WO2008001612A1 - Film anti-reflet et procédé de production de ce film - Google Patents

Film anti-reflet et procédé de production de ce film Download PDF

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Publication number
WO2008001612A1
WO2008001612A1 PCT/JP2007/061905 JP2007061905W WO2008001612A1 WO 2008001612 A1 WO2008001612 A1 WO 2008001612A1 JP 2007061905 W JP2007061905 W JP 2007061905W WO 2008001612 A1 WO2008001612 A1 WO 2008001612A1
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Prior art keywords
group
layer
organic
antireflection film
refractive index
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PCT/JP2007/061905
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English (en)
Japanese (ja)
Inventor
Toshihide Aoshima
Koichi Kawamura
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Fujifilm Corporation
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Publication of WO2008001612A1 publication Critical patent/WO2008001612A1/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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • 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

Definitions

  • the present invention relates to an antireflection film and a method for producing the same, and more particularly relates to an antireflection film having an antifouling surface to which oily stains and the like hardly adhere and a method for producing the same.
  • An antireflection film is generally used for an image display device such as a cathode ray tube display (CRT), a plasma display panel (PDP), and a liquid crystal display (LCD).
  • CTR cathode ray tube display
  • PDP plasma display panel
  • LCD liquid crystal display
  • the antireflection film is placed on the outermost surface of the display.
  • a layer having a refractive index sufficiently lower than that of the support is formed in order to reduce the reflectivity.
  • the refractive index of the hard coat layer needs to be 1.40 or less in order to make the required range of 1.6% or less. Refractive index 1.
  • Inorganic materials that can achieve a refractive index of 40 or less include magnesium fluoride and calcium fluoride, and organic materials that have a high fluorine content. ⁇ ⁇ ⁇ The power of fluorine-containing compounds. These fluorine compounds have no cohesive force. The film placed on the outermost surface of the display lacked scratch resistance. Accordingly, there is a need for compounds that achieve sufficient scratch resistance and low refractive index.
  • Patent Document 2 an anti-glare antireflection film using a silicon oxide silicon film by CVD, which has excellent gas barrier properties, antiglare properties, and antireflection properties has been proposed (see, for example, Patent Document 2).
  • Patent Document 2 Has a problem that it is inferior in productivity as compared with film formation by wet coating, and it is particularly difficult to produce a uniform film having a large area.
  • a technique for reducing reflected light by applying a composition comprising a condensate resulting from hydrolysis of an alkoxysilane compound to a plastic substrate surface is disclosed (for example, , See Patent Documents 3 and 4;).
  • the inorganic film strength S wet coating is obtained by the sol-gel method.
  • the inorganic film Although it is an inorganic film, it is expected to have a very high film strength.
  • the inorganic film generally has a defect that it is liable to cause a peeling failure with poor adhesion to many substrates.
  • heating for a long time is indispensable for curing, and there is a disadvantage that productivity is poor.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-287102
  • Patent Document 2 JP-A-7-333404
  • Patent Document 3 Japanese Patent Publication No. 6-98703
  • Patent Document 4 Japanese Patent Laid-Open No. 63-21601
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2000-284102
  • the object of the present invention in consideration of the problems of the prior art as described above is excellent in adhesion to a support, has a low refractive index, has a water / oil repellent treatment surface, and has high antireflection performance and surface antifouling. It is an object to provide an antireflection film having a property and its durability and a method for producing the same.
  • the inventors of the present invention have made extensive studies on an organic-inorganic composite layer including a graft polymer chain directly bonded on a support and a crosslinked structure formed by hydrolysis and polycondensation reaction of alkoxysilane. As a result, it was found that the above-mentioned problems can be solved by applying the organic-inorganic composite layer to an antireflection film, and the present invention was completed.
  • the antireflection film of the present invention includes a transparent support having a refractive index of 1.57 or more, an organic-inorganic composite layer having a refractive index of 1.35 to L49 on the transparent support, A water / oil repellent treatment layer on the surface of the organic / inorganic composite layer, and the organic / inorganic composite layer is formed in a graft polymer layer formed of a graft polymer chain directly bonded to the surface of the transparent support. It is characterized by comprising a crosslinked structure formed by hydrolysis and condensation polymerization of alkoxysilane.
  • Such a graft polymer chain is preferably produced by a polymerization reaction starting from an initiation species generated on the surface of the support.
  • graft polymer chain strength It is preferable to have an alkoxysilyl group and Z or an amide group in the chain.
  • a preferred embodiment is a copolymer of a structural unit having a graft polymer chain strength polar group, preferably an amide group, and a structural unit having an alkoxysilyl group such as a silane coupling group.
  • the method for producing an antireflection film of the present invention includes providing an antiglare hard coat layer containing a polymer having a saturated hydrocarbon or a polyether as a main chain on the surface of a transparent substrate, and having a refractive index.
  • a step of forming 57 or more transparent supports, and a surface of the transparent support A step of forming a graft polymer chain that directly binds, and hydrolysis and condensation polymerization of the alkoxysilane to form a crosslinked structure, thereby forming an organic-inorganic composite layer having a refractive index of 1.35 to L 49
  • a step of subjecting the surface of the organic / inorganic composite layer to a water / oil repellent treatment is provided.
  • the organic / inorganic composite layer according to the present invention includes a graft polymer chain (organic component) directly bonded to the surface of the support in the layer and a crosslinked structure (inorganic component) formed by hydrolysis and condensation polymerization of alkoxysilane. And comprising.
  • a graft polymer chain organic component
  • inorganic component crosslinked structure formed by hydrolysis and condensation polymerization of alkoxysilane. And comprising.
  • Such an organic-inorganic composite layer has a low refractive index because of its structural characteristics, and even a thin layer has increased wear resistance and high durability.
  • the graft polymer chain has a polar group
  • a polar interaction is formed with the cross-linked structure by the function of the polar group, and an organic-inorganic composite layer excellent in strength and durability can be obtained.
  • the graft polymer chain strength has an alkoxysilyl group in the chain
  • the graft polymer chain and the crosslinked structure are covalently bonded to improve the strength and durability of the organic-inorganic composite layer.
  • a covalent bond or a polar interaction is formed between the crosslinked structure in the organic-inorganic composite layer and the compound used for the water / oil repellent treatment, so that it has excellent adhesion to the support.
  • a water / oil repellent surface can be obtained.
  • a low refractive index layer that exhibits excellent antireflection performance due to the functions of a high refractive index support and a low refractive index layer, and has high antifouling properties and durability as described above. It is presumed that an antireflection film excellent in durability formed by firmly bonding to the support surface can be obtained.
  • the reflectance is a spectral reflectance measured at an incident angle of 5 ° in a wavelength region of 380 to 780 nm using a spectrophotometer (manufactured by JASCO Corporation), The value calculated from the average reflectance in the target wavelength region.
  • the refractive index a value measured using an Abbe refractometer (manufactured by Atago Co., Ltd.) is adopted.
  • an antireflection film having excellent adhesion to a support, having a low refractive index and a water- and oil-repellent treated surface, and having high antireflection performance, surface antifouling properties and durability thereof.
  • a stop film and a method for producing the same can be provided.
  • the antireflection film of the present invention comprises a transparent support having a refractive index of 1.57 or more, an organic-inorganic composite layer having a refractive index of 1.35 to L49 on the transparent support, and the surface of the organic-inorganic composite layer
  • the organic / inorganic composite layer is hydrolyzed and polycondensed by alkoxysilane in a graft polymer layer formed of a graft polymer chain directly bonded to the surface of the transparent support. It is characterized by comprising a cross-linked structure formed by
  • a crosslinked structure is formed using Si alkoxide because of the reactivity and the availability of the compound.
  • the above-mentioned crosslinked structure formed by hydrolysis and polycondensation of the alkoxide is hereinafter appropriately referred to as “sol-gel crosslinked structure”.
  • Such an antireflection film of the present invention is produced by the following method for producing an antireflection film of the present invention.
  • the method for producing an antireflection film of the present invention comprises a step of preparing a transparent support surface having a high refractive index, specifically (1) a refractive index of 1.57 or more [hereinafter referred to as “high refractive index as appropriate”. This is called “rate support forming step”. And (2) forming a graft polymer chain directly bonded to the surface of the high refractive index support and forming a graft polymer layer with the graft polymer chain [hereinafter referred to as “graft polymer layer forming step” ".
  • organic-inorganic composite layer forming step a step of forming an organic-inorganic composite layer by carrying out a crosslinking reaction by hydrolysis and condensation polymerization of alkoxysilane in the graft polymer layer
  • organic-inorganic composite layer forming step a step of subjecting the surface of the organic-inorganic composite layer to a water / oil repellent treatment [hereinafter referred to as a “water / oil repellent treatment step” as appropriate. It is preferable that a method having the following is applied.
  • the organic-inorganic composite layer obtained in the steps (2) to (3) constitutes the “low refractive index layer” in the present invention. [0015] ⁇ Preparation of a transparent support having a refractive index of 1. 57 or more>
  • a transparent support can be used as it is as long as the material itself achieves a refractive index of 1.57 or higher, but in order to achieve a controlled high refractive index and durability.
  • it is preferable to form a high refractive index transparent support by providing a hard coat layer on the surface of the transparent substrate as desired and further forming an antiglare hard coat layer.
  • the transparent base material constituting the support having a refractive index of 1.57 or more any material having mechanical strength and dimensional stability and transparent can be used.
  • transparent resin is used.
  • Film is used.
  • the film used as the transparent substrate include polyester films such as polyethylene terephthalate film, polyethylene terephthalate copolymer polyester film, and polyethylene naphthalate film; nylon 66 film, nylon 6 film, metaxylidene diazine Polyamide films such as amine copolymer polyamide films; Polyolefin films such as polypropylene films, polyethylene films and ethylene propylene copolymer films; Polyimide films; Polyamide imide films; Polybulal alcohol films; Ethylene butyl alcohol copolymer films A polyphenylene film; a polysulfone film; a polyphenylene sulfide film; and the like.
  • polyester films such as polyethylene terephthalate film, polyethylene terephthalate copolymer polyester film, and polyethylene naphthalate film
  • nylon 66 film nylon 6 film, metaxylidene diazine
  • Polyamide films such as amine copolymer polyamide films
  • Polyolefin films such
  • polyester films such as a polyethylene terephthalate film
  • polyolefin films such as a polyethylene film and a polypropylene film are preferable from the viewpoints of balance between price and function, film transparency, and the like.
  • These films may be either stretched or unstretched, and even if used alone, films with different properties should be laminated and used.
  • the film used as the transparent substrate may contain various additives and stabilizers or may be applied as long as the effects of the present invention are not impaired.
  • additives include an antioxidant, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant, and a heat stabilizer.
  • the transparent substrate may be subjected to surface treatment such as corona treatment, plasma treatment, glow discharge treatment, ion bombardment treatment, chemical treatment, solvent treatment, and roughening treatment.
  • surface treatment such as corona treatment, plasma treatment, glow discharge treatment, ion bombardment treatment, chemical treatment, solvent treatment, and roughening treatment.
  • the thickness of the transparent base material can be appropriately set in consideration of the suitability of the purpose of use, and thus is not particularly limited. From the viewpoint of general practical use, 3 111 to 1111 111 From the viewpoint of flexibility and cacheability, which is preferably in the range of 10 to 300 / ⁇ ⁇ , it is more preferable.
  • the refractive index of the material constituting the antiglare node coat layer provided on the transparent base is preferably ⁇ 1.57-2.00, more preferably ⁇ 1.60-1.80.
  • the hard coat layer provided between the transparent substrate and the antiglare node coat layer is not essential, but it is preferable that the viewpoint of imparting film strength is provided.
  • the average reflectance of the transparent support according to the present invention constituted by laminating these layers is preferably 1.8% or less.
  • the refractive index of the material forming the antiglare node coat layer in the present invention is preferably 1.57 to 2.00. In this range, suitable antireflection performance is obtained, and a color tone close to transparency is maintained.
  • This high refractive index antiglare coating layer may contain fine particles in order to improve the light scattering property, as will be described later. When such fine particles are contained, the wavelength dependence of reflectance and the occurrence of color unevenness due to optical interference due to the refractive index difference between the antiglare hard coat layer and the support are suppressed by the internal scattering effect of the fine particles. can do.
  • the compound used for forming the anti-glare coating layer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and preferably a polymer having a saturated hydrocarbon as the main chain. Further preferred.
  • the binder polymer is preferably crosslinked.
  • the polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of ethylenically unsaturated monomers. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups.
  • the monomer structure preferably contains at least one selected from the group consisting of an aromatic ring, a halogen atom other than fluorine, sulfur, phosphorus, and nitrogen.
  • Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1, 4— Dicyclohexanediatalylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, dipentaerythritol tetra ( (Meta) acrylate, dipentaerythritol penta (meth) acrylate, penta erythritol hex (meth) acrylate, 1, 2, 3 cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate Butylbenzene and its derivatives (eg, 1,4-dibul), e
  • a monomer having a crosslinkable group is used to form a crosslinkable group in the polymer. It may be introduced and a crosslinked structure may be introduced into the binder polymer by the reaction of the crosslinkable group.
  • the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridin group, an oxazoline group, an aldehyde group, a carboxylic group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group.
  • Bulsulfonic acid, acid anhydrides, cyanate acrylate derivatives, melamine, etherified methylols, esters and urethanes, and metal alkoxides such as tetramethoxysilane can also be used as monomers for introducing a crosslinked structure.
  • a functional group that exhibits crosslinkability as a result of the decomposition reaction such as a block isocyanate group, may be used.
  • the crosslinkable group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group.
  • Examples of the high refractive index monomer include bis (4-methacryloylthiophene) sulfide, urnaphthalene, buluylsulfuride, 4-methacryloxyphenol 4'-methoxyphenyl thioether, and the like. .
  • These monomers having an ethylenically unsaturated group need to be cured by polymerization reaction using ionizing radiation or heat after application using a photo radical initiator or a thermal radical initiator.
  • a polymer having a polyether as a main chain is a ring-opening polymerization reaction of a polyfunctional epoxy compound. It is preferable to synthesize by reaction. It is necessary to use a photoacid generator or a thermal acid generator and to cure it by ionizing radiation or heat polymerization after coating.
  • fine particles may be dispersed as desired to form a refractive index nonuniform layer! /. With such a configuration, the refractive index of the material can be increased.
  • the particles used for improving the refractive index include, for example, a particle size of lOOnm or less composed of at least one oxide selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony.
  • a particle size of lOOnm or less composed of at least one oxide selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony.
  • fine particles of 50 nm or less are mentioned.
  • Specific examples of the material constituting the fine particles include TiO, ZrO, AlO, InO, ZnO, SnO, S
  • Inorganic materials such as 2 2 2 3 2 3 2 b O and ITO are preferred.
  • the amount of these inorganic fine particles added is
  • 10 to 90% of the total mass of the dazzling hard coat layer is preferably 20 to 80%, more preferably 30 to 60%.
  • a layer made of a monomer having two or more ethylenically unsaturated groups having a high refractive index as described above is formed, and selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony.
  • the particle size of the fine particles is sufficiently smaller than the wavelength of light, so that no scattering occurs and the optical uniformity. This is described in, for example, Japanese Patent Application Laid-Open No. 8-110401.
  • the antiglare hard coat layer contains rosin particles or inorganic compound particles for the purpose of imparting antiglare properties and preventing deterioration of reflectance due to interference between the antiglare hard coat layers and preventing uneven color.
  • particles used for the purpose of imparting antiglare properties include silica particles, TiO particles, and crosslinked particles.
  • any of a perfect sphere and an indeterminate form can be used. Two or more different kinds of particles may be used in combination.
  • the amount of particles applied is preferably 10 to lOOOmgZm 2 , More preferably from 30 to lOOmgZm 2.
  • the silica particle force having a particle size larger than one half of the film thickness of the antiglare node coat layer preferably accounts for 40 to 100% of the total silica particles.
  • the particle size distribution can be measured by the Coulter Counter method, the centrifugal sedimentation method, etc., but the distribution is considered in terms of the particle number distribution.
  • the film thickness of the antiglare node coat layer is preferably 1 to 10 m, more preferably 1.2 to.
  • the antireflection film of the present invention uses a transparent high refractive index support obtained by providing an antiglare coating layer and a coating layer on the surface of a transparent resin base material, and further has a detailed description below. Although it has a low refractive index layer composed of a mechanical-inorganic composite layer, a smooth hard coat layer can be provided below the antiglare hard coat layer as necessary.
  • the resin used for the smooth hard coat layer does not contain fine particles used in combination for the purpose of imparting anti-glare properties, except that the resin used in the anti-glare layer and the coat layer is! The same can be mentioned.
  • a smooth hard coat layer is applied between the transparent support and the antiglare hard coat layer as necessary for the purpose of improving the film strength.
  • the film thickness of the smooth hard coat layer is preferably 1 to 10 m. 1.2 to 6 m is more preferable.
  • the transparent support thus obtained may be used as it is as long as the transparent support itself can generate an active species by applying energy, but it is a starting species that forms a graft polymer chain.
  • a surface layer having a polymerization initiating ability may be provided on the support surface.
  • the surface layer having a polymerization initiating ability is preferably a layer containing a low-molecular or high-molecular polymerization initiator.
  • the polymerization initiator layer is formed by fixing a polymerization initiator by a crosslinking reaction.
  • the side chain preferably has a functional group and a crosslinkable group having a polymerization initiating ability.
  • a polymerization initiation layer formed by fixing a polymer by a crosslinking reaction is more preferable.
  • the polymerization initiating layer obtained by fixing a functional group having a polymerization initiating ability in the side chain and a polymer having a crosslinkable group by a crosslinking reaction
  • paragraph numbers [0011] to [0169] of JP-A No. 2004-161995 are disclosed.
  • the polymerization initiation layer can be applied to the present invention.
  • graft polymer layer forming step “organic / inorganic composite layer forming step” for obtaining “low refractive index layer” in the antireflection film of the present invention, and “repellency” for imparting antifouling property to the surface thereof.
  • the “water / oil repellent treatment step” will be described in order.
  • the low refractive index layer described later preferably satisfies the following formula (1) with respect to the wavelength of incident light.
  • m is a positive odd number (generally 1)
  • nl is the refractive index of the low refractive index layer
  • dl is the film thickness (nm) of the low refractive index layer.
  • a graft polymer chain directly bonded to the surface of the transparent support having the specific high refractive index is generated to form a graft polymer layer by the graft polymer chain.
  • a method of generating a graft polymer chain directly bonded to the support surface (1) a method of generating a graft polymer chain by surface graft polymerization of a compound having a polymerizable double bond from the support as a base point. And (2) a method of forming a graft polymer chain by chemically bonding a polymer having a functional group that reacts with the support and the support surface.
  • the surface graft polymerization method is a polymerizable double bond placed on the surface of the support by applying active species on the surface of the support by means of plasma irradiation, light irradiation, heating, etc. This is a method of polymerizing a compound having the above. According to this method, the resulting graft polymer chain The ends of are directly bonded to the support surface and fixed.
  • any known method described in literatures can be used.
  • New Polymer Experiment 10 edited by Society of Polymer Science, 1994, published by Kyoritsu Shuppan Co., Ltd.
  • P135 describes photograft polymerization and plasma irradiation graft polymerization as surface graft polymerization methods.
  • the adsorption technique manual, NTS Co., Ltd. supervised by Takeuchi, published in February 1999, p203, p695 describes radiation-induced graft polymerization methods such as gamma rays and electron beams.
  • a graft polymer chain can be formed by reacting a compound having a heavy bond (for example, a monomer).
  • photograft polymerization is supported by a film as described in JP-A-53-17407 (Kansai Vint) and JP-A-2000-212313 (Dainippon Ink). It can also be carried out by applying a photopolymerizable composition to the surface of the body, bringing the radical polymerizable compound into contact with it and irradiating it with light.
  • a compound useful in producing a graft polymer chain by the method (1) needs to have a polymerizable double bond.
  • it considering the formation of polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming process described later, it has a polymerizable double bond and has a polar group.
  • a compound is preferable.
  • a compound having a polymerizable double bond and an alkoxysilyl group It is preferable that
  • a polymer or an oligomer can be used as long as it has a double bond in the molecule and, if necessary, a polar group and a Z or alkoxysilyl group. These monomers can also be used as monomers.
  • One of the compounds useful in the present invention is a monomer having a polar group.
  • Monomers having a polar group useful in the present invention include positively charged monomers such as ammonia and phosphonium, sulfonic acid groups, carboxyl groups, phosphoric acid groups, phosphonic acid groups, and the like.
  • Examples of the monomer having a negative charge or an acidic group that can be dissociated into a negative charge include, for example, a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, a cyan group, and the like.
  • a monomer having a polar group having a nonionic group can also be used.
  • the monomer having a particularly useful polar group include the following monomers.
  • Macromers having polar groups useful in the present invention can be obtained by the synthesis method described in "New Polymer Experiments 2, Polymer Synthesis and Reactions” edited by Polymer Society of Japan, Kyoritsu Publishing Co., Ltd. 1995. Can do. Also in Yu Yamashita et al., "Chemical Monomer Chemistry and Industry” IPC, 1989 It is described in detail.
  • monomers having the polar groups specifically described above such as acrylic acid, acrylamide, 2-acrylamide-2-methylpropane sulfonic acid, N buracetoamide, etc. are used.
  • Macromers having polar groups can be synthesized according to the method.
  • macromers having a polar group used in the present invention those particularly useful are macromers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid Monomers of styrene sulfonic acid and its salts Derived from sulfonic acid macromers derived from amide macromers such as acrylamide and methacrylamide, N bur forces such as N burecetamide and N bureformamide Hydroxyl-containing monomarkers such as amide macromers, hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, etc.
  • carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid Monomers of styrene sulfonic acid and its salts Derived from sulfonic acid macromers derived from amide macromers such as acrylamide and methacrylamide
  • a macromer having an amide group as a polar group from the viewpoint that a strong polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later is formed. ,.
  • the useful molecular weight is in the range of 400 to 100,000, the preferred range is 1,000 to 50,000, and the preferred range is 1500 to 20,000.
  • the graft polymer chain in the present invention preferably has an Si alkoxide group, that is, an alkoxysilyl group, in the chain.
  • This alkoxysilyl group is a substituent capable of forming a covalent bond through hydrolysis and polycondensation reaction with a crosslinking agent (metal alkoxide) described later.
  • a crosslinking agent metal alkoxide
  • the surface graft polymerization method (1) it is preferable to use a monomer or macromer having an alkoxysilyl group.
  • This alkoxysilyl group will be specifically described by taking a typical silane force coupling group as an example.
  • Examples of the silane coupling group suitable for the present invention include functional groups represented by the following general formula (I).
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms.
  • m represents an integer of 0 to 2, preferably m represents 0 or 1, and more preferably m represents 0.
  • R 1 and R 2 represent a hydrocarbon group
  • examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable.
  • Examples include 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
  • R 1 and R 2 are preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoints of effects and availability.
  • Examples of the monomer having a functional group represented by the general formula (I) include (3 atalyoxypropyl pill) trimethoxysilane, (3-ataryloxypropyl) dimethylmethoxysilane, and (3-acryloxy).
  • a monomer having a polar group or a macro it is preferable to use a monomer and a macromer having a monomer having an alkoxysilyl group such as a silane coupling group or a macromer to produce a graft polymer chain by surface graft polymerization. Among them, it is more preferable to use a monomer or macromer having an amide group as a polar group.
  • a polymer having a functional group that reacts with the support at the end of the main chain or a side chain is used, and the chemical reaction between the functional group and the functional group on the surface of the support is used to convert the draft polymer chain.
  • the functional group that reacts with the support is not particularly limited as long as it can react with the functional group on the surface of the support.
  • a silane coupling group such as alkoxysilane, an isocyanate group, an amino group, and a hydroxyl group.
  • Compounds particularly useful as polymers having functional groups that react with the support at the main chain ends or side chains are polymers having trialkoxysilyl groups at the polymer ends, polymers having amino groups at the polymer ends, and carboxyl groups at the polymer ends.
  • the polymer used at this time is preferably a polymer having a polar group which preferably has a polar group, specifically, polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, poly-2-acrylamide 2 -Methylpropanesulfonic acid and salts thereof, polyacrylamide, polybuluacetamide and the like.
  • a polymer of a monomer having a polar group used in the above method (1) or a copolymer containing a monomer having a polar group can also be used.
  • a polymer having an amide group as a polar group from the viewpoint of forming a strong polar interaction with the sol-gel crosslinked structure formed in the organic-inorganic composite layer forming step described later.
  • the polymer having a functional group that reacts with the support at the end of the main chain or at the side chain preferably has an alkoxysilyl group.
  • an alkoxysilyl group can be introduced into the resulting graft polymer chain.
  • a covalent bond can be formed between the sol-gel crosslinked structure formed in the later-described organic-inorganic composite layer forming step and the graft polymer chain.
  • an amide group and an alkoxysilyl group as a polymer-polar group having a functional group that reacts with the support at the main chain terminal or side chain.
  • an amide group and Z or alkoxysilyl are formed from the viewpoint of the formation of polar interaction with the sol-gel crosslinked structure and the formation of a covalent bond. It preferably has a group.
  • the amount of amide group introduced into the graft polymer chain is preferably in the range of 10 to 90 mol%, and the amount of alkoxysilyl group introduced is preferably in the range of 10 to 90 mol%.
  • the graft polymer chain in the present invention preferably has a polar group or a specific element alkoxide group as described above in the chain, but in addition to these groups, a crosslinkable group, a polymerizable group, etc. May be introduced and a cross-linked structure may be formed between the graft polymer chains by using these groups.
  • a crosslinking reaction is carried out by hydrolysis and condensation polymerization of Si alkoxide to form an organic-inorganic composite layer.
  • the organic one-inorganic composite layer in the present invention has a crosslinked structure (sol-gel crosslinked structure) formed by performing an organic component such as a graft polymer chain and a crosslinking reaction by hydrolysis and condensation polymerization of Si alkoxide. It is a layer in which the inorganic component consisting of is mixed.
  • crosslinking agent a compound capable of forming a crosslinked structure formed by performing a crosslinking reaction by hydrolysis and polycondensation of Si alkoxide (hereinafter sometimes simply referred to as "crosslinking agent").
  • crosslinking agent a compound represented by the following general formula ( ⁇ ) is used.
  • the compound represented by the following general formula (II) is hydrolyzed and polycondensed with the alkoxysilyl group, so that the graft polymer single chain and the sol-gel crosslinked structure are separated. A covalent bond can be formed. Thereby, a strong organic-inorganic composite layer can be formed.
  • R 3 represents a hydrogen atom, an alkyl group, or an aryl group
  • R 4 represents an alkyl group or an aryl group.
  • m represents an integer of 0 to 2, preferably m represents 0 or 1, and more preferably m is 0.
  • R 3 and R 4 represent an alkyl group
  • the carbon number is preferably 1 to 4.
  • the alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group.
  • This compound is a low molecular compound and preferably has a molecular weight of 1000 or less.
  • the hydrolyzable compound contains a silicon in the molecule.
  • Specific compounds include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane.
  • Aminopuro pills triethoxysilane, phenylalanine trimethoxysilane, phenylalanine triethoxysilane , Phenyltripropoxysilane, diphenyldimethoxysilane, diphenyljetoxysilane, etc. Can be mentioned.
  • tetramethoxysilane tetraethoxysilane
  • methyltrimethoxysilane ethyltrimethoxysilane
  • methyltriethoxysilane methyltriethoxysilane
  • dimethyljetoxysilane phenyltrimethoxysilane
  • phenyltriethoate examples include xylsilane, diphenyldimethoxysilane, diphenyljetoxysilane and the like.
  • the crosslinking agent is dissolved in a solvent such as ethanol, and then a catalyst or the like is added as necessary.
  • a method can be used in which a composition is prepared, applied onto the graft polymer layer, heated and dried. By this method, a sol-gel crosslinked structure is formed by hydrolysis and polycondensation of the crosslinking agent.
  • the heating temperature and the heating time are not particularly limited as long as the solvent in the coating solution is removed and a strong film can be formed, but the heating temperature is 200 ° from the viewpoint of production suitability and the like.
  • the heating time (crosslinking time) that is preferably C or less is preferably within 1 hour.
  • the content of the cross-linking agent in the coating liquid composition may be determined according to the amount of the sol-gel cross-linking structure to be formed, but generally from 5 to 50 in terms of surface hardness and adhesion.
  • the mass% is preferably in the range of 10 to 40 mass%.
  • the content of the crosslinking agent (alkoxysilane) in the coating solution composition is such that the crosslinking in the crosslinking agent is relative to the alkoxysilyl group. It is preferable to adjust the amount so that the functional group (alkoxy group or hydroxyl group) is 5 mol% or more, further 10 mol% or more.
  • the upper limit of the content of the cross-linking agent is not particularly limited as long as it is within a range capable of sufficiently cross-linking with the alkoxysilyl group, but when added in a large excess, the organic agent formed by the cross-linking agent not involved in cross-linking. Problems such as stickiness of the inorganic composite layer may occur.
  • the solvent used in preparing the coating liquid composition is not particularly limited as long as it can uniformly dissolve and disperse the crosslinking agent and other components.
  • methanol, ethanol, An aqueous solvent such as water is preferred.
  • the coating liquid composition promotes hydrolysis and polycondensation reaction of the crosslinking agent. For this reason, it is preferable to use an acidic catalyst or a basic catalyst in combination, and in order to obtain a practically preferable reaction efficiency, a catalyst is essential.
  • this catalyst one that uses an acid or a basic compound as it is, or one dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst and a basic catalyst, respectively) is used. be able to.
  • the concentration at which the catalyst is dissolved in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, etc. Tends to increase the rate of hydrolysis and polycondensation. However, if a basic catalyst with a high concentration is used, a precipitate may be generated in the coating solution composition. If a basic catalyst is used, the concentration should be 1 N or less in terms of concentration in an aqueous solution. Is desirable.
  • the type of acidic catalyst or basic catalyst is not particularly limited. However, if it is necessary to use a concentrated catalyst with high concentration, it will hardly remain in the coating film after drying. Such a catalyst is also preferable.
  • the acidic catalyst is represented by halogen hydrogen such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RC OOH.
  • halogen hydrogen such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RC OOH.
  • Substituted carboxylic acids in which R in the structural formula is substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, etc., and basic catalysts include ammoniacal bases such as ammonia water, ethylamine And amines.
  • various additives can be used according to the purpose as long as the effects of the present invention are not impaired.
  • a surfactant or the like can be added to improve the uniformity of the coating solution.
  • the graft polymer layer and the organic-inorganic composite layer may be formed by the following method.
  • a coating liquid composition containing a graft polymer that is a copolymer of a macromer having a polar group as described above and a structural unit having an alkoxysilyl group, a crosslinking agent, and a catalyst is prepared.
  • the graft polymer layer is formed on the support by the method of coating and drying on the support and then forming a film, and further the organic-inorganic composite layer can be formed. it can.
  • a hydrophilic polymer may be separately contained.
  • the hydrophilic polymer can be obtained by polymerizing a monomer having a polar group useful for forming the graft polymer chain mentioned above.
  • the content of the hydrophilic polymer is preferably 10% by mass or more and less than 50% by mass in terms of solid content. When the content is 50% by mass or more, the film strength tends to decrease. When the content is less than 10% by mass, the film characteristics are decreased, and the possibility of cracks in the film increases. Absent.
  • the formation of the organic-inorganic composite layer in the present invention uses the sol-gel method.
  • Sakuo Sakuo Science of Sol-Gel Method” (Agne Jofusha Co., Ltd.) (1988), Satoshi Hirashima “Technology Center for Functional Thin Films Using the Latest Sol-Gel Method” ) (1992) and the like, and the methods described therein can be applied to the formation of the organic-inorganic composite layer in the present invention.
  • the present invention it is preferable from the viewpoint of low refractive index expression to add fine silica and hollow silica fine particles to the coating composition for forming the organic-inorganic composite layer.
  • hollow silica fine particles are contained for the purpose of achieving both a low refractive index and scratch resistance.
  • the hollow silica fine particles used here have a refractive index of 1.17 to L40, more preferably 1.17 to L35, and most preferably 1.17 to L30.
  • the refractive index here represents the refractive index of the entire particle, and the refractive index of the silica material itself constituting the hollow silica fine particles is not necessarily within this range.
  • the void ratio X is calculated by the following equation (2), where a is the radius of the cavity in the hollow silica fine particle and b is the radius of the outer shell of the particle.
  • the hollow silica fine particles those having a porosity X force of 10 to 60% calculated from the above formula (2) are preferably used.
  • the porosity (X) is more preferably in the range of 20 to 60%, most preferably 30 to 60%.
  • the upper limit of the porosity is about 60%. Therefore, the lower limit of the refractive index that can be achieved by the hollow silica fine particles themselves is about 1.17.
  • the refractive index of the entire low refractive index layer can be controlled by adding such hollow silica fine particles to the organic-inorganic composite layer.
  • the average particle size of the hollow silica fine particles is from 5 nm to 200 nm, preferably from 20 nm to 150 ⁇ m, more preferably from 30 nm to 80 nm, and even more preferably from 40 nm to 60 nm.
  • the particle diameter of the hollow silica fine particles is in the above range, an appropriate decrease in refractive index is achieved, and there is no concern about deterioration in appearance or integrated reflectance due to fine irregularities on the surface of the low refractive index layer.
  • Organic - coating amount of the hollow silica fine particles in the inorganic composite layer is, lmg / m 2 ⁇ : LOOmg Zm 2 is more preferably preferably instrument 5mgZm 2 ⁇ 80mgZm 2, more preferably at lOmgZm 2 ⁇ 60mgZm 2 is there.
  • LOOmg Zm 2 is more preferably preferably instrument 5mgZm 2 ⁇ 80mgZm 2, more preferably at lOmgZm 2 ⁇ 60mgZm 2 is there.
  • the silica in the outer shell part constituting the hollow silica fine particles may be crystalline or amorphous.
  • the size distribution of the hollow silica fine particles is preferably monodispersed particles, but may be polydispersed particles or aggregated particles as long as a predetermined particle size is satisfied.
  • the spherical shape is most preferable, but there is no problem even if it is indefinite.
  • the average particle diameter of the hollow silica fine particles can be determined by an electron microscopic photographic power.
  • the amount of the hollow silica fine particles added to the coating composition for forming the organic / inorganic composite layer is preferably 5 to 80% by mass in terms of solid content from the viewpoint of low refractive index expression. % Is more preferable.
  • the thickness of the organic-inorganic composite layer can be selected depending on the application of the antireflection film, etc., but in general, the range of 50 nm to 300 nm is preferred from the viewpoint of flexibility. Especially preferred is the nm range.
  • sol-gel component The above alkoxysilane hydrolysis / condensation product contributes to improving the film strength and scratch resistance.
  • the surface of the organic / inorganic composite layer obtained by the organic / inorganic composite layer forming step that is, the surface of the low reflectance layer is subjected to water / oil repellent treatment.
  • the compound (water repellent) and the treatment method used in the water / oil repellent treatment in the present invention are no particular limitations on the compound (water repellent) and the treatment method used in the water / oil repellent treatment in the present invention, but it is preferred that fluorine or an alkyl group is imparted to the surface of the organic-inorganic composite layer.
  • an organometallic compound such as a silylating agent, a titanate coupling agent, or alkylaluminum is preferably used, and a silylating agent is more preferably used.
  • the water and oil repellent treated surface is excellent in adhesion to the support.
  • the silylating agent is a silane compound having a hydrolyzable group having affinity or reactivity for the sol-gel cross-linked structure in the present invention, an alkyl group, an aryl group, a fluoroalkyl group containing fluorine, etc. And a compound with a fluoroalkyl group or the like bonded thereto.
  • the hydrolyzable group bonded to silicon in the silylating agent include an alkoxy group, a halogen atom, an acetoxy group, and a silazane. Specifically, it is preferable to use a perfluoroalkylsilane compound or an alkylsilane compound.
  • the critical inclination angle of the water- and oil-repellent treated surface (that is, the inclination angle of the plate on which a certain amount of water droplets placed on the surface of the antireflection film placed horizontally begins to roll) is reduced to cause the water droplets to fall.
  • a polydimethylsiloxane compound may be used as a water repellent.
  • the water repellent is hydrolyzed as necessary to provide a coating for the water repellent layer.
  • the surface treatment with the water repellent as described above is carried out by spraying, flow coating, spin coating, dipping and lifting, or surface adsorption by liquid phase adsorption.
  • the substrate treated with the water repellent is dried and then at a temperature of 300 ° C or lower, preferably 100 ° C to 25 ° C. Heat at 0 ° C for 10 minutes to 1 hour.
  • the water-repellent agent forms a monomolecular layer on the surface of the organic-inorganic composite layer, it exhibits water-repellent performance.
  • the preferred thickness of the water and oil repellent layer after heat treatment is 1 to 1 Onm.
  • the antireflection film of the present invention has adhesion between the water / oil repellent treated surface and the organic / inorganic composite layer which is the low refractive index layer, and has a high reflectance with the organic / inorganic composite layer. Excellent adhesion to a transparent support. As a result, the water / oil repellent treated surface has excellent adhesion to the support.
  • the antireflection film of the present invention is excellent in antireflection ability and surface antifouling property, and further, in the sustainability and durability of those functions.
  • a PET support was obtained by performing oxygen glow treatment under the following conditions.
  • the following coating solution A for antiglare hard coat layer is applied to the surface of the PET support substrate using a bar coater, dried at 120 ° C, and then air-cooled metal halide lamp (Graphics) of 160W / cm. Was used, and the coating layer was cured by irradiating ultraviolet rays with an illuminance of 400 mWZcm 2 and an irradiation amount of 300 mjZcm 2 to form an antiglare node coat layer having a thickness of 6 m. About 50% of the silica particles are larger than 3 ⁇ m, which is a half of the hard coat layer thickness.
  • the obtained transparent support was a non-uniform refractive index layer as described above, and the refractive indexes at five power points near both ends and near the center were measured to be 1.57 or more. confirmed.
  • the refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.53. Furthermore, 10 g of amorphous silica particles with an average particle size of 3 ⁇ m (trade name: Mizukasil P-526, manufactured by Mizusawa Chemical Co., Ltd.) were added to this solution, and the mixture was stirred and dispersed at 5000 rpm for 1 hour with a high speed dispaper. Thereafter, the mixture was filtered through a polypropylene filter having a pore diameter of 30 m to prepare a coating solution A for an antiglare node coat layer. The thickness of the antiglare node coat layer was 3 m.
  • the PET support on which the above antiglare node coat layer was formed was immersed in this mixed solution at 70 ° C. for 7 hours.
  • the substrate after immersion is thoroughly washed with ethanol, and the specific element alkoxide group is present in the structure.
  • a graft polymer layer in which a graft polymer chain having a silane coupling group and an amide group was directly bonded to the surface of the support was formed.
  • the support A was a PET support having this graft polymer layer and an antiglare node coat layer.
  • a coating solution composition 1 containing ethanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred on a support for 24 hours at room temperature, and heated at 100 ° C for 10 minutes. By drying to form an organic-inorganic composite layer, an organic-inorganic hybrid film A was obtained.
  • the formed organic-inorganic hybrid layer had a thickness of 150 nm.
  • the obtained organic-inorganic hybrid film A was immersed in 0.1% by mass of 1 1H, 2H, 2H perfluorodecyltrichlorosilane / hexane solution for 10 minutes, pulled up, and then dried by heating (100 (Anti-reflective film A having a surface water and oil repellent treatment) was obtained.
  • a mother liquor was prepared and warmed to 95 ° C.
  • the pH of this reaction mother liquor was 10.5.
  • a dispersion of Al 2 O porous material precursor particles was prepared. [0086] Next, this porous material precursor particle dispersion lOOg was collected, and 340g of pure water was added and heated to 98 ° C. While maintaining this temperature, the aqueous sodium silicate solution was subjected to cation exchange. Add 600 g of caustic acid solution obtained by dealkalizing with fat (SiO concentration 3.5% by mass)
  • a silica protective film was formed on the surface of the porous material precursor particles.
  • the obtained dispersion liquid of porous substance precursor particles is washed with an ultrafiltration membrane to adjust the solid content concentration to 15% by mass, and then the obtained porous material precursor particles having a solid content concentration of 15% by mass
  • the aluminum salt dissolved in the ultrafiltration membrane was separated while preparing a particle precursor dispersion to prepare a particle precursor dispersion.
  • particles having a silica outer shell layer and a cavity inside the outer shell layer were produced. It was then concentrated to a solid content concentration of 5 wt% with an evaporator, the concentration of ammonia water 15 mass 0/0 and mosquito ⁇ Ete PHIO, and 180 ° C, 2 hours of heat treatment in an autoclave, using an ultrafiltration membrane A dispersion of inorganic compound particles (hollow silica fine particles) having a solid content concentration of 20% by mass in which the solvent was replaced with ethanol was prepared.
  • the particles had cavities formed inside the outer shell layer.
  • the average particle diameter of the particles was 50 nm, and the refractive index was 1.25.
  • Example 1 The same as in Example 1, except that 4.5 g of the hollow silica fine particle dispersion obtained above (solid content concentration 20% by mass) was added to "Coating liquid composition 1" used in Example 1.
  • the antireflection film B was obtained by the method.
  • the average coating amount of the hollow silica fine particles was 40 mgZm 2 .
  • Example 1 ⁇ Formation of graft polymer layer 1> was changed to ⁇ Formation of graft polymer layer 2> below to produce support B, and further, formation of organic-inorganic composite layer 1> An antireflection film C was obtained in the same manner as in Example 1 except that the support A used in V was changed to the support B to produce an organic-inorganic hybrid film B. [0090] ⁇ Formation of graft polymer layer 2>
  • Example 2 An aqueous acrylamide solution (concentration: 50% by mass) was subjected to nitrogen publishing.
  • the PET support used in Example 1 was immersed in this aqueous solution at 70 ° C for 7 hours.
  • the immersed PET support was thoroughly washed with distilled water to form a graft polymer layer in which a graft polymer chain having an amide group in the structure was directly bonded to the support surface.
  • the PET support having this graft polymer layer was designated as support B.
  • a methacryloxypropyltriethoxysilane / ethanol solution (concentration: 50% by mass) was nitrogen-published.
  • the PET support having the antiglare node coat layer used in Example 1 was soaked at 70 ° C. for 7 hours.
  • the PET support after immersion was thoroughly washed with distilled water to form a graft polymer layer in which graft polymer chains having a silane coupling group, which is a specific element alkoxide group, were directly bonded to the support surface. .
  • the PET support having this graft polymer layer was designated as Support C.
  • a coating solution composition 2 containing 2-propanol, water, tetraethoxysilane, and phosphoric acid in the following amounts was stirred on the obtained support C for 5 hours at room temperature.
  • Organic-inorganic nano-film and hybrid film C were obtained by heating and drying for a minute to form an organic-inorganic composite layer.
  • the thickness of the formed organic-inorganic nano-bridging layer was 180 nm.
  • the obtained organic / inorganic hybrid film C was subjected to the same treatment as the water and oil repellent treatment in Example 1 for 1 hour to obtain an antireflection film D having a surface water and oil repellent treatment.
  • Example 5 Example 4 except that 4.5 g of the same hollow silica fine particle dispersion (solid content concentration 20% by mass) as obtained in Example 2 was added to “Coating liquid composition 2” used in Example 4. An antireflection film E was obtained in the same manner as above.
  • Example 1 instead of the support A used in the above, an antiglare node coat layer similar to that in the support A is formed on the surface of the substrate A, and then a graft polymer layer is not formed. Body D. An antireflection film F was obtained in the same manner as in Example 1 except that the support A was changed to the support D.
  • the water- and oil-repellent treated surfaces are manufactured by Kyowa Interface Science Co., Ltd., CA — Z. Used, the angle after 20 seconds after the addition of pure water was measured. A water droplet contact angle of 150 ° or more was marked as ⁇ . The results are shown in Table 1.
  • the refractive index at 25 ° C. was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.).
  • the antireflection films A to E of the examples having the organic-inorganic composite layer have water repellency, antireflection ability, and adhesion between the support and the low reflectance layer treated with water and oil repellency. It turns out that it is favorable. Further, the antireflection films A to E of Examples are excellent in initial antifouling property and repeated antifouling property. From these facts, it can be seen that the antireflection film of the present invention is excellent in antireflection performance, antifouling property and sustainability thereof.
  • the antireflective film of the present invention has a low refractive index, high antireflective ability, surface antifouling property and its durability, so that window materials such as window glass' show window ', LCD' PDP display, etc. It can be suitably used for a wide range of applications such as instrument panels.

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Abstract

L'invention concerne un film anti-reflet comprenant un corps de support transparent et une couche composite organique/inorganique directement collée sur la surface du corps de support transparent. Dans ce film anti-reflet, la surface de la couche composite organique/inorganique est soumise à un traitement hydrofuge et oléofuge. L'indice de réfraction du corps de support transparent est inférieur à 1,57. La couche de composite organique/inorganique contient une partie organique constituée d'un polymère d'une chaîne de polymères greffés et d'une partie inorganique constituée d'une structure réticulée formée par polymérisation par hydrolyse et par polymérisation par condensation d'un alkoxysilane. L'indice de réfraction de la couche de composite organique/inorganique est compris entre 1,35 et 1, 49.
PCT/JP2007/061905 2006-06-30 2007-06-13 Film anti-reflet et procédé de production de ce film WO2008001612A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012237941A (ja) * 2011-05-13 2012-12-06 Asahi Glass Co Ltd 光学部品、光学装置
JP2016505162A (ja) * 2012-11-07 2016-02-18 エルジー・ハウシス・リミテッドＬｇ Ｈａｕｓｙｓ，Ｌｔｄ． シロキサン化合物を含む超親水性反射防止コーティング組成物、それを用いた超親水性反射防止フィルムおよびその製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021879A1 (fr) * 1999-09-17 2001-03-29 Daikin Industries, Ltd. Agent de traitement de surface comprenant un matiere mixte organique/inorganique
JP2005037927A (ja) * 2003-06-26 2005-02-10 Nippon Zeon Co Ltd 光学積層フィルム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001021879A1 (fr) * 1999-09-17 2001-03-29 Daikin Industries, Ltd. Agent de traitement de surface comprenant un matiere mixte organique/inorganique
JP2005037927A (ja) * 2003-06-26 2005-02-10 Nippon Zeon Co Ltd 光学積層フィルム

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012237941A (ja) * 2011-05-13 2012-12-06 Asahi Glass Co Ltd 光学部品、光学装置
JP2016505162A (ja) * 2012-11-07 2016-02-18 エルジー・ハウシス・リミテッドＬｇ Ｈａｕｓｙｓ，Ｌｔｄ． シロキサン化合物を含む超親水性反射防止コーティング組成物、それを用いた超親水性反射防止フィルムおよびその製造方法

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