WO2010016369A1 - Film optique, procédé de production du film optique, plaque polarisante, et dispositif d'affichage à cristaux liquides - Google Patents

Film optique, procédé de production du film optique, plaque polarisante, et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2010016369A1
WO2010016369A1 PCT/JP2009/062878 JP2009062878W WO2010016369A1 WO 2010016369 A1 WO2010016369 A1 WO 2010016369A1 JP 2009062878 W JP2009062878 W JP 2009062878W WO 2010016369 A1 WO2010016369 A1 WO 2010016369A1
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Prior art keywords
film
resin
acid
particles
optical film
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PCT/JP2009/062878
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English (en)
Japanese (ja)
Inventor
亮太 久木
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コニカミノルタオプト株式会社
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Priority to JP2010523818A priority Critical patent/JPWO2010016369A1/ja
Publication of WO2010016369A1 publication Critical patent/WO2010016369A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
    • 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
    • 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
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • G02F1/133528—Polarisers

Definitions

  • the present invention relates to an optical film, a method for producing the optical film, a polarizing plate, and a liquid crystal display device.
  • a plastic film used for a polarizing plate protective film for a liquid crystal display (LCD) is generally manufactured by a solution casting method.
  • a polymer such as triacetyl cellulose is dissolved in a solvent with appropriate addition of various additives to form a dope, and then endless endless support It is cast onto a metal drum or band, which is a body, and peeled off using a peeling roll or the like when it has self-supporting properties.
  • the strip-shaped wet film peeled from the endless support is conveyed while gripping both side edges of the film with a tenter device, dried and stretched in the width direction. Since both side edges (ear portions) of this film are gripped and deformed, the ear portions are cut by the ear-cutting device arranged on the downstream side of the tenter device, and the film is processed into a predetermined width. .
  • a stretched film becomes brittle due to work hardening, and the cutting property is deteriorated, so that the possibility of product failure due to adhesion of the foreign matter is further increased. Furthermore, the adhesion of the pieces of the stretched film becomes a bright spot foreign material, which has a great adverse effect on the optical quality.
  • the cellulose ester film may contain various particles as described in Patent Document 2 or be applied. It has been known.
  • Patent Document 3 proposes an addition method that employs particles having a methyl group on the surface in order to improve aggregation of fine particles to be contained for the above purpose.
  • a few fine particle aggregates that have not been a problem until now have become problems as foreign matters, and these particles and aggregates of particles are scattered when the film is cut, resulting in foreign matters. It was found that this was a factor causing failure.
  • JP 2006-187855 A JP-A-1-299847 Japanese Patent Laid-Open No. 7-11055
  • an object of the present invention is to provide an optical film having good slipping property (blocking resistance) and having no foreign matter failure, a method for producing the optical film, a polarizing plate using the optical film, The object is to provide a liquid crystal display device.
  • the resin film contains particles, the arithmetic mean roughness Ra of the film surface is in the range of 1.0 to 2.0 nm, and the structural surface parameter Mr1 (%) specified in JIS B0671: 2002 An optical film having a value of 12% or less.
  • the resin film has an acrylic resin (A) having a weight average molecular weight (Mw) of 80000 or more, a total acyl group substitution degree (T) of 2.00 to 2.99, and an acetyl group substitution degree (ac) of 0.10.
  • the optical film according to any one of 1 to 3 the resin and particles are heated and melted and kneaded to prepare a heated melt, and then the heated melt is dissolved in a solvent to obtain a resin solution, A method for producing an optical film, wherein a film is formed by a solution casting method using a resin solution.
  • a polarizing plate characterized by using the optical film according to any one of 1 to 3 on at least one surface.
  • a liquid crystal display device comprising the polarizing plate according to 5 above on at least one surface of a liquid crystal cell.
  • slip property (blocking resistance) is favorable and can provide the optical film without a foreign material failure
  • the manufacturing method of this optical film, a polarizing plate using this optical film, and liquid crystal A display device can be provided.
  • the optical film of the present invention contains particles in a resin film, the arithmetic average roughness Ra of the film surface is in the range of 1.0 to 2.0 nm, and the structural surface is defined by JIS B0671: 2002
  • the value of the parameter Mr1 (%) is 12% or less, and the optical film having the above structure has good slipping property (blocking resistance), and an effect that an optical film free from foreign matter failure can be obtained. It plays.
  • the arithmetic average roughness Ra of the film surface is in the range of 1.0 to 2.0 nm, and the structural surface used in JIS B0671
  • Mr1 (%) is 12% or less, it has good slipperiness (blocking resistance), and foreign matter such as chips and chips is generated at the time of cutting, or the film from the cut surface. It has been found that it is effectively prevented that the sheet is broken and a conveyance failure occurs.
  • the cut surface of the optical film according to the configuration of the present invention is smooth, whereas a minute crack (crack) is seen near the surface of the cut surface of the film outside the above range, It is thought that this minute crack (crack) becomes a cutting defect and causes foreign matter failure and breakage.
  • the surface shape within the scope of the present invention was formed as a result of extremely high dispersibility of the particles by using small-sized particles in the optical film and limiting the preparation of the resin and solution used. It is considered a thing.
  • the arithmetic average roughness Ra of the film surface is the parameter that is not affected at all by the variation in the size of the protrusions on the surface, with the average value of the two-dimensional roughness being the arithmetic average roughness.
  • Mr1 (%) is called the load length ratio of the core part, and shows a larger value as the number of large protrusions increases than the average protrusion.
  • Fig. 1 shows an evaluation method for height measurement (JIS B0671: 2002) using a linear load curve.
  • Rk Core level difference Difference between the upper and lower levels of the core part
  • Rpk Protrusion peak height Average height of the protrusive peak part above the core part
  • Rvk Protrusion trough depth Under the core part Average depth of a certain projecting trough Mr1 Load length ratio of the core part: Load length ratio of the intersection of the projecting mountain part and core part separation line and the load curve Mr2 Load length ratio of the core part: projecting trough part and core
  • FIG. 2 is a schematic diagram showing the difference in surface shape depending on the value of Mr1 (%).
  • the extending support is mirror-finished to improve the smoothness, and the stretching ratio, temperature, and amount of residual solvent are set. This can be achieved by appropriate selection.
  • the surface of the take-up roll and the drawing roll immediately after the melt extrusion is made into a mirror surface, the nip between the mirror-like rolls immediately after taking up with the roll, the temperature of the vertical and / or horizontal drawing, This is achieved by appropriately selecting the magnification and the stretching speed. It is also effective to reduce Ra by sharpening the lip edge of the melt-extrusion die or mirroring the surface in contact with the molten resin inside the die.
  • Mr1 (%) exceeds 12%, the protruding large protrusion is the cause, and the occurrence of cracks, and actually setting Mr1 (%) to 0 is too large for production,
  • a preferable range of Mr1 is 0.1% to 12% or less, more preferably 0.5% to 10% or less.
  • the resin film is preferably easy to manufacture and optically transparent. Any of these may be used, for example, cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate ionate film, cellulose diacetate film, cellulose acetate butyrate film, polyethylene terephthalate, polyethylene naphthalate, etc.
  • cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate ionate film, cellulose diacetate film, cellulose acetate butyrate film, polyethylene terephthalate, polyethylene naphthalate, etc.
  • Polyester film such as phthalate, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Shinji Otectic polystyrene film, norbornene resin film, polymethylpentene
  • examples include, but are not limited to, film, polyether ketone film, polyether ketone imide film, polyamide film, fluororesin film, nylon film, cycloolefin polymer film, polymethyl methacrylate film or acrylic film. Absent.
  • a cellulose ester film, a polycarbonate film, a norbornene resin film, and a polyester film are preferable, and in the present invention, in particular, a cellulose ester film is manufactured, cost, isotropic, adhesiveness, and This is preferable because the object and effects of the present invention can be suitably obtained.
  • Cellulose ester film A cellulose ester film (hereinafter also referred to as a cellulose ester film) will be described.
  • 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, such as cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A-10-45804 and 08-231761.
  • Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used.
  • the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.
  • cellulose triacetate those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%.
  • Cellulose triacetate When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.
  • the cellulose ester preferred in the present invention has a total acyl group substitution degree (T) of 2.00 to 2.99, an acetyl group substitution degree (ac) of 0.10 to 1.89, and a moiety other than the acetyl group.
  • T total acyl group substitution degree
  • ac acetyl group substitution degree
  • a moiety other than the acetyl group a cellulose ester resin (B) which is substituted with an acyl group composed of 3 to 7 carbon atoms and the degree of substitution (r) is 1.10 to 2.89.
  • the portion other than the acetyl group is preferably a propionyl group or a butyryl group, and more preferably a propionyl group.
  • the method for measuring the substitution degree of the acyl group can be measured according to ASTM-D817-96.
  • the molecular weight of the cellulose ester is preferably a number average molecular weight (Mn) of 60,000 to 300,000, more preferably 70,000 to 200,000, particularly preferably 100,000 to 200,000.
  • the cellulose ester used in the present invention preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 4.0 or less, more preferably 1.4 to 2.3.
  • the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.
  • the measurement conditions are as follows.
  • a cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination.
  • a cellulose ester synthesized from cotton linter hereinafter sometimes simply referred to as linter
  • linter a cellulose ester synthesized from cotton linter
  • particles in the present invention in order to control the arithmetic average roughness Ra of the film surface and the value of the parameter Mr1 (%) of the structure surface, it is particularly preferable to contain particles in the resin film.
  • the particles are not particularly limited, such as inorganic particles or organic particles, but inorganic particles having an average primary particle size of 1 nm to 10 nm are preferably used.
  • the average primary particle diameter is obtained by subjecting 500 particles to visual observation or image processing from an image photograph of secondary electron emission obtained by a scanning electron microscope (SEM) or the like, or a dynamic light scattering method, It can be measured by a particle size distribution meter using a static light scattering method or the like.
  • the average primary particle diameter here refers to the number average particle diameter.
  • a particle when a particle is not spherical, it means the diameter of a circle corresponding to the projected area.
  • Preferred inorganic particles include, for example, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate and the like. These inorganic particles may be used in combination of two or more different types and average particle diameters, and those obtained by subjecting the surface of the particles to an organic substance are also preferably used.
  • Particularly preferred inorganic particles are silicon dioxide among these.
  • silicon dioxide having an average primary particle diameter of 1 nm to 10 nm
  • commercially available products having trade names such as Aerosil R812, R976, R200, R300 (above Nippon Aerosil Co., Ltd.) can be preferably used.
  • the shape of the particles can be used without any particular limitation, such as indefinite shape, needle shape, flat shape, and spherical shape. However, the use of spherical particles is particularly preferable because it is easy to adjust the haze.
  • the refractive index of the particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65.
  • the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes.
  • the refractive index of the solvent can be measured by measuring with an Abbe refractometer.
  • the content of the inorganic particles is preferably 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the resin that is the main component of the resin film, and more preferably 0.05 mass for obtaining the effects of the present invention. Part to 0.30 part by mass.
  • the particles may be dispersed by being contained in an organic solvent together with a resin and other additives at the time of preparing a composition (dope) for producing a resin film, or may be dispersed alone in the organic solvent. Good.
  • a method for dispersing the particles it is preferable that the particles are preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force.
  • dope preparation it is also preferable to disperse particles in a large amount of organic solvent, merge with the resin solution, and mix with an in-line mixer to form a dope.
  • a resin and particles are heated and melted and kneaded to prepare a heated melt (pellet), and then the heated melt is dissolved in an organic solvent to obtain a resin solution.
  • a heated melt pellet
  • Forming a film by a drawing method is the most preferable method for obtaining an optical film having a uniform particle distribution.
  • Pelletization can be performed by a known method. For example, dry resins, plasticizers, and other additives are supplied together with the particles to an extruder using a feeder, and are kneaded using a single-screw or twin-screw extruder. It can be extruded into strands, water-cooled or air-cooled, and cut into pellets.
  • Particles, dry resin, plasticizer, and other 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.
  • the resin film preferably contains an acrylic resin (A) having a weight average molecular weight (Mw) of 80000 or more in order to keep the dispersibility of contained particles extremely high.
  • the acrylic resin (A) includes a methacrylic resin.
  • the resin is not particularly limited, but a resin comprising 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith is preferable.
  • 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.
  • Examples thereof include unsaturated nitrile, maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, and the like. These can be used alone or in combination of two or more.
  • 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 acrylic resin (A) preferably has a weight average molecular weight (Mw) of 80,000 to 1,000,000 from the viewpoint of mechanical strength as a film and fluidity when producing the film, in addition to the dispersibility of the particles.
  • Mw weight average molecular weight
  • a weight average molecular weight (Mw) can be measured using said high performance liquid chromatography.
  • the method for producing the acrylic resin (A) is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used.
  • 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.
  • a film composed of cellulose ester resin (B) and acrylic resin (A) has a softening point of 105 to 145 ° C. and does not cause ductile fracture. preferable.
  • Ductile fracture is caused by the application of a greater stress than the strength of a certain material, and is defined as a fracture that involves significant elongation or drawing of the material before final fracture.
  • a specific method for measuring the tension softening point temperature for example, a cellulose ester resin / acrylic resin film is cut out by 120 mm (length) ⁇ 10 mm (width) using a Tensilon tester (ORIENTEC, RTC-1225A). The temperature can be raised at a rate of 30 ° C./min while pulling with a tension of 10 N, and the temperature at the time when the pressure reaches 9 N is measured three times, and the average value can be obtained.
  • a cellulose ester resin / acrylic resin film is simply cut out at 100 mm (length) ⁇ 10 mm (width), folded in a central part in the vertical direction once in each of a mountain fold and a valley fold.
  • This evaluation can be evaluated by measuring three times and “breaking” or “not folding”. In this evaluation, “break” means to break and separate into two or more pieces.
  • the cellulose ester resin / acrylic resin film preferably has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, it is 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.
  • Tg glass transition temperature
  • the glass transition temperature is determined by using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer) at a heating rate of 20 ° C./min, and determined in accordance with JIS K7121 (1987). Tmg).
  • the cellulose ester resin / acrylic resin film preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, as measured in accordance with 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 cellulose ester resin / acrylic resin film is preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ 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 film composed of the acrylic resin (A) and the cellulose ester resin (B) is prepared from 95: 5 to 30:70 from the acrylic resin (A) and the cellulose ester resin (B) in terms of both workability and heat resistance. It is preferable to contain by mass ratio.
  • the total mass of the acrylic resin (A) and the cellulose ester resin (B) is 55 to 100% by mass, preferably 60 to 99% by mass, of the cellulose ester resin / acrylic resin film.
  • the cellulose ester resin / acrylic resin film may contain other acrylic resins.
  • the cellulose ester film and the cellulose ester resin / acrylic resin film may be either produced by a solution casting method or produced by a melt casting method, but preferably at least stretched in the width direction.
  • the film is stretched by 1.01 to 1.5 times in the width direction when the amount of residual peeling is 3 to 40% by mass. More preferably, it is biaxially stretched in the width direction and the longitudinal direction, and when the residual dissolution amount is 3 to 40% by mass, it is stretched by 1.01 to 1.5 times in the width direction and the longitudinal direction, respectively. It is desirable that The draw ratio at this time is particularly preferably 1.03 to 1.45.
  • the length of these resin films is preferably 100 m to 5000 m, and the width is preferably 1.2 m or more, more preferably 1.4 to 4 m. By setting the length and width of the resin film within the above ranges, the handleability and productivity are excellent.
  • the resin film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.
  • the cellulose ester film or cellulose ester resin / acrylic resin film preferably contains the following plasticizer.
  • plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters.
  • a plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.
  • phosphate plasticizers triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc.
  • phthalate ester plasticizers diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, and other trimellitic plasticizers such as tributyl trimellitate, triphenyl trimellitate, triethyl
  • trimellitate such as trimellitate, tetrabutyl pyromellitate, tetrafluoro
  • glycolate plasticizers such as nilpyromellitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc., citrate plasticizer
  • polyester plasticizer a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used.
  • the aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used.
  • glycol ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.
  • the polyhydric alcohol ester plasticizer is composed of an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid.
  • preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl- 1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,
  • triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.
  • monocarboxylic acid used for polyhydric alcohol ester Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid can be raised.
  • Examples of preferable alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
  • Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid.
  • Aromatic monocarboxylic acids or derivatives thereof can be raised. Particularly preferred is benzoic acid.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750.
  • the larger one is preferable in terms of improving the retention, and the smaller one is preferable in terms of moisture permeability and compatibility with the cellulose ester.
  • the carboxylic acid used in the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are.
  • These plasticizers are preferably used alone or in combination. The amount of these plasticizers used is preferably from 1 to 20% by weight, particularly preferably from 3 to 13% by weight, based on the cellulose ester, from the viewpoints of film performance and processability.
  • the cellulose ester film or the cellulose ester resin / acrylic resin film may contain an ultraviolet absorber. Next, the ultraviolet absorber will be described.
  • the ultraviolet absorber those which are excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and have little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.
  • Specific examples include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like.
  • benzotriazole-based ultraviolet absorber examples include the following specific examples, but the present invention is not limited thereto.
  • UV-1 2- (2'-hydroxy-5'-methylphenyl) benzotriazole
  • UV-2 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole
  • UV-3 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole
  • UV-4 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole
  • UV-5 2- (2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole
  • UV-6 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
  • UV-7 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-ch
  • UV-10 2,4-dihydroxybenzophenone
  • UV-11 2,2'-dihydroxy-4-methoxybenzophenone
  • UV-12 2-hydroxy-4-methoxy-5-sulfobenzophenone
  • UV-13 Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
  • a benzotriazole UV absorber and a benzophenone UV absorber which are highly transparent and excellent in preventing the deterioration of polarizing plates and liquid crystals, are preferable, and benzotriazole UV absorption with less unnecessary coloring is preferable.
  • An agent is particularly preferably used.
  • an ultraviolet absorber having a distribution coefficient of 9.2 or more as described in Japanese Patent Application No. 11-295209 can be used, and in particular, an ultraviolet absorber having a distribution coefficient of 10.1 or more is suitable for the surface quality of the base film. Is preferable from the standpoint of maintaining good.
  • the polymer ultraviolet absorber (or the general formula (1) or the general formula (2) of JP-A-6-148430 and the general formulas (3), (6) and (7) described in Japanese Patent Application No. 2000-156039 (or A UV-absorbing polymer) is also preferably used.
  • PUVA-30M manufactured by Otsuka Chemical Co., Ltd.
  • the like are commercially available.
  • the dope preferably contains an organic solvent from the viewpoint of film forming properties and productivity.
  • Any organic solvent can be used without limitation as long as it dissolves cellulose ester and other additives simultaneously.
  • methylene chloride methyl acetate,
  • the dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent.
  • an alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability, boiling point of these inner dopes, relatively good drying, and no toxicity.
  • the concentration of cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 100 to 500 poise (P) in order to obtain good film surface quality.
  • a dope by heating and melting and kneading the resin and particles to prepare a heated melt (pellet) in advance and dissolving the heated melt in an organic solvent.
  • a higher resin concentration in the dope is preferable because the drying load after casting on the metal support can be reduced.
  • 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 is preferably a mirror-finished surface because the roughness Ra value can be reduced.
  • a stainless steel belt or a drum whose surface is plated with a casting is preferably used. It is done.
  • the cast width can be 1 to 4 m.
  • 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 preferable 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 web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • 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.
  • warm air considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. .
  • 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. And particularly preferably 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, and 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, so that the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less.
  • the content is preferably 0 to 0.01% by mass or less.
  • a roll drying method (a method in which a plurality of rolls arranged at the top and bottom are alternately passed through the web for drying) or a tenter method for drying while conveying the web is employed.
  • the resin film can also be formed by a melt film forming method.
  • the melt film-forming method refers to heating and melting a composition containing a resin and an additive such as a plasticizer to a temperature exhibiting fluidity, and then casting the melt containing the fluid resin.
  • 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. Among these, in order to obtain a resin film excellent in mechanical strength and surface accuracy, the melt extrusion method is excellent.
  • a plurality of raw materials used for melt extrusion are usually kneaded and pelletized in advance.
  • 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 solidified while the film is nipped by a cooling roll and an elastic touch roll.
  • the extrusion flow rate is preferably carried out stably by introducing a gear pump. Further, 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.
  • a touch roll disclosed in registered patent 3194904, registered patent 3422798, Japanese Patent Application Laid-Open No. 2002-36332, Japanese Patent Application Laid-Open No. 2002-36333, or the like can be preferably used. These can also use what is marketed.
  • the film obtained as described above is stretched by the stretching operation after passing through the step of contacting the cooling roll.
  • 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 ends Prior to winding, the ends may be slit and cut to the width of the product, and knurling (embossing) 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.
  • ⁇ Other resins used> it is preferable to use at least one resin selected from a polycarbonate resin, an acrylic resin, an olefin resin, a cycloolefin resin, and a polyester resin in addition to the cellulose ester resin.
  • the resin film using the following resin may be a film produced by a solution casting method or a film produced by a melt casting method in the same manner as the cellulose ester film.
  • Olefin resin polypropylene or polyethylene resin is preferably used as the olefin resin, but is not limited thereto. Two or more compatible resins may be used as these resins. Specific examples include compounds described in JP-A-2007-316603.
  • the cycloolefin resin (Cycloolefin resin)
  • the cycloolefin resin used in the present invention is made of a polymer resin containing an alicyclic structure.
  • a preferred cycloolefin resin is a resin obtained by polymerizing or copolymerizing a cyclic olefin.
  • cyclic olefin examples include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2,4, Polycyclic unsaturated hydrocarbons such as 6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclo Examples thereof include monocyclic unsaturated hydrocarbons such as octene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene,
  • cyclic olefins may have a polar group as a substituent.
  • the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Or a carboxylic anhydride group is preferred.
  • Preferred cycloolefin resins may be those obtained by addition copolymerization of monomers other than cyclic olefins.
  • addition copolymerizable monomers include ethylene, ⁇ -olefins such as ethylene, propylene, 1-butene and 1-pentene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- And dienes such as 1,4-hexadiene and 1,7-octadiene.
  • the cyclic olefin is obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction.
  • the polymerization is carried out in the presence of a catalyst.
  • the addition polymerization catalyst include a polymerization catalyst composed of a vanadium compound and an organoaluminum compound.
  • a polymerization catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound, and a reducing agent; or titanium, vanadium, zirconium, tungsten, molybdenum And a polymerization catalyst composed of a metal halide such as acetylacetone compound and an organoaluminum compound.
  • the polymerization temperature, pressure and the like are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of ⁇ 50 ° C. to 100 ° C. and a polymerization pressure of 0 to 490 N / cm 2 .
  • the cycloolefin-based resin is obtained by polymerizing or copolymerizing a cyclic olefin and then performing a hydrogenation reaction to change the unsaturated bond in the molecule to a saturated bond.
  • the hydrogenation reaction is performed by blowing hydrogen in the presence of a known hydrogenation catalyst.
  • hydrogenation catalysts examples include cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, transition metal compounds such as titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium / alkyl.
  • Homogeneous catalyst consisting of a combination of metal compounds; heterogeneous metal catalyst such as nickel, palladium, platinum; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth And a heterogeneous solid-supported catalyst in which a metal catalyst such as palladium / alumina is supported on a carrier.
  • the norbornene-based resin preferably has a norbornene skeleton as a repeating unit, and specific examples thereof include, for example, JP-A-62-252406, JP-A-62-2252407, and JP-A-2-133413.
  • ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, APPEL manufactured by Mitsui Chemicals, Inc. (APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) and the like are preferably used.
  • the molecular weight of the cycloolefin resin is appropriately selected according to the purpose of use, but is converted to polyisoprene or polystyrene measured by gel permeation chromatography method of cyclohexane solution (toluene solution when polymer resin is not dissolved)
  • the weight average molecular weight is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, the mechanical strength and molding processability of the molded product are highly balanced. is there.
  • Polycarbonate resin The polycarbonate resin will be described.
  • polycarbonate resins and aromatic polycarbonates are preferable from the viewpoint of chemical properties and physical properties, and bisphenol A polycarbonates are particularly preferable.
  • a bisphenol A derivative in which a benzene ring, a cyclohexane ring or an aliphatic hydrocarbon group is introduced into bisphenol A, but these groups are introduced asymmetrically with respect to the central carbon.
  • a polycarbonate having a structure in which the anisotropy in the unit molecule is reduced, obtained by using the obtained derivative is preferable.
  • polycarbonate resins obtained by use are preferred.
  • 4,4′-dihydroxydiphenylalkane or a halogen-substituted product thereof can be obtained by a phosgene method or a transesterification method.
  • 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane 4,4'-dihydroxydiphenylbutane and the like can be mentioned. It is done.
  • polyester resin As the monomer used in the polyester-based resin, general dicarboxylic acid or a derivative thereof and dialcohol are used. In particular, when the content of the carboxylic acid group or sulfonic acid group at the terminal of the monomer is low, the chargeability is increased. And a good toner can be produced.
  • dicarboxylic acids and derivatives thereof include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid dichloride, terephthalic acid dibromide, diethyl terephthalate, dimethyl terephthalate, dipropyl terephthalate.
  • aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid dichloride, terephthalic acid dibromide, diethyl terephthalate, dimethyl terephthalate, dipropyl terephthalate.
  • dialcohol examples include aliphatic glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, methylpentanediol, nonanediol, and ethylbutylpropanediol.
  • aliphatic glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, methylpentanediol, nonanediol, and ethylbutylpropanediol.
  • xylene glycol phenylene glycol, phenylene glycol Tylene oxide adduct, bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, bisphenol AP, bisphenol C, bisphenol E, bisphenol F, bisphenol S, bisphenol Z and their ethylene oxide, propylene oxide addition Examples include, but are not limited to:
  • polycarboxylic acids or polyhydric alcohols may be added and used.
  • polycarboxylic acids examples include succinic acid, adipic acid, sebacic acid, azelaic acid, octyl succinic acid, benzenetricarboxylic acid, cyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimesic acid and acid anhydrides thereof. Products, halides, lower alkyl esters and the like.
  • polyhydric alcohol examples include, but are not limited to, polyethylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, polypropylene glycol, polytetramethylene glycol and the like.
  • polyester resin used in the present invention may also be a polyester polyol having both ends terminated with a hydroxyl group and urethane-modified by reacting with an organic diisocyanate compound.
  • organic diisocyanate compounds used include hexamethylene diisocyanate, tetramethylene diisocyanate, dimethoxybiphenylene diisocyanate, xylylene diisocyanate, diisocyanate methylcyclohexane, diisocyanate dicyclohexane, diisocyanate cyclohexylmethane, isophorone diisocyanate, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, Examples thereof include, but are not limited to, phenylene diisocyanate, naphthalene diisocyanate, dimethylbiphenylene diisocyanate, and diisocyanate diphenyl ether.
  • the above-described compounds are used as the polycarboxylic acid and the polyol, and the ratio of the polyol and the polycarboxylic acid is usually 2 as the equivalent ratio (OH) / (COOH) of the hydroxyl group (OH) and the carboxyl group (COOH).
  • / 1-1 to 1/1 is preferable, 1.5 / 1 to 1/1 is more preferable, and 1.2 / 1 to 1.02 / 1 is still more preferable.
  • the method for synthesizing the polyester resin used in the present invention is not particularly limited, and can be obtained, for example, by a polyester polycondensation reaction according to a conventional method.
  • the weight-average molecular weight of the polyester-based resin has a maximum value in the range of 2 ⁇ 10 2 to 3 ⁇ 10 4 as a polystyrene-converted value by gel permeation chromatography from the viewpoint of heat resistant storage property, powder flow characteristics, and melt viscosity.
  • the maximum value of the molecular weight is preferably 3 ⁇ 10 3 to 3 ⁇ 10 4 .
  • the optical film of the present invention can be provided with a functional layer on the surface thereof.
  • the functional layer examples include an undercoat layer, a hard coat layer, a light diffusion layer, an antiglare layer, an adhesive layer, an antistatic layer, an antireflection layer, an antifouling layer, and the like. It is preferable to provide an antistatic layer and an antireflection layer. In particular, in the case of a polarizing plate protective film, it is preferable to provide a hard coat layer to increase the surface hardness of the optical film.
  • the hard coat layer is preferably a resin layer formed by polymerizing a component containing an ethylenically unsaturated monomer.
  • the actinic radiation curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as an electron beam in addition to ultraviolet rays.
  • Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an actinic ray other than ultraviolet rays or an electron beam may be used.
  • Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.
  • UV-curable acrylic urethane resins are obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer and further adding 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate). And can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (see, for example, JP-A-59-151110).
  • UV curable polyester acrylate resins can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers (see, for example, JP-A-59-151112). .
  • ultraviolet curable epoxy acrylate resins include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoreaction initiator added thereto (for example, JP-A-1- No. 105738).
  • a photoreaction initiator for example, JP-A-1- No. 105738.
  • the photoinitiator one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.
  • ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc.
  • the said photoinitiator can also be used as a photosensitizer.
  • specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and the like.
  • a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.
  • the photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying can be added in an amount of usually 1 to 10% by mass of the composition, and 2.5 to 6 It is preferable that it is mass%.
  • the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond.
  • Monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.
  • Adekaoptomer KR / BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by ADEKA Corporation), or Koei Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8 MAG-1-P20, AG-106, M-101-C (Gorei Chemical Co., Ltd.), or Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, (Manufactured by Nissei Kagaku Co., Ltd.), or KRM7033, KRM7039, KRM7130
  • the UV curable resin layer can be applied by a known method.
  • the solvent for coating the ultraviolet curable resin layer for example, it can be appropriately selected from hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or a mixture thereof can be used.
  • propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether preferably propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass.
  • the solvent contained above is used.
  • any light source that generates ultraviolet rays can be 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 irradiation conditions vary depending on individual lamps, but the amount of light irradiated may if 20 ⁇ 10000mJ / cm 2 degrees, preferably 50 ⁇ 2000mJ / cm 2.
  • the near ultraviolet region to the visible light region it can be used by using a sensitizer having an absorption maximum in that region.
  • the UV curable resin composition is coated and dried and then irradiated with UV light from a light source.
  • the irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 due to the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.
  • inorganic or organic fine particles it is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance.
  • the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of the organic fine particles include polymethacrylic acid.
  • Methyl acrylate resin powder acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder
  • Polyamide-based resin powder, polyimide-based resin powder, or polyfluorinated ethylene-based resin powder, and the like can be added to the ultraviolet curable resin composition.
  • the average particle size of these fine particle powders is preferably 0.005 ⁇ m to 1 ⁇ m, and particularly preferably 0.01 to 0.1 ⁇ m.
  • the proportion of the ultraviolet curable resin composition and the fine particle powder is 0.1 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • the layer formed by curing the ultraviolet curable resin thus formed is a hard coat layer having a center line average roughness Ra of 1 to 50 nm as defined in JIS B 0601, and Ra is 0.1 to 1 ⁇ m.
  • An antiglare layer of a degree may be used.
  • the liquid film thickness (also referred to as wet film thickness) during coating is about 1 to 100 ⁇ m, preferably 0.1 to 30 ⁇ m, and more preferably 0.5 to 15 ⁇ m.
  • the dry thickness of the hard coat layer is preferably 1 to 20 ⁇ m.
  • the optical film of the present invention preferably further comprises the following antireflection layer on the hard coat layer.
  • the antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference.
  • the antireflective layer is composed of a low refractive index layer having a lower refractive index than that of the support, or a combination of a high refractive index layer having a higher refractive index than that of the support and the low refractive index layer. It is preferable from the point that the function is further enhanced.
  • 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 and a lower refractive index than the high refractive index layer) / high refractive index layer / low refractive index layer.
  • a layer laminated in order is also preferably used, and an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
  • the low refractive index layer preferably contains silica-based fine particles, and the refractive index is lower than the refractive index of the film substrate as a support, and is 1.30 to 1.45 when measured at 23 ° C. and wavelength of 550 nm. A range is preferable.
  • An antireflective film in which a low refractive index layer is laminated directly or via another layer on the hard coat layer is particularly preferable because of excellent adhesion and chemical resistance after a weather resistance test.
  • the film thickness of the low refractive index layer is preferably 5 nm to 0.5 ⁇ m, more preferably 10 nm to 0.3 ⁇ m, and most preferably 30 nm to 0.2 ⁇ m.
  • the composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles.
  • the particles having the outer shell layer and having a porous or hollow interior are preferably hollow silica-based fine particles.
  • composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1), a hydrolyzate thereof, or a polycondensate thereof.
  • OSi-1 organosilicon compound represented by the following general formula (OSi-1)
  • hydrolyzate thereof a hydrolyzate thereof
  • polycondensate thereof a polycondensate thereof.
  • R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.
  • a solvent and if necessary, a silane coupling agent, a curing agent, a surfactant and the like may be added.
  • the hollow silica-based fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the contents are solvent, gas or porous It is a hollow particle filled with a porous material. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.
  • the hollow particles are particles having cavities inside, and the cavities are covered with a coating layer (also referred to as 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 fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm.
  • the average particle diameter of the hollow fine particles used is preferably in the range of 3/2 to 1/10, preferably 2/3 to 1/10, of the average film thickness of the low refractive index layer to be formed.
  • These hollow fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer.
  • the dispersion medium water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohol (for example, diacetone alcohol), or a mixed solvent containing these is preferable.
  • alcohol for example, methanol, ethanol, isopropyl alcohol
  • ketone for example, methyl ethyl ketone, methyl isobutyl ketone
  • ketone alcohol for example, diacetone alcohol
  • 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 refractive index of the particles is increased by entering the voids inside the composite particles, and the effect of low refractive index 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. In the case of hollow particles, if 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. .
  • 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 when the silica is represented by SiO 2 and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 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. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.
  • the pore volume of such porous particles can be determined by a mercury intrusion method.
  • the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles.
  • the solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like.
  • what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.
  • the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed.
  • the composite particles are composed of silica and an inorganic compound other than silica
  • hollow fine particles are 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 the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid 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. Usually, these sols are used. Can do.
  • 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 having a uniform particle size 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. Particle deposition occurs on the top. 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.
  • the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, it is also possible to form a silica protective film using a silicic acid solution.
  • a silicic acid solution is used, 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 alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a 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 addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer is not limited as long as 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 with 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.
  • the hollow silica-based fine particles those commercially available from Catalyst Kasei Co., Ltd. can be preferably used.
  • the content of hollow silica-based fine particles having an outer shell layer and porous or hollow inside is preferably 10 to 50% by mass in the low refractive index layer.
  • the content is preferably 15% by mass or more, and when it exceeds 50% by mass, the binder component is decreased and the film strength becomes insufficient.
  • the amount is particularly preferably 20 to 50% by mass.
  • a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of the tetraalkoxysilane, pure water, and alcohol is added to the dispersion of the hollow silica fine particles.
  • the silicic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles.
  • tetraalkoxysilane, 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.
  • silica-based fine particles produced by the production method described in WO 2007/099814 may be used.
  • the low refractive index layer may contain a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (OSi-2).
  • the fluorine-substituted alkyl group-containing silane compound represented by the general formula (OSi-2) will be described.
  • R 1 to R 6 are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, 6 to 12 carbon atoms, preferably 6 carbon atoms.
  • Rf represents-(CaHbFc)-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24.
  • Rf is preferably a group having a fluoroalkylene group and an alkylene group.
  • fluorine-containing silicone compounds include (MeO) 3 SiC 2 H 4 C 2 F 4 C 2 H 4 Si (MeO) 3 , (MeO) 3 SiC 2 H 4 C 4 F 8 C 2 H 4 Si (MeO) 3 , (MeO) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (MeO) 3, (H 5 C 2 O) 3 SiC 2 H 4 C 4 F 8 C 2 H 4 Si (OC 2 H 5) 3, include methoxy disilane compound or the like represented by (H 5 C 2 O) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (OC 2 H 5) 3.
  • the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer which is the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.
  • a fluorine-substituted alkyl group-containing silane compound when included as a binder, not only the hydrophobic property but also the slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch strength can be obtained. Can do.
  • the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage rate of the binder is equivalent to that of the conductive layer. Therefore, it is possible to form a transparent film having excellent adhesion to the conductive layer.
  • the conductive layer is not peeled off due to the difference in shrinkage rate, and a portion having no electrical contact is not generated in the transparent conductive layer. For this reason, sufficient electroconductivity can be maintained as a whole film.
  • a transparent film containing a fluorine-substituted alkyl group-containing silane compound and hollow silica-based fine particles having the outer shell layer and being porous or hollow inside has high scratch strength and is evaluated by eraser strength or nail strength.
  • the film strength is high, the pencil hardness is high, and a transparent film excellent in strength can be formed.
  • the low refractive index layer may contain a silane coupling agent.
  • Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane.
  • 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 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 may contain a silicon compound represented by CF 3 (CF 2 ) nCH 2 CH 2 Si (OR 1 ) 3 .
  • R1 represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12).
  • Specific compounds include trifluoropropyltrimethoxysilane and trifluoropropyl.
  • Examples include triethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and these are used alone or in combination of two or more. Can be used.
  • a silicon compound having a ureido group (H 2 NCONH—) at the terminal position represented by H 2 NCONH (CH) m Si (OR 2) 3 may be contained.
  • R2 represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 5.
  • Specific compounds include ⁇ -ureidopropyltrimethoxysilane, ⁇ -ureido Examples thereof include propyltriethoxysilane and ⁇ -ureidopropyltripropoxysilane. Of these, ⁇ -ureidopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, and the like are particularly preferable.
  • the low refractive index layer can use, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, etc. as a binder. .
  • binder for the low refractive index layer examples include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin.
  • the low refractive index layer preferably contains 5 to 80% by mass of binder as a whole.
  • the binder has a function of adhering the hollow silica-based fine particles and maintaining the structure of the low refractive index layer including voids.
  • the usage-amount of a binder is suitably adjusted so that the intensity
  • the low refractive index layer preferably contains an organic solvent.
  • organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate).
  • toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.
  • the solid content concentration in the low refractive index layer coating composition is preferably 1 to 4% by mass.
  • the solid content concentration is 4% by mass or less, coating unevenness is less likely to occur, and the solid content concentration is 1% by mass or more. By doing so, the drying load is reduced.
  • the antireflection layer may have the following high refractive index layer.
  • metal oxide fine particles are contained in the high refractive index layer.
  • 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
  • a metal oxide having at least one element selected from the above can be used, and these metal oxide fine particles are doped with a small amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. There may be. A mixture of these may also be used.
  • At least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as the main 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 specifically higher than the refractive index of the film as the support, and is preferably in the range of 1.5 to 2.2 when measured at 23 ° C. and 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 metal oxide fine particles may be surface-treated with an organic compound.
  • an organic compound By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . Therefore, the amount of surface modification with a preferable organic compound is 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass with respect to the metal oxide particles.
  • the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more surface treatments may be combined.
  • the thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 ⁇ m, more preferably 10 nm to 0.2 ⁇ m, and most preferably 30 nm to 0.1 ⁇ m.
  • the ratio of the metal oxide fine particles to be used and a binder such as an actinic ray curable resin to be described later varies depending on the kind of metal oxide fine particles, the particle size, etc. The latter one is preferable.
  • the amount of the metal oxide fine particles used is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, and most preferably 20 to 75% by mass in the high refractive index layer.
  • the metal oxide fine particles are supplied to a coating liquid for forming a high refractive index layer in a dispersion state dispersed in a medium.
  • a dispersion medium for metal oxide particles a liquid having a boiling point of 60 to 170 ° C. is preferably used.
  • the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol).
  • Esters eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate
  • aliphatic hydrocarbons eg, hexane, cyclohexane
  • halogenated hydrocarbons eg, methylene) Chloride, chloroform, carbon tetrachloride
  • aromatic hydrocarbons eg, benzene, toluene, xylene
  • amides eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone
  • ethers eg, diethyl ether, dioxane, Tiger hydrofuran
  • ether alcohols e.g., 1-methoxy-2-propanol
  • propylene glycol monomethyl ether propylene glycol monomethyl ether
  • the metal oxide fine particles can be dispersed in the medium using a disperser.
  • the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill.
  • a sand grinder mill and a high-speed impeller mill are particularly preferred.
  • preliminary dispersion processing may be performed.
  • the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder. It is also preferable to contain a dispersant.
  • metal oxide fine particles having a core / shell structure may be contained.
  • One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance.
  • the core is preferably completely covered by the shell.
  • titanium oxide rutile type, anatase type, amorphous type, etc.
  • zirconium oxide zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, etc.
  • Titanium may be the main component.
  • the shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component.
  • an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used.
  • silicon dioxide silicon dioxide
  • alumina aluminum oxide
  • zirconium oxide zirconium oxide
  • zirconia zirconium oxide
  • a mixture of these may also be used.
  • the coating amount of the shell with respect to the core is 2 to 50% by mass in average coating amount.
  • the amount is preferably 3 to 40% by mass, more preferably 4 to 25% by mass.
  • the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated.
  • Two or more inorganic fine particles may be used in combination.
  • the titanium oxide used as the core can be prepared by a liquid phase method or a gas phase method. Further, as a method of forming the shell around the core, for example, US Pat. No. 3,410,708, Japanese Patent Publication No. 58-47061, US Pat. No. 2,885,366, and US Pat. No. 3,437,502 No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. Can do.
  • the high refractive index layer or the aforementioned low refractive index layer can contain a compound represented by the following general formula (CL1) or a chelate compound thereof, and can improve physical properties such as hardness.
  • M represents a metal atom
  • A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group
  • B represents an atomic group covalently or ionically bonded to the metal atom M.
  • x represents the valence of the metal atom M
  • n represents an integer of 2 or more and x or less.
  • hydrolyzable functional group A examples include an alkoxyl group, a halogen such as a chloro atom, an ester group, an amide group, and the like.
  • the metal compound belonging to the general formula (CL1) includes an alkoxide having two or more alkoxyl groups directly bonded to a metal atom, or a chelate compound thereof.
  • Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount.
  • Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of promoting the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.
  • titanium alkoxide examples include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.
  • zirconium alkoxide examples include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium, etc. Is mentioned.
  • Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less.
  • the addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.
  • an actinic ray curable resin as a binder for the metal oxide fine particles in order to improve the film formability and physical properties of the coating film.
  • the actinic ray curable resin include monomers or oligomers having two or more functional groups that cause polymerization reaction directly by irradiation of actinic rays such as ultraviolet rays and electron beams or indirectly by the action of a photopolymerization initiator. Can be used.
  • a polyol acrylate, an epoxy acrylate, a urethane acrylate, a polyester acrylate or a mixture thereof is preferable.
  • the polyfunctional acrylate compound described in the hard coat layer is preferable.
  • the amount of the actinic ray curable resin added is preferably 15% by mass or more and less than 50% by mass in the solid content in the high refractive index composition.
  • the photopolymerization initiator and the acrylic compound having two or more polymerizable unsaturated bonds in the molecule are in a mass ratio of 3: 7 to 1: It is preferable to contain 9.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
  • Examples of the organic solvent used for coating the high refractive index layer include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol).
  • alcohols for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol).
  • polyhydric alcohols for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thio Diglycol etc.
  • polyhydric alcohol ethers for example, ethylene glycol monomethyl ether, Tylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, ethylene glycol monophenyl ether, propylene glycol monophenyl acetate, triethylene glycol monomethyl ether
  • a gravure coater As a method for applying the antireflection layer, a gravure coater, a dip coater, a wire bar coater, a reverse coater, an extrusion coater, or the like can be used.
  • the optical film of the present invention is preferably used for a polarizing plate protective film.
  • a method of laminating a polarizing plate protective film by using a completely saponified polyvinyl alcohol aqueous solution on both sides of a polarizer prepared by subjecting the obtained optical film to an alkali treatment and immersing and stretching the polyvinyl alcohol film in an iodine solution It is preferable to directly bond the optical film of the present invention to a polarizer on one side.
  • the thickness of the protective film is preferably 10 to 500 ⁇ m. In particular, it is preferably 20 ⁇ m or more, and more preferably 35 ⁇ m or more. Moreover, 150 micrometers or less, Furthermore 120 micrometers or less are preferable. Particularly preferred is 35 to 90 ⁇ m. If the optical film is thicker than the above region, the polarizing plate after polarizing plate processing becomes too thick, so that it is not suitable for the purpose of thin and light in liquid crystal displays used for notebook personal computers and mobile electronic devices. On the other hand, if it is thinner than the above region, the film has high moisture permeability, and the ability to protect the polarizer from humidity decreases, which is not preferable.
  • the polarizing plate can be produced by a general method.
  • the back side of the optical film of the present invention is subjected to alkali saponification treatment, and the treated optical film is bonded to at least one surface of a polarizer produced by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. It is preferable.
  • the optical film may be used on the other surface, or another polarizing plate protective film may be used.
  • the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, an optical compensation having a retardation of 20 to 70 nm and a thickness direction retardation Rt of 100 to 400 nm.
  • a film (retardation film). These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395.
  • a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal.
  • the optically anisotropic layer can be formed by the method described in JP-A-2003-98348.
  • a non-oriented film having a retardation Ro of 590 nm at 0 to 5 nm and an Rt of ⁇ 20 to +20 nm described in JP-A No. 2003-12859 is also preferably used.
  • KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR-1, -2, KC8UE, KC4UE (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.
  • a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
  • a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
  • iodine is dyed on a system film
  • a dichroic dye is dyed, but it is not limited to this.
  • a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound.
  • a polarizer having a thickness of 5 to 30 ⁇ m, preferably 8 to 15 ⁇ m is preferably used.
  • one surface of the optical film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.
  • the optical film of the present invention is preferably used for various image display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper.
  • the optical film of the present invention is incorporated in the polarizing plate, and is a reflective type, transmissive type, transflective type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type. It is preferably used in liquid crystal display devices of various driving systems such as OCB type.
  • the size of the pellet was a cube of 10 mm ⁇ 10 mm ⁇ 10 mm.
  • Formation of optical film 1 The produced dope liquid was uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the film was peeled off from the stainless steel band support with a peeling tension of 162 N / m.
  • the web of cellulose ester resin / acrylic resin that has been peeled is evaporated at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while stretching 1.1 times in the width direction with a tenter. I let you. At this time, the amount of residual solvent when starting stretching with a tenter was 10%.
  • the draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.
  • the residual solvent amount of the optical film 1 shown in Table 1 was 0.1%, the film thickness was 60 ⁇ m, and the winding length was 4000 m.
  • the resin 1 is appropriately selected from the resins A to F listed in Table 2
  • the acrylic resin 1 is the acrylic resins AC1 to AC3 listed in Table 1
  • the particles 1 are appropriately selected as the particles A to E listed in Table 3.
  • Optical films 2 to 25 shown in Table 4 were produced in the same manner except that the changes were made.
  • acyl groups of the cellulose ester resins shown in Table 2 represent ac for acetyl groups and pr for propionyl groups.
  • optical film 26 was produced in the same manner except that the particles 1 were not added when the heated melt 1 was prepared.
  • Ra and Mr1 were determined by measuring the surface of an area of 120 ⁇ m ⁇ 90 ⁇ m with an objective lens 50 ⁇ and image zoom 1.0 ⁇ .
  • ⁇ No blocking ⁇ ⁇ : There is no trace or deformation in the sample to the extent that a light peeling sound is made. ⁇ : There is no deformation but a trace remains in the sample. ⁇ ⁇ : There is no deformation but a trace remains clearly. Unevenness remains on the sample. XX: Strong resistance when loosening the sample. An on-line defect inspection machine was installed immediately before the film take-up section, and the number of foreign object failures of 50 ⁇ m or more per 100 m 2 of each of the 10 optical films was counted and averaged.
  • the optical film of the present invention is superior to the optical film of the comparative example in terms of cut surface, blocking property, foreign matter failure, and bright spot foreign matter.
  • optical films 7 to 9, 12, 13, 15, and 16 of the present invention prepared according to the structure of claim 3 showed the evaluation results that the above characteristics were further excellent.
  • Example 2 ⁇ Preparation of antireflection films 1 to 28> On the optical films 1 to 28 produced above, an antistatic layer, a backcoat layer and a low refractive index layer were provided by the following procedure to produce antireflection films 1 to 28.
  • antistatic hard coat layer composition 1 filtered through a polypropylene filter having a pore size of 0.4 ⁇ m is applied to the surface of cellulose ester film 1 using a micro gravure coater, dried at a temperature of 80 ° C., and then irradiated with ultraviolet light. Using a lamp, the irradiance of the irradiated part was 100 mW / cm 2 , the irradiation amount was 0.2 J / cm 2 , and the coating layer was cured to form an antistatic layer having a refractive index of 1.55 and a dry film thickness of 10 ⁇ m.
  • the following back coat layer composition 1 was applied to the surface opposite to the surface coated with the antistatic hard coat layer of the optical film by an extrusion coater so as to have a wet film thickness of 14 ⁇ m, and dried at a temperature of 50 ° C. Then, a back coat layer was provided.
  • Antistatic hard coat layer composition 1 90 parts by mass of dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) Pentaerythritol triacrylate 20 parts by mass Pentaerythritol tetraacrylate 60 parts by mass Urethane acrylate 10 parts by mass (trade name U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd.) 90 parts by mass of methanol-dispersed phosphorus-doped tin oxide sol (50% solid content, product name Celnax CX-S501M, manufactured by Nissan Chemical Industries, Ltd.) Irgacure 184 (manufactured by Ciba Japan) 5 parts by mass Irgacure 907 (manufactured by Ciba Japan) 7 parts by mass Silicone surfactant 3 parts by mass (trade name: KF-351A, manufactured by Shin-Etsu Chemical Co., Ltd.) Propylene
  • a silica coating layer was formed and washed with an ultrafiltration membrane while adding 5 L of pure water to obtain an aqueous dispersion of silica-based fine particles having a silica coating layer with a solid content concentration of 20% by mass.
  • ammonia water is added to the silica-based fine particle dispersion with the silica coating layer formed thereon to adjust the pH to 10.5, aged at 150 ° C. for 11 hours, cooled to room temperature, and ionized by a cation exchange resin. Exchange and ion exchange with an anion exchange resin were repeated, and then a hollow silica-based particle dispersion 1 having a solid content concentration of 20% by mass was prepared by replacing the solvent with ethanol using an ultrafiltration membrane.
  • the thickness of the outer shell layer of the hollow silica-based particles was 10 nm, the average particle size was 55 nm, MOX / SiO 2 (molar ratio) was 0.0019, and the refractive index was 1.24.
  • the average particle diameter was measured by a dynamic light scattering method.
  • the low-refractive-index layer coating composition 1 is applied to the surface of the antistatic hard coat layer prepared above with a microgravure coater so that the film thickness after drying is 85 nm, dried at a temperature of 80 ° C. for 1 minute, and then irradiated with ultraviolet rays.
  • Anti-reflective films 1 to 28 were produced by forming a low refractive index layer by curing using a lamp under the conditions of an illuminance of the irradiated portion of 200 mW / cm 2 and an irradiation amount of 0.35 J / cm 2 .
  • the refractive index of the low refractive index layer of the obtained antireflection film was 1.34.
  • polarizing plates were produced as follows, and these polarizing plates were incorporated into a liquid crystal display panel (image display device) to evaluate the visibility.
  • the obtained PVA film had an average thickness of 40 ⁇ m, a moisture content of 4.4%, and a film width of 3 m.
  • the obtained PVA film was successively processed in the order of pre-swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to produce a polarizer. That is, the PVA film was pre-swelled by immersing in water at a temperature of 30 ° C. for 30 seconds, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C. for 3 minutes.
  • the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under the condition that the tension applied to the film was 700 N / m, and the potassium iodide concentration was 40 g / liter and the boric acid concentration was 40 g / liter. Then, it was immersed in an aqueous solution having a zinc chloride concentration of 10 g / liter and a temperature of 30 ° C. for 5 minutes for fixing. Thereafter, the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further heat-treated at a temperature of 100 ° C. for 5 minutes.
  • the obtained polarizer had an average thickness of 13 ⁇ m, a polarization performance of 43.0% transmittance, a polarization degree of 99.5%, and a dichroic ratio of 40.1.
  • Step 1 An optical compensation film (KC8UCR-5, manufactured by Konica Minolta Opto) and an antireflection film are immersed in a 2 mol / L sodium hydroxide solution at a temperature of 60 ° C. for 90 seconds, then washed with water and dried. It was. A surface of each antireflection film provided with a low refractive index layer was previously protected with a peelable protective film (PET).
  • K8UCR-5 manufactured by Konica Minolta Opto
  • the above-mentioned optical compensation film was immersed in a 2 mol / L sodium hydroxide solution at a temperature of 60 ° C. for 90 seconds, then washed with water and dried.
  • Step 2 The aforementioned polarizer was immersed in a storage tank of a polyvinyl alcohol adhesive solution 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 removed, and the polarizer was sandwiched between the optical compensation film and the antireflection film subjected to alkali treatment in Step 1 and laminated.
  • the antireflection film was disposed so that the surface of the antireflection layer was opposite to the polarizer.
  • Step 4 The laminate was laminated with two rotating rollers at a pressure of 20 to 30 N / cm 2 and a speed of about 2 m / min. At this time, it was carried out with care to prevent bubbles from entering.
  • Step 5 The sample prepared in Step 4 was dried in a dryer at a temperature of 80 ° C. for 2 minutes to prepare polarizing plates 1 to 28.
  • each polarizing plate 1 to 28 having the polarization direction was pasted thereto.
  • the liquid crystal panels 1 to 28 thus obtained are placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S • D / MX Panasonic Corporation is placed on the ceiling 3 m high from the floor. 10 sets of 40W ⁇ 2 pieces were arranged at 1.5 m intervals.
  • the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling portion from the evaluator's overhead to the rear.
  • Each liquid crystal panel was tilted by 25 ° from the vertical direction with respect to the desk, and the visibility (visibility) of the screen was evaluated by dividing it into the following ranks so that a fluorescent lamp was reflected, and the results are shown in Table 6.
  • A There is no glare due to foreign matter failure, and you are not concerned about the reflection of the nearest fluorescent light, and you can clearly read characters with a font size of 8 or less.
  • B There is no glare due to foreign matter failure, and nearby fluorescent light I'm a little worried about the reflection of the image, but I don't care about the distance, and I can read some characters with a font size of 8 or less.
  • C There is a slight glare due to a foreign object failure, and I am also concerned about the reflection of a distant fluorescent light. Therefore, it is difficult to read characters with a font size of 8 or less.
  • D There is glare due to a foreign object failure, and the reflection of the fluorescent lamp is quite worrisome. The following characters cannot be read
  • the antireflection film of the comparative example and the liquid crystal panel using the polarizing plate were evaluated as C to D, whereas the antireflection film of the present invention and the liquid crystal panel using the polarizing plate were All were evaluation results of B or higher, and visibility was better.
  • liquid crystal panels 7 to 9, 12, 13, 15, 16 are: All were the evaluation results of A and were excellent.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention porte sur un film optique qui possède une bonne capacité à coulisser (résistance de blocage) et ne provoque pas de défaillance due à des matières étrangères. L'invention porte également sur un procédé de production du film optique. L'invention porte également sur une plaque polarisante et sur un dispositif d'affichage à cristaux liquides chacun produit à l'aide du film optique. Le film optique comprend un film de résine et des particules contenues dans le film de résine. La surface du film a une dureté moyenne arithmétique (Ra) de 1,0 à 2,0 nm. Dans le film, le paramètre Mr1 (%) de la surface de structure comme défini selon JIS B0671:2002 est inférieur ou égal 12 %.
PCT/JP2009/062878 2008-08-05 2009-07-16 Film optique, procédé de production du film optique, plaque polarisante, et dispositif d'affichage à cristaux liquides WO2010016369A1 (fr)

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WO2011121817A1 (fr) * 2010-03-30 2011-10-06 コニカミノルタオプト株式会社 Film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
JP2011215171A (ja) * 2010-03-31 2011-10-27 Nippon Shokubai Co Ltd 光学フィルム
WO2012005207A1 (fr) * 2010-07-06 2012-01-12 コニカミノルタオプト株式会社 Procédé de production d'un dopant pour film optique, procédé de production de film optique, film optique, plaque polarisante, et dispositif d'affichage à cristaux liquides
WO2012005208A1 (fr) * 2010-07-06 2012-01-12 コニカミノルタオプト株式会社 Procédé de production d'un dopant pour film optique, procédé de production de film optique, film optique, plaque polarisante, et dispositif d'affichage à cristaux liquides
WO2012140901A1 (fr) * 2011-04-13 2012-10-18 コニカミノルタアドバンストレイヤー株式会社 Procédé de production de composition de résine, film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
WO2012144016A1 (fr) * 2011-04-19 2012-10-26 コニカミノルタアドバンストレイヤー株式会社 Film optique, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP2013064813A (ja) * 2011-09-16 2013-04-11 Konica Minolta Advanced Layers Inc 偏光板保護フィルム、偏光板保護フィルムの製造方法、偏光板及び液晶表示装置
JP5740980B2 (ja) * 2008-11-11 2015-07-01 コニカミノルタ株式会社 セルロースエステルフィルムの製造方法、偏光板及び液晶表示装置
JP5821849B2 (ja) * 2010-07-30 2015-11-24 コニカミノルタ株式会社 セルロースアセテートフィルムの製造方法
WO2017057564A1 (fr) * 2015-09-30 2017-04-06 旭硝子株式会社 Structure de projection vidéo et procédé de projection vidéo

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JP2006240228A (ja) * 2005-03-07 2006-09-14 Konica Minolta Opto Inc 光学フィルム、及びその製造方法
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JP2006327068A (ja) * 2005-05-27 2006-12-07 Konica Minolta Medical & Graphic Inc 感光性平版印刷版用支持体及び感光性平版印刷版材料。

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JP2006240228A (ja) * 2005-03-07 2006-09-14 Konica Minolta Opto Inc 光学フィルム、及びその製造方法
JP2006274015A (ja) * 2005-03-29 2006-10-12 Fuji Photo Film Co Ltd セルロースアシレートフィルム及びその製造方法
JP2006327068A (ja) * 2005-05-27 2006-12-07 Konica Minolta Medical & Graphic Inc 感光性平版印刷版用支持体及び感光性平版印刷版材料。

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JP5590116B2 (ja) * 2010-03-30 2014-09-17 コニカミノルタ株式会社 光学フィルム、偏光板および液晶表示装置
WO2011121720A1 (fr) * 2010-03-30 2011-10-06 コニカミノルタオプト株式会社 Film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
WO2011121817A1 (fr) * 2010-03-30 2011-10-06 コニカミノルタオプト株式会社 Film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
JP2011215171A (ja) * 2010-03-31 2011-10-27 Nippon Shokubai Co Ltd 光学フィルム
JP5626347B2 (ja) * 2010-07-06 2014-11-19 コニカミノルタ株式会社 光学フィルム用ドープの製造方法、光学フィルムの製造方法、光学フィルム、偏光板、及び液晶表示装置
KR101464065B1 (ko) 2010-07-06 2014-11-20 코니카 미놀타 어드밴스드 레이어즈 인코포레이티드 광학 필름용 도프의 제조 방법, 광학 필름의 제조 방법, 광학 필름, 편광판 및 액정 표시 장치
JP5614450B2 (ja) * 2010-07-06 2014-10-29 コニカミノルタ株式会社 光学フィルム用ドープの製造方法、光学フィルムの製造方法、光学フィルム、偏光板、及び液晶表示装置
WO2012005207A1 (fr) * 2010-07-06 2012-01-12 コニカミノルタオプト株式会社 Procédé de production d'un dopant pour film optique, procédé de production de film optique, film optique, plaque polarisante, et dispositif d'affichage à cristaux liquides
WO2012005208A1 (fr) * 2010-07-06 2012-01-12 コニカミノルタオプト株式会社 Procédé de production d'un dopant pour film optique, procédé de production de film optique, film optique, plaque polarisante, et dispositif d'affichage à cristaux liquides
JP5821849B2 (ja) * 2010-07-30 2015-11-24 コニカミノルタ株式会社 セルロースアセテートフィルムの製造方法
WO2012140901A1 (fr) * 2011-04-13 2012-10-18 コニカミノルタアドバンストレイヤー株式会社 Procédé de production de composition de résine, film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
WO2012144016A1 (fr) * 2011-04-19 2012-10-26 コニカミノルタアドバンストレイヤー株式会社 Film optique, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP2013064813A (ja) * 2011-09-16 2013-04-11 Konica Minolta Advanced Layers Inc 偏光板保護フィルム、偏光板保護フィルムの製造方法、偏光板及び液晶表示装置
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WO2017057564A1 (fr) * 2015-09-30 2017-04-06 旭硝子株式会社 Structure de projection vidéo et procédé de projection vidéo
CN108139660A (zh) * 2015-09-30 2018-06-08 旭硝子株式会社 映像投影结构体以及映像投影方法
JPWO2017057564A1 (ja) * 2015-09-30 2018-07-19 旭硝子株式会社 映像投影構造体および映像投影方法
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