.
- the objective effect of this invention is exhibited favorably by not containing substantially the resin which is.
- the internal haze is preferably 0 to 0.5%.
- the internal haze can be measured by the following procedure.
- a few drops of silicone oil are dropped on the front and back surfaces of the antiglare film and sandwiched between two glass plates (micro slide glass product number S 9111, manufactured by MATSUNAMI) having a thickness of 1 mm from the front and back.
- An anti-glare film sandwiched between front and back glass is optically brought into intimate contact with two glass plates, and haze (Ha) is measured in accordance with JIS-K7105 and JIS K7136 in this state.
- several drops of silicone oil are dropped between two glass plates and sandwiched to measure glass haze (Hb).
- internal haze (Hi) is computable by drawing glass haze (Hb) from the haze (Ha) which pinched
- the surface haze (the haze resulting from the surface scattering of the film) is preferably 3 to 40%.
- the surface haze is obtained by subtracting the internal haze from the total haze.
- the total haze is preferably 3% to 40%.
- the antiglare film of the present embodiment has a projection shape in which the antiglare layer forms surface irregularities, the projection shape is a projection having an irregular shape in the longitudinal direction, and the arrangement thereof is also irregular arrangement. It is preferable. By having such a protrusion shape, the object effect of the present invention is exhibited well.
- the “irregularly shaped protrusions” included in the antiglare layer of the antiglare film of the present embodiment means that the surface irregularities do not have a regular shape periodically in the length direction formed by embossing. This refers to protrusions of various shapes whose sizes are not fixed. Although not limited thereto, for example, protrusions having different widths and heights shown in FIG. 2 are exemplified as irregularly shaped protrusions.
- the “irregular arrangement” means that the irregularly-protruding protrusions are not regularly arranged (for example, at regular intervals), but are irregularly arranged at random intervals, It may be isotropic or anisotropic.
- the surface shape thereof is controlled at a high temperature, for example, the processing temperature of the rate-decreasing drying section in the drying process of the antiglare layer coating composition. It can be obtained by a method in which a convection of the resin is generated, a non-uniform state is formed on the surface of the antiglare layer, and the coating is formed by curing in this non-uniform surface state. By forming the coating film by such a method, the film strength of the antiglare layer is improved.
- the method of controlling the treatment temperature in the decreasing rate drying section in the drying process of the antiglare layer coating composition is preferable in terms of excellent productivity.
- the manufacturing method of the said anti-glare film will not be specifically limited if what has the anti-glare layer which has the above characteristics on a base film can be manufactured.
- an actinic radiation curable resin having a viscosity at 25 ° C. in the range of 20 to 3000 mPa ⁇ s is diluted with at least one solvent selected from esters, glycol ethers or alcohols.
- the antiglare layer coating composition is formed at least through the coating process, the drying process and the curing process, and the temperature of the decreasing rate drying section in the drying process is maintained within the range of 90 to 160 ° C.
- the manufacturing method provided with processing on the conditions which were carried out is mentioned.
- the application is not particularly limited as long as it is a method capable of applying the antiglare layer coating composition on the base film so that the thickness after curing becomes a predetermined thickness. Specifically, a coating method as described later can be used. Drying and curing are not particularly limited as long as the above conditions are satisfied and an antiglare layer can be formed on the base film, and examples thereof include the methods described below.
- the antiglare layer according to this embodiment contains an actinic radiation curable resin, that is, a resin that is cured through a crosslinking reaction when irradiated with actinic rays (also referred to as active energy rays) such as ultraviolet rays and electron beams. It is a layer.
- actinic radiation curable resin that is, a resin that is cured through a crosslinking reaction when irradiated with actinic rays (also referred to as active energy rays) such as ultraviolet rays and electron beams. It is a layer.
- an actinic radiation curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams.
- Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but the resin that is cured by ultraviolet irradiation is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable.
- the ultraviolet curable resin examples include an ultraviolet curable acrylate resin, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet ray.
- a curable epoxy resin or the like is preferably used. Of these, ultraviolet curable acrylate resins are preferred.
- polyfunctional acrylate is preferable.
- the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
- the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.
- polyfunctional acrylate monomer examples include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate.
- the active energy ray-curable isocyanurate derivative is not particularly limited as long as it is a compound having a structure in which one or more ethylenically unsaturated groups are bonded to the isocyanuric acid skeleton, but three or more in the same molecule.
- a compound having an ethylenically unsaturated group and one or more isocyanurate rings is preferred. More specifically, for example, isocyanuric acid triacrylate compound, isocyanuric acid diacrylate compound, ⁇ -caprolactone-modified tris- (acryloxyethyl) isocyanurate, and the like can be mentioned.
- Adekaoptomer N series Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries, Ltd.) SP-1509, SP-1507, Aronix M-6100, M-8030, M-8060, Aronix M-215, Aronix M-315, Aronix M-313, Aronix M-327 (manufactured by Toagosei Co., Ltd.), NK-ester A-TMM-3L, NK-ester AD-TMP, NK-ester ATM-35E, NK ester A-DOG, NK ester A-IBD-2E, A-9300, A-9300-1CL (Shin Nakamura Chemical) Industrial Co., Ltd.), Light Acrylate TMP-A, PE-3A (Kyoeisha Chemical Co., Ltd.)
- monofunctional acrylate may be used.
- Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate.
- Such monofunctional acrylates can be obtained from Nippon Kasei Co., Ltd., Shin-Nakamura Chemical Co., Ltd., Osaka Organic Chemical Co., Ltd., etc.
- a monofunctional acrylate 70: 30 to 99: 2 in terms of mass ratio of polyfunctional acrylate and monofunctional acrylate.
- Actinic radiation curable resins may be used alone or in combination of two or more.
- the viscosity of the actinic radiation curable resin at 25 ° C. is preferably 20 mPa ⁇ s or more and 3000 mPa ⁇ s or less, more preferably 20 mPa ⁇ s or more and 2000 mPa ⁇ s or less.
- the above-described protrusion shape and arithmetic average roughness Ra are easily obtained.
- the viscosity of the actinic radiation curable resin is 20 mPa ⁇ s or higher, a monomer having a high functionality can be used, and sufficiently high curability is obtained. If the viscosity is 3000 mPa ⁇ s or lower, the drying step In this case, it is easy to obtain sufficient fluidity of the actinic radiation curable resin.
- the said viscosity is the value measured on 25 degreeC conditions using the B-type viscosity meter.
- the antiglare layer preferably contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin.
- Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof. In particular, it is not limited to these.
- a commercial item may be used for such a photoinitiator, for example, Irgacure 184, Irgacure 907, Irgacure 651, etc. by BASF Japan Ltd. are mentioned as a preferable illustration.
- the antiglare layer may contain a conductive agent in order to impart antistatic properties.
- a conductive agent include ⁇ -conjugated conductive polymers and ionic liquids.
- the antiglare layer may contain a silicone surfactant, a fluorine surfactant, an acrylic surfactant, a fluorine-siloxane graft compound, or a compound having an HLB value of 3 to 18 from the viewpoint of coatability. good.
- a compound having an HLB value of 3 to 18 will be described.
- the HLB value is Hydrophile-Lipophile-Balance, hydrophilic-lipophilic-balance, and is a value indicating the hydrophilicity or lipophilicity of a compound. The smaller the HLB value, the higher the lipophilicity, and the higher the value, the higher the hydrophilicity.
- the HLB value can be obtained by the following calculation formula.
- HLB 7 + 11.7Log (Mw / Mo)
- Mw represents the molecular weight of the hydrophilic group
- Mo represents the molecular weight of the lipophilic group
- Mw + Mo M (molecular weight of the compound).
- HLB value 20 ⁇ total formula weight of hydrophilic part / molecular weight (J. Soc. Cosmetic Chem., 5 (1954), 294) and the like.
- Specific examples of the compound having an HLB value of 3 to 18 are listed below, but are not limited thereto. Figures in parentheses indicate HLB values.
- Emulgen 102KG (6.3), Emulgen 103 (8.1), Emulgen 104P (9.6), Emulgen 105 (9.7), Emulgen 106 (10.5), Emulgen 108 (12. 1), Emulgen 109P (13.6), Emulgen 120 (15.3), Emulgen 123P (16.9), Emulgen 147 (16.3), Emulgen 210P (10.7), Emulgen 220 (14.2) , Emulgen 306P (9.4), Emulgen 320P (13.9), Emulgen 404 (8.8), Emulgen 408 (10.0), Emulgen 409PV (12.0), Emulgen 420 (13.6), Emulgen 430 (16.2), Emulgen 705 (10.5), Emulgen 707 (12.1), Emulgen 09 (13.3), Emulgen 1108 (13.5), Emulgen 1118S-70 (16.4), Emulgen 1135S-70 (17.9), Emulgen 2020G-HA (13.0), Emulgen 2025G (15.
- Emulgen LS-106 (12.5), Emulgen LS-110 (13.4), Emulgen LS-114 (14.0), manufactured by Nissin Chemical Industry Co., Ltd .: Surfynol 104E (4), Surfynol 104H (4), Surfinol 104A (4), Surfinol 104BC (4), Surfinol 104DPM (4), Surfinol 104PA (4), Surfinol 104PG-50 (4), Surfinol 104S (4), Surfy Knoll 420 (4), Surfynol 440 (8), Surfynol 4 5 (13), Surfynol 485 (17), Surfynol SE (6), manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-4272 (7), X-22-6266 (8), KF-351 (12) KF-352 (7), KF-353 (10), KF-354L (16), KF-355A (12), KF-615A (10), KF-9
- silicone surfactant examples include polyether-modified silicone, and the KF series manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
- acrylic surfactant examples include commercially available compounds such as BYK-350 and BYK-352 manufactured by BYK Japan.
- fluorosurfactant examples include Megafac RS series, Megafac F-444 and Megafac F-556 manufactured by DIC Corporation.
- the fluorine-siloxane graft compound is a copolymer compound obtained by grafting polysiloxane containing siloxane and / or organosiloxane alone and / or organopolysiloxane to at least a fluorine resin.
- Examples of commercially available products include ZX-022H, ZX-007C, ZX-049, ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.
- the antiglare layer is prepared by diluting the above-described components for forming the antiglare layer with a solvent as an antiglare layer coating composition, and applying, drying and curing the antiglare layer coating composition on the film substrate in the following manner. Thus, it is preferable to provide an antiglare layer.
- Solvents include ketones (methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, etc.), alcohols (ethanol, methanol, butanol, etc.) , N-propyl alcohol, isopropyl alcohol, diacetone alcohol), hydrocarbons (toluene, xylene, benzene, cyclohexane), glycol ethers (propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, etc.), etc.
- ketones methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, etc.
- esters methyl acetate, ethy
- the antiglare layer is applied after the antiglare layer coating composition is applied to the base film.
- the solvent of the coating composition evaporates, convection of the resin is likely to occur, and as a result, the antiglare layer is irregular in the longitudinal direction and also on the base film. It is preferable because surface roughness having an irregular protrusion shape is easily developed and the arithmetic average roughness Ra is easily controlled.
- the coating amount of the antiglare layer is suitably 0.1 to 40 ⁇ m as a wet film thickness, and preferably 0.5 to 30 ⁇ m.
- the dry film thickness is from 0.1 to 30 ⁇ m, preferably from 1 to 20 ⁇ m, particularly preferably from 2 to 15 ⁇ m.
- an antiglare layer coating composition for forming an antiglare layer is applied, dried after application, irradiated with actinic radiation (also referred to as UV curing treatment), and, if necessary, after UV curing It can be formed by heat treatment.
- the heat treatment temperature after UV curing is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher.
- Drying is preferably performed by high-temperature treatment at a temperature of 90 ° C. or higher in the rate of drying section. More preferably, the temperature of the decreasing rate drying section is 90 ° C or higher and 150 ° C or lower.
- the temperature of the reduced rate drying section is 90 ° C or higher and 150 ° C or lower.
- the drying process changes from a constant state to a gradually decreasing state when drying starts.
- the decreasing section is called the decreasing rate drying section.
- the constant rate drying section the amount of heat flowing in is all consumed for solvent evaporation on the coating film surface, and when the solvent on the coating film surface decreases, the evaporation surface moves from the surface to the inside and enters the decreasing rate drying section.
- the temperature of the coating film surface rises and approaches the hot air temperature, and the temperature of the actinic radiation curable resin of the coating film rises.
- the convection of the coating film resin is caused by the decrease in the viscosity of the actinic radiation curable resin and the increase in fluidity.
- any light source that generates ultraviolet rays can be used without limitation.
- a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
- Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 50 to 1000 mJ / cm 2 , preferably 50 to 300 mJ / cm 2 .
- the tension to be applied is preferably 30 to 300 N / m.
- the method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.
- the antiglare layer may further contain an ultraviolet absorber described in the base film described later.
- the antiglare layer is preferably composed of two or more layers, and the antiglare layer in contact with the base film preferably contains the ultraviolet absorber.
- the film thickness of the antiglare layer in contact with the base film is preferably in the range of 0.05 to 2 ⁇ m.
- Two or more layers may be formed as a simultaneous multilayer.
- the simultaneous multi-layering means that two or more anti-glare layers are applied on a wet substrate on a substrate without passing through a drying step to form the anti-glare layer.
- the layers are stacked one after another with an extrusion coater or simultaneously with a slot die having a plurality of slits. Can be done.
- the anti-glare film in this embodiment has a pencil hardness, which is an index of hardness, of H or higher, more preferably 3H or higher. If it is 3H or more, it is not only difficult to be scratched in the polarizing plate forming step of the liquid crystal display device, but also used for outdoor applications, and is a surface protective film for large liquid crystal display devices and liquid crystal display devices for digital signage. Excellent mechanical properties when used. More preferably, the pencil hardness is 4H or more.
- the pencil hardness was determined by adjusting the humidity of the produced antiglare film for 2 hours or more under conditions of a temperature of 23 ° C. and a relative humidity of 55%, and then using a test pencil specified by JIS S 6006 under a load of 500 g. It is a value measured according to the pencil hardness evaluation method specified by K5400. Next, the base film will be described.
- the base film is preferably easy to manufacture, easily adheres to the antiglare layer, and is optically isotropic. Moreover, in this embodiment, a base film is used as a polarizing plate protective film.
- cellulose ester-based films such as triacetyl cellulose film, cellulose acetate propionate film, cellulose diacetate film, and cellulose acetate butyrate film, polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Syndiotactic polystyrene film, norbornene resin film, polymethylpente Films, polyether ketone films, polyether ketone imide film, a polyamide film, a fluorine resin film, nylon film, can be used cycloolefin polymer film, a polymethyl methacrylate film or an acrylic film or the like.
- polyester film such as naphthalate, polycarbonate film, polyarylate film, polysulfone (including polyether
- cellulose ester films for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UE, KC4UE, and KC12UR (above, Konica Minolta Opto Co., Ltd., Polycarbonate Film)
- An olefin polymer film and a polyester film are preferable, and in the present invention, the cellulose ester film is preferable from the viewpoint of ease of obtaining the above-described protruding shape by the antiglare layer, productivity and cost.
- the refractive index of the base film is preferably 1.30 to 1.70, and more preferably 1.40 to 1.65.
- the refractive index is measured by the method of JIS K7142 using an Atpe refractometer 2T manufactured by Atago Co., Ltd.
- the cellulose ester film is not particularly limited as long as it has the above characteristics, but the cellulose ester resin (hereinafter also referred to as cellulose ester) is preferably a lower fatty acid ester of cellulose.
- the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms.
- mixed fatty acid esters such as cellulose acetate butyrate can be used.
- the lower fatty acid esters of cellulose particularly preferably used are cellulose diacetate, cellulose triacetate, and cellulose acetate propionate. These cellulose esters can be used alone or in combination.
- Cellulose diacetate preferably has an acetyl group substitution degree of 2.0 to 2.5.
- Commercially available products include Daicel L20, L30, L40, and L50, and Eastman Chemical's Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S.
- cellulose triacetate those having an acetyl group substitution degree of 2.75 to 2.95 are preferably used.
- a preferred cellulose ester other than cellulose triacetate has an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution degree of propionyl group or butyryl group is Y, It is a cellulose ester containing the cellulose ester which satisfy
- cellulose acetate propionate is preferably used, and among them, 1.9 ⁇ X ⁇ 2.5 and 0.1 ⁇ Y ⁇ 0.9 are preferable.
- the cellulose ester preferably has a number average molecular weight (Mn) of 125,000 or more and less than 180000, and the cellulose ester has a weight average molecular weight Mw / number average molecular weight Mn ratio of 1.5 to 5.5. It is preferably used, particularly preferably 2.0 to 5.0, more preferably 2.5 to 5.0, and still more preferably 3.0 to 5.0 cellulose ester.
- the number average molecular weight (Mn) and molecular weight distribution (Mw) of cellulose ester can be measured using high performance liquid chromatography.
- the measurement conditions are as follows.
- the raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable.
- a cotton linter is preferably used from the viewpoint of peelability during film formation.
- the cellulose ester made from these can be mixed suitably or can be used independently.
- the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.
- 1 g of cellulose ester is added to 20 ml of pure water (electric conductivity 0.1 ⁇ S / cm or less, pH 6.8), and the pH when stirred in a nitrogen atmosphere at 25 ° C. for 1 hr is 6 It is preferable that the electric conductivity is 1 to 100 ⁇ S / cm.
- Acrylic resin includes methacrylic resin.
- the acrylic resin is not particularly limited, but is preferably composed of 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith.
- Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 alkyl carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, alkyl acrylates such as acrylic acid and methacrylic acid.
- Unsaturated group-containing divalent carboxylic acids such as saturated acid, maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, Examples thereof include maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like, and these can be used alone or in combination of two or more monomers.
- methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
- n-Butyl acrylate is particularly preferably used.
- the weight average molecular weight (Mw) is preferably 80,000 to 500,000, and more preferably 110,000 to 500,000.
- the weight average molecular weight of the acrylic resin can be measured by gel permeation chromatography including the measurement conditions.
- a manufacturing method of an acrylic resin You may use any well-known methods, such as suspension polymerization, emulsion polymerization, block polymerization, or solution polymerization.
- a polymerization initiator a normal peroxide type and an azo type can be used, and a redox type can also be used.
- the polymerization temperature may be 30 to 100 ° C. for suspension or emulsion polymerization, and 80 to 160 ° C. for bulk or solution polymerization.
- polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
- alkyl mercaptan Commercial products can also be used.
- Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned.
- Two or more acrylic resins can be used in combination.
- the acrylic resin may be a graft copolymer obtained by grafting a (meth) acrylic resin to a copolymer of (meth) acrylic rubber and an aromatic vinyl compound.
- a copolymer of (meth) acrylic rubber and an aromatic vinyl compound forms a core, and the (meth) acrylic resin forms a shell around the copolymer.
- -A shell-type graft copolymer is preferred.
- the total mass of the acrylic resin and the cellulose ester resin in the base film is preferably 55% by mass or more of the base film, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
- the base film may be configured to contain resins and additives other than thermoplastic acrylic resins and cellulose ester resins.
- the base film may contain acrylic particles because it is excellent in improving brittleness.
- An acrylic particle represents the acrylic component which exists in the state of particle
- the acrylic particles are not particularly limited, but are preferably multi-layered acrylic granular composites.
- Examples of commercially available acrylic granular composites that are multi-layer structured polymers include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kaneace” manufactured by Kaneka Chemical Co., Ltd., “Paralloid” manufactured by Kureha Chemical Co., Ltd., Rohm and “Acryloid” manufactured by Haas, “Staffyroid” manufactured by Ganz Kasei Kogyo Co., Ltd., “Parapet SA” manufactured by Kuraray Co., Ltd., and the like can be used alone or in combination of two or more.
- the refractive index of the mixture of the acrylic resin and the cellulose ester resin is close to the refractive index of the acrylic particles in order to obtain a highly transparent film.
- the refractive index difference between the acrylic particles and the acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.
- Acrylic fine particles are in a range of 0.5: 100 to 30: 100 in terms of the content of acrylic fine particles: acrylic resin and cellulose ester resin with respect to the total mass of acrylic resin and cellulose ester resin constituting the film.
- the base film is, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate. It is preferable to contain inorganic fine particles such as calcium phosphate and a matting agent such as a crosslinked polymer. Among these, silicon dioxide is preferably used because it can reduce the haze of the film.
- the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm.
- a plasticizer can also be used in combination with the base film in order to improve the fluidity and flexibility of the composition.
- the plasticizer include phthalate ester, fatty acid ester, trimellitic ester, phosphate ester, polyester, and epoxy. Of these, polyester plasticizers are preferably used. Polyester plasticizers are superior in non-migration and extraction resistance compared to phthalate ester plasticizers such as dioctyl phthalate. It can be applied to a wide range of uses by selecting or using these plasticizers according to the use.
- the polyester plasticizer is a reaction product of a monovalent or tetravalent carboxylic acid and a monovalent or hexavalent alcohol, and is mainly obtained by reacting a divalent carboxylic acid with a glycol.
- Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like.
- the polyester plasticizer is preferably an aromatic terminal ester plasticizer.
- an aromatic terminal ester plasticizer an ester compound having a structure obtained by reacting phthalic acid, adipic acid, at least one benzene monocarboxylic acid and at least one alkylene glycol having 2 to 12 carbon atoms is preferable.
- benzene monocarboxylic acid component examples include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like. Most preferred is benzoic acid. Moreover, these can be used as a 1 type, or 2 or more types of mixture, respectively.
- alkylene glycol component having 2 to 12 carbon atoms examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1, 3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol 1 , 6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexan
- the aromatic terminal ester plasticizer may be either an oligoester type or a polyester type, and the molecular weight is preferably in the range of 100 to 10,000, but is preferably in the range of 350 to 3000.
- the acid value is 1.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.5 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.
- the aromatic terminal ester plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the base film. Specific examples thereof include, but are not limited to, the following compounds (B-1 to B-10).
- the base film may contain the following sugar ester compound.
- the sugar ester compound is a compound obtained by esterifying all or part of the OH group of a sugar such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide. As a more specific example, a general formula (1) And the like.
- R1 to R8 represent a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms, and R1 to R8 are the same. Or it may be different.
- the compounds represented by the general formula (1) are shown more specifically (compound 1-1 to compound 1-23), but are not limited thereto.
- the “average degree of substitution” in the table below indicates the degree of substitution of R.
- an average degree of substitution of 6.0 indicates that the number of R1 to R8 substituted for R is an average of 6.
- R1 to R8 in the compound represented by the general formula (1) are unsubstituted except for those substituted with R, that is, a hydrogen atom is bonded.
- the base film preferably contains an ultraviolet absorber, and examples of the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
- the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
- 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone And benzophenones.
- UV absorbers with a molecular weight of 400 or more are difficult to volatilize at high boiling points and are difficult to disperse even during high temperature molding, so that the weather resistance can be effectively improved with a relatively small amount of addition. Can do.
- Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Such as til] -4- [3- (3,5-di-tert-butyl
- 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.
- TINUVIN such as TINUVIN 109, TINUVIN 171, TINUVIN 234, TINUVIN 326, TINUVIN 327, TINUVIN 328, and TINUVIN 928 manufactured by BASF Japan Ltd.
- various antioxidants can also be added to the base film in order to improve the thermal decomposability and thermal colorability during molding. It is also possible to add an antistatic agent to give the base film antistatic performance.
- a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used.
- Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.
- triphenyl phosphate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
- the base film is required to withstand use in a higher temperature environment, and if the tension softening point of the base film is 105 ° C. to 145 ° C., it is judged that the base film exhibits sufficient heat resistance. In particular, 110 ° C. to 130 ° C. is preferable.
- a Tensilon tester (ORIENTEC Co., RTC-1225A) is used to cut out the optical film at 120 mm (length) ⁇ 10 mm (width) and pull it with a tension of 10 N.
- the temperature can be continuously increased at a temperature increase rate of 30 ° C./min, and the temperature at 9 N can be measured three times, and the average value can be obtained.
- the glass transition temperature referred to here is an intermediate value determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min. Point glass transition temperature (Tmg).
- the dimensional change rate (%) is preferably less than 0.5%, and more preferably less than 0.3%.
- the base film preferably has a defect of 5 ⁇ m or more in diameter in the film plane of 1 piece / 10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.
- the diameter of the defect indicates the diameter when the defect is circular, and when the defect is not circular, the range of the defect is determined by observing with a microscope by the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
- the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object.
- the defect is a change in the surface shape, such as transfer of a roll flaw or an abrasion
- the size is confirmed by observing the defect with the reflected light of a differential interference microscope.
- the film When the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film during processing in a later process, the film may be broken with the defect as a starting point and productivity may be reduced. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
- the coating agent may not be formed uniformly, resulting in defects (coating defects).
- the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign substance in the film forming stock solution, or a foreign substance mixed in the film forming process. This refers to the foreign matter (foreign matter defect) in the film.
- the base film preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more in the measurement based on JIS-K7127-1999.
- the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
- the thickness of the base film is preferably 10 ⁇ m or more. More preferably, it is 20 ⁇ m or more.
- the upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 ⁇ m from the viewpoint of applicability, foaming, solvent drying and the like. The thickness of the film can be appropriately selected depending on the application.
- the base film preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film. Also, reduce the surface roughness of the film surface by reducing the surface roughness of the film contact part (cooling roll, calender roll, drum, belt, coating substrate in solution casting, transport roll, etc.) during film formation. It is also effective to reduce the diffusion and reflection of light on the film surface by reducing the refractive index of the acrylic resin.
- a production method such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, a hot press method, or the like can be used.
- melt casting film forming method From the viewpoint of suppressing the residual solvent using a cellulose ester resin or an acrylic resin for dissolution, a method of producing by a melt casting film forming method is preferable.
- Methods formed by melt casting can be classified into melt extrusion molding methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like.
- the melt extrusion method is preferable, in which a film having excellent mechanical strength and surface accuracy can be obtained.
- solution casting by casting is preferred.
- a method of extruding and forming a film forming material on a drum or an endless belt after the film forming material is heated to express its fluidity is also included as a melt casting film forming method.
- Organic solvent useful for forming the dope when the base film is produced by the solution casting method can be used without limitation as long as it dissolves acrylic resin, cellulose ester resin, and other additives at the same time. .
- methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
- Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.
- the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
- a linear or branched aliphatic alcohol having 1 to 4 carbon atoms When the proportion of alcohol in the dope increases, the web gels and peeling from the metal support becomes easy, and when the proportion of alcohol is small, the acrylic resin and cellulose ester resin dissolve in a non-chlorine organic solvent system.
- a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms at least 15 to 45 mass in total of at least three kinds of acrylic resin, cellulose ester resin, and acrylic particles are used. It is preferable that the dope composition is dissolved in%.
- linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.
- the base film can be produced by a solution casting method.
- a step of preparing a dope by dissolving a resin and an additive in a solvent a step of casting the dope on a belt-like or drum-like metal support, and a step of drying the cast dope as a web , A step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
- the concentration of cellulose ester in the dope, and the concentration of cellulose ester resin / acrylic resin is preferably higher because the drying load after casting on the metal support can be reduced. The load increases, and the filtration accuracy deteriorates.
- the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
- the metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
- the cast width can be 1 ⁇ 4m.
- the surface temperature of the metal support in the casting step is set to ⁇ 50 ° C. to below the temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.
- a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably 5 to 30 ° C.
- the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
- the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% by mass.
- the amount of residual solvent is defined by the following formula.
- Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100
- M is the mass of a sample collected during or after the production of the web or film
- N is the mass after heating M at 115 ° C. for 1 hour.
- the web is peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less, more preferably 0. 0.1 mass% or less, particularly preferably 0 to 0.01 mass% or less.
- a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.
- the film in the stretching step, can be sequentially or simultaneously stretched in the longitudinal direction (MD direction) and the width direction (TD direction) of the film.
- the draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 1.0 to 2.0 times in the MD direction and 1.07 to 2.0 times in the TD direction, respectively. It is preferably performed in the range of 1.0 to 1.5 times and 1.07 to 2.0 times in the TD direction.
- width maintenance or width direction stretching in the film forming step is preferably performed by a tenter, and may be a pin tenter or a clip tenter.
- the film transport tension in the film forming process such as in the tenter depends on the temperature, but is preferably 120 N / m to 200 N / m, and more preferably 140 N / m to 200 N / m. 140 N / m to 160 N / m is most preferable.
- the glass transition temperature of the substrate film is Tg, (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C., and more preferably (Tg-5) to (T Tg + 20) ° C.
- the Tg of the base film can be controlled by the type of material constituting the film and the ratio of the constituting materials.
- the Tg when the film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.
- the glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower.
- the Tg of the film can be determined by the method described in JIS K7121.
- the surface is preferably roughened. Roughening the film surface is preferable because it improves not only the slipperiness but also the surface processability, particularly the adhesion of the antiglare layer.
- the base film may be formed by a melt film forming method.
- the melt film-forming method refers to heating and melting a composition containing an additive such as a resin and a plasticizer to a temperature exhibiting fluidity, and then casting a melt containing a fluid cellulose ester.
- the molding method for heating and melting can be further classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like.
- the melt extrusion method is preferable from the viewpoint of mechanical strength and surface accuracy. It is preferable that a plurality of raw materials used for melt extrusion are usually kneaded in advance and pelletized.
- Pelletization may be performed by a known method. For example, dry cellulose ester, plasticizer, and other additives are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder, and formed into a strand from a die. It can be done by extrusion, water cooling or air cooling and cutting.
- Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
- a small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.
- the extruder is preferably processed at as low a temperature as possible so that it can be pelletized so as to suppress the shearing force and prevent the resin from deteriorating (molecular weight reduction, coloring, gel formation, etc.).
- a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
- Film formation is performed using the pellets obtained as described above.
- the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.
- the melting temperature at the time of extrusion is about 200 to 300 ° C, filtered through a leaf disk type filter, etc. to remove foreign matter, and then formed into a film from the T die.
- the film is nipped by a cooling roll and an elastic touch roll, and solidified on the cooling roll.
- the extrusion flow rate is preferably carried out stably by introducing a gear pump.
- a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.
- the stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.
- Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
- the film temperature on the touch roll side when the film is nipped by the cooling roll and the elastic touch roll is preferably Tg or more and Tg + 110 ° C. or less of the film.
- a well-known roll can be used for the roll which has the elastic body surface used for such a purpose.
- the elastic touch roll is also called a pinching rotator.
- As the elastic touch roll a commercially available one can be used.
- the film obtained as described above is stretched by the stretching operation after passing through the step of contacting the cooling roll.
- the stretching method a known roll stretching machine or tenter can be preferably used.
- the stretching temperature is usually preferably in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.
- the end Before winding, the end may be slit and cut to the product width, and knurled (embossed) may be applied to both ends to prevent sticking or scratching during winding.
- the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.
- grip part of the clip of both ends of a film is cut out and reused.
- the film thickness of the substrate film in the present embodiment is not particularly limited, but 10 to 200 ⁇ m is used. In particular, the film thickness is particularly preferably 10 to 100 ⁇ m. More preferably, it is 20 to 60 ⁇ m.
- the base film according to this embodiment has a width of 1 to 4 m. Particularly, those having a width of 1.4 to 4 m are preferably used, and particularly preferably 1.6 to 3 m. If it exceeds 4 m, conveyance becomes difficult.
- the arithmetic average roughness Ra of the base film is preferably 2.0 nm to 4.0 nm, more preferably 2.5 nm to 3.5 nm.
- the antiglare film according to the present embodiment can be provided with functional layers such as a backcoat layer and an antireflection layer.
- the anti-glare film according to the present embodiment is a back surface for preventing sticking when a curl or anti-glare film is stored in a roll on the surface opposite to the side on which the anti-glare layer of the base film is provided.
- a coat layer may be provided.
- the back coat layer preferably contains fine particles for the above purpose, and the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined silicic acid. Mention may be made of calcium, tin oxide, indium oxide, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Moreover, it is preferable to contain a solvent in order to disperse the fine particles and to dissolve a binder described later to form a coating composition. As the solvent, the solvents described in the antiglare layer are preferable.
- the particles contained in the back coat layer are preferably 0.1 to 50% by mass with respect to the binder. When the back coat layer is provided, the increase in haze is preferably 1.5% or less, and 0.5% or less. Further, it is preferable to use a cellulose ester resin such as diacetyl cellulose as the binder.
- the antiglare film of the present embodiment provides a low refractive index layer, which is an antireflection layer, directly on the antiglare layer or via another layer, thereby improving the adhesion between the low refractive index layer and the antiglare layer. It is preferable to use the antiglare film of the present invention for the antiglare antireflection film because it is excellent and can further suppress the occurrence of spotted unevenness in the low refractive index layer and an excellent appearance can be obtained.
- the antireflection layer composed of the low refractive index layer may have a single layer configuration consisting of only the low refractive index layer, but may also be a multilayer.
- a high refractive index layer having a higher refractive index than the support and a low refractive index layer having a lower refractive index than the support can be combined. Further, three layers having different refractive indexes from the support side are divided into a medium refractive index layer (a layer having a higher refractive index than the support or the antiglare layer and a lower refractive index than the high refractive index layer) / high refractive index layer / low. You may laminate
- Base film / Anti-glare layer / Low refractive index layer Base film / Anti-glare layer / High refractive index layer / Low refractive index layer Base film / Anti-glare layer / Medium refractive index layer / High refractive index layer / Low refractive index layer
- ⁇ An antifouling layer can be further provided on the outermost low refractive index layer so that dirt and fingerprints can be easily wiped off.
- the antifouling layer fluorine-containing organic compounds are preferably used.
- an intermediate layer may be provided as appropriate.
- an antistatic layer containing conductive polymer fine particles (for example, crosslinked cation fine particles) or metal oxide fine particles (for example, SnO 2 , ITO) is preferable.
- ⁇ Low refractive index layer> In the low refractive index layer, a layer lower than the refractive index of the base film is formed, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and wavelength of 550 nm.
- the thickness of the low refractive index layer is not particularly limited, but is preferably 5 nm to 0.5 ⁇ m, more preferably 10 nm to 0.3 ⁇ m, and more preferably 30 nm to 0.2 ⁇ m. Most preferred.
- the low refractive index layer preferably uses hollow spherical silica-based fine particles from the viewpoint of refractive index adjustment and mechanical strength.
- the hollow spherical fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the content is a solvent, gas or porous Cavity particles filled with a substance. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.
- the cavity particles are particles having a cavity inside, and the cavity is surrounded by a particle wall.
- the cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such hollow spherical fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm.
- the hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. Is desirable.
- These hollow spherical fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer.
- an appropriate medium for example, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.
- the thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably 1 to 20 nm, preferably 2 to 15 nm.
- the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later.
- the inside of the composite particles may enter and the internal porosity may decrease, and the low refractive index effect may not be sufficiently obtained.
- the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible.
- the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.
- the coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica.
- components other than silica may be contained, and specifically, Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , CeO 2 , P 2 O 3 , Sb 2 O 3. , MoO 3 , ZnO 2 , WO 3 and the like.
- the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF 2 , NaF, NaAlF 6 , MgF, and the like.
- porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable.
- inorganic compounds other than silica include Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , CeO 2 , P 2 O 3 , Sb 2 O 3 , MoO 3 , ZnO 2 and WO 3. 1 type or 2 types or more can be mentioned.
- the molar ratio MOX / SiO 2 is 0.0001 to 1.0, preferably 0 when silica is represented by SiO 2 and inorganic compounds other than silica are represented by oxide (MOX). It is desirable to be in the range of .001 to 0.3.
- the pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g.
- the pore volume of such porous particles can be determined by a mercury intrusion method.
- Such hollow spherical fine particles can be produced from the following first to third steps.
- First Step Preparation of Porous Particle Precursor
- an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance.
- a mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.
- alkali metal, ammonium or organic base silicate is used as the silica raw material.
- Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate.
- the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine.
- the ammonium silicate or organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound, or the like to a silicate solution.
- alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica.
- an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc. an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.
- the aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction
- a dispersion of seed particles can be used as a starting material.
- the seed particles are not particularly limited, but inorganic oxides such as SiO 2 , Al 2 O 3 , TiO 2 or ZrO 2 or fine particles of these composite oxides are used, and usually these sols can be used. .
- the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion.
- the pH of the seed particle dispersion is adjusted to 10 or higher, and then an aqueous solution of the compound is added to the above-mentioned alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion.
- seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.
- the silica raw material and inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.
- the composite ratio of silica and an inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOX), and the molar ratio of MOX / SiO 2 is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small.
- the molar ratio of MOX / SiO 2 is preferably in the range of 0.25 to 2.0.
- Second step Removal of inorganic compound other than silica from porous particles
- inorganic compounds other than silica elements other than silicon and oxygen
- the porous particle precursor obtained in the first step At least a portion is selectively removed.
- the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.
- the porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen.
- fluorine-substituted obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film.
- the thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.
- silica protective film By forming such a silica protective film, inorganic compounds other than silica can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.
- the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content.
- a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.
- the amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor.
- tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.
- a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed.
- the produced silicic acid polymer is deposited on the surface of the inorganic oxide particles.
- alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion.
- the alkali catalyst ammonia, an alkali metal hydroxide, or an amine can be used.
- the acid catalyst various inorganic acids and organic acids can be used.
- a silica protective film can be formed using a silicic acid solution.
- a silicic acid solution a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles.
- the porous particle dispersion prepared in the second step contains a fluorine-substituted alkyl group-containing silane compound.
- a hydrolyzable organosilicon compound or silicic acid solution By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.
- a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilanes, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, hollow particle precursor).
- the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors).
- alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion.
- the alkali catalyst ammonia, an alkali metal hydroxide, or an amine can be used.
- the acid catalyst various inorganic acids and organic acids can be used.
- the silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.
- the silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface.
- alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors).
- a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane.
- the amount of the organosilicon compound or silicic acid solution used for forming the coating layer may be such that the surface of the colloidal particles can be sufficiently covered, and the finally obtained silica coating layer has a thickness of 1 to 20 nm.
- the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.
- the particle dispersion having the coating layer formed thereon is heat-treated.
- the heat treatment in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained.
- the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.
- the heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C.
- the heat treatment temperature is less than 80 ° C.
- the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time.
- the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.
- the refractive index of the inorganic fine particles thus obtained is as low as less than 1.42.
- Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.
- Specific examples of commercially available particles include P-4 manufactured by Catalyst Chemical Industry Co., Ltd.
- the content (mass) of the hollow spherical silica-based fine particles having an outer shell layer and porous or hollow inside in the low refractive index layer coating solution is preferably 10 to 80% by mass, more preferably 20 to 60% by mass. %.
- the low refractive index layer preferably contains a tetraalkoxysilane compound or a hydrolyzate thereof as a sol-gel material.
- a silicon oxide having an organic group in addition to the inorganic silicon oxide.
- sol-gel materials metal alcoholates, organoalkoxy metal compounds and hydrolysates thereof can be used.
- alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable.
- Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. Tetraalkoxysilane and its hydrolyzate are particularly preferable.
- organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, ⁇ -glycidyloxypropyltrialkoxysilane, ⁇ -glycidyloxypropylmethyl dialkoxysilane, ⁇ - (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, ⁇ -methacryloyloxypropyltrialkoxysilane, ⁇ -aminopropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ -chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds (for example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxys
- the low refractive index layer preferably contains the silicon oxide and the following silane coupling agent.
- silane coupling agent examples include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane.
- silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and ⁇ -glycidyloxypropylmethyldiethoxysilane.
- ⁇ -acryloyloxypropylmethyldimethoxysilane, ⁇ -acryloyloxypropylmethyldiethoxysilane, ⁇ -methacryloyloxypropylmethyldimethoxysilane, ⁇ -methacryloyloxypropylmethyldiethoxy are those having a disubstituted alkyl group with respect to silicon.
- Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, ⁇ -acryloyloxypropyltrimethoxysilane and ⁇ -methacryloyloxy Particularly preferred are propyltrimethoxysilane, ⁇ -acryloyloxypropylmethyldimethoxysilane, ⁇ -acryloyloxypropylmethyldiethoxysilane, ⁇ -methacryloyloxypropylmethyldimethoxysilane and ⁇ -methacryloyloxypropylmethyldiethoxysilane.
- silane coupling agent examples include KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE- manufactured by Shin-Etsu Chemical Co., Ltd. 503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.
- silane coupling agents Two or more coupling agents may be used in combination.
- other silane coupling agents may be used.
- Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and hydrolysates thereof.
- the low refractive index layer can also contain a polymer in an amount of 5 to 50% by mass.
- the polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids.
- the amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids.
- the amount of the polymer is preferably 10 to 30% by mass with respect to the total amount of the low refractive index layer.
- the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder.
- the polymer to be bonded to the surface treating agent (1) is preferably the shell polymer (2) or the binder polymer (3).
- the polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer.
- the polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and by polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to implement a combination of two or all of the above (1) to (3), and to implement a combination of (1) and (3), or (1) to (3) all combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.
- the surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out by chemical surface treatment alone or a combination of physical surface treatment and chemical surface treatment.
- a coupling agent an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used.
- the fine particles are made of SiO 2, the surface treatment with the above-described silane coupling agent can be carried out particularly effectively.
- the surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days.
- inorganic acids for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid
- organic acids for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid
- salts thereof eg, metal salts, ammonium salts
- the polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain.
- a polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred.
- Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred.
- the refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases.
- the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms.
- the polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom.
- Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Examples thereof include esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.
- fluoroolefins eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole
- the polymer forming the shell may be a copolymer comprising a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom.
- the repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom.
- ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyl toluene, ⁇ -methyl styrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides
- a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking.
- the shell polymer may have crystallinity.
- Tg glass transition temperature
- the core-shell fine particles preferably contain 5 to 90% by volume, more preferably 15 to 80% by volume of a core composed of inorganic fine particles. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.
- Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain.
- the binder polymer is preferably crosslinked.
- the polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups.
- Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol).
- esters of polyhydric alcohols and (meth) acrylic acid eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol.
- 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg divinyl sulfone), acrylamide (eg methylene bisacrylamide) and methacrylamide Can be mentioned.
- the polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound.
- a crosslinked structure may be introduced into the binder polymer by reaction of a crosslinkable group.
- crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups.
- Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure.
- a functional group that exhibits crosslinkability as a result of the decomposition reaction such as a block isocyanate group, may be used.
- the cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group.
- the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable.
- photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums.
- acetophenones examples include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.
- benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone.
- phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- the binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.
- a polymer for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin
- the low refractive index layer may be a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”).
- fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group.
- fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (Osaka Organic Chemical Co., Ltd.) and M-2020 (Daikin Industries, Ltd.)), Examples include fully or partially fluorinated vinyl ethers.
- Examples of the monomer for imparting a crosslinkable group include glycidyl methacrylate, vinyltrimethoxysilane, ⁇ -methacryloyloxypropyltrimethoxysilane, vinylglycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule.
- Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.).
- crosslinkable group examples include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group.
- the fluorine-containing copolymer When the fluorine-containing copolymer is crosslinked by heating with a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, it is a thermosetting type.
- a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator
- it is a thermosetting type.
- crosslinking by irradiation with light preferably ultraviolet rays, electron beams, etc.
- the ionizing radiation curable type is used.
- a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking.
- the monomer that can be used in combination is not particularly limited.
- olefins ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.
- acrylic esters methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl
- methacrylic acid esters methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.
- styrene derivatives styrene, divinylbenzene, vinyl toluene, ⁇ -methyl styrene, etc.
- vinyl ethers methyl vinyl ether) Etc.
- vinyl esters vinyl acetate, vinyl propionate, vinyl cinnamate, etc.
- acrylamides N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.
- methacrylamides Ronitoriru derivatives and the like
- polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties.
- polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.
- the proportion of each monomer used to form the fluorinated copolymer before cross-linking is preferably 20 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer,
- the amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.
- the fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means of solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like.
- Fluorine-containing resin before crosslinking is commercially available and can be used.
- Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass Co., Ltd.), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass Co., Ltd.), OPSTAR (Manufactured by JSR) and the like.
- the low refractive index layer comprising a crosslinked fluorine-containing resin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.
- the low refractive index layer may contain a cationically polymerizable compound as a binder.
- Any cationically polymerizable compound can be used as long as it undergoes cationic polymerization by irradiation with energy active rays or heat to form a resin.
- Specific examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group.
- a compound having a functional group such as an epoxy group or a vinyl ether group is preferably used in the present embodiment.
- Examples of the cationically polymerizable compound having an epoxy group or a vinyl ether group include phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, 3,4-epoxycyclohexylmethyl-3 ′.
- oxetane compound may be a compound having at least one oxetane ring in the molecule.
- a (co) polymer containing a monomer having a hydrogen bond forming group and a reactive polymer having an oxetanyl group in the main chain or side chain and having a number average molecular weight of 20,000 or more can also be used.
- the above cationic polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the low refractive layer coating composition.
- Examples of the compound that accelerates the polymerization of the cationic polymerizable compound include known acids and photoacid generators.
- Examples of the photoacid generator include a cationic polymerization photoinitiator, a dye photodecoloring agent, a photochromic agent, a known compound used in a microresist, and a mixture thereof. Specific examples include onium compounds, organic halogen compounds, and disulfone compounds, and onium compounds are preferable.
- As the onium compound diazonium salts, sulfonium salts, iodonium salts and the like represented by the following formulas are preferably used.
- Ar represents an aryl group
- R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different
- Z— Represents a non-basic and non-nucleophilic anion.
- the aryl group represented by Ar or R is also typically phenyl or naphthyl, and these may be substituted with an appropriate group.
- Specific examples of the anion represented by Z ⁇ include tetrafluoroborate ion (BF 4 ⁇ ), tetrakis (pentafluorophenyl) borate ion (B (C 6 F 5 ) 4 ⁇ ), hexafluorophosphate ion.
- PF 6 ⁇ hexafluoroarsenate ion
- AsF 6 ⁇ hexafluoroantimonate ion
- SbF 6 ⁇ hexafluoroantimonate ion
- SbCl 6 ⁇ hexachloroantimonate ion
- HSO 4 ⁇ hydrogen sulfate ion
- ClO 4 ⁇ perchloric acid Ions
- onium compounds include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, boron salts and the like.
- diazonium salts iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the material stability of the compound.
- initiators include, for example, “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd., and “Adekaoptomer SP-150” (trade name) sold by ADEKA Co., Ltd. Product name), “Adekaoptomer SP-300” (product name), “RHODORSIL PHOTOINITIAOR 2074” (product name) sold by Rhodia Japan Co., Ltd., and the like.
- Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate
- organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate
- Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.
- Aromatic polycarboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, or anhydrides thereof, maleic acid, maleic anhydride, succinic acid, succinic anhydride Aliphatic polycarboxylic acids such as or anhydrides thereof are also included.
- acids and photoacid generators are preferably added in an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the cationic polymerizable compound. is there.
- the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity, and the like.
- the low refractive index layer can also contain a radical polymerizable compound as a binder.
- a radical polymerizable group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a compound having a (meth) acryloyl group is preferable.
- a radically polymerizable compound it is preferable to contain the polyfunctional monomer which contains a 2 or more radically polymerizable group in a molecule
- the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
- the addition amount of the radical polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the low refractive layer coating composition from the viewpoint of the stability of the low refractive layer coating composition.
- Radar polymerization accelerator In order to accelerate the curing of the radical polymerizable compound, it is preferable to use a photopolymerization initiator in combination with the radical polymerizable compound.
- a photopolymerization initiator and a radical polymerizable compound are used in combination, the photopolymerization initiator and the radical polymerizable compound are preferably contained in a mass ratio of 20: 100 to 0.01: 100.
- photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
- the low refractive index layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a known method such as an inkjet method, and the above coating composition for forming the low refractive index layer is applied, and after coating, It is formed by heat drying and curing treatment as necessary.
- the coating amount is suitably 0.05 to 100 ⁇ m, preferably 0.1 to 50 ⁇ m, as the wet film thickness. Further, the solid content concentration of the coating composition is adjusted so that the dry film thickness becomes the above film thickness.
- the method may include a step of performing heat treatment at a temperature of 50 to 160 ° C. after forming the low refractive index layer.
- the period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably a period of 3 days or more and less than 30 days, and if it is 160 ° C., a range of 10 minutes or more and 1 day or less is preferable.
- the curing method include a method of thermosetting by heating, a method of curing by irradiation with light such as ultraviolet rays, and the like. In the case of thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, more preferably 80 to 150 ° C.
- the exposure amount of the irradiation light is preferably 10 mJ / cm 2 to 1 J / cm 2 , and more preferably 100 mJ / cm 2 to 500 mJ / cm 2 .
- the wavelength range of the irradiated light is not particularly limited, but light having a wavelength in the ultraviolet region is preferably used.
- a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
- the high refractive index layer and the middle refractive index layer preferably contain metal oxide fine particles.
- the kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S Having at least one element selected from
- a metal oxide can be used, and these metal oxide fine particles may be doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. A mixture of these may also be used.
- at least one metal oxide fine particle selected from organic titanium compounds, zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is mainly used. It is particularly preferable to use it as a component. In particular, it is preferable to contain zinc antimonate particles.
- the average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and is particularly preferably 10 to 150 nm.
- the average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased.
- the shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.
- the refractive index of the high refractive index layer is preferably higher than the refractive index of the base film, and is preferably in the range of 1.5 to 2.3 when measured at 23 ° C. and a wavelength of 550 nm.
- the means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60. More preferably, it is 1.85 to 2.50.
- the refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the base film and the refractive index of the high refractive index layer.
- the refractive index of the middle refractive index layer is preferably 1.55 to 1.80.
- the thickness of the high refractive index layer and the middle refractive index layer is preferably 5 nm to 1 ⁇ m, more preferably 10 nm to 0.2 ⁇ m, and most preferably 30 nm to 100 nm.
- the high refractive index layer and the medium refractive index layer preferably contain metal oxide particles as fine particles, and further contain a binder polymer.
- a crosslinked polymer As the binder polymer of the high refractive index layer and the medium refractive index layer, a crosslinked polymer is preferable.
- a monomer having two or more ethylenically unsaturated groups is most preferable. Examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate).
- 1,4-dichlorohexanediacrylate pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate Relate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone
- a photopolymerization reaction or a thermal polymerization reaction can be used for the polymerization reaction of the polymer.
- a photopolymerization reaction is particularly preferable.
- a polymerization initiator is preferably used for the polymerization reaction.
- the thermal polymerization initiator mentioned later used in order to form the binder polymer of a hard-coat layer, and a photoinitiator are mentioned.
- a commercially available polymerization initiator may be used as the polymerization initiator.
- a polymerization accelerator may be used.
- the addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers.
- the coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application
- the middle and high refractive index layers can be provided by coating, drying and curing on the antiglare layer as a coating layer composition by diluting the above-described components forming the middle and high refractive index layers with a solvent.
- a light source for curing any light source that generates ultraviolet rays can be used without limitation.
- a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
- the amount of irradiation light is preferably 20 mJ / cm 2 to 1 J / cm 2, more preferably 100 mJ / cm 2 to 500 mJ / cm 2 .
- the antireflection layer of the antiglare antireflection film has an average reflectance at 450 nm to 650 nm of preferably 1.5% or less, particularly preferably 1.2% or less. Further, the minimum reflectance in this range is preferably 0.00 to 0.5%.
- the refractive index and film thickness of the antireflection layer can be calculated and calculated by measuring the spectral reflectance.
- the reflection optical characteristic of the anti-glare antireflection film having the antireflection layer thus produced can be measured for reflectance under the condition of regular reflection at 5 degrees using a spectrophotometer.
- the light absorption treatment is performed with a black spray, or the light absorption treatment is performed by attaching a black acrylic plate or the like.
- the reflectance can be measured by preventing reflection of the back light of the film.
- the transmittance at a transmittance of 550 nm is measured using a spectrophotometer with reference to air.
- the antiglare antireflection film of this embodiment preferably has a flat reflection spectrum in the wavelength region of visible light. Reflective hues are often colored red and blue due to the high reflectance in the short-wavelength and long-wavelength regions in the visible light region due to the design of the antireflection layer. In contrast, when used on the surface of an image display device or the like, a neutral color tone is preferred. In this case, generally preferred reflection hue ranges are 0.17 ⁇ x ⁇ 0.27 and 0.07 ⁇ y ⁇ 0.17 on the XYZ color system (CIE1931 color system).
- the color tone can be calculated from the refractive index of each layer in accordance with a conventional method in consideration of the reflectance and the color of reflected light.
- the polarizing plate according to the present embodiment is provided with the antiglare film according to the present embodiment. Since such a polarizing plate includes the antiglare film, it improves both visibility and reduces moire fringes.
- the polarizing plate includes, for example, a polarizing film and a transparent protective film (polarizing plate protective film) disposed on the surface of the polarizing film, and the transparent protective film is an antiglare film according to this embodiment. Some are listed.
- reference numeral 11 denotes an antiglare film
- 12 denotes an antiglare layer
- 13 denotes a base film
- 14 denotes a polarizing film
- 15 denotes an optical film
- 16 denotes an adhesive layer.
- the polarizing plate 10 has an anti-glare film 11 on the surface of the polarizing film 14 on the side to be visually recognized so that the anti-glare layer 12 is on the outside and the base film 13 is on the inside.
- the optical film 15 is disposed on the surface of the polarizing film 14 opposite to the surface on the viewing side, and the adhesive layer 16 that can be attached to other members is disposed outside the polarizing film 14. The thing which was done is mentioned.
- the optical film 15 for example, the polarizing plate protective film etc. which are mentioned later are mentioned.
- the polarizing plate can be produced by a general method.
- the back surface side of the antiglare film according to the present invention is subjected to alkali saponification treatment, and a fully saponified polyvinyl alcohol aqueous solution is formed on at least one surface of a polarizing film prepared by immersing and stretching the treated antiglare film in an iodine solution. It is preferable to stick together.
- the antiglare film may be used on the other surface, or another polarizing plate protective film may be used.
- the above retardation can be calculated from the value obtained by measuring a sample conditioned at 23 ° C. and 55% RH in an automatic birefringence meter (KOBRA21DH, Oji Scientific Co., Ltd.) at 590 nm by the following formula.
- Ro (nx ⁇ ny) ⁇ d (nm)
- Rt ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d (nm)
- Ro represents the in-plane retardation value in the film
- Rt represents the retardation value in the thickness direction in the film
- D represents the thickness (nm) of the optical film
- nx represents the maximum refractive index in the plane of the film
- ny represents the refractive index in the direction perpendicular to the slow axis in the film plane
- nz represents the refractive index of the film in the thickness direction.
- an optical compensation film (retardation film) having a retardation of in-plane retardation Ro of 590 nm, 20 to 70 nm, and Rt of 70 to 400 nm may be used to obtain a polarizing plate capable of widening the viewing angle. it can.
- an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal.
- polarizing plate protective films preferably used include KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-2, KC4FR-2, KC4FR-2, KC8FR-2 KC4UE (Konica Minolta Opto Co., Ltd.) etc. are mentioned.
- the polarizing film which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction.
- a typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film.
- iodine is dyed on a system film
- a dichroic dye is dyed, but it is not limited to this.
- As the polarizing film a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound.
- a polarizing film having a thickness of 5 to 30 ⁇ m, preferably 8 to 15 ⁇ m is preferably used.
- the pressure-sensitive adhesive layer used on one side of the protective film to be bonded to the substrate of the liquid crystal cell is preferably optically transparent and exhibits moderate viscoelasticity and adhesive properties.
- the adhesive layer include adhesives or adhesives such as acrylic copolymers, epoxy resins, polyurethane, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers.
- adhesives or adhesives such as acrylic copolymers, epoxy resins, polyurethane, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers.
- a polymer such as an agent
- a film can be formed and cured by a drying method, a chemical curing method, a heat curing method, a heat melting method, a photocuring method, or the like.
- the acrylic copolymer can be preferably used because it is most easy to control the physical properties of the adhesive and is excellent in transparency, weather resistance, durability and the like.
- ⁇ Image display device> By using the antiglare film of this embodiment in an image display device, performance with excellent visibility is exhibited.
- a reflection type, a transmission type, a semi-transmission type liquid crystal display device, a liquid crystal display device of various drive systems such as a TN type, STN type, OCB type, VA type, IPS type, ECB type, etc., organic electroluminescence Examples include a display device having an element and a plasma display.
- the use of the antiglare film of the present embodiment for the polarizing plate of a liquid crystal display device is preferable from the viewpoint of excellent visibility.
- FIG. 4 shows a polarizing plate which is an embodiment of the present invention.
- the use of a polarizing plate composed of the antiglare film of the present embodiment on the rear side (backlight side) of the liquid crystal cell (FIG. 6) of the liquid crystal display device generates moiré fringes. It is preferable at the point which is excellent in prevention.
- reference numeral 20 is a liquid crystal display device
- 21 is a liquid crystal cell
- 22 is a polarizing film
- 23 is an optical film
- 24 is a clear hard coat film
- 25 is an antiglare film
- 26 is an adhesive layer
- 27 is an adhesive layer.
- Polarizing plates 28 are polarizing plates.
- reference numeral 30 denotes a liquid crystal cell
- 31 denotes liquid crystal
- 32 denotes an alignment film
- 33 denotes a color filter
- 34 denotes a glass substrate
- 35 denotes a spacer
- 36 denotes a polarizing plate
- 37 denotes a polarizing plate.
- the liquid crystal panel 20 includes an anti-glare film 25 on the surface of the liquid crystal cell 21 on the rear (backlight) side (the side opposite to the viewing side surface).
- the polarizing plate 28 is disposed so that is on the outside.
- the liquid crystal panel 20 includes a liquid crystal cell 21 in which a polarizing plate 27 different from the polarizing plate 28 is disposed on the surface on the viewing side.
- the polarizing plate 27 include a polarizing plate including a clear hard coat film 24 instead of an antiglare film.
- the liquid crystal cell is a cell in which a liquid crystal substance is filled between a pair of electrodes. By applying a voltage to this electrode, the alignment state of the liquid crystal is changed and the amount of transmitted light is controlled.
- the liquid crystal cell 30 includes two stacked bodies in which an alignment film 32, a color filter 33, and a glass substrate 34 are stacked.
- the liquid crystal 31 is disposed between the alignment films 32 and the like.
- a transparent electrode for applying a voltage to the liquid crystal 31 may be disposed between the alignment film 32 and the color filter 33.
- the antiglare film according to the present embodiment may be used for a touch panel member.
- the touch panel member according to the present embodiment is provided with the antiglare film according to the present embodiment. Since such a member for touch panels is equipped with the said anti-glare film, it is preferable at the point which is excellent also in durability (a damage
- an anti-glare film with a conductive film as shown in FIG.
- reference numeral 40 denotes an antiglare film with a conductive film for a touch panel
- 41 denotes a base film
- 42 denotes an antiglare layer
- 43 denotes a transparent conductive thin film (ITO layer).
- the antiglare film 40 with a conductive film is a member for a touch panel, and includes an antiglare film including an antiglare layer 42 on the surface of the base film 41.
- the antiglare film includes an antiglare layer 42 on both surfaces of the base film 41.
- the anti-glare film 40 with a conductive film is equipped with the transparent conductive thin film (ITO layer) 43 on one surface of this anti-glare film.
- the anti-glare film of the present invention when used as a member for a touch panel of an image display device with a touch panel, it is preferable in that it is excellent in letter blurring and pen input durability (scratches due to sliding, etc.).
- FIG. 8 is a schematic diagram of a liquid crystal display device 50 with a resistive touch panel using the antiglare film of this embodiment as a touch panel.
- reference numeral 50 denotes a resistive touch panel liquid crystal display device
- 51 denotes a spacer
- 52 denotes a transparent conductive thin film (ITO layer)
- 53 denotes a glass substrate
- 54 denotes an LCD (liquid crystal display panel).
- a touch panel can be configured.
- An electrode (not shown) is disposed on the end of the conductive antiglare film and the glass substrate.
- the transparent conductive thin film of the conductive anti-glare film comes into contact with the transparent conductive thin film on the glass substrate. .
- a dot-shaped spacer is arrange
- a liquid crystal display device with a touch panel can be configured by mounting the touch panel on an LCD (liquid crystal display device).
- One aspect of the present invention is an antiglare film having an antiglare layer containing an actinic radiation curable resin on a substrate film, wherein the antiglare layer is not in contact with fine particles and the actinic radiation curable resin.
- the resin having no compatibility is substantially not contained, the arithmetic average roughness Ra of the antiglare layer is 300 to 1500 nm, and haze due to internal scattering of the antiglare layer is 0 to 1.0%. It is an anti-glare film characterized by being.
- the arithmetic average roughness Ra of the antiglare layer is preferably 350 to 1300 nm. Thereby, the above-mentioned effect can be obtained more reliably.
- the arithmetic average roughness Ra of the antiglare layer is preferably 500 to 1300 nm. Thereby, the above-mentioned effect can be obtained more reliably.
- the surface of the antiglare layer has an irregular protrusion shape having no period in the longitudinal direction. As a result, the above-described effect is exhibited better.
- the viscosity of the actinic radiation curable resin at 25 ° C. is preferably in the range of 20 to 3000 mPa ⁇ s.
- Another aspect of the present invention is an antiglare antireflection film characterized in that a low refractive index layer is laminated directly or via another layer on the antiglare layer of the antiglare film. .
- the anti-glare antireflection film excellent in visibility can be obtained.
- a further aspect of the present invention is a method for producing an antiglare film for producing the antiglare film, wherein an actinic radiation curable resin having a viscosity at 25 ° C. in the range of 20 to 3000 mPa ⁇ s is used.
- An anti-glare layer coating composition diluted with at least one solvent selected from esters, glycol ethers or alcohols, forming an anti-glare layer through at least a coating step, a drying step and a curing step; and
- a process for producing an antiglare film characterized in that the treatment is carried out under the condition that the temperature of the decreasing rate drying section in the drying step is maintained within a range of 90 to 160 ° C.
- Further aspect of the present invention is a polarizing plate characterized in that the antiglare film and the antiglare antireflection film are provided on at least one surface. According to such a configuration, a polarizing plate having excellent visibility can be obtained.
- a further aspect of the present invention is an image display device comprising the antiglare film and the antiglare antireflection film. According to such a configuration, an image display device having excellent visibility can be obtained.
- the polarizing plate is provided on at least one surface of the liquid crystal cell. According to such a configuration, an image display device with excellent visibility can be obtained more reliably.
- the polarizing plate is preferably used on the rear side of the liquid crystal cell. Such a configuration is preferable in that it is further excellent in preventing the occurrence of moire fringes.
- the image display device is preferably an image display device with a touch panel, and the antiglare film or the antiglare antireflection film is provided as a constituent member of the touch panel. According to such a configuration, it is preferable in that it is also excellent in durability against letter blurring and pen input (scratches caused by sliding, etc.).
- Example 1 ⁇ Preparation of base film 1> (Preparation of silicon dioxide dispersion) Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd., average diameter of primary particles: 7 nm) 10 parts by mass Ethanol 90 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution. The mixture was filtered with a fine particle dispersion dilution filter (Advantech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
- a fine particle dispersion dilution filter Advancedtech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).
- the belt was cast evenly on a stainless steel band support using a belt casting apparatus.
- the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off.
- the cellulose ester film web was evaporated at 35 ° C., slit to 1.65 m width, and stretched 1.3 times in the TD direction (film width direction) with a tenter, and the MD direction draw ratio was 1.01 times. While stretching, the film was dried at a drying temperature of 160 ° C. The residual solvent amount at the start of drying was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C.
- the base film 1 was obtained.
- the residual solvent amount of the base film was 0.2%, the film thickness was 40 ⁇ m, and the number of turns was 3900 m.
- the following antiglare layer coating composition 1 filtered through a polypropylene filter having a pore diameter of 0.4 ⁇ m was applied onto the base film 1 produced above using an extrusion coater, and a constant rate drying zone temperature of 95 ° C., a reduced rate drying zone. After drying at a temperature of 85 ° C., while purging with nitrogen so that the oxygen concentration is 1.0 volume% or less, the illuminance of the irradiated part is 100 mW / cm 2 using an ultraviolet lamp and the irradiation amount is 0.25 J / cm 2.
- the coating layer was cured as 2 to form an antiglare layer having a dry film thickness of 8 ⁇ m.
- the anti-glare layer After forming the anti-glare layer, it was wound up into a roll and the anti-glare film 1 was produced.
- an optical interference surface roughness meter (New View 5030, manufactured by Zygo Corporation), irregular projection shapes irregularly in the longitudinal direction and the width direction as shown in FIG. It was found that they are arranged in
- Anti-Glare Layer Coating Composition 1 The following antiglare layer coating composition 1 was stirred and mixed with a disper to obtain an antiglare layer coating composition 1.
- Antiglare films 2 to 8 were produced in the same manner as the antiglare film 1 except that the conditions for changing the temperature of the decreasing rate drying section were changed as shown in Table 1 in the production of the antiglare film 1.
- the antiglare layer coating composition 1 was changed to the following antiglare layer coating composition 2, and the temperature in the decreasing rate drying section in the drying step was changed to 100 ° C. in the same manner. A dazzling film 9 was produced.
- Anti-Glare Layer Coating Composition 2 The following antiglare layer coating composition 2 was stirred and mixed with a disper to obtain an antiglare layer coating composition 2.
- the antiglare layer coating composition 1 was changed to the following antiglare layer coating composition 3 and the temperature in the decreasing rate drying section in the drying step was changed to 100 ° C. in the same manner. A dazzling film 10 was produced.
- Anti-glare layer coating composition 3 The following antiglare layer coating composition 3 was stirred and mixed with a disper to obtain an antiglare layer coating composition 3.
- Antiglare films 11 to 17 were produced in the same manner as in the antiglare film 7 except that the conditions for changing the temperature of the decreasing rate drying section in the production of the antiglare film 7 were changed as shown in Table 1.
- the antiglare layer coating composition 4 containing an incompatible resin component prepared by referring to Example 1 of JP-A-2006-106290 was prepared as the antiglare layer coating composition 1.
- the antiglare layer was prepared in the same manner except that the drying temperature was changed to 70 ° C., which was the same as that in Example 1 of JP-A-2006-106290.
- a thermosetting fluorine-containing compound coating solution manufactured by Nissan Chemical Co., Ltd., LR-202B, solid content 1 mass%) is dried to a film thickness of 100 nm. Then, it was cured by drying at 90 ° C. for 5 minutes to produce an antiglare film 18.
- Anti-Glare Layer Coating Composition 4 The following antiglare layer coating composition 4 was stirred and mixed with a disper to obtain an antiglare layer coating composition 4.
- the antiglare layer coating composition 5 containing an incompatible resin component prepared by referring to Example 1 of JP2008-225195A was prepared.
- the antiglare film 19 was produced in the same manner as the antiglare film 1 except that the drying temperature was changed to 70 ° C. as in Example 1 of JP-A-2008-225195.
- Anti-Glare Layer Coating Composition 5 The following antiglare layer coating composition 5 was stirred and mixed with a disper to obtain an antiglare layer coating composition 5.
- the antiglare layer coating composition 6 containing an incompatible resin component prepared by referring to Example 3 of JP-A-2007-58204 was prepared.
- the antiglare film 20 was produced in the same manner as the antiglare film 1 except that the drying temperature was changed to 80 ° C. as in Example 3 of JP-A-2007-58204.
- Anti-glare layer coating composition 6 The following antiglare layer coating composition 6 was stirred and mixed with a disper to obtain an antiglare layer coating composition 6.
- an antiglare film 21 was produced in the same manner as the antiglare film 4 except that the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 7.
- an antiglare film 22 was produced in the same manner as the antiglare film 4 except that the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 8.
- Anti-Glare Layer Coating Composition 8 The following antiglare layer coating composition 8 was stirred and mixed with a disper to obtain an antiglare layer coating composition 8.
- the anti-glare film 23 was changed in the same manner except that the anti-glare layer composition 1 was changed to the following anti-glare layer composition 9 and the temperature of the reduced drying section was changed to 120 ° C. Was made.
- Anti-Glare Layer Coating Composition 9 The following antiglare layer composition 9 was stirred and mixed with a disper to obtain an antiglare layer coating composition 9.
- an antiglare film 24 was produced in the same manner except that the antiglare layer composition 1 was changed to the following antiglare layer composition 10.
- Anti-Glare Layer Coating Composition 10 The following antiglare layer coating composition 10 was stirred and mixed with a disper to obtain an antiglare layer coating composition 10.
- an antiglare film 24 was produced in the same manner except that the antiglare layer composition 1 was changed to the following antiglare layer composition 11.
- Anti-glare layer coating composition 11 The following antiglare layer coating composition 11 was stirred and mixed with a disper to obtain an antiglare layer coating composition 11.
- the arithmetic average roughness Ra of the antiglare layer of each antiglare film was measured 10 times using an optical interference type surface roughness meter (New View 5030 manufactured by Zygo), and each antiglare property was determined from the average of the measurement results. The arithmetic average roughness Ra of the film was determined.
- Antiglare films 1 to 25 are stored for 50 days in a constant temperature and humidity chamber at 70 ° C and 90% relative humidity, assuming outdoor use, and then cycle thermostat (-40 ° C, 45 minutes, then 110 ° C, 500 cycles were thrown every other time.
- Fine particle addition liquid 1 The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
- a main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose acetate was added to a pressurized dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.
- the above composition was put into a closed container and dissolved while stirring to prepare a dope solution.
- an endless belt casting apparatus was used to uniformly cast the dope solution on a stainless steel belt support at a temperature of 33 ° C. and a width of 2000 mm. The temperature of the stainless steel belt was controlled at 30 ° C.
- the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
- the film is stretched 1.4 times in the width direction by a tenter set at 170 ° C., then dried by being transported in a drying zone set at 130 ° C. for 30 minutes, trimmed at both ends,
- the optical film 1 having a film thickness of 40 ⁇ m having a knurling of 1 cm width and 6 ⁇ m height was prepared, and wound up with a width of 1.49 m and 3900 m.
- the in-plane retardation value Ro of the optical film 1 was 50 nm, and the thickness direction retardation Rt was 130 nm.
- ⁇ Preparation of polarizing plate> A 120 ⁇ m-thick polyvinyl alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizer.
- step 6 the adhesive layer was bonded to each of the polarizing plates 1 to 25.
- Step 1 An anti-glare film 1 to 25 and an optical film 1 that are immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to saponify the side to be bonded to a polarizer. Obtained.
- Step 2 The polarizer was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
- Step 3 Excess adhesive adhered to the polarizer in Step 2 was lightly wiped off, and the antiglare films 1 to 25 treated in Step 1 and the optical film 1 were placed on the back side.
- Step 4 The films laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
- Step 5 A sample obtained by bonding the polarizer prepared in Step 4 to each of the antiglare films 1 to 25 and the optical film 1 in a drier at 80 ° C. is dried for 2 minutes, wound into a roll, and polarizing plate 1 to 22 were produced.
- Step 6 A commercially available acrylic adhesive is applied to the optical film 1 of each polarizing plate prepared in Step 5 so that the thickness after drying is 25 ⁇ m, and dried in an oven at 110 ° C. for 5 minutes to form an adhesive layer. Then, a peelable protective film was attached to the adhesive layer. This polarized light was cut (punched) to produce polarizing plates 1 to 25.
- Each anti-glare film is conditioned at 23 ° C. and 55% RH for 12 hours, and is flexible according to the cylindrical mandrel method using a type 1 test apparatus in accordance with JIS K5600-5-1. evaluated. It shows that it is excellent in the flexibility, so that the numerical value of the diameter of a mandrel is low.
- JIS K5600-5-1 the cylindrical mandrel has a diameter of only 2 mm, so a 1 mm diameter was prototyped. It represents that it is excellent in the flexibility (flexibility of a film), so that the numerical value of a diameter is small.
- Table 1 The obtained results are shown in Table 1.
- the antiglare layer does not substantially contain a resin that is incompatible with the fine particles or the actinic radiation curable resin, and the arithmetic average roughness Ra of the antiglare layer is 300 to 1500 nm.
- the antiglare film of the present invention in which the internal haze of the antiglare layer is 0 to 1.0% is found to be excellent in transmission image clarity and flexibility after the durability test.
- the antiglare film of the present invention having an arithmetic average roughness Ra of 350 to 1300 nm is particularly excellent in visibility when used in a liquid crystal display device, transmission image properties as a film, and flexibility.
- Antiglare coating composition in which actinic radiation curable resin having a viscosity at 25 ° C. in the range of 20 to 3000 mPa ⁇ s is diluted with glycol ethers such as PGME and EPGE, alcohols such as ethanol and methanol, or esters such as butyl acetate.
- glycol ethers such as PGME and EPGE
- alcohols such as ethanol and methanol
- esters such as butyl acetate.
- the arithmetic average of the antiglare layer is obtained by treating the product under the condition that it is formed through at least the coating process, the drying process, and the curing process, and the drying rate of the drying process is maintained at 90 to 150 ° C. It can be seen that the roughness Ra and the internal haze can be easily controlled within the scope of the present invention, and the object and effects of the present invention can be obtained satisfactorily.
- the antiglare film of the present invention in which the internal haze of the antiglare layer is 0 to 0.5% is preferable because the objective effect of the present invention can be obtained well.
- irregular projection shapes are irregular as in the antiglare film 1 They were arranged in the longitudinal direction and the width direction.
- the antiglare films 1 to 25 using a test pencil specified by JIS-S6006, in accordance with the pencil hardness evaluation method specified by JIS-K5400, an antiglare layer with a pencil of each hardness using a 500 g weight. Was repeatedly scratched and the pencil hardness was evaluated.
- all of the antiglare films of the present invention were 3H or more and had good hard coat properties.
- the pencil hardness of the antiglare film of the present invention having an arithmetic average roughness Ra of 500 to 1300 nm of the present invention was 4H, which was particularly excellent.
- Example 2 ⁇ Preparation of antiglare antireflection films 1 to 7>
- the nitrogen purge was not performed, and the illuminance of the irradiated part was 100 mW / cm 2 using an ultraviolet lamp, and the irradiation amount was 0.1 J / cm 2.
- antiglare films 26 to 32 were produced and wound into a roll.
- the roll-shaped anti-glare films 26 to 32 subjected to the durability test under the conditions described in Example 1 were drawn out again to apply the coating composition 1 for the low refractive index layer on the surface of the anti-glare layer.
- a low refractive index layer was formed to produce antiglare antireflection films 1 to 7.
- the refractive index of the low refractive index layer was 1.37.
- the temperature in the autoclave was kept as it was, and the reaction was continued for 8 hours.
- the pressure reached 3.2 kg / cm 2
- the heating was stopped and the mixture was allowed to cool.
- the internal temperature decreased to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out.
- reaction solution was poured into a large excess of hexane, and the solvent was removed by decantation to take out the precipitated polymer. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove residual monomers and dried to obtain 28 g of a polymer.
- 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of fluorinated polymer 1.
- the following materials were stirred and mixed to obtain a coating composition 1 for a low refractive index layer.
- Antiglare antireflection film Cut each anti-glare anti-reflection film with a size of 150cm x 150cm, perform light absorption treatment using black spray on the back, observe the reflection of the fluorescent lamp from the front, the appearance (spotted unevenness) is as follows The visual evaluation was performed based on the criteria. The obtained results are shown in Table 2.
- Each anti-glare antireflection film was put into a cycle thermo (-40 ° C for 30 minutes, then left at 85 ° C for 30 minutes alternately) for 500 cycles, and then a weather resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.) ) For 120 hours.
- the peeled area ratio was less than 10% ⁇ : The peeled area ratio was 10% or more and less than 20% ⁇ : The peeled area ratio was 20% or more Met
- the anti-glare antireflection film of the present invention composed of the anti-glare layer of the present invention is better for spot unevenness (appearance) and adhesion than the comparative example. It can be seen that it has excellent performance.
- anti-glare antireflection films 1 to 7 a black acrylic plate with an adhesive was attached to the back coat surface, and light absorption treatment was performed. From the low refractive index layer surface, CM-3700d (manufactured by Konica Minolta Sensing Co., Ltd.) As a result, the average reflectance of the antiglare antireflection film of the present invention was 1.2% or less and had a good antireflection function.
- Example 3 ⁇ Preparation of clear hard coat film 1>
- ⁇ Preparation of polarizing plate> A 120 ⁇ m-thick polyvinyl alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizer.
- the polarizer, the clear hard coat film 1 and the optical film 1 are aligned with the back surface side in the longitudinal direction, and bonded together by roll-to-roll to produce a polarizing plate.
- the adhesive layer was bonded together.
- Step 1 Soaked in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to saponify the side to be bonded to the polarizer to obtain a clear hard coat film 1 and an optical film 1 .
- Step 2 The polarizer was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
- Step 3 The excess adhesive adhered to the polarizer in Step 2 was gently wiped off, and the clear hard coat film 1 treated in Step 1 and the optical film 1 were placed on the back side.
- Step 4 The films laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm 2 and a conveyance speed of about 2 m / min.
- Step 5 A sample obtained by bonding the polarizer, the clear hard coat film 1 and the optical film 1 prepared in Step 4 in a dryer at 80 ° C. is dried for 2 minutes, wound into a roll, and the polarizing plate 100 is produced. did.
- Step 6 Apply a commercially available acrylic adhesive to the protective film of the polarizing plate prepared in Step 5 so that the thickness after drying is 25 ⁇ m, and dry in an oven at 110 ° C. for 5 minutes to form an adhesive layer. A peelable protective film was attached to the adhesive layer. This polarized light was cut (punched) to produce a polarizing plate 100.
- the polarizing plate 1 produced in Example 1 was peeled off from the peelable protective film of the pressure-sensitive adhesive layer as shown in FIG. 5, and was bonded to the rear (backlight) side through the glass of the liquid crystal cell. Furthermore, the peelable protective film of the pressure-sensitive adhesive layer of the produced polarizing plate 100 is peeled off and bonded to the front side to produce a liquid crystal panel 101. The liquid crystal panel 101 is removed from the SONY notebook PC VAIO TYPE B panel. The liquid crystal display device 101 was manufactured by fitting.
- Liquid crystal display devices 102 to 125 were prepared in the same manner except that the rear polarizing plate 1 was changed to polarizing plates 2 to 25 in the production of the liquid crystal display device 101.
- the manufactured liquid crystal display devices 101 to 125 were observed for moire fringes and evaluated according to the following criteria. The obtained results are shown in Table 3.
- the liquid crystal display device used on the rear side using the polarizing plate composed of the antiglare film of the present invention was excellent in preventing the generation of moire fringes because no moire fringes were observed.
- Example 4 Preparation of antiglare film 1 with conductive film>
- the surface resistivity is about 200 ⁇ on one side of the antiglare layer.
- a transparent conductive thin film of indium tin (ITO) was provided using a sputtering method to produce the antiglare film 1 with a conductive film shown in FIG.
- ⁇ Preparation of antiglare films 2 to 25 with conductive film> In the same manner as the production of the antiglare film 1 with a conductive film, after providing an antiglare layer on both sides, a transparent conductive thin film of ITO having a surface resistivity of about 200 ⁇ on one side of the antiglare layer is sputtered. Were used to prepare antiglare films 2 to 25 with a conductive film.
- resistive touch panel liquid crystal display devices 202 to 225 In the production of the resistive touch panel liquid crystal display device 1, the resistive touch panel liquid crystal display device 202 ⁇ is similarly manufactured except that the antiglare film 1 with conductive film is changed to the antiglare films 2-25 with conductive film. 225 was made.
- the antiglare film with a conductive film of the present invention and the resistive film type touch panel liquid crystal display device using the film were excellent in visibility and pen sliding resistance.
- the present invention has wide industrial applicability in the technical fields of antiglare films, polarizing plates, image display devices, and touch panels.
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Abstract
Description
本発明でいう防眩性フィルムとは、フィルム基材の表面に反射した像や外光の輪郭をぼかす層(すなわち、防眩層)をフィルム基材の表面に設けることで、液晶ディスプレイ、有機ELディスプレイ、プラズマディスプレイといった画像表示装置等の使用時に、外光や反射像の映り込みが気にならないようにしたフィルムのことである。なお、本願において、「~」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。また、「表面ヘイズ値」及び「内部ヘイズ値」は、それぞれ、単に「表面ヘイズ」、「内部ヘイズ」とも表現する。
本実施形態の防眩性フィルムは、防眩層の算術平均粗さRa(JIS B0601:1994)が300~1500nmで有ることを一つの特徴としている。算術平均粗さRaは、更に好ましくは350~1300nmであり、特に好ましくは500~1300nmである。算術平均粗さRa350~1300nmで本発明の目的効果がより良好に発揮され、更に算術平均粗さRa500~1300nmでは、鉛筆硬度評価法(試験方法の詳細は後述)による硬度試験において、引っ掻いた鉛筆の防眩層での滑り性が増し、傷が付きにくい事で、薄膜でも高硬度(4H以上)が得られるため好ましい。
また、前記防眩性フィルムの製造方法は、基材フィルム上に上述したような特徴を有する防眩層を有するものを製造することができれば、特に限定されない。この製造方法は、具体的には、25℃における粘度が20~3000mPa・sの範囲内にある活性線硬化型樹脂をエステル類、グリコールエーテル類或いはアルコール類から選ばれる少なくとも1種の溶剤で希釈した防眩層塗布組成物を、少なくとも塗布工程、乾燥工程及び硬化工程を経由して防眩層を形成し、かつ前記乾燥工程における減率乾燥区間の温度を90~160℃の範囲内に維持した条件下で処理することを備える製造方法が挙げられる。このような製造方法によれば、安定した表面凹凸が形成され、耐久性試験後の防眩性フィルムの微小白濁ムラや微小クラックの発生がなく、画像表示装置に用いた場合、視認性(写り込み防止性能と鮮鋭性)に優れる防眩性フィルムが得られる。前記塗布は、硬化後の厚みが所定の厚みになるように、基材フィルム上に防眩層塗布組成物を塗布できる方法であれば、特に限定されない。具体的には、後述するような塗布方法が挙げられる。乾燥及び硬化は、上記の条件を満たし、基材フィルム上に防眩層を形成できる方法であれば、特に限定されず、後述する方法が挙げられる。
本実施形態に係る防眩層は、活性線硬化樹脂を含有すること、すなわち、紫外線や電子線のような活性線(活性エネルギー線ともいう)照射により、架橋反応を経て硬化する樹脂を主たる成分とする層である。
式中、Mwは親水基の分子量、Moは親油基の分子量を表し、Mw+Mo=M(化合物の分子量)である。或いはグリフィン法によれば、HLB値=20×親水部の式量の総和/分子量(J.Soc.Cosmetic Chem.,5(1954),294)等が挙げられる。HLB値が3~18の化合物の具体的化合物を下記に挙げるが、これに限定されるものでない。( )内はHLB値を示す。
基材フィルムは製造が容易であること、防眩層と接着し易いこと、光学的に等方性であることが好ましい。また、本実施形態では基材フィルムを偏光板保護フィルムとして使用する。
次に基材フィルムとして好ましい、セルロースエステルフィルムについてより詳細に説明する。セルロースエステルフィルムは上記特徴を有するものであれば特に限定はされないが、セルロースエステル樹脂(以下、セルロースエステルともいう)は、セルロースの低級脂肪酸エステルであることが好ましい。セルロースの低級脂肪酸エステルにおける低級脂肪酸とは炭素原子数が6以下の脂肪酸を意味し、例えば、セルロースアセテート、セルロースジアセテート、セルローストリアセテート、セルロースプロピオネート、セルロースブチレート等や、セルロースアセテートプロピオネート、セルロースアセテートブチレート等の混合脂肪酸エステルを用いることができる。
式(II) 0≦X≦2.5
カラム:Shodex K806、K805、K803G
(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度:0.1質量%
検出器:RI Model 504(GLサイエンス社製)
ポンプ:L6000(日立製作所(株)製)
流量:1.0ml/min
校正曲線:標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=1000000~500迄の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いることが好ましい。
また、基材フィルムは、熱可塑性アクリル樹脂とセルロースエステル樹脂とを含有し、熱可塑性アクリル樹脂とセルロースエステル樹脂の含有質量比が、熱可塑性アクリル樹脂:セルロースエステル樹脂=95:5~50:50であるフィルムを用いることも好ましい。
基材フィルムは脆性の改善に優れる点から、アクリル粒子を含有しても良い。アクリル粒子とは、前記熱可塑性アクリル樹脂及びセルロースエステル樹脂を相溶状態で含有する基材フィルム中に粒子の状態(非相溶状態ともいう)で存在するアクリル成分を表す。
基材フィルムは、取扱性を向上させる為、例えば二酸化ケイ素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、カオリン、タルク、焼成ケイ酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム、リン酸カルシウム等の無機微粒子や架橋高分子などのマット剤を含有させることが好ましい。中でも二酸化ケイ素がフィルムのヘイズを小さくできるので好ましく用いられる。
基材フィルムには、組成物の流動性や柔軟性を向上するために、可塑剤を併用することもできる。可塑剤としては、フタル酸エステル系、脂肪酸エステル系、トリメリット酸エステル系、リン酸エステル系、ポリエステル系、あるいはエポキシ系等が挙げられる。この中で、ポリエステル系の可塑剤が好ましく用いられる。ポリエステル系可塑剤は、フタル酸ジオクチルなどのフタル酸エステル系の可塑剤に比べて非移行性や耐抽出性に優れる。用途に応じてこれらの可塑剤を選択、あるいは併用することによって、広範囲の用途に適用できる。
次に、基材フィルムの製膜方法の例を説明するが、これに限定されるものではない。基材フィルムの製膜方法としては、インフレーション法、T-ダイ法、カレンダー法、切削法、流延法、エマルジョン法、ホットプレス法等の製造法が使用できる。
基材フィルムを溶液流延法で製造する場合のドープを形成するのに有用な有機溶媒は、アクリル樹脂、セルロースエステル樹脂、その他の添加剤を同時に溶解するものであれば制限なく用いることが出来る。
基材フィルムは、溶液流延法によって製造することが出来る。溶液流延法では、樹脂および添加剤を溶剤に溶解させてドープを調製する工程、ドープをベルト状もしくはドラム状の金属支持体上に流延する工程、流延したドープをウェブとして乾燥する工程、金属支持体から剥離する工程、延伸または幅保持する工程、更に乾燥する工程、仕上がったフィルムを巻き取る工程により行われる。
延伸工程では、フィルムの長手方向(MD方向)、及び幅手方向(TD方向)に対して、逐次または同時に延伸することができる。互いに直交する2軸方向の延伸倍率は、それぞれ最終的にはMD方向に1.0~2.0倍、TD方向に1.07~2.0倍の範囲とすることが好ましく、MD方向に1.0~1.5倍、TD方向に1.07~2.0倍の範囲で行うことが好ましい。例えば、複数のロールに周速差をつけ、その間でロール周速差を利用してMD方向に延伸する方法、ウェブの両端をクリップやピンで固定し、クリップやピンの間隔を進行方向に広げてMD方向に延伸する方法、同様に横方向に広げてTD方向に延伸する方法、或いはMD/TD方向同時に広げてMD/TD両方向に延伸する方法などが挙げられる。製膜工程のこれらの幅保持或いは幅手方向の延伸はテンターによって行うことが好ましく、ピンテンターでもクリップテンターでもよい。
基材フィルムは、溶融製膜法によって製膜しても良い。溶融製膜法は、樹脂および可塑剤などの添加剤を含む組成物を、流動性を示す温度まで加熱溶融し、その後、流動性のセルロースエステルを含む溶融物を流延することをいう。
本実施形態における基材フィルムの膜厚は、特に限定はされないが10~200μmが用いられる。特に膜厚は10~100μmであることが特に好ましい。更に好ましくは20~60μmである。
本実施形態に係る防眩性フィルムは、バックコート層、反射防止層等の機能性層を設けることができる。
本実施形態に係る防眩性フィルムは、基材フィルムの防眩層を設けた側と反対側の面に、カールや防眩性フィルムを巻き状で保管した際のくっつき防止の為に、バックコート層を設けてもよい。
本実施形態の防眩性フィルムは、防眩層上に直接又は他の層を介して反射防止層である低屈折率層を設けることで、低屈折率層と防眩層との密着性に優れ、更に低屈折率層の斑点ムラの発生を良好に抑制でき、優れた外観が得られる点から、防眩性反射防止フィルムに本発明の防眩性フィルムを用いることが好ましい。低屈折率層からなる反射防止層は、低屈折率層のみの単層構成でもよいが、多層でも良い。具体的には、支持体よりも屈折率の高い高屈折率層と、支持体よりも屈折率の低い低屈折率層を組み合わせて構成したりできる。また、支持体側から屈折率の異なる3層を、中屈折率層(支持体又は防眩層よりも屈折率が高く、高屈折率層よりも屈折率の低い層)/高屈折率層/低屈折率層の順に積層されても良い。更に、2層以上の高屈折率層と2層以上の低屈折率層とを交互に積層した4層以上の層構成の反射防止層も好ましく用いられる。反射防止層の好ましい層構成の例を下記に示す。ここで/は積層配置されていることを示している。
基材フィルム/防眩層/高屈折率層/低屈折率層
基材フィルム/防眩層/中屈折率層/高屈折率層/低屈折率層
低屈折率層では、基材フィルムの屈折率より低い層を形成し、該屈折率は23℃、波長550nm測定で、屈折率が1.30~1.45の範囲であることが好ましい。
中空球状微粒子は、(I)多孔質粒子と該多孔質粒子表面に設けられた被覆層とからなる複合粒子、又は(II)内部に空洞を有し、かつ内容物が溶媒、気体又は多孔質物質で充填された空洞粒子である。なお、低屈折率層には(I)複合粒子又は(II)空洞粒子のいずれかが含まれていればよく、また双方が含まれていてもよい。
第1工程では、予め、シリカ原料とシリカ以外の無機化合物原料のアルカリ水溶液を個別に調製するか、又は、シリカ原料とシリカ以外の無機化合物原料との混合水溶液を調製しておき、この水溶液を目的とする複合酸化物の複合割合に応じて、pH10以上のアルカリ水溶液中に攪拌しながら徐々に添加して多孔質粒子前駆体を調製する。
第2工程では、前記第1工程で得られた多孔質粒子前駆体から、シリカ以外の無機化合物(珪素と酸素以外の元素)の少なくとも一部を選択的に除去する。具体的な除去方法としては、多孔質粒子前駆体中の無機化合物を鉱酸や有機酸を用いて溶解除去したり、又は、陽イオン交換樹脂と接触させてイオン交換除去する。
第3工程では、第2工程で調製した多孔質粒子分散液(空洞粒子の場合は空洞粒子前駆体分散液)に、フッ素置換アルキル基含有シラン化合物を含有する加水分解性の有機珪素化合物又はケイ酸液等を加えることにより、粒子の表面を加水分解性有機珪素化合物又はケイ酸液等の重合物で被覆してシリカ被覆層を形成する。
低屈折率層には、ゾルゲル素材としてテトラアルコキシシラン化合物又はその加水分解物が含有されることが好ましい。低屈折率層用の素材として、前記無機珪素酸化物以外に有機基を有する珪素酸化物を用いることも好ましい。これらは一般にゾルゲル素材と呼ばれるが、金属アルコレート、オルガノアルコキシ金属化合物及びその加水分解物を用いることができる。特に、アルコキシシラン、オルガノアルコキシシラン及びその加水分解物が好ましい。これらの例としては、テトラアルコキシシラン(テトラメトキシシラン、テトラエトキシシラン等)、アルキルトリアルコキシシラン(メチルトリメトキシシラン、エチルトリメトキシシラン等)、アリールトリアルコキシシラン(フェニルトリメトキシシラン等)、ジアルキルジアルコキシシラン、ジアリールジアルコキシシラン等が挙げられる。特にテトラアルコキシシラン及びその加水分解物が好ましい。
微粒子(特に無機微粒子)には、表面処理を実施して、ポリマーとの親和性を改善することが好ましい。表面処理は、プラズマ放電処理やコロナ放電処理のような物理的表面処理と、カップリング剤を使用する化学的表面処理に分類できる。化学的表面処理のみ、又は物理的表面処理と化学的表面処理の組み合わせで実施することが好ましい。カップリング剤としては、オルガノアルコキシメタル化合物(例、チタンカップリング剤、シランカップリング剤)が好ましく用いられる。微粒子がSiO2からなる場合は、前述のシランカップリング剤による表面処理が特に有効に実施できる。
シェルを形成するポリマーは、飽和炭化水素を主鎖として有するポリマーであることが好ましい。フッ素原子を主鎖又は側鎖に含むポリマーが好ましく、フッ素原子を側鎖に含むポリマーが更に好ましい。ポリアクリル酸エステル又はポリメタクリル酸エステルが好ましく、フッ素置換アルコールとポリアクリル酸又はポリメタクリル酸とのエステルが最も好ましい。シェルポリマーの屈折率は、ポリマー中のフッ素原子の含有量の増加に伴い低下する。低屈折率層の屈折率を低下させるため、シェルポリマーは35~80質量%のフッ素原子を含むことが好ましく、45~75質量%のフッ素原子を含むことが更に好ましい。フッ素原子を含むポリマーは、フッ素原子を含むエチレン性不飽和モノマーの重合反応により合成することが好ましい。フッ素原子を含むエチレン性不飽和モノマーの例としては、フルオロオレフィン(例えば、フルオロエチレン、ビニリデンフルオライド、テトラフルオロエチレン、ヘキサフルオロプロピレン、パーフルオロ-2,2-ジメチル-1,3-ジオキソール)、フッ素化ビニルエーテル及びフッ素置換アルコールとアクリル酸又はメタクリル酸とのエステルが挙げられる。
バインダーポリマーは、飽和炭化水素又はポリエーテルを主鎖として有するポリマーであることが好ましく、飽和炭化水素を主鎖として有するポリマーであることが更に好ましい。バインダーポリマーは架橋していることが好ましい。飽和炭化水素を主鎖として有するポリマーは、エチレン性不飽和モノマーの重合反応により得ることが好ましい。架橋しているバインダーポリマーを得るためには、二以上のエチレン性不飽和基を有するモノマーを用いることが好ましい。2以上のエチレン性不飽和基を有するモノマーの例としては、多価アルコールと(メタ)アクリル酸とのエステル(例えば、エチレングリコールジ(メタ)アクリレート、1,4-ジクロヘキサンジアクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ペンタエリスリトールヘキサ(メタ)アクリレート、1,2,3-シクロヘキサンテトラメタクリレート、ポリウレタンポリアクリレート、ポリエステルポリアクリレート)、ビニルベンゼン及びその誘導体(例えば、1,4-ジビニルベンゼン、4-ビニル安息香酸-2-アクリロイルエチルエステル、1,4-ジビニルシクロヘキサノン)、ビニルスルホン(例えば、ジビニルスルホン)、アクリルアミド(例えば、メチレンビスアクリルアミド)及びメタクリルアミドが挙げられる。ポリエーテルを主鎖として有するポリマーは、多官能エポシキ化合物の開環重合反応により合成することが好ましい。2以上のエチレン性不飽和基を有するモノマーの代わり又はそれに加えて、架橋性基の反応により、架橋構造をバインダーポリマーに導入してもよい。架橋性官能基の例としては、イソシアナート基、エポキシ基、アジリジン基、オキサゾリン基、アルデヒド基、カルボニル基、ヒドラジン基、カルボキシル基、メチロール基及び活性メチレン基が挙げられる。ビニルスルホン酸、酸無水物、シアノアクリレート誘導体、メラミン、エーテル化メチロール、エステル及びウレタンも、架橋構造を導入するためのモノマーとして利用できる。ブロックイソシアナート基のように、分解反応の結果として架橋性を示す官能基を用いてもよい。また、架橋基は、上記化合物に限らず上記官能基が分解した結果反応性を示すものであってもよい。バインダーポリマーの重合反応及び架橋反応に使用する重合開始剤は、熱重合開始剤や、光重合開始剤が用いられるが、光重合開始剤の方がより好ましい。光重合開始剤の例としては、アセトフェノン類、ベンゾイン類、ベンゾフェノン類、ホスフィンオキシド類、ケタール類、アントラキノン類、チオキサントン類、アゾ化合物、過酸化物類、2,3-ジアルキルジオン化合物類、ジスルフィド化合物類、フルオロアミン化合物類や芳香族スルホニウム類がある。アセトフェノン類の例としては、2,2-ジエトキシアセトフェノン、p-ジメチルアセトフェノン、1-ヒドロキシジメチルフェニルケトン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-4-メチルチオ-2-モルフォリノプロピオフェノン及び2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノンが挙げられる。ベンゾイン類の例としては、ベンゾインメチルエーテル、ベンゾインエチルエーテル及びベンゾインイソプロピルエーテルが挙げられる。ベンゾフェノン類の例としては、ベンゾフェノン、2,4-ジクロロベンゾフェノン、4,4-ジクロロベンゾフェノン及びp-クロロベンゾフェノンが挙げられる。ホスフィンオキシド類の例としては、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキシドが挙げられる。
低屈折率層は、バインダーとしてカチオン重合性化合物を含有しても良い。カチオン重合性化合物としては、エネルギー活性線照射や熱によってカチオン重合を起こして樹脂化するものであればいずれも使用できる。具体的には、エポキシ基、環状エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル化合物、ビニルオキソ基等が挙げられる。中でもエポキシ基やビニルエーテル基などの官能基を有する化合物が本実施形態においては、好適に用いられる。エポキシ基またはビニルエーテル基を有するカチオン重合性化合物としては、例えば、フェニルグリシジルエーテル、エチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ビニルシクロヘキセンジオキサイド、リモネンジオキサイド、3,4-エポキシシクロヘキシルメチル-3′,4′-エポキシシクロヘキサンカルボキシレート、ビス-(6-メチル-3,4-エポキシシクロヘキシル)アジペート、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、ジエチレングリコールジビニルエーテル、ポリエチレングリコールジビニルエーテル、1,4-シクロヘキサンジメタノールジビニルエーテル等が挙げられる。また、オキセタン化合物も挙げることができる。オキセタン化合物としては、分子中に少なくとも1個のオキセタン環を有する化合物であればよい。
カチオン重合性化合物の重合を促進する化合物として、公知の酸や光酸発生剤を挙げることができる。光酸発生剤としては、カチオン重合の光開始剤、色素類の光消色剤、光変色剤、或いは、マイクロレジスト等に使用されている公知の化合物及びそれらの混合物等が挙げられる。具体的には、例えば、オニウム化合物、有機ハロゲン化合物、ジスルホン化合物が挙げられ、好ましくは、オニウム化合物である。オニウム化合物としては、以下の各式に示されるジアゾニウム塩、スルホニウム塩、ヨードニウム塩などが好適に使用される。
(R)3S+Z-、
(R)2I+Z-
また低屈折率層は、バインダーとしてラジカル重合性化合物を含有することもできる。ラジカル重合性基としては、(メタ)アクリロイル基、ビニルオキシ基、スチリル基、アリル基等のエチレン性不飽和基等が挙げられ、中でも、(メタ)アクリロイル基を有する化合物が好ましい。また、ラジカル重合性化合物としては、分子内に2個以上のラジカル重合性基を含有する多官能モノマーを含有することが好ましい。多官能アクリレートとしては、ペンタエリスリトール多官能アクリレート、ジペンタエリスリトール多官能アクリレート、ペンタエリスリトール多官能メタクリレート、及びジペンタエリスリトール多官能メタクリレートよりなる群から選ばれることが好ましい。ラジカル重合性化合物の添加量は、低屈折層塗布組成物中では固形分中の15質量%以上70質量%未満であることが、低屈折層塗布組成物の安定性の点から、好ましい。
ラジカル重合性化合物の硬化促進のために、光重合開始剤をラジカル重合性化合物と併用して用いることが好ましい。光重合開始剤とラジカル重合性化合物とを併用して用いる場合には、光重合開始剤とラジカル重合性化合物とを質量比で20:100~0.01:100含有することが好ましい。
高屈折率層及び中屈折率層には、金属酸化物微粒子が含有されることが好ましい。金属酸化物微粒子の種類は特に限定されるものではなく、Ti、Zr、Sn、Sb、Cu、Fe、Mn、Pb、Cd、As、Cr、Hg、Zn、Al、Mg、Si、P及びSから選択される少なくとも一種の元素を有する。
高屈折率層及び中屈折率層は、微粒子として金属酸化物粒子を含み、更にバインダーポリマーを含むことが好ましい。
防眩性反射防止フィルムの反射防止層は、450nm~650nmにおける平均反射率が、1.5%以下が好ましく、特に好ましくは1.2%以下である。また、この範囲における最低反射率は0.00~0.5%にあることが好ましい。
本実施形態に係る防眩性フィルムを用いた本実施形態の偏光板について述べる。
式(II):Rt={(nx+ny)/2-nz}×d(nm)
〔上式中、Roはフィルム内の面内リターデーション値を表し、Rtはフィルム内の厚さ方向のリターデーション値を表す。また、dは光学フィルムの厚さ(nm)を表し、nxはフィルムの面内の最大の屈折率を表す。nyはフィルム面内で遅相軸に直角な方向の屈折率を表し、nzは厚さ方向におけるフィルムの屈折率を表す。〕
液晶セルの基板と貼り合わせるために保護フィルムの片面に用いられる粘着剤層は、光学的に透明であることはもとより、適度な粘弾性や粘着特性を示すものが好ましい。
本実施形態の防眩性フィルムは、画像表示装置に使用することで、視認性に優れた性能が発揮される。画像表示装置としては、反射型、透過型、半透過型液晶表示装置または、TN型、STN型、OCB型、VA型、IPS型、ECB型等の各種駆動方式の液晶表示装置、有機エレクトルミネッセンス素子を有する表示装置やプラズマディスプレイ等が挙がられる。これら画像表示装置の中でも液晶表示装置の偏光板に本実施形態の防眩性フィルムを用いることで、視認性に優れる点から好ましい。
次に、本実施形態の防眩性フィルムをタッチパネルに用いた場合の一例を示す。図8は、本実施形態の防眩性フィルムをタッチパネルに用い抵抗膜方式タッチパネル付き液晶表示装置50の概略図である。図8中、符号50は抵抗膜方式タッチパネル液晶表示装置、51はスペーサ、52は透明導電性薄膜(ITO層)、53はガラス基板、54はLCD(液晶表示パネル)をぞれぞれ示す。導電性防眩性フィルム40を透明導電性薄膜52が形成されたガラス基板53と、透明導電性薄膜同士が向き合うように一定の間隔(スペーサー51)をあけて対向させることにより、抵抗膜方式のタッチパネルを構成することができる。導電性防眩性フィルム、及びガラス基板の端部には不図示の電極が配置されている。抵抗膜方式のタッチパネルは、ユーザが導電性防眩性フィルムを指やペン等で押下することにより、導電性防眩性フィルムの透明導電性薄膜が、ガラス基板上の透明導電性薄膜と接触する。この接触を端部の電極を介して電気的に検出することにより、押下された位置が検出される仕組みである。ガラス基板の透明導電性薄膜上には、必要に応じてドット状のスペーサが配置される。また、タッチパネルをLCD(液晶表示装置)上に搭載することにより、タッチパネル付き液晶表示装置を構成することができる。
<基材フィルム1の作製>
(二酸化珪素分散液の調製)
アエロジルR812(日本アエロジル(株)製、一次粒子の平均径7nm) 10質量部
エタノール 90質量部
以上をディゾルバーで30分間撹拌混合した後、マントンゴーリンで分散を行った。二酸化珪素分散液に88質量部のメチレンクロライドを撹拌しながら投入し、ディゾルバーで30分間撹拌混合し、二酸化珪素分散希釈液を作製した。微粒子分散希釈液濾過器(アドバンテック東洋(株):ポリプロピレンワインドカートリッジフィルターTCW-PPS-1N)で濾過した。
(ドープ組成物)
セルローストリアセテート(Mn=148000、Mw=310000 アセチル基置換度2.92)
90質量部
芳香族末端エステル系可塑剤(B-4) 10質量部
チヌビン900(BASFジャパン(株)製) 2.5質量部
二酸化珪素分散希釈液 4質量部
メチレンクロライド 432質量部
エタノール 38質量部
以上を密閉容器に投入し、加熱し、撹拌しながら、完全に溶解し、安積濾紙(株)製の安積濾紙No.24を使用して濾過し、ドープ液を調製した。
上記作製した基材フィルム1上に孔径0.4μmのポリプロピレン製フィルターで濾過した下記防眩層塗布組成物1を、押出しコーターを用いて塗布し、恒率乾燥区間温度95℃、減率乾燥区間温度85℃で乾燥後、酸素濃度が1.0体積%以下の雰囲気になるように窒素パージしながら、紫外線ランプを用い照射部の照度が100mW/cm2で、照射量を0.25J/cm2として塗布層を硬化させ、ドライ膜厚8μmの防眩層を形成した。防眩層を形成後、ロール状に巻き取り、防眩性フィルム1を作製した。防眩性フィルム1の防眩層表面を光学干渉式表面粗さ計(Zygo社製 New View 5030)で観察した結果、図3のように不規則な突起形状が不規則に長手方向及び幅方向に配列していることが分かった。
下記防眩層塗布組成物1をディスパーにて撹拌混合し、防眩層塗布組成物1を得た。
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製)
90質量部
トリメチロールプロパントリアクリレート
(NKエステルA-TMPT、新中村化学工業(株)製)
10質量部
(光重合開始剤)
イルガキュア184(BASFジャパン社製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(溶剤)
プロピレングリコールモノメチルエーテル(PGME) 100質量部
上記防眩層塗布組成物1の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、550mPa・sであった。
防眩性フィルム1の作製において、減率乾燥区間の温度を表1に記載したように条件変更した以外は、防眩性フィルム1と同様にして、防眩性フィルム2~8を作製した。
防眩性フィルム1の作製において、防眩層塗布組成物1を下記防眩層塗布組成物2とし、かつ乾燥工程における減率乾燥区間の温度を100℃に変更した以外は同様にして、防眩性フィルム9を作製した。
下記防眩層塗布組成物2をディスパーにて撹拌混合し、防眩層塗布組成物2を得た。
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製)
90質量部
トリメチロールプロパントリアクリレート
(NKエステルA-TMPT、新中村化学工業(株)製)
10質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(溶剤)
エタノール 100質量部
上記防眩層塗布組成物2の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、550mPa・sであった。
防眩性フィルム1の作製において、防眩層塗布組成物1を下記防眩層塗布組成物3とし、かつ乾燥工程における減率乾燥区間の温度を100℃に変更した以外は、同様にして防眩性フィルム10を作製した。
下記防眩層塗布組成物3をディスパーにて撹拌混合し、防眩層塗布組成物3を得た。
ジトリメチロールプロパンテトラアクリレート
(NKエステルAD-TMP、新中村化学工業(株)製)
60質量部
エトキシ化ペンタエリスリトールテトラアクリレート
(NKエステルATM-35E、新中村化学工業(株)製)
40質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(溶剤)
プロピレングリコールモノメチルエーテル(PGME) 50質量部
メタノール 50質量部
上記防眩層塗布組成物3の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、740mPa・sであった。
防眩性フィルム7の作製において、減率乾燥区間の温度を表1に記載したように条件変更した以外は、防眩性フィルム7と同様にして、防眩性フィルム11~17を作製した。
防眩性フィルム1の作製において、防眩層塗布組成物1を特開2006-106290号公報の実施例1を参考にして調製した非相溶の樹脂成分を含有する防眩層塗布組成物4に変更し、更に乾燥温度を特開2006-106290号公報の実施例1と同じ70℃とした以外は同様にして防眩層を作製した。次に、防眩層上に押出しコーターを用いて、熱硬化性含フッ素化合物塗工液(日産化学(株)製、LR-202B、固形分1質量%)を、乾燥後の膜厚が100nmとなるように塗布し、90℃で5分間乾燥させることで熱硬化させ、防眩性フィルム18を作製した。
下記防眩層塗布組成物4をディスパーにて撹拌混合し、防眩層塗布組成物4を得た。
サイクロマーP(ACA)320(不飽和基含有アクリル樹脂混合物、ダイセル化学工業(株)製)
5.04質量部
ジペンタエリスリトールヘキサアクリレート(DPHA、ダイセル・サイテック(株)製)
6.4質量部
(非相溶性樹脂)
セルロースアセテートプロピオネート(CAP-482-20、イーストマンケミカル社製)
0.9質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 0.2質量部
(溶剤)
メチルエチルケトン(MEK) 20質量部
シクロヘキサノン(CYC) 5質量部
上記防眩層塗布組成物4の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、10600mPa・sであった。なお、表1でセルロースアセテートプロピオネートをCAPと示した。
防眩性フィルム1の作製において、防眩層塗布組成物1を特開2008-225195号公報の実施例1を参考にして調整した非相溶の樹脂成分を含有する防眩層塗布組成物5に変更し、更に乾燥温度を特開2008-225195号公報の実施例1と同じ70℃とした以外は防眩性フィルム1と同様にして、防眩性フィルム19を作製した。
下記防眩層塗布組成物5をディスパーにて撹拌混合し、防眩層塗布組成物5を得た。
サイクロマーP(ACA)320(不飽和基含有アクリル樹脂混合物、ダイセル化学工業(株)製)
5.65質量部
ジペンタエリスリトールヘキサアクリレート(DPHA、ダイセル・サイテック(株)製)
6.3質量部
(非相溶性樹脂)
ポリメタクリル酸メチル(重量平均分子量480000;三菱レイヨン(株)製、BR88)
0.9質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 0.5質量部
(溶剤)
メチルエチルケトン(MEK) 0.1質量部
ブタノール 5.4質量部
プロピレングリコールモノメチルエーテル(PGME)
1.89質量部
上記防眩層塗布組成物5の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、10500mPa・sであった。なお、表1でポリメタクリル酸メチルをPMMAと示した。
防眩性フィルム1の作製において、防眩層塗布組成物1を特開2007-58204号公報の実施例3を参考にして調整した非相溶の樹脂成分を含有する防眩層塗布組成物6に変更し、更に乾燥温度を特開2007-58204号公報の実施例3と同じ80℃に変更した以外は防眩性フィルム1と同様にして、防眩性フィルム20を作製した。
下記防眩層塗布組成物6をディスパーにて撹拌混合し、防眩層塗布組成物6を得た。
ジペンタエリスリトールヘキサアクリレート(DPHA、ダイセル・サイテック(株)製)
92質量部
(非相溶性樹脂)
メタアクリレート共重合ポリマー(サフトマーST3600,三菱化学株式会社)
15質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 4質量部
(溶剤)
エタノール 45質量部
トルエン 15質量部
上記防眩層塗布組成物6の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、6000mPa・sであった。なお、表1でメタアクリレート共重合ポリマーをMACPと示した。
防眩性フィルム4の作製において、防眩層塗布組成物1を防眩層塗布組成物7に変更した以外は防眩性フィルム4と同様にして、防眩性フィルム21を作製した。
下記配合割合の溶媒に平均粒径2μmのシリカ微粒子(商品名:ハイプレシカTS、宇部日東化成社製)5質量部を混ぜた後、エアーディスパーにて30分間攪拌し、粒子分散液を得た。この粒子分散液に他の素材を混合、攪拌し、防弦層塗布組成物7を調整した。
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製)
90質量部
トリメチロールプロパントリアクリレート
(NKエステルA-TMPT、新中村化学工業(株)製)
10質量部
(光重合開始剤)
イルガキュア184(BASFジャパン社製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(微粒子)
平均粒径2μmのシリカ微粒子 5質量部
(溶剤)
プロピレングリコールモノメチルエーテル(PGME) 100質量部
上記防眩層塗布組成物7の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、450mPa・sであった。
防眩性フィルム4の作製において、防眩層塗布組成物1を防眩層塗布組成物8に変更した以外は防眩性フィルム4と同様にして、防眩性フィルム22を作製した。
下記防眩層塗布組成物8をディスパーにて撹拌混合し、防眩層塗布組成物8を得た。
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製)
90質量部
トリメチロールプロパントリアクリレート
(NKエステルA-TMPT、新中村化学工業(株)製)
10質量部
(光重合開始剤)
イルガキュア184(BASFジャパン社製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(溶剤)
エチレングリコールモノプロピルエーテル(EGPE) 100質量部
上記防眩層塗布組成物8の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、450mPa・sであった。
防眩性フィルム1の作製において、防眩層組成物1を下記防眩層層組成物9に変更し、減率乾燥区間温度を120℃に変更した以外は同様にして、防眩性フィルム23を作製した。
下記防眩層組成物9をディスパーにて撹拌混合し、防眩層塗布組成物9を得た。
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製)
75質量部
イソシアヌル酸EO変性ジアクリレート
(アロニックスM-215、東亞合成(株)製) 25質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 100質量部
上記防眩層塗布組成物9の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、2800mPa・sであった。
防眩性フィルム4の作製において、防眩層組成物1を下記防眩層層組成物10に変更した以外は同様にして、防眩性フィルム24を作製した。
下記防眩層塗布組成物10をディスパーにて撹拌混合し、防眩層塗布組成物10を得た。
トリメチロールプロパントリアクリレート
(ライトアクリレートTMP-A、共栄社化学(株)製)
80質量部
4-ヒドロキシブチルアクリレート(4-HBA、大阪有機化学工業(株)製)
20質量部
(光重合開始剤)
イルガキュア184(BASFジャパン(株)製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(溶剤)
プロピレングリコールモノメチルエーテル 100質量部
上記防眩層塗布組成物10の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、35mPa・sであった。
防眩性フィルム4の作製において、防眩層組成物1を下記防眩層層組成物11に変更した以外は同様にして、防眩性フィルム24を作製した。
下記防眩層塗布組成物11をディスパーにて撹拌混合し、防眩層塗布組成物11を得た。
ペンタエリスリトールトリ/テトラアクリレート
(NKエステルA-TMM-3L、新中村化学工業(株)製)
90質量部
トリメチロールプロパントリアクリレート
(NKエステルA-TMPT、新中村化学工業(株)製)
10質量部
(光重合開始剤)
イルガキュア184(BASFジャパン社製) 5質量部
(レベリング剤)
ポリエーテル変性シリコーン(KF-889、信越化学工業社製)
2質量部
(溶剤)
酢酸ブチル 100質量部
上記防眩層塗布組成物11の活性線硬化型樹脂だけをディスパーにて撹拌混合して、25℃の条件にてB型粘度計を用いて測定したところ、樹脂粘度は、550mPa・sであった。
《ヘイズ及び算術平均粗さRa測定》
上記作製した防眩性フィルム1~25について、ヘイズ測定を行い、内部ヘイズ(Hi)を求めた。また、算術平均粗さRaについても下記条件で測定した。
各防眩性フィルムの表裏面にシリコーンオイルを数滴滴下した。次にシリコーンオイルを滴下した防眩性フィルムを厚さ1mmのガラス板(ミクロスライドガラス品番S 9111、MATSUNAMI製)2枚で裏表より挟み、完全に2枚のガラス板と得られた防眩性フィルムを光学的に密着させた。この光学的に密着させ、表面ヘイズを除去したサンプルのヘイズ(Ha)を日本電色工業(株)製の測定機(NDH2000)を用いて測定した。
各防眩性フィルムの防眩層の算術平均粗さRaを、光学干渉式表面粗さ計(Zygo社製 New View 5030)を用いて10回測定し、その測定結果の平均から各防眩性フィルムの算術平均粗さRaを求めた。
防眩性フィルム1~25を、屋外での使用を想定して70℃相対湿度90%の恒温恒湿槽で50日保存後、更にサイクルサーモ(-40℃・45分放置、次いで110℃・45分放置を交互)に500サイクルを投入した。
耐久試験後の各防眩性フィルム1~25と下記偏光子と裏面側に下記手順で作製した光学フィルム1とを長手方向を合わせるようにロール・トゥ・ロールで貼り合わせて偏光板を各々作製した。偏光板の概略図を図4に示す。
〈微粒子分散液1〉
微粒子(アエロジル R972V 日本アエロジル(株)製)
11質量部
エタノール 89質量部
以上をディゾルバーで50分間攪拌混合した後、マントンゴーリンで分散を行った。
メチレンクロライドを入れた溶解タンクに十分攪拌しながら、微粒子分散液1をゆっくりと添加した。更に、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液1を調製した。
微粒子分散液1 5質量部
下記組成の主ドープ液を調製した。まず加圧溶解タンクにメチレンクロライドとエタノールを添加した。溶剤の入った加圧溶解タンクにセルロースアセテートを攪拌しながら投入した。これを加熱し、攪拌しながら、完全に溶解し。これを安積濾紙(株)製の安積濾紙No.244を使用して濾過し、主ドープ液を調製した。
メチレンクロライド 340質量部
エタノール 64質量部
アセチル基置換度2.4のセルロースアセテート(Mn80000)
100質量部
糖エステル化合物(1-23) 10質量部
芳香族末端エステル系可塑剤(2-23) 2.5質量部
紫外線吸収剤(チヌビン928(BASFジャパン(株)製))
2.3質量部
微粒子添加液1 1.0質量部
上記組成物を密閉容器に投入し、攪拌しながら溶解してドープ液を調製した。次いで、無端ベルト流延装置を用い、ドープ液を温度33℃、2000mm幅でステンレスベルト支持体上に均一に流延した。ステンレスベルトの温度は30℃に制御した。
厚さ120μmのポリビニルアルコールフィルムを一軸延伸(温度110℃、延伸倍率5倍)した。これをヨウ素0.075g、ヨウ化カリウム5g、水100gからなる水溶液に60秒間浸漬し、次いでヨウ化カリウム6g、ホウ酸7.5g、水100gからなる68℃の水溶液に浸漬した。これを水洗、乾燥し偏光子を得た。次いで、下記工程1~5に従って偏光子と各防眩性フィルム1~25と裏面側に光学フィルム1を長手方向で合わせるようにして、ロール・トゥ・ロールで貼り合わせて各偏光板1~25を作製し、更に工程6で粘着層をそれぞれの偏光板1~25に貼り合わせた。
SONY製32型ディスプレイBRAVIA KDL-32EXの予め貼合されていたパネル前側の偏光板を剥がして、上記作製した各偏光板1~22の粘着層をそれぞれ液晶セルのガラス面の前面に貼合した。その際、その偏光板の貼合の向きは、防眩性フィルムの防眩層が、視認側となるように、かつ、予め貼合されていた偏光板と同一の方向に吸収軸が向くように行い、液晶表示装置1~25を各々作製した。
(視認性評価)
上記作製した各液晶表示装置1~25について、80℃の条件で250時間放置した後、23℃、55%RHに戻し、視認性を評価した。評価者30人で画像の視認性の官能評価を行い、その平均点を求めた。10点が最も良好で、写り込みが少なく、鮮鋭性も高い。1点が最も劣る。7点以上が許容レベルである。
上記耐久性試験後の防眩性フィルム1~25について、以下の項目を評価した。
各防眩性フィルムについて、スガ試験機株式会社の写像性測定器ICM-IDPを用い、櫛幅0.25mmにおける透過写像性を測定した。数値が高いほど、透過写像性に優れていることを示す。
各防眩性フィルムを23℃55%RHの雰囲気下で12時間調湿後、JIS K5600-5-1に準拠する方法で、タイプ1の試験装置を用いて円筒型マンドレル法により可とう性を評価した。マンドレルの直径の数値が低い程、可とう性に優れることを示す。なお、JIS K5600-5-1では、円筒型マンドレルは直径2mmまでしかないため、直径1mmは試作した。直径の数値が小さいほど、可とう性(フィルムのフレキシブル性)に優れていることを表す。得られた結果を表1に示した。
<防眩性反射防止フィルム1~7の作製>
実施例1の防眩性フィルム4、9、13及び18~21の作製において、窒素パージを行わず、更に紫外線ランプを用い照射部の照度が100mW/cm2で、照射量を0.1J/cm2として塗布層を硬化させた以外は、同様にして防眩性フィルム26~32を作製し、ロール状に巻き取った。次いで、実施例1に記載の条件で、耐久性試験を実施した各ロール状防眩性フィルム26~32を再び繰り出して、防眩層表面上に低屈折率層用塗布組成物1を塗布して、低屈折率層を形成して、防眩性反射防止フィルム1~7を作製した。なお、低屈折率層の屈折率は1.37であった。
(含フッ素ポリマー1の調製)
内容量100mlのステンレス製撹拌機付オートクレーブに、酢酸エチル40ml、ヒドロキシエチルビニルエーテル14.7g、及び過酸化ジラウロイル0.55gを仕込み、反応系内を脱気して、窒素ガスで置換した。更にヘキサフルオロプロピレン(HFP)25gをオートクレーブ中に導入して、温度65℃まで昇温した。オートクレーブ内の温度が65℃に達した時点の圧力は、5.4kg/cm2であった。オートクレーブ内の温度をそのまま保持し、8時間反応を続け、圧力が3.2kg/cm2に達した時点で加熱をやめ、放冷した。室温まで内温が下がった時点で、未反応のモノマーを追い出し、オートクレーブを開放して、反応液を取り出した。
メチルエチルケトン 460質量部
シクロヘキサノン 300質量部
(ラジカル重合性化合物)
含フッ素ポリマー1 30質量部
ペンタエリスリトールトリアクリレート 20質量部
ペンタエリスリトールテトラアクリレート 14質量部
(光重合性開始剤)
イルガキュア907(BASFジャパン(株)製) 3質量部
(添加剤)
シリコーン化合物(FZ-2207、日本ユニカー株式会社製)の10%プロピレン
グリコールモノメチルエーテル液 6.5質量部
(微粒子)
イソプロピルアルコール分散中空シリカ微粒子ゾル 50質量部
(固形分20%、触媒化成工業社製シリカゾル、商品名:ELCOM V-8209)
《フィルム評価》
得られた防眩性フィルム26~32、及び防眩性反射防止フィルム1~7について、以下の項目を評価した。得られた結果を表2に示した。
防眩性フィルム26~32の内部ヘイズ(Hi)、及び算術平均粗さRaを実施例1に記載した方法で測定した。得られた結果を表2に示した。
(外観評価)
各防眩性反射防止フィルムを150cm×150cmサイズでカットし、裏面に黒色のスプレーを用いて光吸収処理を行い、表面から蛍光灯の反射を観察して、外観(斑点状のムラ)について以下の基準で目視評価した。得られた結果を表2に示した。
◎:斑点状のムラが全く認められない
○:斑点状のムラが僅かに認められる
△:斑点状のムラがやや認められる。実用上問題がある
×:斑点状のムラが認められる
各防眩性反射防止フィルムをサイクルサーモ(-40℃・30分放置、次いで85℃・30分放置を交互)に500サイクル投入後、耐候性試験機(アイスーパーUVテスター、岩崎電気株式会社製)にて、120時間光照射した。
○:剥離された面積割合が10%未満であった
△:剥離された面積割合が10%以上~20%未満であった
×:剥離された面積割合が20%以上であった
<クリアハードコートフィルム1の作製>
実施例1で作製した基材フィルム1上に孔径0.4μmのポリプロピレン製フィルターで濾過した下記クリアハードコート塗布組成物1を、マイクログラビアコーターを用いて塗布し、恒率乾燥区間温度80℃、減率乾燥区間温度80℃で乾燥後、酸素濃度が1.0体積%以下の雰囲気になるように窒素パージしながら、紫外線ランプを用い照射部の照度が100mW/cm2で、照射量を0.25J/cm2として塗布層を硬化させ、ドライ膜厚5μmのクリアハードコート層を形成した。クリアハードコート層を形成後、ロール状に巻き取り、クリアハードコートフィルム1を作製した。クリアハードコートフィルム1の全ヘイズを日本電色工業(株)製の測定機(NDH2000)を用いて測定した結果、0.3%であり、クリア性に優れていた。
下記クリアハードコート層塗布組成物1をディスパーにて撹拌混合し、クリアハードコート層塗布組成物1を得た。
ジペンタエリスリトールポリアクリレート
(NKエステルA-9550、新中村化学工業(株)製)
100質量部
(光重合開始剤)
イルガキュア184(BASFジャパン社製) 5質量部
(レベリング剤)
アクリル共重合物(BYK-350、ビックケミー・ジャパン社製)
2質量部
(溶剤)
プロピレングリコールモノメチルエーテル(PGME) 10質量部
メチルエチルケトン 45質量部
酢酸メチル 45質量部
<偏光板の作製>
クリアハードコートフィルム1と下記偏光子と裏面側に実施例1で作製した光学フィルム1とを長手方向を合わせるようにロール・トゥ・ロールで貼り合わせて偏光板100を作製した。
厚さ120μmのポリビニルアルコールフィルムを一軸延伸(温度110℃、延伸倍率5倍)した。これをヨウ素0.075g、ヨウ化カリウム5g、水100gからなる水溶液に60秒間浸漬し、次いでヨウ化カリウム6g、ホウ酸7.5g、水100gからなる68℃の水溶液に浸漬した。これを水洗、乾燥し偏光子を得た。次いで、工程1~5に従って偏光子とクリアハードコートフィルム1と裏面側に光学フィルム1を長手方向で合わせるようにして、ロール・トゥ・ロールで貼り合わせて偏光板を作製し、更に工程6で粘着層を貼り合わせた。
実施例1で作製した偏光板1を図5に示したように粘着剤層の剥離性保護フィルムを剥がし、液晶セルのガラスを介在してリア(バックライト)側に貼合した。更に、上記作製した偏光板100の粘着剤層の剥離性保護フィルムを剥がしフロント側に貼合し、液晶パネル101を作製し、この液晶パネル101をSONY製ノート型PC VAIO TYPE Bのパネルを外してはめ込み、液晶表示装置101を作製した。
液晶表示装置101の作製において、リア側の偏光板1を偏光板2~25に、それぞれ変更した以外は同様にして液晶表示装置102~125を作製した。
(モアレ縞評価)
◎ :モアレ縞が全く確認できない
○ :注視すると僅かにモアレ縞の確認できる
△ :ぼんやりであるがモアレ縞の存在が容易に確認できる
× :モアレ縞の存在が確認できる。実用上問題のあるレベル
××:モアレ縞の発生が明確に確認できる
<導電性膜付き防眩性フィルム1の作製>
防眩性フィルム1の作製において、両面に防眩層塗布層組成物1を塗設して、両面に防眩層を設けた後、防眩層の片面に表面抵抗率が約200Ωである酸化インジウム錫(ITO)の透明導電性薄膜を、スパッタリング法を用いて設け、図7に示した導電性膜付き防眩性フィルム1を作製した。
導電性膜付き防眩性フィルム1の作製と同様にして、両面に防眩層を設けた後、防眩層の片面に表面抵抗率が約200ΩであるITOの透明導電性薄膜を、スパッタリング法を用いて設け、導電性膜付き防眩性フィルム2~25を作製した。
市販の抵抗膜方式タッチパネル液晶表示装置(型名:LCD-USB10XB-T、I-O DATA社製)の導電性光学フィルムを剥がし、上記作製した導電性膜付き防眩性フィルム1を図8のように貼合して、抵抗膜方式タッチパネル液晶表示装置201を作製した。
抵抗膜方式タッチパネル液晶表示装置1の作製において、導電性膜付き防眩性フィルム1を導電性膜付き防眩性フィルム2~25に変更した以外は同様にして抵抗膜方式タッチパネル液晶表示装置202~225を作製した。
実施例1と同様にして抵抗膜方式タッチパネル液晶表示装置202~225の視認性の評価を行った。得られた結果を表4に示した。
(耐ペン摺動性)
導電性膜付き防眩性フィルム2~25については、以下の条件で耐ペン摺動性について評価を行った。得られた結果を表4に示した。
Claims (13)
- 基材フィルム上に、活性線硬化型樹脂を含有する防眩層を有する防眩性フィルムであって、前記防眩層が微粒子及び前記活性線硬化型樹脂に対し非相溶性である樹脂を実質的に含有せず、前記防眩層の算術平均粗さRaが300~1500nmであり、かつ該防眩層の内部散乱に起因するヘイズが0~1.0%であることを特徴とする防眩性フィルム。
- 前記防眩層の算術平均粗さRaが350~1300nmであることを特徴とする請求項1に記載の防眩性フィルム。
- 前記防眩層の算術平均粗さRaが500~1300nmであることを特徴とする請求項1または2に記載の防眩性フィルム。
- 前記防眩層の内部散乱に起因するヘイズが0~0.5%であることを特徴とする請求項1~3のいずれか1項に記載の防眩性フィルム。
- 前記防眩層の表面が長手方向に周期をもたない不規則な突起形状を有していることを特徴とする請求項1~4のいずれか1項に記載の防眩性フィルム。
- 前記活性線硬化型樹脂の25℃における粘度が20~3000mPa・sの範囲内であることを特徴とする請求項1~5のいずれか1項に記載の防眩性フィルム。
- 請求項1~6のいずれか1項に記載の防眩性フィルムの防眩層上に直接又は他の層を介して低屈折率層が積層されたことを特徴とする防眩性反射防止フィルム。
- 請求項1~6のいずれか1項に記載の防眩性フィルムを製造する防眩性フィルムの製造方法であって、25℃における粘度が20~3000mPa・sの範囲内にある活性線硬化型樹脂をエステル類、グリコールエーテル類或いはアルコール類から選ばれる少なくとも1種の溶剤で希釈した防眩層塗布組成物を、少なくとも塗布工程、乾燥工程及び硬化工程を経由して防眩層を形成し、かつ前記乾燥工程における減率乾燥区間の温度を90~150℃の範囲内に維持した条件下で処理することを特徴とする防眩性フィルムの製造方法。
- 請求項1~6のいずれか1項に記載の防眩性フィルム及び請求項7に記載の防眩性反射防止フィルムが、少なくとも一方の面に具備されていることを特徴とする偏光板。
- 請求項1~6のいずれか1項に記載の防眩性フィルム及び請求項7に記載の防眩性反射防止フィルムが具備されていることを特徴とする画像表示装置。
- 請求項9に記載の偏光板が液晶セルの少なくとも一方の面に具備されていることを特徴とする請求項10に記載の画像表示装置。
- 請求項9に記載の偏光板を液晶セルのリア側に用いることを特徴とする請求項10に記載の画像表示装置。
- 前記画像表示装置がタッチパネル付き画像表示装置であって、かつ当該タッチパネルの構成部材として、請求項1~6のいずれか1項に記載の防眩性フィルム、または請求項7に記載の防眩性反射防止フィルムが具備されていることを特徴とする請求項10に記載の画像表示装置。
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JP2014142630A (ja) * | 2012-12-27 | 2014-08-07 | Fujifilm Corp | 偏光板保護フィルム、偏光板、並びに液晶表示装置 |
JPWO2013054673A1 (ja) * | 2011-10-14 | 2015-03-30 | 大日本印刷株式会社 | パターン位相差フィルム及びその製造方法 |
WO2015098685A1 (ja) * | 2013-12-27 | 2015-07-02 | コニカミノルタ株式会社 | 光学フィルム、偏光板および画像表示装置 |
JP2015533228A (ja) * | 2012-10-08 | 2015-11-19 | コーニング インコーポレイテッド | 改善されたディスプレイコンポーネントを提供するための方法及び装置 |
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