WO2005037901A1 - Procede de production d'article en resine revetu par un film antitaches - Google Patents

Procede de production d'article en resine revetu par un film antitaches Download PDF

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Publication number
WO2005037901A1
WO2005037901A1 PCT/JP2004/016055 JP2004016055W WO2005037901A1 WO 2005037901 A1 WO2005037901 A1 WO 2005037901A1 JP 2004016055 W JP2004016055 W JP 2004016055W WO 2005037901 A1 WO2005037901 A1 WO 2005037901A1
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Prior art keywords
film
group
layer
underlayer
antifouling
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PCT/JP2004/016055
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English (en)
Japanese (ja)
Inventor
Koji Takahashi
Toyoyuki Teranishi
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Nippon Arc Co., Ltd.
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Publication of WO2005037901A1 publication Critical patent/WO2005037901A1/fr

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    • 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
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • 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
    • C08J7/04—Coating
    • 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
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • 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
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/02—Polysilicates

Definitions

  • the present invention relates to a method for producing a resin article coated with an antifouling film. More specifically, the present invention relates to a method for producing an antifouling film-coated resin article in which the surface of a transparent resin substrate or a transparent resin film used for a display screen of a display is provided with antifouling properties.
  • Transparent plastics have optical properties, light weight, and can be processed and thinly written.
  • the optical-related market such as liquid crystal-related materials and optical disks or in the film market.
  • display screens such as liquid crystal displays, projection displays, plasma displays, and EL displays
  • transparent plastic materials are mainly used in combination with glass or alone as a main material.
  • the purpose of this display is to provide an explosion-proof auxiliary effect, antistatic effect, transmittance adjustment effect, antireflection effect, antifouling effect, and the like.
  • a laminated body formed by laminating on a resin film to be formed is attached to glass to form a display screen substrate, or a laminate obtained by directly laminating the laminated body on a transparent resin sheet and forming a display screen substrate by itself is used. .
  • a film in which a hard coat film, a transparent conductive film, an antireflection film, and an antifouling film are laminated in this order on a PET film is known.
  • the antifouling film means a film provided with a function that makes it difficult for dirt such as fingerprints to adhere to the surface thereof and that once the dirt is adhered, the dirt is easily removed.
  • Japanese Patent Application Laid-Open No. 7-16940 discloses an optical article having an optical thin film mainly composed of silicon dioxide, and a perfluoroalkyl (meth) acrylate relay on the optical thin film. It is known to form a thin film of a copolymer of a monomer and a monomer having an alkoxysilane group.
  • Japanese Patent Application Laid-Open No. 2000-3227818 discloses a perethoxy group-containing triethoxy compound.
  • a coating agent obtained by adding a perfluoro group-containing phosphoric acid ester as a catalyst to a solution containing a run as a solute is applied on the antireflection film of an optical article having an antireflection film having a SiO 2 layer on its surface. To form an antifouling layer.
  • JP-A-2001-188102 discloses a perfluoropolyether group-containing silane coupling agent as an uppermost layer of an antireflection film having an antireflection layer on the upper surface of a transparent film substrate. It has been proposed to form an antifouling layer by forming a film by vacuum evaporation.
  • Japanese Patent Application Laid-Open No. H11-16882 discloses that the surface is treated in advance with a plasma or corona atmosphere containing oxygen to make it hydrophilic, or that the surface of the base material is placed in an atmosphere containing oxygen.
  • a method for producing a water-repellent product which comprises applying a solution containing a silane compound having a fluoroalkyl group and a fluorinated alkyl group-containing compound and then drying the solution to form a water-repellent film.
  • the technique disclosed in Japanese Patent Application Laid-Open No. 7-169040 has a problem in that the reaction after coating takes a long time, resulting in low production efficiency. According to the methods disclosed in Japanese Patent Application Laid-Open Nos. 2000-0-327818 and Hei11-71682, it takes a long time to develop the antifouling property, and the antifouling performance is low. And there is a problem that the antifouling property tends to decrease with use. Further, in the technique disclosed in Japanese Patent Application Laid-Open No. 2001-188102, a special apparatus such as a vacuum evaporation apparatus is required. Disclosure of the invention
  • the present invention prevents the attachment of dirt such as fingerprints, sebum, sweat, and cosmetics to the surface of a transparent resin substrate such as an anti-reflection film, and prevents water droplets from being easily wiped off even if attached.
  • a transparent resin substrate such as an anti-reflection film
  • the purpose is to provide.
  • a transparent base material having at least a base layer made of a siliceous resin or an inorganic compound on the surface thereof, A coating solution containing a silicon alkoxide, a fluoralkyl group-containing silane compound and an acid on the undercoat layer, and drying to form an antifouling layer. Achieved by the method.
  • an underlayer made of a resin or an inorganic compound is provided on at least the surface of the transparent resin substrate, the surface being siliceous. It is preferable content of S i 0 2 or S i 10 at the surface of the resin base layer or an inorganic compound base layer is 2 0% by weight or less. The following five types can be given as embodiments of the underlayer.
  • At least the surface is made of a siliceous material.
  • the hard coat layer of the siliceous force can be cited. This hard coat layer has the following formula (1)
  • R 1 is an alkyl group having 1 to 4 carbon atoms, a hydrocarbon group having an epoxy group having 2 to 12 carbon atoms, an aryl group or a halogenated alkyl group having 6 to 12 carbon atoms, methacryloxy alkyl group having 5 to 8 carbon atoms, ureido alkylene group having a carbon number of 2 to 1 0, the aromatic ureido alkylene group, an aromatic alkylene group, a main mercaptoethyloleates alkylene group
  • R 2 is c 1 -C
  • R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an acyl group, an arylalkyl group, and a Is 1, 2, or 3, and b is 0, 1, or 2, a compound represented by the formula:
  • This hard coat layer preferably has a thickness of 1 to 10 m.
  • the organic silane compound represented by the above formula (1) include trimethylmethoxysilane and phenyl.
  • the mixing ratio of each component is preferably from 40 to 900 parts by weight, more preferably from 250 to 500 parts by weight, based on 100 parts by weight of the compound represented by the above formula (1). Good.
  • the coating liquid is prepared as a dispersion containing a predetermined amount of the above-mentioned active ingredient in a liquid medium such as alcohol.
  • colloidal silica for example, 1 0-5 0% by weight of S i 0 2, preferably a particle size 1 to 2 0 O nm, more preferably the active ingredient S i 0 2 particles 1 to 1 0 O nm Colloidal silica sol or particle size of 1 to 200 nm, more preferably 1 to 200 nm
  • the composite oxide is a composite of S I_ ⁇ 2 and a metal oxide is a metal oxide, A l, S n, S b, T a, C e, L a, F e, Z n, W, Zr, Pd, I Oxides of one or more metals selected from the group consisting of n and Ti can be mentioned. Specific examples A 1 2 0 3, Sn0 2 , Sb 2 ⁇ 5, Ce0 2, Ta 2 0 5, L a 2 0 3, Fe 2 ⁇ 3, ZnO, W_ ⁇ 3, Z r0 2, Pd0 2 , I there are n 2 0 3 and T i O 2.
  • the composite oxide fine particles containing Si 2 there are composite oxide fine particles of titanium and silicon (T i 0 2 ⁇ S i 0 2 ), and composite oxide fine particles of titanium, cerium and gay (T i 0 2- ce0 2 - S i 0 2) , titanium composite oxide fine particles of iron and Gay-containing (T I_ ⁇ 2 ⁇ Fe 2 0 3 ⁇ S i 0 2), the composite oxide fine particles (T of titanium and zirconium and Gay-containing i 0 2 'Z r0 2' S i 0 2), the composite oxide fine particles of titanium and aluminum and Kei element (I_ ⁇ 2 ⁇ a 1 2 0 3 ⁇ S i 0 2) and the like.
  • It preferably contains S i 0 2 component 5 mol% or more in these composite Sani ⁇ particles.
  • the composite oxide may be surface-modified with an organic silane compound to enhance dispersibility in a solvent.
  • the amount of the organic silane compound used is preferably 20% by weight or less based on the weight of the composite oxide fine particles.
  • the surface treatment may be performed with the organic silane compound used for the treatment having a carohydrate decomposing group or after the hydrolysis. Examples of this organic silane compound include trimethylmethoxysilane, phenyldimethylmethoxysilane, vinyldimethylmethoxysilane, acryloxypropyldimethylmethoxysilane, r-mercaptopropyldimethylmethoxysilane, and N-i3 (aminoethyl).
  • Monofunctional silanes such as aminopropyl dimethylmethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane; dimethyldimethylmethoxysilane, phenylmethyldimethoxysilane, vinylmethyldisilane
  • tetrafunctional silanes such as tetraethylorthosilicate and tetramethylorthosilicate it can.
  • the complex oxide is treated with such a silane compound, it is preferably carried out in, for example, water, alcohol, or another organic medium.
  • the siliceous hard coat layer is obtained by applying a hard coat solution containing (A) a polyfunctional acrylate, (B) aminosilane and (C) colloidal silica, and irradiating with ultraviolet light.
  • This hard coat layer preferably has a thickness of 1 to 10 m.
  • the polyfunctional acrylate as the component (A) is a (meth) acrylate having at least two hydroxyl groups and at least two (meth) acryloyl groups in the molecule.
  • an acryloyl group or a methacryloyl group is referred to as (meth) acryloyl group
  • acrylate or methacrylate is referred to as (meth) acrylate
  • acrylic acid or methacrylic acid is referred to as (meth) acrylic acid.
  • polyfunctional (meth) acrylates include 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, and ethylene glycol diacrylate.
  • the aminosilane as the component (B) is an alkoxysilane having an amino group or a substituted amino group.
  • the following formula (2) is an alkoxysilane having an amino group or a substituted amino group.
  • R 4 is a hydrocarbon radical is a hydrogen atom or a monovalent hydrocarbon group
  • a is an integer from. 1 to 3
  • b is an integer of 0 or from 1 to 6
  • a is preferably 2 or 3
  • b is preferably 0 or 1.
  • Examples of the aminosilane represented by the formula (2) include n- (2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, r- ( 2-aminoethylile) aminopropyltrimethoxysilane, r- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-j3_ (N-acid salt and ani Linopropyltrimethoxysilane can be mentioned.
  • the same colloidal silica as described above can be used.
  • This hard coat liquid preferably contains a photopolymerization initiator for the polymerization of polyfunctional (meth) acrylate.
  • a photopolymerization initiator for example, a radical photopolymerization initiator, a cationic photopolymerization initiator, or the like can be used.
  • radical photopolymerization initiators include benzophenone, [2-hydroxy-2-methyl-11-phenylpropane-1-one], and [1-1 (4-isopropylphenyl) 1-2-hydroxy-1-methylpropane-1-one.
  • the amount of the photopolymerization initiator is preferably from 0.1 to 30 parts by weight, more preferably from 11 to 15 parts by weight, based on 100 parts by weight of the polyfunctional (meth) acrylate of the hard coat composition. .
  • This hard coat liquid preferably contains a hydrolysis catalyst for hydrolysis and polycondensation of aminosilane (B).
  • the hydrolysis catalyst include acid catalysts such as delight acid, acetic acid, propionic acid, butanoic acid, oxalic acid, (meth) acrylic acid, hydrochloric acid, nitric acid, and sulfuric acid, and ammonia, sodium hydroxide, and 7j potassium oxide aqueous solution.
  • a basic catalyst is used. Among these are acid catalysts in the form of aqueous solutions, for example! 3 ⁇ 4, (meth) acrylic acid is preferably used.
  • the amount of the acid catalyst to be added is preferably 5 to 30 parts by weight based on 100 parts by weight of the aminosilane (B).
  • This hard coat solution is preferably used in an amount of 1.5 to 50 parts by weight of the amino functional silane (B), more preferably 8 to 2 parts by weight, based on 100 parts by weight of the polyfunctional (meth) acrylate (A).
  • the colloidal silica (C) contains 5 parts by weight, preferably 10 to 150 parts by weight, more preferably 40 to 85 parts by weight, as a solid content.
  • an antireflection film can be mentioned as an inorganic compound underlayer having at least a surface made of silicon.
  • this antireflection film at least one inorganic compound film layer (a silicon oxide film in the case of one layer, and an oxide film in the case of two or more layers) (A silicon film) with a film thickness of 2011111 to 50/2111 (total film thickness in the case of two or more layers).
  • the inorganic compound include silicon oxide (silicon dioxide, silicon monoxide), and metal oxides such as aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, thorium oxide, antimony oxide, indium oxide, and oxide.
  • the method for forming the antireflection film include a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD method).
  • the CVD method includes a plasma CVD method
  • the PVD method includes a vacuum evaporation method, a reactive evaporation method, an ion beam assist method, a sputtering method, and an ion plating method.
  • SiO 2 film by plasma CVD single-layer anti-reflection film
  • a single-layer antireflection layer composed of silica fine particles can be exemplified.
  • This single antireflection layer can be formed to a thickness of 70 to 350 nm by applying and heating the following low reflection layer solution.
  • the low-reflection layer liquid comprises: (1) a raw material comprising at least one of non-agglomerated sily fine particles having an average particle diameter of 40 to 1,000 nm and chain aggregated sily fine particles having an average primary particle diameter of 10 to L00 nm; Fine particles, (2) hydrolyzable alkoxysilane as a binder, And one or more alkoxysilanes represented by the following formula (4), and water and a solvent.
  • the binder is then hydrolyzed in the presence of the above-mentioned (2) binder in the presence of the fine particles and a catalyst, Next, a liquid to which a curing catalyst has been added.
  • hydrolyzable alkoxysilane for example, a tetraalkoxysilane such as tetraethoxysilane is used, and as the other alkoxysilane, those represented by the following formula (3) can be exemplified.
  • R 7 is an alkyl group having 1 to 4 carbon atoms, an aryl group or a nodogenated alkyl group having 6 to 12 carbon atoms, a methacryloxy acrylyl group having 5 to 8 carbon atoms, and a carbon atom having 2 to 2 carbon atoms.
  • the silica fine particles and the binder are blended in a weight ratio, preferably in a ratio of 60:40 to 95: 5. Further, the non-agglomerated silica fine particles in the low reflection layer liquid preferably have a ratio of the major axis length to the minor axis length of 1.0 to 1.2, and the primary particle diameter standard deviation is preferably It is 1.0 to 1.5.
  • a hard coat layer of a silicon resin As a base layer of a resin having at least a surface having a siliceous property, a hard coat layer of a silicon resin can be given.
  • This hard coat layer has the following formula (5)
  • R 1 is an alkyl group having 1 to 4 carbon atoms, a hydrocarbon group having an epoxy group having 2 to 12 carbon atoms, an aryl group or a halogenated alkyl group having 6 to 12 carbon atoms, methacryloxy alkyl group having a carbon number of 5-8, ureido alkylene group having a carbon number of 2 to 1 0, the aromatic ureido alkylene group, an aromatic alkylene group, a main mercaptoethyloleates alkylene group,
  • R 2 is c 1 -C
  • R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an acyl group, an alkyl acyl group;
  • this one coat layer has a thickness of 1 to 10 zm.
  • the description of the formula (1) in the underlayer 1 can be applied as it is.
  • the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, a polymer thereof (preferably a 19-mer or less) or a hydrolyzate thereof.
  • the mixing ratio of each component is preferably from 40 to 900 parts by weight, more preferably from 250 to 500 parts by weight, per 100 parts by weight of the compound represented by the above formula (5). More preferred. It is prepared as a liquid containing a predetermined amount of the active ingredient in a liquid medium such as alcohol.
  • underlayers 1 to 5 are composed of two layers, for example, an antireflection layer, for example, an underlayer 3 or 4 is provided immediately below the antifouling layer, and a hard coat layer, for example, 2, 5 can be provided.
  • an antireflection layer for example, an underlayer 3 or 4 is provided immediately below the antifouling layer
  • a hard coat layer for example, 2, 5 can be provided.
  • a surfactant an alkali metal salt, conductive fine particles or a charge transfer complex can be added to these underlayers 1 to 5, thereby further imparting an antistatic property or conductivity to the underlayer.
  • a surfactant an alkali metal salt, conductive fine particles or a charge transfer complex
  • surfactant examples include “Electro stripper QN” (anionic), “Electro stripper-AC z” (amphoteric), “Electro stripper F”, “E “Rectrostripper EA” (non-ionic), “Amittle 302 J” (non-ionic, “raw"), “Homogenol L-18” (special polymer), “Homogenol L1820” (special polymer) ( “FZ-2105", “L-7604", “: L-177", “: L-17001", “FZ-2123”, “FZ-2123”, “FZ-2105”, manufactured by Kao Corporation — 2 16 2 ”(all non-ionic).
  • the amount of addition is preferably from 0.05 to 50 parts by weight based on 100 parts by weight of the active ingredient of the membrane.
  • the conductive fine particles include metals such as ATO (antimony tin oxide) having a particle diameter of 1 to 100 nm, metal oxides of ITO, and silver, which are usually in the form of a dispersion liquid. I have.
  • the addition amount is preferably 1 to 80 parts by weight per 100 parts by weight of the active ingredient of the membrane.
  • the fine particles those having a spherical, elliptical, fibrous, or scaly shape are used. In order to increase the conduction efficiency, fibrous or scaly ones are preferred.
  • Examples of the charge transfer complex include boron-based antistatic agent manufactured by Boron International Co., Ltd. such as high boron.
  • the addition amount is preferably 1 to 20 parts by weight based on 100 parts by weight of the active ingredient of the membrane.
  • an antifouling coating solution is applied on the above-described underlayer, and is applied at room temperature for 10 seconds to
  • This antifouling layer having a thickness of preferably 10 to 100 nm, more preferably 10 to 30 nm is formed.
  • This antifouling coating solution contains a silicon alkoxide, a fluoroalkyl group-containing silane compound and an acid.
  • the silicon alkoxide orchid or a polymer thereof (preferably 19 or less) or a hydrolyzate thereof is preferably used.
  • silane compound containing a fluoroalkyl group for example, a silane compound containing a fluoroalkyl group and containing an alkoxy group, an acyloxy group, or a chloro group can be preferably used.
  • a silane compound containing a fluoroalkyl group and containing an alkoxy group, an acyloxy group, or a chloro group can be preferably used.
  • compounds represented by the following chemical formulas (6) and (7) can be mentioned. Among these, one compound can be used alone, or two or more compounds can be used in combination.
  • R 11 is a carbon atom
  • a divalent organic group having 1 to 10 atoms for example, a methylene group or an ethylene group) or a group containing a silicon atom and an oxygen atom
  • X is a monovalent hydrocarbon group having 1 to 4 carbon atoms (for example, an alkyl group, Cycloalkyl group, aryl group) or a substituent selected from these derivatives, or hydrogen
  • p is 0, 1 or 2
  • Y is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group.
  • n is an integer of 0 to 12, preferably 3 to 12, R 12 is a methylene group, an ethylene group, or a group containing a silicon atom and an oxygen atom, X is H or an alkyl group, a cycloalkyl Group, a substituent selected from an aryl group or a derivative thereof, p is 0, 1 or 2)
  • Examples of the silane represented by the above formulas (6) and (7) include C 8 F 17 CH 2 CH 2 1 No. 2 , G 8 J? 17 H 2 CH 2 S i C 13 (3_heptadecafluorodecyltrichlorosilane) and C 8 F 17 CH 2 CH 2 S i (CH 3 ) C 1 2 is particularly preferably used.
  • a volatile acid such as hydrochloric acid, nitric acid, and acetic acid is preferably used.
  • an alcohol-based hydrophilic solvent As a solvent of the antifouling coating solution, an alcohol-based hydrophilic solvent, a ketone-based hydrophilic solvent, or the like is preferably used.
  • alcohol-based, chain-type saturated monohydric alcohols having 3 or less carbon atoms such as methanol, ethanol, 1-propanol and 2-propanol are more preferably used because of their high evaporation rate at room temperature.
  • the ketone-based hydrophilic solvent include acetone-methylethyl ketone.
  • the antifouling coating solution is preferably
  • the weight ratio of acid water is 0.02 or more, preferably 0.02 or more.
  • the antifouling coating solution can be prepared by dissolving the above components (A) to (C) in an alcohol-based solvent.
  • the chlorosilyl group-containing compound and the fluoroarylalkyl group-containing silane compound are converted into an alcohol and / or an alcohol.
  • it can be prepared by dissolving in a solvent containing water and substituting the chloro group of the chlorosilyl group-containing compound with an alkoxyl group or a hydroxyl group.
  • a primer layer can be provided between the underlayer and the transparent resin substrate in order to improve the adhesion between the underlayer and the transparent resin substrate.
  • an antistatic layer can be provided between the underlayer and the transparent resin substrate.
  • the primer layer is not particularly limited, but for example, a urethane-based, acryl-based, urethane acrylate-based or partially silanized main component whose concentration is adjusted with an organic solvent is used.
  • a silicone acryl-based primer solution CP710, manufactured by Nippon ARC Co., Ltd.
  • CP620 urethane-based primer solution
  • the treatment method is obtained by applying a treatment liquid for a primer layer to the surface of a transparent resin substrate and drying.
  • the preferred thickness of this primer layer is 0.5 to 5 m.
  • An organic solvent such as alcohol is used as a solvent for the treatment solution for the primer layer. But it can be water.
  • a film of ITO indium tin oxide
  • a sputtering method or the like can be formed directly below the underlayer by a sputtering method or the like.
  • examples of the material of the transparent resin base material include triacetyl cell mouth resin, polymethyl methyl acrylate resin, polycarbonate resin, polyethylene resin, polyethylene terephthalate resin, polystyrene resin, cycloolefin polymer, and polystyrene resin.
  • Transparent resins such as ether sulfone resin and aryldiglycol-l-ponate can be used. These transparent resin sheets and films are used as the base material.
  • the present invention relates to, for example, a light diffusion treatment film of a light guide plate for a mobile phone, a display, for example, a notebook type personal computer, a monitor, a PDP, a front plate of a projection TV, a surface treatment film of a PDA, and a surface treatment of a sunset panel monitor.
  • a light diffusion treatment film of a light guide plate for a mobile phone a display, for example, a notebook type personal computer, a monitor, a PDP, a front plate of a projection TV, a surface treatment film of a PDA, and a surface treatment of a sunset panel monitor.
  • a resin article coated with an antifouling film with high abrasion resistance and weather resistance that can be easily wiped off even if it adheres can be obtained with high production efficiency without the need for special equipment .
  • the base material, the method for forming the antireflection layer, the method for forming various coating layers, the evaluation method, and the like used in the examples and comparative examples are as follows.
  • Resin base material
  • PC Polycarbonate
  • PET Polyethylene terephthalate resin
  • COP Cycloolefin polymer
  • PMMA Polymethyl methacrylate
  • S i 0 2 is a high-frequency magnetron sputtering method, a sputtering gas and A r gas was 1. 2 / imZh r cities deposition.
  • the refractive index of the SiO 2 film was 1.46.
  • T I_ ⁇ 2 a sputtering gas a mixed gas of A r and 0 2 in a DC magnetron sputtering method was deposited at a rate of 1. 4 mZh r.
  • T i 0 2 film refractive index is 2.30 der seven this.
  • the values in the brackets indicate the values of the optical film thickness (refractive index nx physical film thickness d).
  • This low reflection layer liquid was applied by spin coating and dried at room temperature to a film thickness of 11 Onm.
  • Chain aggregated silica fine particle dispersion (average primary particle diameter 25 nm, average length 100 nm, solid content 15%, Nissan Chemical Co., Ltd. Snowtex II UP) While stirring 56 g, ethanol 20 g, concentrated hydrochloric acid lg was added, then 5.2 g of tetraethoxysilane was added, and the mixture was stirred for 2 hours, and then allowed to stand for 24 hours to react. Thereafter, 164 g of propylene glycol monomethyl ether is added, and aluminum acetylethylacetone is further added as a curing catalyst, followed by stirring to make the mixture uniform. Thereafter, 4 g of Paintant 19 (manufactured by Dow Corning Asia) was added to obtain a low reflection layer liquid. This low reflection layer liquid was applied by spin coating and dried at room temperature to a thickness of 110 nm.
  • a weatherable primer (CP 710, manufactured by Nippon ALC Co., Ltd.) was used as a silicone acryl-based primer solution. This primer solution was applied by spin coating so that the film thickness after curing became about 2 m, and heated at 110 ° C for about 30 minutes to prepare a primer layer 1.
  • primer layer 2 A general primer (CP 620, manufactured by Nippon Radio Co., Ltd.) was used as a urethane-based primer solution. This primer solution was applied by spin coating so that the film thickness after curing became about 2 m, and heated at 50 ° C. for 30 minutes to prepare a primer layer 2 . Formation of hard coat layer 1: ''
  • the hard coat liquid 1 was applied by spin coating so that the film thickness after hardening was 3 m, and heated at a temperature of 120 ° C for 30 minutes to prepare a hard coat layer 1.
  • 1,6-hexanedioldiacrylate 12.4 g 1,6-hexanedioldiacrylate 12.4 g, arnaminopropyl trimethoxysilane 1.6 g, 2-methoxypropanol 6.3 g, acetic acid 4.0 g, photopolymerization 0.8 g of benzophenone as an initiator and "NPC-ST-30" as a colloidal silica (manufactured by Nissan Chemical Co., Ltd., silica fine particles having an average particle diameter of 20 nm are dispersed in n-propyl cellosolve.
  • a flow control agent [Pain evening 19, manufactured by Dow Corning Asia Co., Ltd.] was added and then 100 g of 2-methoxypropanol was added, followed by stirring and homogenization. Disperse to provide scratch resistance Hard coating solution 2 for was obtained.
  • Hard coat liquid 2 is applied by spin coating so that the film thickness after curing becomes 5 m, and then the total UV irradiation energy is adjusted to 1,000 (mJZcm 2 ) by an ultraviolet lamp with an output of 120 WZ cm. Irradiate for 1 to 30 seconds to harden the coating Thus, a hard coat layer 2 was obtained.
  • the total ultraviolet irradiation energy value was measured with an integrated light meter (model: UIT-102 manufactured by Shio Electric Co., Ltd.).
  • Radio frequency (RF) - magnetron sputtering evening device use the I TO as a target, using the A r + 0 2 as a sputtering gas, a substrate temperature of 130 ° C, film formation rate: about 1 ⁇ m / An ITO film was formed at hr.
  • RF Radio frequency
  • This solution contains, in terms of weight ratio, Si derived from 3-heptadecafluorodecyltrimethoxysilane at a ratio of 0.6 to Si 100 derived from tetrachlorosilane, and about ⁇ It had a specified hydrochloric acid concentration, a water concentration of 0.35% by weight, and a pH of about 0.7.
  • the degree of polymerization of the tetraethoxysilane polymer in this solution was 1 to 3.
  • This solution was applied by flow coating at room temperature and a humidity of 30% at room temperature, and dried at room temperature for about 1 minute to obtain an antifouling film-coated resin article coated with an antifouling layer 1 having a thickness of about 60 nm. .
  • This solution contains Si derived from 3-heptadecafluorodecinoletrimethoxysilane at a ratio of 0.6 with respect to Si 100 derived from tetraethoxysilane, and about 0.2 N hydrochloric acid. Concentration, 1.6% by weight It had a water concentration and had a pH of about 0.7. The degree of polymerization of the tetraethoxysilane polymer in this solution was 1-3.
  • ⁇ The oil-based ink pen has repelled into a sphere.
  • Oil-based ink pen does not repel and can be written.
  • the oil-based pen adhering to the substrate surface was wiped off with a cellulose nonwoven fabric (Bencott M-3: manufactured by Asahi Kasei Corporation), and the easiness of removal was visually determined. The criteria are shown below. In addition, the number of times until wiping was measured.
  • the oil-based ink pen can be completely wiped off.
  • Fingerprints adhering to the substrate surface were wiped off with a cellulose nonwoven fabric (Bencott M-3: manufactured by Asahi Kasei Corporation), and the ease of removal was visually determined. The criteria are shown below. In addition, the number of times until wiping was measured.
  • ⁇ The fingerprint can be completely wiped off.
  • ⁇ Trace of fingerprint wiping remains.
  • X Fingerprint wiping marks spread and cannot be wiped off.
  • the surface of the obtained antifouling film-coated resin article was subjected to an abrasion resistance test in which the surface was rubbed 50 times with a load of 250 g / cm 2 using a cellulose nonwoven fabric (Bencott M-3: manufactured by Asahi Ichinari Co., Ltd.). Thereafter, the presence or absence of a scratch was visually determined. The criteria are shown below.
  • CA-DT contact angle meter
  • a water drop with a diameter of 5 mm is placed on the surface of the horizontally disposed antifouling film-coated resin article, and the antifouling film-coated resin article is gradually inclined, and the inclination angle at which the water drop placed on the surface starts to roll ( Critical inclination angle and falling angle) were measured.
  • the smaller the falling angle the better the dynamic water repellency, that is, the antifouling property (easiness of removing dirt).
  • the antifouling film coating of the antifouling film-coated resin article obtained in the present invention has a feature that its surface is very excellent in smoothness.
  • the surface roughness of the antifouling film-coated resin article is measured by arithmetic mean roughness (Ra) and ten-point mean roughness (Rz).
  • the surface roughness characteristics Ra and Rz can be measured by a method in which JIS B 0601-1982 defined in two dimensions is extended in three dimensions.
  • the fluorine concentration on the surface of the antifouling film of the antifouling film-coated resin article obtained in the present invention was measured by X-ray photoelectron spectroscopy (ESCA) as the atomic ratio of F to Si (FZSi).
  • the X-ray photoelectron spectroscopy (ESCA) test conditions were as follows: Anode energy: 146.6 eV, anode output: 150 W, acceleration using monochromated aluminum K-rays as the X-ray source Voltage: 14 kV, X-ray incident angle to the sample: 45 degrees, analysis area: 800 m diameter circle, ij constant thickness: several nm.
  • a primer layer 1 is formed on the polycarbonate sheet substrate, a hard coat layer 1 is formed thereon, and an antifouling layer 2 is further formed thereon, and a PC sheet Z primer layer 1 Z hard coat layer 1 is formed.
  • An antifouling film-coated resin article comprising the antifouling layer 2 was produced.
  • a primer layer, a hard coat layer, a functional film (transparent conductive layer), an antireflection layer, and an antifouling layer are formed in this order on the resin base material shown in Table 1.
  • the product was manufactured, and various performances were measured in the same manner as in Example 1. The results are shown in Table 1.
  • the hard coat liquid 2 instead of the hard coat liquid 2 used in the formation of the hard coat layer 2 in Example 2, the hard coat liquid 2 was further added with a boron-based antistatic agent “Hiboron KB2 12” (active ingredient 10%, manufactured by Boron International). Was added in the same manner as in Example 2 except that an antistatic hard coat solution obtained by adding 30 g of the antifouling film-coated resin article was produced.
  • Antistatic performance 1 0 "showed to 10 12 Omega / mouth. Other performance showed almost the same performance as in Example 2 without imparting antistatic.
  • the surfactant “FZ-2105” was used instead of 4 g of “Paintad 19” added in the preparation of the low reflection layer liquid.
  • Anti-reflective (antistatic) liquid with 5 g A resin article coated with an antifouling film was produced in the same manner as in Example 5 except that it was used. The antistatic performance showed 10 12 to 10 13 ⁇ square. Other performances were almost the same as those of Example 5 in which no antistatic was provided.
  • Example 1 a silicon-based material represented by [R f Si (OEt) 3: R f is a perfluoro group, Et is an ethyl group] containing a perfluoro group 0
  • An antifouling film-coated resin article was manufactured in the same manner as in Example 2 except that the coating solution was applied and dried at 66 ° C to form an antifouling layer, and various properties were measured in the same manner as in Example 2. Table 1 shows the results.
  • Example 8 was repeated except that the hard coat layer 2 formed in Example 8 was replaced with a resin substrate whose surface had been previously treated with a plasma containing oxygen to make it hydrophilic without forming a hard coat layer.
  • An antifouling film-coated resin article was manufactured in the same manner as in Example 1.
  • Various performances were measured in the same manner as in Example 8, and the results are shown in Table 1.
  • Example 4 COP film 2 Conductive film 3 Sol-gel method Si0 2 Fine particles 1 (IT0)
  • Example 5 COP film 1 : 4 sol-gel method Si0 2 chain-like fine particles 1
  • Example 6 PMMA film 2 3 sol-gel method Si0 2 fine particles 2
  • Example 7 COP film 2 High frequency magnetron Si0 2 / TiO / 1 Sputter Si0 2 / Ti0 2 / Si0 2
  • Example 8 PC film ⁇ 2- ⁇ ⁇ ⁇ 1 Comparative example 1
  • Example 1 110 5 1.1 8 ⁇ ⁇ 0 (3) 0.4 3.0 ⁇ 107
  • Example 2 111 4 1.2 0.3 ⁇ ⁇ 0 (3) 0.3 3.2 ⁇ 104
  • Example 3 109 6 1.1 0.2 ⁇ ⁇ 0 (3) 0.3 4.0 ⁇ 103
  • Example 4 111 12 1.2 0.8 ⁇ ⁇ 0 (5) 20 45.0 ⁇ 105
  • Example 5 110 5 1.2 0.5 ⁇ ⁇ 0 (5) 10 29.0 ⁇ 103
  • Example 6 112 13 1.1 0.8 ⁇ ⁇ 0 (5 ) 18 40.0 ⁇ 106
  • Example 7 110 5 1.2 0.2 ⁇ ⁇ 0 (3) 0.4 4.0 ⁇ 102
  • Example 8 111 7 1.28 ⁇ ⁇ 0 (3) 0.4 4.5 ⁇ 103
  • Comparative example 1 95 ⁇ 1 0.5 ⁇ ⁇ 0 ( 5) ⁇ ⁇ ⁇ 70
  • Comparative example 2 95 1 1 8 ⁇ ⁇ 0 (5) 1 ⁇ ⁇ 60

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé de production d'un article en résine revêtu par un film antitaches qui consiste : à disposer une sous-couche qui comprend une résine ou un composé inorganique et dont la surface est siliceuse sur la surface d'un matériau support en résine transparent ; à appliquer un liquide de revêtement contenant un alcoxyde de silicium, un composé silane possédant un groupe fluoroalkyle et un acide sur la sous-couche ; et à sécher. Le procédé de l'invention peut être mis en oeuvre pour la production d'un article en résine revêtu par un film antitaches qui permet de prévenir, sur la surface d'un matériau support en résine transparent, la formation de taches de type empreintes digitales, graisses de la peau, transpiration, produits cosmétiques et analogues ; d'éliminer facilement lesdites taches si celles-ci sont présentes sur le film ; et qui présente en outre une résistance élevée à la formation de taches et à l'altération, sans l'aide d'un dispositif spécial et à une productivité élevée.
PCT/JP2004/016055 2003-10-22 2004-10-22 Procede de production d'article en resine revetu par un film antitaches WO2005037901A1 (fr)

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JP2012088761A (ja) * 2010-10-15 2012-05-10 Hitachi Displays Ltd タッチパネルの製造方法、タッチパネル及び液晶表示素子
CN102019730A (zh) * 2010-12-21 2011-04-20 苏州禾盛新型材料股份有限公司 防污抗指纹抗牛顿环的透明导电复合板材
CN102962183B (zh) * 2012-12-10 2014-05-07 昆山伟翰电子有限公司 有机硅系产品表面封油方法
CN113166920A (zh) * 2018-11-13 2021-07-23 Ａｇｃ株式会社 带拒水拒油层的基材、蒸镀材料及带拒水拒油层的基材的制造方法
WO2020137992A1 (fr) * 2018-12-26 2020-07-02 Ａｇｃ株式会社 Substrat avec couche hydrofuge et oléofuge ainsi que procédé de fabrication de celui-ci, et matériau de dépôt en phase vapeur

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JP2002006107A (ja) * 2000-06-16 2002-01-09 Reiko Co Ltd 反射防止フイルム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002006107A (ja) * 2000-06-16 2002-01-09 Reiko Co Ltd 反射防止フイルム

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