WO2010035571A1 - Composition pour couche antireflet, film antireflet, plaque polarisante et dispositif d’affichage d’image - Google Patents

Composition pour couche antireflet, film antireflet, plaque polarisante et dispositif d’affichage d’image Download PDF

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Publication number
WO2010035571A1
WO2010035571A1 PCT/JP2009/063260 JP2009063260W WO2010035571A1 WO 2010035571 A1 WO2010035571 A1 WO 2010035571A1 JP 2009063260 W JP2009063260 W JP 2009063260W WO 2010035571 A1 WO2010035571 A1 WO 2010035571A1
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Prior art keywords
acid
film
particles
mass
layer
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PCT/JP2009/063260
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English (en)
Japanese (ja)
Inventor
洋 渡邉
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コニカミノルタオプト株式会社
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Priority to JP2010530776A priority Critical patent/JPWO2010035571A1/ja
Publication of WO2010035571A1 publication Critical patent/WO2010035571A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/107—Porous materials, e.g. for reducing the refractive index
    • 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
    • G02F1/133502—Antiglare, refractive index matching layers

Definitions

  • the present invention relates to an antireflection composition, an antireflection film, a polarizing plate, and an image display device.
  • an antireflection film is used for an image display device such as a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display device (LCD).
  • CTR cathode ray tube display device
  • PDP plasma display
  • ELD electroluminescence display
  • LCD liquid crystal display device
  • it has a function of reducing the reflectance by the light interference of the multilayer thin film, and is disposed on the outermost surface of the display.
  • a method is known in which a plurality of hollow silica particles having a porous or hollow interior are used, and a binder for a low refractive index layer is formed by a so-called sol-gel method while maintaining a low refractive index due to voids (Patent Document 1). ).
  • Patent Document 2 a technique has been proposed in which a cured product by active energy rays is used as a binder instead of forming a binder by a sol-gel method.
  • the present invention relates to an antireflective composition for achieving a low refractive index layer having a sufficiently low refractive index but also having excellent scratch resistance and adhesion, and a reflection having a layer obtained by curing the composition. It aims at providing a prevention film, a polarizing plate, and an image display apparatus.
  • the object of the present invention was achieved by the following.
  • An antireflection layer composition comprising (A) hollow silica particles, (B) a cationic polymerizable compound represented by the following general formula (1), and (C) a photocationic polymerization initiator.
  • R 1 represents a cationically polymerizable group having 1 to 10 carbon atoms.
  • R 2 represents a group selected from a methyl group, an ethyl group, and a propyl group.
  • n represents 0, 1, or 2.
  • R 1 of the compound represented by the general formula (1) is a group having an epoxy structure or an oxetane structure.
  • An antireflection film comprising a layer obtained by curing the composition according to 1 or 2 above.
  • an antireflective composition for achieving a low refractive index layer excellent in scratch resistance and adhesion while having a sufficiently low refractive index, a layer obtained by curing the composition, An antireflection film, a polarizing plate and an image display device can be provided.
  • the antireflective composition of the present invention is a composition capable of producing an antireflective layer, particularly a low refractive index layer, by applying the composition to, for example, a film as a substrate and then curing the composition.
  • the basic composition is characterized by containing (A) hollow silica particles, (B) a cationically polymerizable compound represented by the following general formula (1) and (C) a photocationic polymerization initiator.
  • A) Hollow silica particles The hollow silica particles of the present invention are preferably hollow silica particles having an outer shell layer and porous or hollow inside.
  • the hollow silica particles having an outer shell layer and the inside is porous or hollow
  • Composite particles comprising porous particles and a coating layer provided on the surface of the porous particles
  • Cavity particles having a cavity inside and filled with a solvent, a gas or a porous substance, It is.
  • the cavity particles are particles having a cavity inside, and the cavity is surrounded by a particle wall.
  • the cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation.
  • the average particle size of such hollow silica particles is 5 to 200 nm, preferably 10 to 70 nm.
  • the particle diameter of the hollow silica particles is preferably monodispersed with a coefficient of variation of 1 to 40%.
  • the average particle diameter of the hollow silica particles used 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.
  • the average particle diameter of the hollow silica particles used in the present invention is appropriately selected according to the thickness of the transparent film of the low refractive index layer to be formed, and is preferably less than 100% of the film thickness of the low refractive index layer. .
  • These hollow silica particles are preferably used in a state of being dispersed in a suitable medium in order to form a low refractive index layer.
  • water for example, methanol, ethanol, isopropyl alcohol
  • ketone for example, methyl ethyl ketone, methyl isobutyl ketone
  • ketone alcohol for example, diacetone alcohol
  • propylene monomethyl ether propylene glycol monomethyl ether acetate and the like
  • the thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 40 nm, preferably 1 to 20 nm, more preferably 2 to 15 nm.
  • the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the coating liquid component can easily enter the composite particles to reduce the internal porosity. However, the effect of lowering the refractive index may not be obtained sufficiently.
  • the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of lowering the refractive index cannot be sufficiently obtained. Sometimes.
  • the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even when the thickness exceeds 20 nm, the effect of lowering the refractive index may not be sufficiently exhibited. is there.
  • the coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica.
  • components other than silica may be contained, 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 , sb 2 O 5, SbO 2, 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 Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , CeO 2 , P 2 O 3 , Sb 2 O 3 , Sb 2 O 5 , SbO 2 , MoO 3 , ZnO 2 , or WO 3 and two or more.
  • the molar ratio: MO x / SiO 2 is 0.0001 to 1.0 when silica is represented by SiO 2 and inorganic compounds other than silica are represented by oxides (MO x ).
  • it is in the range of 0.001 to 0.3.
  • Porous particles having a molar ratio of MO x / SiO 2 of less than 0.0001 are difficult to obtain, and even if obtained, the pore volume is small and particles having a low refractive index cannot be obtained. Further, when the molar ratio of the porous particles: MO x / SiO 2 exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it may be difficult to obtain a low refractive index. .
  • the pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g.
  • the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained, and when the pore volume exceeds 1.5 ml / g, the strength of the 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.
  • 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.
  • porous substance examples include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.
  • hollow silica particles As a method for producing such hollow silica particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is preferably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow silica particles can be produced by carrying out 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 mixed aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared in advance.
  • a porous particle precursor is prepared by gradually adding it to an alkaline aqueous solution having a pH of 10 or more while stirring.
  • 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
  • the seed particles are not particularly limited, but inorganic oxides such as SiO 2 , Al 2 O 3 , TiO 2 , or ZrO 2 or fine particles of these composite oxides are used, and usually these sols are used. be able to. Furthermore, 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 more, and then an aqueous solution of the above compound is added to the aqueous alkali solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion.
  • seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.
  • silica raw material and the inorganic compound raw material described above have high solubility on the alkali side.
  • solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of particles.
  • the composite ratio of silica and inorganic compound other than silica in the first step is calculated by converting the inorganic compound to silica into an oxide (MO x ), and the molar ratio of MO x / SiO 2 is 0.05 to 2.0, Preferably it is in 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 MO x / SiO 2 molar ratio is preferably in the range of 0.25 to 2.0.
  • 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 40 nm, preferably 0.5 to 15 nm. Even if a 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 from the porous particle precursor. is there.
  • silica protective film By forming such a silica protective film, inorganic compounds other than silica described above 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. be able to.
  • 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 body, the formed coating layer becomes a particle wall to form hollow particles.
  • the amount of 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.
  • an alkoxysilane represented by the following general formula (1) can be used as the hydrolyzable organosilicon compound used for forming the silica protective film.
  • tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.
  • R n Si (OR ′) 4-n (1)
  • R and R ′ represent a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, and an acrylic group, and n represents 0, 1, 2, or 3.
  • 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 porous particles, and then alkoxysilane, pure water, and alcohol are added.
  • a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of the above is added to a dispersion of porous particles, and a silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of inorganic oxide particles. .
  • alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion.
  • alkali catalyst ammonia, an alkali metal hydroxide, or an amine can be used.
  • 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.
  • a hydrolyzable organosilicon compound or silica containing a fluorine-substituted alkyl group-containing silane compound is added to the porous particle dispersion (in the case of hollow particles, a hollow particle precursor dispersion) prepared in the second step.
  • the porous particle dispersion in the case of hollow particles, a hollow particle precursor dispersion
  • an acid solution or the like the surface of the particles is coated with a hydrolyzable organosilicon compound or a polymer such as a silicic acid solution to form a silica coating layer.
  • the silicic acid solution is an aqueous solution of a low polymer of silicic acid obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.
  • the amount of the organosilicon compound or silicic acid solution used for forming the coating layer may be such that the surface of the colloidal particles can be sufficiently covered, and the finally obtained silica coating layer has a thickness of 1 to 40 nm, Preferably, it is added in an amount of 1 to 20 nm in the dispersion of porous particles (in the case of hollow particles, hollow particle precursor).
  • 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 40 nm, preferably 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, dense particles may be formed, and the effect of lowering the refractive index may not be obtained.
  • the refractive index of the hollow silica particles thus obtained is as low as less than 1.42.
  • Such hollow silica 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 particles are preferably hollow silica particles in which a polymer having a hydrocarbon main chain is covalently bonded to the surface.
  • hollow silica particles in which a polymer having a hydrocarbon main chain is covalently bonded will be described.
  • the polymer having a hydrocarbon main chain is a direct covalent bond, or a binder is interposed between the silica on the surface of the hollow silica particles and the polymer having the hydrocarbon main chain, and the silica and the binder are covalently bonded. It also refers to a covalent bond between a binder and a polymer.
  • a coupling agent is preferably used as the binder.
  • Hollow silica particles with a covalently bonded polymer having a hydrocarbon main chain can (1) form a covalent bond with the hollow silica particle surface in a state where the hollow silica particle surface is untreated or treated with a coupling agent.
  • the polymer can be produced by polymerizing a polymer to grow a polymer chain and surface grafting. As a specific manufacturing method, the method described in JP-A-2006-257308 can be used.
  • a method of polymerizing a monomer from the surface of the hollow silica particles to grow a polymer chain and surface grafting is preferable. More preferred is a method in which hollow silica particles are surface-treated with a coupling agent containing a functional group having a polymerization initiating ability or a chain transfer ability, monomers are polymerized therefrom, polymer chains are grown, and surface grafting is performed.
  • an alkoxy metal compound for example, titanium coupling agent, alkoxysilane compound (silane coupling agent)
  • titanium coupling agent for example, titanium coupling agent, alkoxysilane compound (silane coupling agent)
  • alkoxysilane compound silane coupling agent
  • the hollow silica particles may contain two or more types of hollow silica particles having different average particle diameters.
  • hollow silica particles In the present invention, it is preferable to use hollow silica particles having a conductive metal oxide coating layer for the low refractive index layer because the conductivity can be increased.
  • the metal oxide for forming the conductive metal oxide coating layer is not particularly limited.
  • tin oxide, antimony tin oxide, indium tin oxide, antimony oxide, aluminum zinc oxide, gallium zinc oxide, and these The thing chosen from the mixture of these is mentioned.
  • hollow silica particles coated with antimony oxide are particularly preferable.
  • the average thickness of the conductive metal oxide coating layer is in the range of 1 to 40 nm, more preferably 1 to 20 nm, and the hollow silica particles can be sufficiently coated.
  • the thickness of the coating layer is preferably 1 nm or more from the viewpoint of sufficient conductivity.
  • the thickness of the coating layer is preferably 40 nm or less in that the effect of improving the conductivity is sufficient and the refractive index is sufficient even when the average particle size of the conductive metal oxide-coated hollow silica particles is small.
  • hollow silica particles having a particularly preferable antimony oxide coating layer will be described.
  • the antimony oxide may be any of Sb 2 O 3 , Sb 2 O 5 , SbO 2, etc., and the antimony oxide coating layer may contain tin oxide or the like. The total content of these antimony oxides in the antimony oxide coating layer is preferably 10% or more.
  • the antimony oxide coating layer may be further coated with silica or the like.
  • the volume resistance value of the antimony oxide-coated hollow silica particles is preferably 10 to 5000 ⁇ / cm, and more preferably 10 to 2000 ⁇ / cm.
  • volume resistance value By making the volume resistance value within this range, it is possible to reduce the surface resistance of the low refractive index coating film while keeping the refractive index of the particles low.
  • the volume resistance value can be controlled by adjusting the particle size of the core particles, the film thickness of the surface-coated metal oxide layer, and the composition.
  • the volume resistance value was measured by the following method.
  • a dispersion of porous silica-based particles or silica-based particles having cavities inside is prepared by the method described above.
  • the solid concentration of the dispersion is preferably in the range of 0.1 to 40% by mass, more preferably 0.5 to 20% by mass.
  • the solid content concentration is less than 0.1% by mass, the production efficiency is low, and when the solid content concentration exceeds 40% by mass, the obtained antimony oxide-coated hollow silica particles may be aggregated, and the transparency of the coating is low. It may decrease or haze may deteriorate.
  • a dispersion (aqueous solution) of antimonic acid is prepared.
  • the antimonic acid preparation method is not particularly limited as long as the antimony oxide coating layer can be formed on the particle surface without filling the pores and cavities of the porous silica particles or the silica particles having cavities inside. However, the following method is preferable because a uniform and thin antimony oxide coating layer can be formed.
  • an antimonic acid (gel) dispersion is prepared by treating an alkali antimonate aqueous solution with a cation exchange resin, and then treated with an anion exchange resin.
  • a cation exchange resin for example, an alkali antimonate aqueous solution described in JP-A-2-180717, which is used in a method for producing an antimony oxide sol, is suitable.
  • the alkali antimonate aqueous solution is preferably obtained by reacting antimony trioxide (Sb 2 O 3 ), an alkali substance and hydrogen peroxide, and the molar ratio of antimony oxide, alkali substance and hydrogen peroxide is 1: 2.0 to 2.5: 0.8 to 1.5, preferably 1: 2.1 to 2.3: 0.9 to 1.2, and the system containing antimony trioxide and an alkaline substance is peroxidized. It is obtained by adding hydrogen at a rate of 0.2 mol / hr or less per mol of antimony trioxide.
  • the antimony trioxide used at this time is preferably a powder, particularly a fine powder having an average particle size of 10 ⁇ m or less, and examples of the alkaline substance include LiOH, KOH, NaOH, Mg (OH) 2 , and Ca (OH). 2, etc. Among them, alkali metal hydroxides such as KOH and NaOH are preferable. These alkaline substances have the effect of stabilizing the resulting antimonic acid solution.
  • an antimony trioxide suspension a predetermined amount of an alkaline substance and antimony trioxide are added to water to prepare an antimony trioxide suspension.
  • the antimony trioxide concentration of the antimony trioxide suspension is preferably in the range of 3 to 15% by mass as Sb 2 O 3 .
  • this suspension was heated to 50 ° C. or higher, preferably 80 ° C. or higher, and hydrogen peroxide having a concentration of 5 to 35% by mass was added to 0.2 mol / hr or less of antimony trioxide. Add at a rate.
  • the alkali antimonate aqueous solution (when MHSbO 3 : M is an alkali metal) obtained by the above reaction is separated from an undissolved residue as necessary, and further diluted as necessary, and treated with a cation exchange resin. Then, an antimonic acid gel (HSbO 3 ⁇ ) n dispersion is prepared by removing alkali ions.
  • the alkali antimonate aqueous solution may contain an aqueous solution containing a doping agent such as an alkali stannate aqueous solution or a sodium phosphate aqueous solution.
  • a doping agent such as an alkali stannate aqueous solution or a sodium phosphate aqueous solution.
  • the concentration of the alkali antimonate aqueous solution in the treatment with the cation exchange resin is preferably in the range of 0.01 to 5% by mass, more preferably 0.1 to 3% by mass as the solid content Sb 2 O 5 .
  • the solid content is less than 0.01% by mass, the production efficiency is low, and when it exceeds 5% by mass, a large aggregate of antimonic acid may be formed, and it is difficult to coat the hollow silica particles with antimonic acid. May be non-uniform.
  • the amount of the cation exchange resin used is preferably such that the resulting antimonic acid dispersion has a pH of 1 to 4, more preferably 1.5 to 3.5.
  • the pH is less than 1, there is a tendency that aggregated particles are generated instead of chain particles, and when the pH exceeds 4, monodispersed particles tend to be generated.
  • the pH is less than 1, it is difficult to coat a predetermined amount of antimony oxide because the solubility of antimony oxide is high.
  • the pH exceeds 4 the obtained antimony oxide-coated hollow silica particles may become an aggregate. The dispersibility in the film may be lowered, and the antistatic effect may be insufficient.
  • the antimonic acid dispersion and porous silica particles or a dispersion of silica particles having cavities inside are mixed and aged at a temperature of 50 to 250 ° C., preferably 70 to 120 ° C., usually for 1 to 24 hours.
  • a temperature of 50 to 250 ° C. preferably 70 to 120 ° C., usually for 1 to 24 hours.
  • the mixing ratio of the antimonic acid dispersion to the silica-based particle dispersion is 100 parts by mass with the silica-based particles as solids and 1 to 200 parts by mass, preferably 5 to 100 parts by mass with antimonic acid as Sb 2 O 5. Add as follows.
  • the coating is uneven or the thickness of the coating layer becomes insufficient, and the effect of coating with antimony oxide, that is, the effect of imparting and improving conductivity is sufficient. May not be obtained.
  • the mixing ratio of antimonic acid exceeds 200 parts by mass, the antimony oxide not contributing to the coating does not increase, and the conductivity of the obtained antimony oxide-coated hollow silica particles is not further improved, and the refractive index is 1.60. May be higher than
  • the concentration of the mixed dispersion is preferably in the range of 1 to 40% by mass, more preferably 2 to 30% by mass as the solid content.
  • concentration of the mixed dispersion is less than 1% by mass, the coating efficiency of antimony oxide is insufficient or the production efficiency is lowered.
  • the obtained antimony oxide-coated hollow silica particles may aggregate when the amount of antimonic acid used is large.
  • the amount of hollow silica particles added to the low refractive index layer is preferably 10% by mass to 60% by mass, and more preferably 20% by mass to 60% by mass with respect to the entire solid content of the low refractive index layer.
  • the low refractive index layer of the present invention is characterized by containing a cationically polymerizable compound of the general formula (1).
  • R 1 represents a cationically polymerizable group having 1 to 10 carbon atoms.
  • R 2 represents a group selected from a methyl group, an ethyl group, and a propyl group.
  • n represents 0, 1, or 2.
  • the cationically polymerizable group of R 1 is preferably a group having a vinyl ether structure, a group having an epoxy structure, or a group having an oxetane structure, and more preferably any one of the following Ra, Rb, and Rc. More preferably, it is any of the following Ra and Rc.
  • n is preferably 0 or 1.
  • Examples of the compound represented by the general formula (1) are commercially available from Shin-Etsu Chemical Co., Ltd. as KBM-403, KBE-402, and KBE-403.
  • the cationically polymerizable compound other than the general formula (1) include known compounds such as epoxy compounds, oxetane compounds, phenol compounds, aldehyde compounds, vinyl ether compounds, styrene compounds, cyclic ether compounds, lactone compounds, episulfide compounds, and silicones. It is done.
  • the above cationic polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content of the low refractive index layer composition.
  • ⁇ (C) Photocationic polymerization initiator Known compounds and photoacid generators can be used as the compound that functions as the photocationic polymerization initiator of the present invention.
  • the photoacid generator include a cationic polymerization photoinitiator, a dye photodecoloring agent, a photochromic agent, a known compound used in a microresist, and a mixture thereof.
  • onium compounds examples include onium compounds, organic halogen compounds, and disulfone compounds, and onium compounds are preferred.
  • Onium compound diazonium salts, sulfonium salts, iodonium salts and the like represented by the following formulas are preferably used, and sulfonium salts are particularly preferable.
  • Ar represents an aryl group
  • R represents an alkyl group having an aryl group or having 1 to 20 carbon atoms, when appearing more than R are times in one molecule may be different from each other in the same
  • Z - is Represents a non-basic and non-nucleophilic anion.
  • the aryl group represented by Ar or R is also typically phenyl or naphthyl, and these may be substituted with an appropriate group.
  • anion represented by Z ⁇ examples include tetrafluoroborate ion (BF 4 ⁇ ), tetrakis (pentafluorophenyl) borate ion (B (C 6 F 5 ) 4 ⁇ ), hexafluorophosphate ion. (PF 6 ⁇ ), hexafluoroarsenate ion (AsF 6 ⁇ ), hexafluoroantimonate ion (SbF 6 ⁇ ), hexachloroantimonate ion (SbCl 6 ⁇ ), hydrogen sulfate ion (HSO 4 ⁇ ), perchloric acid Ions (ClO 4 ⁇ ) and the like.
  • onium compounds examples include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, boron salts and the like.
  • onium compounds examples include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, boron salts and the like.
  • diazonium salts iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the material stability of the compound.
  • onium salts that can be suitably used include, for example, an amylated sulfonium salt described in paragraph No. [0035] of JP-A No. 9-268205, and paragraph Nos. Of JP-A No. 2000-71366.
  • Diaryl iodonium salts or triarylsulfonium salts described in [0010] to [0011] sulfonium salts of thiobenzoic acid S-phenyl ester described in paragraph [0017] of JP-A-2001-288205, JP-A-2001-133696 Examples thereof include onium salts described in paragraph numbers [0030] to [0033].
  • the acid generator examples include a photoacid generator having an organometallic / organic halide and an o-nitrobenzyl type protecting group described in paragraphs [0059] to [0062] of JP-A-2002-29162. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.).
  • initiators include, for example, “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd., and “Adekaoptomer SP-150” (trade name) sold by ADEKA Co., Ltd. Product name), “Adekaoptomer SP-300” (product name), “RHODORSIL PHOTOINITIAOR 2074” (product name) sold by Rhodia Japan Co., Ltd., and the like.
  • a sulfonium salt in terms of curability, and examples of a preferable sulfonium salt include a sulfonium salt of the general formula (2), (3), (4) or (5). preferable.
  • R 1 to R 17 each represent a hydrogen atom or a substituent
  • R 1 to R 3 do not simultaneously represent a hydrogen atom
  • R 4 to R 7 do not simultaneously represent a hydrogen atom
  • R 8 to R 11 do not represent hydrogen atoms at the same time
  • R 12 to R 17 do not represent hydrogen atoms at the same time.
  • X ⁇ represents a non-nucleophilic anionic residue.
  • acids that function as a cationic photopolymerization initiator in the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, and the like Examples include Bronsted acids such as organic acids, Lewis acids such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, and the like
  • Aromatic polycarboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, or anhydrides thereof, maleic acid, maleic anhydride, succinic acid, succinic anhydride Aliphatic polyvalent carboxylic acid or anhydride thereof such as
  • These acids and photoacid generators are preferably added in an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the cationic polymerizable compound. is there.
  • the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity and the like.
  • ⁇ Antireflection layer composition other than (A), (B), (C)> In addition to (A), (B), and (C), it is preferable to add the following compounds to the composition for an antireflection layer of the present invention.
  • the antireflection layer composition preferably contains a catalyst.
  • the catalyst include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, organic bases such as triethylamine and pyridine, metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium, and metal chelate compounds described later. Of these, metal chelate compounds are preferably used.
  • a chelate compound having a metal selected from Zr, Ti, and Al as a central metal can be suitably used without particular limitation.
  • Specific examples include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis ( Zirconium chelate compounds such as acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetate) titanium, diisopropoxybis (acetylacetone) titanium, etc.
  • Titanium chelate compound diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonatoal Ni, isopropoxy bis (ethyl acetoacetate) aluminum, isopropoxy bis (acetylacetonate) aluminum, tris (ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonato bis (ethyl acetoacetate) aluminum, etc.
  • aluminum chelate compound examples include titanium chelate compound, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonatoal Ni, isopropoxy bis (ethyl acetoacetate) aluminum, isopropoxy bis (acetylacetonate) aluminum, tris (ethyl acetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonato bis (ethyl acetoacetate
  • metal chelate compounds tri-n-butoxyethyl acetoacetate zirconium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are particularly preferably used. These metal chelate compounds can be used either alone or in combination.
  • the antireflective composition may contain an organosilicon compound represented by the following general formula (6), a hydrolyzate thereof, or a polycondensate thereof.
  • R 0 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group
  • X is a hydroxyl group or a hydrolyzable substituent
  • m is an integer of 0 to 3.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group and the like.
  • aryl group examples include a phenyl group and a naphthyl group.
  • Examples of the hydrolyzable substituent of X include an alkoxy group, a halogen group, and a carboxyl group.
  • Specific examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane.
  • composition for an antireflection layer of the present invention 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).
  • alcohols eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol
  • ketones eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
  • esters eg, methyl acetate, ethyl acetate.
  • aliphatic hydrocarbons eg, hexane, cyclohexane
  • halogenated hydrocarbons eg, methylene
  • toluene methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, isopropanol, and propylene glycol monomethyl ether are particularly preferable.
  • the solid content concentration of the composition for the antireflection layer is preferably 1 to 4% by mass, and by setting the solid content concentration to 4% by mass or less, coating unevenness is less likely to occur and should be 1% by mass or more. As a result, the drying load is reduced.
  • the coating composition for forming the low refractive index layer preferably contains a fluorine-based or silicone-based surfactant. Inclusion of the surfactant is effective for reducing coating unevenness and improving the antifouling property of the film surface.
  • Fluorosurfactants include perfluoroalkyl group-containing monomers, oligomers, and polymers as the core, and include derivatives such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene. It is done.
  • fluorosurfactants can also be used.
  • Surflon S-381, S-382, SC-101, SC-102, SC-103, SC-104 manufactured by Asahi Glass Co., Ltd.
  • FLORARD FC-430, FC-431, FC-173 Fluorochemical-manufactured by Sumitomo 3M
  • F-top EF352, EF301, EF303 manufactured by Shin-Akita Kasei Co., Ltd.
  • Schwegau Fluer 8035, 8036 Manufactured by Schwegman
  • BM1000, BM1100 manufactured by BM Himmy
  • MegaFuck F-171, F-470 both manufactured by DIC Corporation
  • the fluorine content of the fluorosurfactant is 0.05 to 2% by mass, preferably 0.1 to 1% by mass.
  • One or two or more of the above fluorosurfactants can be used in combination.
  • Silicone surfactants can be broadly classified into straight silicone oil and modified silicone oil depending on the type of organic group bonded to the silicon atom.
  • the straight silicone oil refers to one in which a methyl group, a phenyl group, or a hydrogen atom is bonded as a substituent.
  • a modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil.
  • Silicone oil 1. Straight silicone oil 1-1.
  • Non-reactive silicone oil dimethyl, methylphenyl substitution, etc.
  • Reactive silicone oil methyl hydrogen substitution and the like.
  • Modified silicone oil Modified silicone oil is born by introducing various organic groups into dimethyl silicone oil.
  • Non-reactive modified silicone oil alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc.
  • Alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is substituted with a long-chain alkyl group or a phenylalkyl group.
  • Polyether-modified silicone oil is a surfactant in which hydrophilic polyoxyalkylene is introduced with hydrophobic dimethyl silicone.
  • Higher fatty acid-modified silicone oil is a silicone oil in which a part of methyl group of dimethylsilicone oil is replaced with higher fatty acid ester.
  • Amino-modified silicone oil is a silicone oil having a structure in which a part of methyl group of silicone oil is substituted with aminoalkyl group.
  • the epoxy-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with an epoxy group-containing alkyl group.
  • the carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group.
  • polyether-modified silicone oil is preferably added.
  • the number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the drying property of the coating film decreases, and conversely, the number average molecular weight is When it exceeds 100,000, it becomes difficult to bleed out to the coating film surface.
  • Specific products include L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ- from Toray Dow Corning. 3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF351A, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, BYK series surfactants BYK series, BYK-300 / 302, BYK-306, BYK-307, B K-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK
  • the silicone surfactant is a surfactant obtained by substituting a part of the methyl group of the silicone oil with a hydrophilic group.
  • the position of substitution includes a side chain of silicone oil, both ends, one end, both end side chains, and the like.
  • the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.
  • silicone surfactant a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.
  • a nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution.
  • a hydrophilic group includes a hydroxyl group of a polyhydric alcohol, a polyoxyalkylene chain (poly Oxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer.
  • nonionic surfactant examples include silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, Toray Dow Corning, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ- 2164, FZ-2166, FZ-2191, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, and the like.
  • Preferred structures of these nonionic surfactants comprising a hydrophobic group of dimethylpolysiloxane and a hydrophilic group of polyoxyalkylene include linear structures in which dimethylpolysiloxane structural portions and polyoxyalkylene chains are alternately and repeatedly bonded.
  • a block copolymer is preferred. It is preferable from unevenness suppression and leveling properties when a coating composition for forming a low refractive index layer is applied.
  • Specific examples thereof include silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, FZ-2222, etc., manufactured by Toray Dow Corning.
  • the coating composition for forming the low refractive index layer has a reactive modified silicone resin (also referred to as a reactive modified silicone oil) described below from the standpoint of easily exhibiting desirable performance after a durability test under more severe conditions. It is preferable to contain.
  • a reactive modified silicone resin also referred to as a reactive modified silicone oil
  • Reactive modified silicone oil amino, epoxy, carboxyl, alcohol substitution, etc.
  • the reactive modified silicone resin is a reactive type modified silicone resin substituted with amino, epoxy, carboxyl, hydroxyl group, methacryl, mercapto, phenol or the like at the side chain, one end or both ends of polysiloxane.
  • amino-modified silicone resins include KF-860, KF-861, X-22-161A, X-22-161B (above, manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3311, FM-3325 (above, Manufactured by Chisso Corporation), epoxy-modified silicone resins such as KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above, Shin-Etsu Chemical Co., Ltd.), polyether-modified X-22-4272 and X-22-4952 as silicone resins, X-22-3701E and X-22-3710 (above, Shin-Etsu Chemical Co., Ltd.) as carboxyl-modified silicone
  • hydroxyl group-modified silicone resin examples include FM-4411, FM-4421, FM-DA21, FM-DA26 (manufactured by Chisso Corporation).
  • X-22-170DX, X-22-2426, X-22-176F manufactured by Shin-Etsu Chemical Co., Ltd.
  • the above-mentioned surfactants may be used in combination with other surfactants.
  • anionic surfactants such as sulfonate-based, sulfate-based, phosphate-based, etc.
  • You may use together with nonionic surfactants, such as an ether type
  • the addition amount of the above-mentioned surfactant is 0.05 to 3.0% by mass in the low refractive index layer coating composition, not only improving the water repellency, oil repellency and antifouling property of the coating film. From the viewpoint of exerting an effect also on the scratch resistance of the surface.
  • the surfactant described above can also be contained in the antistatic layer for the purpose of reducing coating unevenness.
  • the antireflection film of the present invention is an antireflection film obtained by laminating a low refractive index layer having a refractive index lower than that of the base film directly or via another layer on the base film.
  • the refractive index layer curing the composition for an antireflection layer containing (A) hollow silica particles, (B) a cationic polymerizable compound of the general formula (1), and (C) a cationic photopolymerization initiator.
  • the layer is a produced layer.
  • the adhesion is extremely excellent, and the reflection can withstand the light resistance test assuming use under severe conditions for a long period of time. It becomes possible to provide a prevention film.
  • the base film contains a cellulose ester resin, or a cellulose ester resin and an acrylic resin, and further includes a cellulose ester resin, an acrylic resin, and acrylic particles, thereby providing a base material having further excellent adhesion. It becomes possible.
  • ⁇ Layer structure of antireflection film> The example of the preferable layer structure of the antireflection film of this invention is shown below. Here, “/” indicates that they are stacked. However, the present invention is not limited to the following layer structure.
  • 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.
  • cellulose ester films for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UE, KC4UE, and KC12UR (above, manufactured by Konica Minolta Opto, Polycarbonate Film)
  • An olefin polymer film and a polyester film are preferable, and in the present invention, a cellulose ester film is particularly preferable in terms of production, cost, isotropy, adhesiveness, and the object effects of the present invention.
  • the refractive index of the base film of the present invention is 1.30 to 1.70, preferably 1.40 to 1.65.
  • the refractive index is measured by the method of JISK7142 using an Upe refractometer 2T manufactured by Atago Co., Ltd.
  • a cellulose ester film (hereinafter, also referred to as a cellulose ester film) that is preferable as a base 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 that are 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.
  • Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy
  • cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ⁇ X ⁇ 2.5 and 0.1 ⁇ Y ⁇ 0.9.
  • the portion that is not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods. 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
  • the cellulose ester film preferably contains an acrylic resin and acrylic particles from the viewpoint that the objective effect of the present invention is better exhibited.
  • Acrylic resin also includes 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 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 the film is produced.
  • 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. Further, in order to control the reduced viscosity of the produced copolymer, polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
  • the cellulose ester film preferably contains an acrylic resin and further acrylic particles because the objective effect of the present invention is exhibited well and the pencil hardness is excellent.
  • Acrylic particles for example, a PTFE membrane having a pore diameter less than the average particle diameter of acrylic particles when a predetermined amount of the prepared acrylic resin-containing film is collected, dissolved in a solvent, stirred, and sufficiently dissolved and dispersed. It is preferable that the weight of the insoluble matter filtered and collected using a filter is 90% by mass or more of the acrylic particles added to the acrylic resin-containing film.
  • the acrylic particles are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and more preferably the following multilayer structure acrylic granular composite.
  • the multilayer structure acrylic granular composite is formed by laminating the innermost hard layer polymer, the cross-linked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer from the central portion toward the outer peripheral portion.
  • Preferred embodiments of the multilayer structure acrylic granular composite used in the acrylic resin composition include the following.
  • (c) the innermost hard In the presence of a polymer comprising a layer and a crosslinked soft layer, a monomer mixture comprising 80 to 99% by mass of methyl methacrylate and 1 to 20% by mass of alkyl
  • Outermost hard layer polymer obtained by And the obtained three-layer structure polymer has an innermost hard layer polymer (a) of 5 to 40% by mass, a soft layer polymer (b) of 30 to 60% by mass, and an outermost layer polymer.
  • a hard layer polymer (c) comprising 20 to 50% by mass, having an insoluble part when fractionated with acetone, and an acrylic granular composite having a methyl ethyl ketone swelling degree of 1.5 to 4.0 in the insoluble part, Can be mentioned.
  • the innermost hard layer polymer (a) constituting the multilayer structure acrylic granular composite is 80 to 98.9% by mass of methyl methacrylate and 1 to 20 mass of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. % And a monomer mixture consisting of 0.01 to 0.3% by mass of a polyfunctional grafting agent is preferred.
  • examples of the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like. And n-butyl acrylate are preferably used.
  • the proportion of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass.
  • the thermal decomposability of the polymer is increased, while the unit is 20% by mass. If it exceeds 50%, the glass transition temperature of the innermost hard layer polymer (c) is lowered, and the impact resistance imparting effect of the three-layer structure acrylic granular composite is lowered.
  • polyfunctional grafting agent examples include polyfunctional monomers having different polymerizable functional groups, such as allyl esters of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, and allyl methacrylate is preferably used.
  • the polyfunctional grafting agent is used to chemically bond the innermost hard layer polymer and the soft layer polymer, and the ratio used during the innermost hard layer polymerization is 0.01 to 0.3% by mass. .
  • the crosslinked soft layer polymer (b) constituting the acrylic granular composite is an alkyl acrylate having from 9 to 8 carbon atoms having an alkyl group of 1 to 8 in the presence of the innermost hard layer polymer (a). What is obtained by polymerizing a monomer mixture consisting of 10% by mass, 0.01 to 5% by mass of a polyfunctional crosslinking agent and 0.5 to 5% by mass of a polyfunctional grafting agent is preferred.
  • n-butyl acrylate or 2-ethylhexyl acrylate is preferably used as the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group.
  • Examples of other monofunctional monomers that can be copolymerized include styrene and substituted styrene derivatives. As the ratio of the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group and styrene increases, the glass transition temperature of the produced polymer (b) decreases as the former increases, that is, it can be softened.
  • the refractive index of the soft layer polymer (b) at room temperature is set to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard heat. It is more advantageous to make it closer to the plastic acrylic resin, and the ratio between them is selected in consideration of these.
  • polyfunctional grafting agent those mentioned in the section of the innermost layer hard polymer (a) can be used.
  • the polyfunctional grafting agent used here is used to chemically bond the soft layer polymer (b) and the outermost hard layer polymer (c), and the proportion used during the innermost hard layer polymerization is impact resistance. From the viewpoint of the effect of imparting properties, 0.5 to 5% by mass is preferable.
  • polyfunctional crosslinking agent generally known crosslinking agents such as divinyl compounds, diallyl compounds, diacrylic compounds, dimethacrylic compounds and the like can be used, but polyethylene glycol diacrylate (molecular weight 200 to 600) is preferably used.
  • the polyfunctional cross-linking agent used here is used to generate a cross-linked structure during the polymerization of the soft layer (b) and to exhibit the effect of imparting impact resistance.
  • the polyfunctional crosslinking agent is not an essential component because the crosslinked structure of the soft layer (b) is generated to some extent. Is preferably 0.01 to 5% by weight from the viewpoint of imparting impact resistance.
  • the outermost hard layer polymer (c) constituting the multilayer structure acrylic granular composite is 80 to 99 mass% of methyl methacrylate in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). % And a monomer mixture comprising 1 to 20% by mass of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is preferred.
  • the acrylic alkylate those described above are used, but methyl acrylate and ethyl acrylate are preferably used.
  • the proportion of the alkyl acrylate unit in the outermost hard layer (c) is preferably 1 to 20% by mass.
  • an alkyl mercaptan or the like can be used as a chain transfer agent to adjust the molecular weight for the purpose of improving compatibility with the acrylic resin.
  • the outermost hard layer with a gradient such that the molecular weight gradually decreases from the inside toward the outside in order to improve the balance between elongation and impact resistance.
  • the monomer mixture for forming the outermost hard layer is divided into two or more, and the molecular weight is increased from the inside by a method of sequentially increasing the amount of chain transfer agent added each time. It is possible to make it smaller toward the outside.
  • the molecular weight formed at this time can also be examined by polymerizing the monomer mixture used each time under the same conditions, and measuring the molecular weight of the obtained polymer.
  • the particle diameter of the acrylic granular composite that is a multilayer structure polymer is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, and more preferably 20 nm or more and 500 nm or less. In particular, the thickness is most preferably from 50 nm to 400 nm.
  • the mass ratio of the core and the shell is not particularly limited, but when the total multilayer structure polymer is 100 parts by mass, the core layer is 50 parts by mass.
  • the content is preferably 90 parts by mass or less, and more preferably 60 parts by mass or more and 80 parts by mass or less.
  • Examples of such commercially available multilayered acrylic granular composites include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kane Ace” manufactured by Kaneka Chemical Co., Ltd., “Paralloid” manufactured by Kureha Chemical Co., Ltd., Rohm and Haas “Acryloid” manufactured by KK, “Staffyroid” manufactured by Gantz Kasei Kogyo Co., Ltd., “Parapet SA” manufactured by Kuraray Co., Ltd., and the like can be used alone or in combination of two or more.
  • acrylic particles (c-1) which are graft copolymers suitably used as the acrylic particles include an unsaturated carboxylic acid ester monomer, an unsaturated carboxylic acid in the presence of a rubbery polymer.
  • examples thereof include a graft copolymer obtained by copolymerizing a monomer mixture comprising a monomer, an aromatic vinyl monomer, and, if necessary, other vinyl monomers copolymerizable therewith.
  • the rubbery polymer used for the acrylic particles as the graft copolymer but diene rubber, acrylic rubber, ethylene rubber, and the like can be used.
  • Specific examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer.
  • the refractive indexes of the acrylic resin and the acrylic particles are close to each other because the transparency of the base film can be obtained.
  • the refractive index difference between the acrylic particles and the acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.
  • the difference in refractive index referred to here is a solvent-soluble portion obtained by sufficiently dissolving an acrylic resin-containing film under a suitable condition in a solvent in which the acrylic resin is soluble to form a cloudy solution. And the soluble part (acrylic resin) and the insoluble part (acrylic particles) are purified respectively, and the difference in the measured refractive index (23 ° C., measurement wavelength: 550 nm) is shown.
  • the method of blending acrylic particles with acrylic resin is not particularly limited, and after blending acrylic resin and other optional components in advance, usually at 200 to 350 ° C., a single or twin screw extruder while adding acrylic particles Thus, a method of uniformly melting and kneading is preferably used.
  • acrylic particles can also be used.
  • metabrene W-341 (manufactured by Mitsubishi Rayon Co., Ltd.)
  • Chemisnow MR-2G (C3)
  • MS-300X (manufactured by Soken Chemical Co., Ltd.) and the like can be mentioned.
  • the acrylic particles preferably contain 0.5 to 45% by mass of acrylic particles based on the total mass of the cellulose ester resin and the acrylic resin.
  • a film made of cellulose ester resin and acrylic resin is preferably a film having a tension softening point of 105 to 145 ° C. and not causing ductile fracture.
  • 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.
  • the tension softening point temperature for example, using a Tensilon tester (ORIENTEC, RTC-1225A), an acrylic resin-containing film is cut out at 120 mm (length) ⁇ 10 mm (width), and 10N The temperature can be raised at a rate of 30 ° C./min while pulling with tension, and the temperature at 9 N is measured three times, and the average value can be obtained.
  • ORIENTEC Tensilon tester
  • RTC-1225A Tensilon tester
  • the film made of cellulose ester resin and acrylic resin 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 film composed of a cellulose ester resin and an acrylic resin preferably has a breaking elongation of 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 film made of cellulose ester resin and acrylic resin is preferably 20 ⁇ m or more.
  • the upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 ⁇ m from the viewpoint of applicability, foaming, solvent drying, and the like.
  • the thickness of the film can be appropriately selected depending on the application.
  • the film comprising a cellulose ester resin and an acrylic resin preferably contains an acrylic resin and a cellulose ester resin in a mass ratio of 95: 5 to 30:70 from the viewpoint of both workability and heat resistance.
  • the acyl group has a total substitution degree (T) of 2.00 to 3.00, an acetyl group substitution degree (ac) of 0 to 1.89, and an acyl group other than the acetyl group has 3 to 7 carbon atoms, and the weight
  • the average molecular weight (Mw) is preferably 75,000 to 280000.
  • the total mass of the acrylic resin and the cellulose ester resin is 55 to 100% by mass, preferably 60 to 99% by mass of the acrylic resin-containing film.
  • the film made of a cellulose ester resin and an acrylic resin may contain other acrylic resins.
  • a cellulose ester film or a film made of a cellulose ester resin and an acrylic resin may be produced by a solution casting method or a melt casting method, but preferably at least stretched in the width direction. In particular, it is preferable that the film is stretched by 1.01 to 1.5 times in the width direction when the amount of residual solution after peeling is 3 to 40% by mass in the solution casting step.
  • the draw ratio at this time is particularly preferably 1.03 to 1.45.
  • the length of the base film is preferably 100 m to 5000 m and the width is preferably 1.2 m or more, more preferably 1.4 to 4 m.
  • the cellulose ester 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
  • carboxylic acid esters examples include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.
  • 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.
  • 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.
  • Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these.
  • triethylene glycol 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.
  • an alicyclic monocarboxylic acid or an aromatic monocarboxylic acid in terms of improving moisture permeability and retention.
  • preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a straight-chain or side-chain fatty acid 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 When acetic acid is contained, 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 acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples 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.
  • 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.
  • all 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 base 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.
  • polymer ultraviolet absorbers or ultraviolet rays described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039.
  • Absorbable polymers are also preferably used.
  • PUVA-30M manufactured by Otsuka Chemical Co., Ltd.
  • PUVA-30M manufactured by Otsuka Chemical Co., Ltd.
  • particle Internal haze, for example, by adding particles with a refractive index different from that of the base film to the base film, and controlling the addition amount and particle size of the particles, generating haze due to internal scattering, and adjusting this Can be achieved.
  • Particles are classified into inorganic particles and organic particles.
  • the inorganic particles are not particularly limited, and examples thereof include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate.
  • the organic particles are not particularly limited.
  • fluorinated acrylic resin powder, polystyrene resin powder, polymethacrylic acid methyl acrylate resin powder, silicone resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin examples thereof include powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluoroethylene resin powder.
  • inorganic particles and organic particles may be used in combination of two or more different types and average particle diameters, and those obtained by treating the surface of the particles with an organic substance are also preferably used.
  • Particularly preferred inorganic particles are silicon dioxide among these.
  • silicon dioxide include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.), Seahoster KE-P10, Seahoster KE-P30, Commercial products with trade names such as Seahoster KE-P50 (above, made by Nippon Shokubai Co., Ltd.), Silo Hovic 100 (made by Fuji Silysia), Nip Seal E220A (made by Nippon Silica Kogyo), Admafine SO (made by Admatechs), etc. Can be preferably used.
  • the shape of the particles can be used without particular limitation such as indefinite shape, needle shape, flat shape, spherical shape, etc. However, the use of spherical particles is preferable because it is easy to adjust the haze.
  • Fluorine-containing acrylic resin particles are particularly suitable as the organic particles.
  • Fluorine-containing acrylic resin particles are, for example, particles formed from a fluorine-containing acrylic ester or methacrylic ester monomer or polymer.
  • fluorine-containing acrylic acid ester or methacrylic acid ester include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acryl
  • the vinyl monomer copolymerizable with fluorine-containing (meth) acrylic acid is not particularly limited as long as it has a vinyl group.
  • alkyl methacrylates such as methyl methacrylate and butyl methacrylate, and methyl acrylate.
  • Alkyl acrylates such as ethyl acrylate, and styrenes such as styrene and ⁇ -methylstyrene. These may be used alone or in combination.
  • the crosslinking agent used in the polymerization reaction is not particularly limited, but those having two or more unsaturated groups are preferably used.
  • bifunctional dimethacrylates such as ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate are used.
  • the polymerization reaction for producing the fluorine-containing polymethyl methacrylate particles may be either random copolymerization or block copolymerization. Specifically, for example, the method described in JP-A No. 2000-169658 can also be mentioned.
  • fluorine-containing acrylic resin particles may be used alone or in combination of two or more. Moreover, the state of these fluorine-containing acrylic resin particles may be added in any state such as powder or emulsion.
  • fluorine-containing crosslinked particles described in paragraphs 0028 to 0055 of JP-A-2004-83707 may be used.
  • polystyrene particles examples include commercially available products such as those manufactured by Soken Kagaku; SX-130H, SX-200H, SX-350H), Sekisui Plastics, SBX series (SBX-6, SBX-8).
  • melamine-based particles examples include a product made by Nippon Shokubai: benzoguanamine / melamine / formaldehyde condensate (trade name: eposter, grade; M30, product name: eposter GP, grade: H40 to H110), and made by Nippon Shokubai: melamine / formaldehyde condensation.
  • Commercial products such as products (trade name: eposter, grade; S12, S6, S, SC4) can be mentioned.
  • core-shell type spherical composite cured melamine resin particles in which the core is made of melamine resin and the shell is filled with silica are also exemplified. Specifically, it can be produced by the method described in JP-A No. 2006-171033, and commercially available products such as melamine resin / silica composite particles (trade name: Opto Beads) manufactured by Nissan Chemical Industries, Ltd. can be mentioned.
  • poly ((meth) acrylate) particles and cross-linked poly ((meth) acrylate) particles include: Sokenken; MX150, MX300, Nippon Shokubai; Eposta MA, Grade; MA1002, MA1004, MA1006, MA1010, Eposter MX (Emulsion), grade: MX020W, MX030W, MX050W, MX100W, manufactured by Sekisui Plastics: MBX series (MBX-8, MBX12) and the like.
  • crosslinked poly (acryl-styrene) particles include commercially available products such as FS-201 and MG-351 manufactured by Nippon Paint.
  • benzoguanamine-based particles include a product manufactured by Nippon Shokubai Co., Ltd .: benzoguanamine / formaldehyde condensate (trade name: eposter, grade; L15, M05, MS, SC25).
  • the average particle size of the particles added to the base film is preferably 0.3 to 1 ⁇ m, and more preferably 0.4 to 0.7 ⁇ m.
  • the average particle size can be determined by visual observation from an image photograph of secondary electron emission obtained by scanning electron microscope (SEM) or the like of 500 particles or by image processing, or by dynamic light scattering, static It can be measured by a particle size distribution meter using an automatic light scattering method or the like.
  • SEM scanning electron microscope
  • the average particle diameter here refers to the number average particle diameter.
  • an average particle diameter means the average particle diameter of an aggregate, when particle
  • a particle when not spherical, it means the diameter of a circle corresponding to the projected area.
  • 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 a solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes.
  • the refractive index of the solvent can be measured by measuring with an Abbe refractometer.
  • the refractive index difference between the resin used for the base film and the particles is preferably 0.02 or more and 0.20 or less in order to increase the internal haze using the light scattering effect.
  • a more preferable range of the refractive index difference is 0.05 or more and 0.15 or less.
  • the content of the inorganic or organic particles is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin for producing the base film, and more preferably 5 parts by mass to 25 parts by mass for obtaining the internal haze. Part.
  • the particles may be dispersed together with cellulose ester, other additives and an organic solvent when preparing a composition (dope) for producing a base film, or may be dispersed alone in a solution. .
  • the particles are preliminarily dispersed in an organic solvent and then finely dispersed with a disperser (high pressure disperser) having a high shearing force.
  • a dope preparation method it is preferable to disperse particles in a large amount of organic solvent, merge with a cellulose ester solution, and mix with an in-line mixer to form a dope.
  • an ultraviolet absorbent may be added to the particle dispersion to form an ultraviolet absorbent liquid.
  • the above-mentioned deterioration inhibitor and ultraviolet absorber may be added together with a solvent, cellulose ester, cellulose ester resin and acrylic resin, It may be added during or after solution preparation.
  • 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.
  • Cellulose ester film, and cellulose ester resin / acrylic resin film are produced by a solution casting method.
  • a step of preparing a dope by dissolving cellulose ester or cellulose ester resin / acrylic resin and an additive in a solvent, and belting the dope A step of casting on a metal support in the form of a drum or a drum, a step of drying the cast dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a finished film It is performed by a winding process.
  • the concentration of cellulose ester in the dope, and the concentration of cellulose ester resin / acrylic resin is preferably higher because the drying load after casting on a metal support can be reduced. The load increases, and the filtration accuracy deteriorates.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 ⁇ 4m.
  • the surface temperature of the metal support in the casting step is set to ⁇ 50 ° C. to below the temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.
  • a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably 5 to 30 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected at any time during or after 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 to make the residual solvent amount 1% by mass or less. Is 0.1% by mass or less, particularly preferably 0 to 0.01% by mass.
  • 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 transporting the web is employed.
  • the cellulose ester film and the cellulose ester resin / acrylic resin film are also preferably formed by a melt film forming method.
  • a melt film-forming method a composition containing a cellulose ester, a cellulose ester resin / acrylic resin, and an additive such as a plasticizer is heated and melted to a temperature showing fluidity, and then a melt containing a fluid cellulose ester. It means to cast.
  • 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.
  • melt extrusion method is excellent.
  • a plurality of raw materials used for melt extrusion are usually kneaded and pelletized in advance.
  • Pelletization may be performed by a known method. For example, dry cellulose ester, plasticizer, and other additives are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder, and formed into a strand from a die. It can be done by extrusion, water cooling or air cooling and cutting.
  • Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
  • a small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.
  • the extruder is preferably processed at as low a temperature as possible so that it can be pelletized so as to suppress the shearing force and prevent the resin from deteriorating (molecular weight reduction, coloring, gel formation, etc.).
  • a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
  • Film formation is performed using the pellets obtained as described above.
  • the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.
  • the melting temperature at the time of extrusion is about 200 to 300 ° C, filtered through a leaf disk type filter, etc. to remove foreign matter, and then formed into a film from the T die. And solidified on a cooling 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.
  • touch rolls disclosed in registered patent 3194904, registered patent 3422798, Japanese Patent Application Laid-Open No. 2002-36332, Japanese Patent Application Laid-Open No. 2002-36333, and 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.
  • the stretching method a known roll stretching machine or tenter can be preferably used.
  • the stretching temperature is usually preferably in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.
  • the 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.
  • ⁇ Hard coat layer> In the antireflection film according to the present invention, it is possible to provide a layer containing an actinic radiation curable resin as a hard coat layer between the base film and the low refractive index layer. This is preferable because the film is less likely to be scratched in the step of forming the polarizing plate described later.
  • the actinic radiation curable resin layer according to the present invention refers to a layer mainly composed of a resin that cures through a crosslinking reaction upon irradiation with actinic rays (also referred to as actinic energy rays) such as ultraviolet rays and electron beams.
  • actinic radiation curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams.
  • Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but the resin that is cured by ultraviolet irradiation is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable.
  • an ultraviolet curable urethane acrylate resin for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.
  • polyfunctional acrylate is preferable.
  • the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
  • the polyfunctional acrylate is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.
  • polyfunctional acrylate monomer examples include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate.
  • the hard coat layer contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
  • the cured resin layer thus obtained may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index.
  • silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated silicic acid Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate.
  • silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.
  • Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin. Powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, or the like can be added.
  • Preferred fine particles include crosslinked polystyrene particles (for example, SX-130H, SX-200H, SX-350H manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150 and MX300 manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles.
  • fluorine-containing acrylic resin fine particles include commercially available products such as FS-701 manufactured by Nippon Paint.
  • acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.
  • the average particle size of these fine particle powders is not particularly limited, but is preferably 0.01 to 5 ⁇ m, more preferably 0.1 to 5.0 ⁇ m, and even more preferably 0.1 to 4.0 ⁇ m. It is also preferable to contain two or more kinds of fine particles having different particle diameters. It is desirable that the proportion of the ultraviolet curable resin composition and fine particles is 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.
  • the average particle diameter of the fine particles can be measured by, for example, a laser diffraction particle size distribution measuring apparatus.
  • These hard coat layers are coated using a known method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, ink jet method, and the like. And can be formed by UV curing.
  • the coating amount is suitably 0.1 to 40 ⁇ m, preferably 0.5 to 30 ⁇ m, as the wet film thickness.
  • the dry film thickness is from 0.1 to 30 ⁇ m, preferably from 1 to 20 ⁇ m, particularly preferably from 6 to 15 ⁇ m.
  • any light source that generates ultraviolet rays can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm 2 , preferably 5 to 200 mJ / cm 2 .
  • irradiating active rays it is preferably performed while applying tension in the film transport direction, more preferably while applying tension in the width direction.
  • the tension to be applied is preferably 30 to 300 N / m.
  • the method for applying tension is not particularly limited, and tension may be applied in the conveying direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.
  • the hard coat layer of the present invention may contain a conductive agent in order to impart antistatic properties, and preferred conductive agents include metal oxide particles or ⁇ -conjugated conductive polymers.
  • preferred conductive agents include metal oxide particles or ⁇ -conjugated conductive polymers.
  • the ionic liquid mentioned later is also preferably used as a conductive compound.
  • the type of metal oxide 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 can be used. Further, these metal oxide particles may be doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta.
  • At least one metal oxide selected from antimony oxide, tin oxide, zinc oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), phosphorus-containing tin oxide (PTO), and zinc antimonate. It is preferable to use physical particles as the main component.
  • PTO phosphorus-containing tin oxide
  • zinc antimonate particles it is preferable to contain either phosphorus-containing tin oxide (PTO) or zinc antimonate particles.
  • the average particle diameter of the primary particles of these metal oxide particles is in the range of 10 nm to 200 nm, more preferably 20 to 150 nm, and particularly preferably 30 to 100 nm.
  • the average particle diameter of the metal oxide particles can be measured from an electron micrograph using a scanning electron microscope (SEM) or the like. Further, it may be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method.
  • SEM scanning electron microscope
  • the shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.
  • the metal oxide particles may be surface treated with an organic compound.
  • an organic compound By modifying the surface of the metal oxide 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. .
  • the surface modification amount with a preferable organic compound is 0.1 to 5% by mass, more preferably 0.5 to 3% by mass with respect to the metal oxide particles.
  • organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more surface treatments may be combined.
  • the metal oxide particles are supplied to a coating liquid for forming a hard coat 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.
  • dispersion solvent examples 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).
  • 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
  • Tetrahydrofuran ether alcohols (e.g., 1-methoxy-2-propanol)
  • propylene glycol monomethyl ether propylene glycol monomethyl ether
  • the metal oxide particles can be dispersed in the medium using a disperser.
  • a 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 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.
  • the ⁇ -conjugated conductive polymer used in the present invention can be any organic polymer having a main chain composed of a ⁇ -conjugated system.
  • examples thereof include polythiophenes, polypyrroles, polyanilines, polyphenylenes, polyacetylenes, polyphenylene vinylenes, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of ease of polymerization and stability, polythiophenes, polypyrroles, and polyanilines are preferred.
  • the ⁇ -conjugated conductive polymer can provide sufficient conductivity and solubility in a binder resin even if it is not substituted, but in order to further improve conductivity and solubility, an alkyl group, a carboxy group, a sulfo group, an alkoxy group.
  • a functional group such as a group, a hydroxy group, or a cyano group may be introduced.
  • ⁇ -conjugated conductive polymers include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3 -Cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythio) Phen), poly (3-octyloxythi
  • a dopant component may be added to these ⁇ -conjugated conductive polymers.
  • the dopant component include low molecular weight dopants such as halogens, Lewis acids, proton acids, transition metal halides, and polymers such as polyanions.
  • a polyanion is a polymer having an anionic group that functions as a dopant for a ⁇ -conjugated conductive polymer, and is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted Substituted polyamides, substituted or unsubstituted polyesters, and copolymers thereof, comprising a structural unit having an anionic group and a structural unit having no anionic group.
  • Polyalkylene is a polymer whose main chain is composed of repeating methylene, and examples thereof include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, polyacrylonitrile, polyacrylate, polystyrene, and the like.
  • Polyalkenylene is a polymer composed of structural units containing one or more unsaturated bonds in the main chain.
  • propenylene 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropene Nylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2-butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-phenyl-1-butenylene, 2- Butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene, -Methyl-2-
  • polyimides examples include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-tetracarboxydiphenyl ether dianhydride, 2,2'-[4 , 4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride and the like, and a polyimide comprising diamine such as oxydiamine, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
  • diamine such as oxydiamine, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
  • Polyamide includes polyamide 6, polyamide 6,6, polyamide 6,10 and the like.
  • polyester examples include polyethylene terephthalate and polybutylene terephthalate.
  • the anion group of the polyanion may be a functional group that can undergo chemical oxidation doping to the ⁇ -conjugated conductive polymer, but from the viewpoint of ease of production and stability, a monosubstituted sulfate group and a monosubstituted phosphate ester Group, phosphoric acid group, carboxy group, sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the ⁇ -conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.
  • polyanion examples include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene.
  • These homopolymers may be used, or two or more types of copolymers may be used.
  • polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polyacrylic acid butyl sulfonic acid are preferable.
  • These polyanions have high compatibility with the binder resin, and can further increase the conductivity of the obtained conductive layer.
  • the following donor or acceptor dopants can be used.
  • Donor dopants include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, quaternary compounds such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium and dimethyldiethylammonium. An amine compound etc. are mentioned.
  • acceptor dopant examples include halogen compounds such as Cl 2 , Br 2 , I 2 , ICl, IBr, and IF, Lewis acids such as PF 5 , AsF 5 , SbF 5 , BF 5 , BCl 5 , BBr 5 , and SO 3 , Tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone, tetracyanoquinodimethane, tetracyanoazanaphthalene and other organic cyano compounds, proton acids, organometallic compounds, fullerenes, hydrogenated fullerenes, hydroxylated fullerenes, Carboxy oxide fullerene, sulfonated fullerene and the like can be used.
  • halogen compounds such as Cl 2 , Br 2 , I 2 , ICl, IBr, and IF
  • Lewis acids such as PF 5 , AsF 5
  • Examples of proton acids include inorganic acids and organic acids.
  • Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, perchloric acid and the like.
  • organic carboxylic acid, organic sulfonic acid, etc. are mentioned as an organic acid.
  • organic carboxylic acid aliphatic, aromatic, cycloaliphatic or the like containing one or more carboxy groups
  • organic sulfonic acid aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups or a polymer containing sulfo groups can be used.
  • Examples of those containing one sulfo group include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, colistin methanesulfone Acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 3-aminopropanesulf
  • Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid.
  • Xylene disulfonic acid chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3 Benzenedisulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1 Acetamide-8-hydroxy-3,6-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulf
  • an ionic liquid may be contained as a conductive agent.
  • a compound consisting of an organic cation and an anion, and a compound having a melting point of 25 ° C. or less is preferable.
  • examples of the organic cation include imidazolium, pyridinium, piperidinium, quaternary ammonium, and phosphonium.
  • the conductive agent is preferably 0.01 part by weight to 300 parts by weight, more preferably 0.1 part by weight to 100 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin used as the binder.
  • the coating composition for forming the hard coat layer may contain a solvent.
  • the organic solvent contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), These may be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or may be used by mixing them.
  • organic solvent propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is preferable.
  • the content of the organic solvent is preferably 5 to 80% by mass in the coating composition.
  • the hard coat layer has a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 ⁇ m, or a fine layer or the like is added to adjust Ra to 0.1 to 1 ⁇ m.
  • An antiglare hard coat layer may also be used.
  • the center line average roughness (Ra) is preferably measured by an optical interference type surface roughness measuring instrument, and can be measured, for example, using a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.
  • an uneven shape may be formed on the hard coat surface by embossing with a roll or a master.
  • the hard coat layer contains the following silicone surfactant or polyoxyether compound described in the low refractive index layer. These enhance the applicability. Further, these components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.
  • polyoxyether compound examples include polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ether compounds such as polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Polyoxyalkyl phenyl ether compounds such as ethylene octyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyldodecyl ether and the like can be mentioned.
  • polyoxyethylene alkyl ether Commercially available products of polyoxyethylene alkyl ether include Emulgen 1108, Emulgen 1118S-70 (above, manufactured by Kao Corporation), and commercially available products of polyoxyethylene lauryl ether include Emulgen 103, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 147, Emulgen 150, Emulgen 130K (above, manufactured by Kao Corporation), and polyoxyethylene cetyl ether are commercially available products of Emulgen 210P, Emulgen 220 (above, Kao Corporation) As commercially available products of polyoxyethylene stearyl ether, Emulgen 220, Emulgen 306P (above, manufactured by Kao Corporation), and commercially available products of polyoxyalkylene alkyl ether include Examples of commercially available products of Rugen LS-106, Emulgen LS-110, Emulgen LS-
  • polyoxyethylene oleyl ether compounds are preferable, and are compounds represented by the following general formula (3).
  • n 2 to 40.
  • the average number (n) of ethylene oxide added to the oleyl moiety is 2 to 40, preferably 2 to 10.
  • the compound of the said General formula (3) is obtained by making ethylene oxide and oleyl alcohol react.
  • Emulgen 404 [polyoxyethylene (4) oleyl ether], Emulgen 408 [polyoxyethylene (8) oleyl ether], Emulgen 409P [polyoxyethylene (9) oleyl ether], Emulgen 420 [polyoxy Ethylene (13) oleyl ether], Emulgen 430 [polyoxyethylene (30) oleyl ether] (above, manufactured by Kao Corporation), NOFBLEEAO-9905 (polyoxyethylene (5) oleyl ether) manufactured by NOF Corporation.
  • () represents the number of n.
  • Polyoxyether compounds may be used alone or in combination of two or more.
  • the preferable content of the polyoxyether compound and the silicone surfactant in the hard coat layer is preferably 0.1 to 8.0% by mass, more preferably 0.2 to 4.0% by mass in terms of the total content of both. %, It is stably present in the hard coat layer by adding in this range.
  • a fluorine surfactant an acrylic copolymer, an acetylene glycol compound or a nonionic surfactant, a radical polymerizable nonionic surfactant, or the like may be used in combination.
  • Nonionic surfactants include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyalkyl ester compounds such as polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, etc. Sorbitan ester compounds, and the like.
  • acetylene glycol compounds examples include Surfinol 104E, Surfinol 104PA, Surfinol 420, Surfinol 440, Dinol 604 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
  • radical polymerizable nonionic surfactant examples include polyoxyalkylene alkylphenyl ether (meth) acrylates such as RMA-564, RMA-568, and RMA-1114 (above, trade name, manufactured by Nippon Emulsifier Co., Ltd.). Examples thereof include system polymerizable surfactants.
  • the hard coat layer may contain a polyfunctional thiol compound as a curing aid, such as 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1 , 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like.
  • a polyfunctional thiol compound such as 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1 , 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like.
  • a polyfunctional thiol compound such as 1,4-bis (3-mercaptobutyryloxy)
  • the polyfunctional thiol compound is preferably added in the range of 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, with respect to 100 parts by mass of the ultraviolet curable resin. By adding in this range, it acts suitably as a curing aid, and also exists stably in the hard coat layer.
  • the hard coat layer may have a multilayer structure of two or more layers.
  • One of the layers may be, for example, a so-called clear hard coat layer that does not contain metal oxide particles, and a color tone adjusting agent (dye or pigment, etc.) having a color tone adjusting function as a color correction filter for various display elements. ), Or may contain an electromagnetic wave blocking agent or an infrared absorber so as to have each function.
  • a back coat layer may be provided on the surface of the base film opposite to the side on which the hard coat layer and the low refractive index layer are provided.
  • the back coat layer is provided in order to correct curling caused by providing a hard coat layer or a low refractive index layer. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward.
  • the backcoat layer is preferably applied also as an antiblocking layer, and in this case, particles of an inorganic compound or an organic compound are added to the backcoat layer coating composition in order to provide an antiblocking function. Is preferred.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.
  • These particles include, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.), Seahoster KE-P10, KE-P30, KE- P50, KE-P100, KE-P150, KE-P250 (above, manufactured by Nippon Shokubai Co., Ltd.) are commercially available and can be used.
  • organic compounds examples include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (manufactured by GE Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
  • Aerosil 200V, Aerosil R972V, Seahoster KE-P30, KE-P50, and KE-P100 are particularly preferred because they have a large anti-blocking effect while keeping haze low.
  • the particles contained in the backcoat layer are 0.1 to 50% by mass, preferably 0.1 to 10% by mass with respect to the binder.
  • the increase in haze is preferably 1.5% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less.
  • the coating composition used for coating the backcoat layer contains a solvent.
  • the solvent include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, chloroform, water, methanol, ethanol, Examples include n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or hydrocarbons (toluene, xylene). .
  • Examples of the resin used as the binder for the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer.
  • Vinyl-based polymers or copolymers nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetylcellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, Polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile
  • acrylic resin Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M -4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR- 80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (made by Mitsubishi Rayon Co., Ltd.) And
  • a resin used as a binder it is preferable to use a blend of cellulose ester such as cellulose diacetate and cellulose acetate prothionate and an acrylic resin, and the refractive index of the particles and the binder using particles made of an acrylic resin. By setting the difference to 0 to less than 0.02, a highly transparent back coat layer can be obtained.
  • the dynamic coefficient of friction of the backcoat layer is preferably 0.9 or less, particularly preferably 0.1 to 0.9.
  • the above-described coating composition for forming the backcoat layer is formed using a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or spray coating, inkjet coating, or the like. It is preferable to apply a wet film thickness of 1 to 100 ⁇ m on the surface of the transparent resin film, but it is particularly preferable that the thickness is 5 to 30 ⁇ m.
  • the back coat layer is formed by heating and drying after coating and curing as necessary.
  • the content described in the low refractive index layer can be used for the curing treatment.
  • the back coat layer can be applied in two or more steps. Further, the backcoat layer may also serve as an easy adhesion layer for improving the adhesion with the polarizer.
  • the antistatic layer is provided between the film base and the hard coat layer, or between the hard coat layer and the low refractive index layer, thereby imparting antistatic properties to the antireflection film.
  • the antistatic layer is a layer containing a conductive compound, and is preferably a layer having a surface specific resistance adjusted to 10 13 ⁇ / cm 2 (25 ° C., 55% RH) or less, More preferably, it is 10 10 ⁇ / cm 2 (25 ° C., 55% RH) or less, and particularly preferably 10 9 ⁇ / cm 2 (25 ° C., 55% RH) or less.
  • the measurement of the surface specific resistance is a value measured using a resistivity meter after conditioning the sample for 24 hours under the conditions of 25 ° C. and 55% RH.
  • a resistivity meter device for example, Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation can be used.
  • the measurement of the surface specific resistance value is substantially the same as the surface specific resistance value of the outermost surface layer on the side where the antistatic layer is provided. It is defined as the surface specific resistance value.
  • the aforementioned metal oxide fine particles, ⁇ -conjugated conductive polymer, ionic liquid, and the like are preferable compounds.
  • the conductive compound is preferably 0.01 part by weight to 300 parts by weight, and more preferably 0.1 part by weight to 100 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin used as the binder.
  • a curable resin is preferable, and among them, an actinic radiation curable resin is preferable from the viewpoint of excellent film-forming properties and physical characteristics of the coating film and adhesion to the laminated film.
  • an actinic radiation curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and actinic radiation curable resin layer is formed by curing by irradiating actinic radiation such as ultraviolet rays or electron beams.
  • actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin is particularly preferable.
  • the curable resin includes a thermosetting resin.
  • thermosetting resin include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, thermosetting polyamide imides, and the like.
  • the unsaturated polyester resin for example, orthophthalic acid resin, isophthalic acid resin, terephthalic acid resin, bisphenol resin, propylene glycol-maleic acid resin, dicyclopentadiene or derivatives thereof are introduced into the unsaturated polyester composition.
  • Low-shrinkage resin with low styrene volatile resin and thermoplastic resin polyvinyl acetate resin, styrene / butadiene copolymer, polystyrene, saturated polyester, etc.
  • thermoplastic resin polyvinyl acetate resin, styrene / butadiene copolymer, polystyrene, saturated polyester, etc.
  • Reactive types such as bromating unsaturated polyester directly with Br 2 or copolymerizing heptic acid or dibromoneopentyl glycol, halides such as chlorinated paraffin, tetrabromobisphenol, antimony trioxide, phosphorus compounds
  • Additive-type flame retardant resin that uses sesame or aluminum hydroxide as an additive, toughness resin that is hybridized with polyurethane or silicone, or toughened with IPN (high strength, high elastic modulus, high elongation), etc. is there.
  • epoxy resin examples include glycidyl ether type epoxy resins including bisphenol A type, novolak phenol type, bisphenol F type, brominated bisphenol A type, glycidyl amine type, glycidyl ester type, cyclic aliphatic type, and heterocyclic epoxy type.
  • the special epoxy resin containing can be mentioned.
  • vinyl ester resins include those obtained by dissolving an oligomer obtained by a ring-opening addition reaction between an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid in a monomer such as styrene. There are also special types such as vinyl monomers having vinyl groups at the molecular ends and side chains.
  • vinyl ester resins of glycidyl ether type epoxy resins include bisphenol type, novolak type, brominated bisphenol type, etc.
  • special vinyl ester resins include vinyl ester urethane type, isocyanuric acid vinyl type, side chain vinyl ester type, etc.
  • the phenol resin is obtained by polycondensation using phenols and formaldehydes as raw materials, and there are a resol type and a novolac type.
  • thermosetting polyimide resins include maleic acid-based polyimides such as polymaleimide amine, polyamino bismaleimide, bismaleimide, diallyl bisphenol-A resin, bismaleimide / triazine resin, nadic acid-modified polyimide, and acetylene-terminated polyimide. There is.
  • the antistatic layer may contain the inorganic particles or organic particles.
  • the average particle size of these particles is preferably 0.01 to 5 ⁇ m, more preferably 0.1 to 5.0 ⁇ m, and particularly preferably 0.1 to 4.0 ⁇ m.
  • the particles are desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the curable resin.
  • the antistatic layer has a vinyl group and a carboxyl group in the side chain of the polyurethane resin as a curing aid, has a weight average molecular weight of 10,000 to 30,000, and a double bond equivalent of 500 to 2,000.
  • Examples of other functional thiol compounds include 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.
  • Showa Denko Co., Ltd. make, brand name Karenz MT series, etc. are mentioned.
  • a fluorine-acrylic copolymer resin may be contained.
  • the fluorine-acrylic copolymer resin is a copolymer resin comprising a fluorine monomer and an acrylic monomer, and a block copolymer comprising a fluorine monomer segment and an acrylic monomer segment is particularly preferred.
  • the molecular weight of the fluorine-acrylic copolymer resin is preferably 5,000 to 1,000,000 in terms of number average molecular weight, preferably 10,000 to 300,000, more preferably 10,000 to 100,000.
  • polymeric peroxide was used as a polymerization initiator. It can be produced by a known production process (for example, Japanese Patent Publication No. 5-41668 and Japanese Patent Publication No. 5-59942).
  • Polymeric peroxide is a compound having two or more peroxy bonds in one molecule.
  • the polymer peroxide one or more of various polymer peroxides described in JP-B-5-59942 can be used.
  • fluorine-acrylic copolymer resins examples include Nippon Oil & Fats Co., Ltd., Modiper F-200, Modiper F-600, and Modiper F-2020.
  • the antistatic layer may contain the silicone surfactant described in the low refractive index layer, the fluorine compound, and the polyoxyether compound, or the nonionic surfactant described in the hard coat layer. It is preferable in that the productivity can be improved by giving high-speed coating suitability while improving the surface uniformity.
  • the antistatic layer may contain a color tone adjusting agent (dye or pigment, etc.) having a color tone adjusting function as a color correction filter for various display elements, an electromagnetic wave blocking agent, an infrared absorber or the like.
  • a color tone adjusting agent die or pigment, etc.
  • an electromagnetic wave blocking agent an infrared absorber or the like.
  • the antistatic layer preferably contains a cellulose ester resin or an acrylic resin in order to maintain easy adhesion with the overcoat layer.
  • cellulose ester resin examples include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate.
  • acrylic resins examples include Acrypet MD, VH, MF, V (Mitsubishi Rayon Co., Ltd.), Hyperl M4003, M-4005, M-4006, M-4202, M-5000, M -5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR- 79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (manufactured by Mitsubishi Rayon Co., Ltd.)
  • the following solvents are preferably used.
  • hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents can be appropriately mixed and used, but are not particularly limited thereto.
  • hydrocarbons examples include benzene, toluene, xylene, hexane, cyclohexane and the like
  • examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert- Examples include butanol, pentanol, 2-methyl-2-butanol, and cyclohexanol.
  • ketones examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • esters include methyl formate, ethyl formate, Examples thereof include methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, and methyl lactate.
  • glycol ethers (C1 to C4) include methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl.
  • propylene glycol monoethyl ether As propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, or propylene glycol mono (C1-C4) alkyl ether esters, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, and other solvents include methylene chloride and N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.
  • a wet film thickness of 0 is applied to one surface of the base film using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. .1 to 100 ⁇ m, preferably 0.5 to 30 ⁇ m, and the dry film thickness is an average film thickness of 0.1 to 30 ⁇ m, preferably 1 to 20 ⁇ m. Formed.
  • the curing process is performed by heat treatment or UV curing treatment.
  • any light source that generates ultraviolet rays can be used without limitation.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm 2 , preferably 5 to 200 mJ / cm 2 .
  • tensile_strength in the conveyance direction of a film More preferably, it is performing applying tension
  • the tension to be applied is preferably 30 to 500 N / m.
  • the method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.
  • the antistatic layer may be a single layer or a multilayer structure of two or more layers. ⁇ Coating and curing method of composition for antireflection layer>
  • the low refractive index layer which is the antireflection layer of the present invention, is a composition that forms a low refractive index layer using a known method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, and ink jet method. Is applied on each layer so as to have the above-described layer structure, and after coating, it is dried by heating and cured.
  • each layer Before applying the composition for an antireflection layer of the present invention, it is also preferable to subject each layer to a surface treatment such as corona discharge or plasma discharge.
  • the coating amount is suitably 0.05 to 100 ⁇ m, preferably 0.1 to 50 ⁇ m, as the wet film thickness. Moreover, the solid content concentration of the composition is adjusted so that the dry film thickness becomes the above-mentioned film thickness.
  • the exposure amount of irradiation light is preferably 10 mJ / cm 2 to 10 J / cm 2 , and more preferably 100 mJ / cm 2 to 500 mJ / cm 2 .
  • the wavelength range of the irradiated light is not particularly limited, but light having a wavelength in the ultraviolet region is preferably used.
  • a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • thermosetting by heating can be used in combination, and the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, more preferably 80 to 150 ° C.
  • a step of performing heat treatment at a temperature of 50 to 160 ° C. after forming the low refractive index layer may be included.
  • the period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably a period of 3 days or more and less than 30 days, and if it is 160 ° C., a range of 10 minutes or more and 1 day or less is preferable. .
  • the substrate film is unwound in a roll form with a width of 1.4 to 4 m, applied, dried and cured, and then rolled. It is preferable to be wound around.
  • the antireflection film can be manufactured by a manufacturing method in which an antireflection layer is laminated and then wound in a roll shape, and heat treatment is performed at a temperature of 50 to 160 ° C. This is preferable from the viewpoint of efficiency and stability.
  • the heat treatment period may be appropriately determined depending on the set temperature. For example, if the temperature is 50 ° C., it is preferably 3 days or more, less than 30 days, if the temperature is 160 ° C., 10 minutes or more, 1 day The following ranges are preferred.
  • it is preferably set at a relatively low temperature so that the heat treatment effect on the outside of the winding, the center of the winding, and the core is not biased, and is preferably performed at a temperature of about 50 to 60 ° C. for about 7 days.
  • the winding core for winding the hard coat film and the antireflection film into a roll shape is not particularly limited as long as it is a cylindrical core, but is preferably a hollow plastic core, and the plastic material can withstand the heat treatment temperature.
  • a heat resistant plastic is preferable, and examples thereof include resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin.
  • thermosetting resin reinforced with a filler such as glass fiber is preferable.
  • the number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.
  • the refractive index of the low refractive index layer of the present invention is lower than that of the substrate film as the support, and is preferably in the range of 1.20 to 1.49 at 23 ° C. and wavelength of 550 nm, and is preferably in the range of 1.25 to 1.44. More preferably, the range of 1.30 to 1.38 is particularly preferable.
  • the film thickness of the low refractive index layer is preferably from 5 nm to 0.5 ⁇ m, more preferably from 10 nm to 0.3 ⁇ m, and even more preferably from 30 nm to 0.2 ⁇ m, from the characteristics as an optical interference layer.
  • 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 25 to 90 ⁇ m.
  • the polarizing plate can be produced by a general method.
  • the back surface side of the antireflective film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizer produced by immersing and stretching the treated antireflective film in an iodine solution. It is preferable to bond them together.
  • the antireflection 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, 20 to 70 nm, and Rt of 70 to 400 nm. It is preferable to use a retardation film.
  • 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 antireflection 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 antireflection film of the present invention is incorporated in the polarizing plate, and is a reflection type, transmission type, transflective liquid crystal display device or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS. It is preferably used in liquid crystal display devices of various driving systems such as a type and OCB type.
  • the antireflection film of the present invention is also preferably used in various image display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper.
  • Example 1 ⁇ Base film 1; Production of cellulose ester film 1>
  • Dope composition 1 The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. .
  • the silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester.
  • This dope was filtered using filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope composition 1.
  • Cellulose triacetate 100 parts by weight Trimethylolpropane tribenzoate 5 parts by weight Ethylphthalylethyl glycolate 5 parts by weight Fine particles of silicon oxide 0.2 parts by weight (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) Tinuvin 109 (manufactured by Ciba Japan Co., Ltd.) 1 part by mass Tinuvin 171 (manufactured by Ciba Japan Co., Ltd.) 1 part by mass Methylene chloride 300 parts by mass Ethanol 40 parts by mass Butanol 5 parts by mass Next, the obtained dope composition 1 was obtained. The web was formed by casting on a support having a temperature of 35 ° C.
  • the web after peeling is transported while being dried with 90 ° C drying air in a transport drying process using a plurality of rolls arranged on the top and bottom, and then grips both ends of the web with a tenter and then stretches in the width direction at a temperature of 130 ° C.
  • the film was stretched to 1.1 times the previous size.
  • After stretching with a tenter the web was dried with a drying air at a temperature of 135 ° C. in a transport drying process using a plurality of rolls arranged vertically.
  • the film After heat-treating for 15 minutes in an atmosphere with an atmosphere substitution rate of 15 (times / hour) in the drying process, the film was cooled to room temperature and wound up, with a width of 1.5 m, a film thickness of 80 ⁇ m, a length of 4000 m, and a refractive index of 1.49. A long cellulose ester film 1 was produced. Further, the film was wound by applying a knurling process with a width of 1 cm and an average height of 10 ⁇ m at both ends.
  • the draw ratio in the web conveyance direction immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.
  • the atmosphere substitution rate in the drying process is a unit time determined by the following equation when the atmosphere capacity of the drying process (heat treatment chamber) is V (m 3 ) and the fresh air flow rate is FA (m 3 / hr). This is the number of times the atmosphere in the heat treatment chamber is replaced with Fresh-air.
  • “Fresh-air” means that the air blown into the heat treatment chamber is not a wind that is recirculated and does not contain volatilized solvent or plasticizer, or means fresh air from which they are removed. Yes.
  • Atmosphere replacement rate FA / V (times / hour) ⁇ Preparation of antireflection film 1>
  • an antireflection film 1 was produced by the following procedure.
  • the refractive index of the low refractive index layer was measured by the following method.
  • the refractive index of the low refractive index layer was determined from the measurement result of the spectral reflectance of the spectrophotometer for the sample in which the low refractive index layer was coated on the hard coat film prepared below.
  • the spectrophotometer is a U-4000 model (manufactured by Hitachi, Ltd.). After the surface on the measurement side of the sample is roughened, it is light-absorbed with a black spray to prevent reflection of light on the back surface. In the atmosphere of 23 ° C. and 55% RH, the reflectance in the visible light region (400 to 700 nm) was measured under the condition of regular reflection at 5 degrees.
  • ⁇ Preparation of hard coat layer 1> The following hard coat layer composition 1 filtered through a polypropylene filter having a pore size of 0.4 ⁇ m is applied to the surface of the cellulose ester film 1 using a micro gravure coater, dried at a temperature of 80 ° C., and then subjected to an ultraviolet lamp.
  • the illuminance of the used irradiation part was 100 mW / cm 2
  • the irradiation amount was 0.2 J / cm 2
  • the coating layer was cured to form a hard coat layer having a dry film thickness of 10 ⁇ m.
  • the following back coat layer composition 1 was applied to the surface of the cellulose ester film 1 opposite to the surface on which the hard coat layer 1 was applied with an extrusion coater so as to have a wet film thickness of 14 ⁇ m. After drying, a back coat layer 1 was provided.
  • the pH of the reaction solution was 12.0.
  • 1125 g of pure water and 100 g of sodium sulfate having a concentration of 0.5% by mass were added to 500 g of the composite oxide fine particle dispersion having a solid concentration of 13% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35). .5% by mass) was dropped to pH 1.0, and dealumination was performed.
  • 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 anion exchange resin were repeated, and then a hollow silica 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 particles was 10 nm, the average particle size was 55 nm, MO X / SiO 2 (molar ratio) was 0.0019, and the refractive index was 1.24.
  • Example 2 An antireflection film 2 was produced in the same manner as in Example 1 except that the following low refractive index layer composition 2 was used as the low refractive index layer composition.
  • Example 1 An antireflection film 3 was produced in the same manner as in Example 1 except that the low refractive index layer composition of Example 1 was used as the low refractive index layer composition 3 below.
  • Example 3 Antireflection films 5 to 12 were produced in the same manner as in Example 1 except that the cationically polymerizable compound and the cationic polymerization initiator of the low refractive index layer composition 1 of Example 1 were changed to those shown in Table 2.
  • Reflectance measurement Using a spectrophotometer V-550 (manufactured by JASCO), the specular reflection spectral reflectance in the wavelength range of 380 to 780 nm was measured at an incident angle of 5 °. In the evaluation of the reflectance, the lowest reflectance in the wavelength region of 450 to 650 nm was used. In addition, after roughening the back surface of the measurement surface of the sample, light absorption treatment was performed with black spray to prevent reflection of light on the back surface, and reflectance measurement was performed.
  • the number of scratches is preferably 5 / cm width or less, more preferably 1 / cm width or less.
  • a Shinto Kagaku Co., Ltd. friction and wear tester (Tribo Station TYPE: 32, moving speed 4000 mm / min.) was used.
  • Adhesion test Using a super xenon weather meter (SX120, manufactured by Suga Test Instruments Co., Ltd.) on the surface of the antireflection film, the light quantity is 100 W / m 2 ; 300 to 400 nm, the black panel temperature is 50 ° C., the humidity is 65%, and the test time is 2000 hours.
  • the UV irradiation test was conducted under the conditions of Thereafter, the scratch resistance was evaluated by the above method, and in accordance with the following JIS K 5600-5-6, a cross-cut tape peeling test was performed in an atmosphere of 23 ° C. and 55% RH to evaluate adhesion.
  • the affected part is 5% or less ⁇ : The affected part exceeds 5%, but 30% or less ⁇ : The affected part exceeds 30%
  • the low refractive index layer comprises (A) hollow silica particles, (B) a cationically polymerizable compound of the general formula (1), and (C) a photocationic polymerization initiator. It can be seen that the antireflection film, which is a layer composed of the curable composition contained, is excellent in both reflectance and scratch resistance.
  • Example 4 Antireflective films 13-22 in the same manner as in Example 1 except that the hollow silica particles, the cationic polymerizable compound, and the cationic polymerization initiator of the low refractive index layer composition 1 of Example 1 were changed to those shown in Table 3. Was made.
  • the produced antireflection films 13 to 22 were evaluated in the same manner as in Example 1 together with the antireflection film 5 produced in Example 3. The evaluation results are shown in Table 3.
  • Example 5 Preparation of antireflection films 23 to 25>
  • the hard coat layer composition and the low refractive index layer composition were changed as shown in Table 4 to produce antireflection films 23 to 25.
  • Antistatic hard coat layer composition ANS1 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 (Ciba Japan Co., Ltd.) 10 parts by mass Silicone surfactant 3 parts by mass (Shin-Etsu Chemical Co., Ltd., trade name: KF-351A) Propylene glycol monomethyl ether 50 parts by weight Methanol 20 parts by weight Methyl e
  • the solvent was evaporated from the peeled acrylic resin web 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. At this time, the residual solvent amount 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.
  • a small amount of the polymer latex thus obtained was collected, and the flat particle size was determined by the absorbance method, which was 0.10 ⁇ m.
  • the remaining latex was poured into a 3% by mass sodium sulfate warm aqueous solution, salted out and coagulated, and then dried after repeated dehydration and washing to obtain acrylic particles having a three-layer structure.
  • MMA methyl methacrylate MA; methyl acrylate BA; n-butyl acrylate ALMA; allyl methacrylate PEGDA; polyethylene glycol diacrylate (molecular weight 200) n-OM; n-octyl mercaptan APS; ammonium persulfate (production of cellulose ester resin / acrylic resin film 1 containing acrylic particles) (Dope solution composition 3) Dianar BR80 (Mitsubishi Rayon Co., Ltd.) 70 parts by mass CAP482-20 30 parts by mass The above prepared acrylic particles 20 parts by mass Tinuvin 109 (Ciba Japan Co., Ltd.) 1 part by mass Tinuvin 171 (Ciba Japan Co., Ltd.) ) 1 part by mass Methylene chloride 300 parts by mass Ethanol 40 parts by mass Butanol 5 parts by mass The above composition was sufficiently dissolved while heating to prepare a dope solution.
  • cellulose ester C1 was synthesized by adjusting the addition amount of propionic acid and acetic acid to adjust the degree of acetyl group substitution and propionyl group substitution as follows. .
  • the degree of substitution of the obtained cellulose ester was calculated based on ASTM-D817-96.
  • the weight average molecular weight of the cellulose ester C1 was 130,000 as a result of measurement using the high performance liquid chromatography.
  • a cellulose ester film 2 was produced by melt casting with the following composition.
  • Cellulose ester film 2 composition Cellulose ester: C1 94 parts by mass Plasticizer: Glycerin tribenzoate 5 parts by mass Irganox 1010 (manufactured by Ciba Japan KK) 0.5 parts by mass Irgafos P-EPG (manufactured by Ciba Japan KK) 0.3 parts by mass HP- 136 (manufactured by Ciba Japan Co., Ltd.) 0.2 parts by mass
  • the above cellulose ester was dried under reduced pressure at 70 ° C. for 3 hours and cooled to room temperature, and then each additive was mixed.
  • the above mixture was formed into a film by a manufacturing apparatus using an elastic touch roll. In a nitrogen atmosphere, it was melted at 240 ° C., extruded from the casting die onto the first cooling roll, and molded by pressing the film between the first cooling roll and the touch roll. Further, silica particles (manufactured by Nippon Aerosil Co., Ltd.) were added as a slip agent from the hopper opening in the middle of the extruder so as to be 0.1 part by mass.
  • the heat bolt was adjusted so that the gap width of the casting die was 0.5 mm within 30 mm from the end in the width direction of the film and 1 mm at other locations.
  • 80 degreeC water was poured as cooling water in the inside.
  • the length L along the surface was set to 20 mm.
  • the temperature T of the melted portion immediately before being sandwiched between the first cooling roll and the touch roll is 1 mm upstream from the nip upstream end P2, and a thermometer (HA-200E manufactured by Anritsu Keiki Co., Ltd.) It was measured by. As a result of the measurement, the temperature T was 141 ° C.
  • the linear pressure of the touch roll against the first cooling roll was 14.7 N / cm.
  • the size of the winding core was 152 mm in inner diameter, 165 to 180 mm in outer diameter, and 1550 mm in length.
  • a prepreg resin obtained by impregnating glass fibers and carbon fibers with an epoxy resin was used as the core material for the core.
  • the surface of the core was coated with an epoxy conductive resin, the surface was polished, and the surface roughness Ra was finished to 0.3 ⁇ m.
  • the film thickness was 40 micrometers
  • the winding length was 3500 m
  • the cellulose-ester film 2 of refractive index 1.49 was produced.
  • the antireflection film 12 produced in Example 3 and the produced antireflection films 26 to 28 were evaluated by the method described in Example 1. Furthermore, each was cut into A4 size, the low refractive index layer was used as the surface, and it was stored for 700 hours in a high-temperature and high-humidity thermo at a temperature of 80 ° C. and a humidity of 90% RH to prepare a wet heat treatment sample. Next, the wet-heat-treated antireflection film was conditioned for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 55%, and pencil hardness was evaluated according to the following method.
  • Base film 1 cellulose ester film 1
  • Base film 2 Cellulose ester resin / acrylic resin film 1
  • Base film 3 Cellulose ester resin / acrylic resin film 2 containing acrylic particles
  • Base film 4 Cellulose ester film 2 (Pencil hardness)
  • the antireflection film was conditioned for 2 hours in an environment of 25 ° C. and 60% RH, and then a scratch test was performed in accordance with JIS K5600-5-4. Using a 1 kg weight, scratching with a pencil of each hardness was performed five times while changing the place, and the hardness until one scratch was found was measured.
  • the term “scratches” here refers to tearing of the coating film, scratches and dents. Higher values indicate higher hardness, preferably 3H or higher.
  • the substrate film is a cellulose ester film
  • even if it is a cellulose ester resin / acrylic resin film, an acrylic particle-containing cellulose ester resin / acrylic resin film, or a cellulose ester film 2 Similarly, it can be seen that the film exhibits excellent low reflectivity and scratch resistance, and also has good light resistance.
  • the base film is a film made of cellulose ester resin / acrylic resin rather than cellulose ester film, or a film composed of cellulose ester resin / acrylic resin and containing acrylic particles. It can be seen that the method is particularly excellent in pencil hardness.
  • Example 7 Using the antireflection films 1 to 12 prepared in Example 1 and Example 2, polarizing plates were prepared as follows, and these polarizing plates were incorporated into a liquid crystal display panel (image display device) to improve visibility. evaluated.
  • each of the antireflection films 1 to 12 produced in Examples 1 and 2 is a cellulose ester optical compensation film, Konica Minolta Tack KC8UCR5 (manufactured by Konica Minolta Opto), each with polarizing plate protection Polarizing plates 101 to 112 were respectively prepared as films.
  • 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.
  • 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 The optical compensation film and the antireflection film were immersed in a 2 mol / L sodium hydroxide solution at a temperature of 60 ° C. for 90 seconds, then washed with water and dried. A surface of each antireflection film provided with a low refractive index layer was previously protected with a peelable protective film (PET).
  • PET peelable protective film
  • 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.
  • 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 101 to 111.
  • the polarizing plate on the outermost surface of a commercially available liquid crystal display panel (VA type) was carefully peeled off, and the polarizing plates 101 to 111 having the same polarization direction were attached thereto.
  • the liquid crystal panels 201 to 211 thus obtained were placed on a desk 80 cm high from the floor, and a daylight direct tube fluorescent lamp (FLR40S • D / MX Matsushita Electric) was placed on the ceiling 3 meters high from the floor.
  • FLR40S • D / MX Matsushita Electric was placed on the ceiling 3 meters high from the floor.
  • Sangyo Co., Ltd. 40W ⁇ 2 were set as one set, and 10 sets were arranged at intervals of 1.5 m.
  • the fluorescent lamp when the evaluator is in front of the display surface of the liquid crystal display panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling 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 a fluorescent lamp was reflected so that the visibility of the screen (visibility) was divided into the following ranks and subjected to sensory evaluation.
  • A I don't care about the reflection of the nearest fluorescent lamp, and I can clearly read characters with a font size of 8 or less.
  • B The reflection of a nearby fluorescent lamp is a little anxious, but I don't care about the distance. Can manage to read characters with a font size of 8 or less
  • C It is difficult to read characters with a font size of 8 or less. Worried, the portion of the reflection cannot read characters with a font size of 8 or less.
  • a liquid crystal panel using the antireflection films 3 to 4 of the comparative example and the polarizing plates 103 to 104 of the comparative example For 203 to 204, the evaluation was C or lower, and the antireflection films 1 to 2 and 5 to 12 of the present invention and the liquid crystal panels 201 to 202 and 205 to 120 using the polarizing plates 101 to 102 and 105 to 112 of the present invention were used. 212 is , Both were B or higher evaluation results, and the visibility was better.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Polarising Elements (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne une composition antireflet, qui peut produire une couche à faible indice de réfraction qui présente d’excellentes résistance à l’abrasion et adhérence, tout en ayant un indice de réfraction suffisamment faible. La présente invention concerne en outre un film antireflet ayant une couche obtenue par durcissement de la composition, une plaque polarisante et un dispositif d’affichage d’image. La présente invention concerne spécifiquement une composition pour des couches antireflet, qui est caractérisée en ce qu’elle contient (A) des particules de silice creuses, (B) un composé polymérisable par voie cationique représenté par la formule générale (1), et (C) un initiateur de photopolymérisation cationique. Dans la formule générale (1), R1 représente un groupe polymérisable par voie cationique ayant de 1 à 10 atomes de carbone ; R2 représente un groupe choisi parmi un groupe méthyle, un groupe éthyle et un groupe propyle ; et n représente 0, 1 ou 2.
PCT/JP2009/063260 2008-09-24 2009-07-24 Composition pour couche antireflet, film antireflet, plaque polarisante et dispositif d’affichage d’image WO2010035571A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019187588A1 (fr) * 2018-03-30 2019-10-03 太陽インキ製造株式会社 Composition de résine durcissable, film sec, objet durci et composant électronique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003255103A (ja) * 2002-02-28 2003-09-10 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板および画像表示装置
JP2004170901A (ja) * 2002-07-05 2004-06-17 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板およびディスプレイ装置
JP2005316415A (ja) * 2004-03-31 2005-11-10 Dainippon Printing Co Ltd 反射防止積層体
WO2005114271A1 (fr) * 2004-05-20 2005-12-01 Fujifilm Corporation Plaque de polarisation à fonction antireflet, processus de fabrication, et écran d'affichage d'image
JP2007034213A (ja) * 2005-07-29 2007-02-08 Fujifilm Corp 反射防止フィルム、それを用いた偏光板及びディスプレイ装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003255103A (ja) * 2002-02-28 2003-09-10 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板および画像表示装置
JP2004170901A (ja) * 2002-07-05 2004-06-17 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板およびディスプレイ装置
JP2005316415A (ja) * 2004-03-31 2005-11-10 Dainippon Printing Co Ltd 反射防止積層体
WO2005114271A1 (fr) * 2004-05-20 2005-12-01 Fujifilm Corporation Plaque de polarisation à fonction antireflet, processus de fabrication, et écran d'affichage d'image
JP2007034213A (ja) * 2005-07-29 2007-02-08 Fujifilm Corp 反射防止フィルム、それを用いた偏光板及びディスプレイ装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019187588A1 (fr) * 2018-03-30 2019-10-03 太陽インキ製造株式会社 Composition de résine durcissable, film sec, objet durci et composant électronique
CN111936575A (zh) * 2018-03-30 2020-11-13 太阳油墨制造株式会社 固化性树脂组合物、干膜、固化物和电子部件

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