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WO2013031738A1 - Film antibuée et article revêtu dudit film antibuée - Google Patents

Film antibuée et article revêtu dudit film antibuée Download PDF

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Publication number
WO2013031738A1
WO2013031738A1 PCT/JP2012/071615 JP2012071615W WO2013031738A1 WO 2013031738 A1 WO2013031738 A1 WO 2013031738A1 JP 2012071615 W JP2012071615 W JP 2012071615W WO 2013031738 A1 WO2013031738 A1 WO 2013031738A1
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Prior art keywords
film
antifogging
water
absorbing composite
composite film
Prior art date
Application number
PCT/JP2012/071615
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English (en)
Japanese (ja)
Inventor
大家　和晃
神谷　和孝
寺西　豊幸
周平 村田
Original Assignee
日本板硝子株式会社
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Publication of WO2013031738A1 publication Critical patent/WO2013031738A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L83/02—Polysilicates
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/75—Hydrophilic and oleophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/02—Polysilicates

Definitions

  • the present invention relates to an antifogging film and an antifogging film-coated article, and more particularly to an antifogging film formed on a hard substrate and an antifogging film-coated article having the antifogging film.
  • the antifogging film coated article in which an antifogging film is provided on a hard substrate is, for example, an antifogging mirror for bathrooms, toilets, etc., an antifogging window glass or antifogging mirror for automobiles, etc. It is used for various applications such as window glass.
  • Patent Document 1 As an antifogging film composed of a single layer film using a water-absorbing polymer compound, a coating type antifogging agent is disclosed in Patent Document 1 after applying only a polyvinyl acetal resin and then drying at room temperature to form an antifogging film. It is disclosed.
  • Patent Document 2 an antifogging layer made of a polyvinyl acetal resin having an acetalization degree of 2 to 40 mol% is provided on the surface of an article such as glass, a mirror, or a plastic film, or a water-soluble resin layer is provided on the article surface.
  • an antifogging article is disclosed in which an antifogging layer comprising a polyvinyl acetal resin having an acetalization degree of 2 to 40 mol% is provided thereon.
  • a water-absorbing composite film in which a polyvinyl acetal resin and an inorganic component are mixed for example, in Patent Document 3 and Patent Document 4, a hydrolyzate of a polyvinyl acetal resin having a degree of acetalization of 10 mol% or less and an alkylsilyl isocyanate or
  • An anti-fogging base material is disclosed in which a water-absorbing composite film in which a partial hydrolyzate is mixed, and a water-permeable protective film and water-repellent layer having a water permeability of 3 to 10 nm are laminated thereon.
  • an anti-fogging film in which a surfactant is dispersed in a film made of a water-absorbing resin for example, in Patent Document 5 and Patent Document 6, a urethane resin in which a surfactant and trialkanolamine are fixed is formed. Agents and antifogging membranes are disclosed.
  • JP-A-6-157794 Japanese Patent Laid-Open No. 6-158031 JP 2001-146585 A JP 2001-152137 A JP 60-85939 A JP 2004-269851 A
  • the water-absorbing composite film single layer cannot obtain high film hardness and wear resistance while maintaining sufficient anti-fogging properties.
  • a protective layer is required on the upper layer of the film. This is because in water-absorbing composite film monolayers, increasing the amount of alkylsilyl isocyanate added increases the proportion of the inorganic component (SiO 2 ) in the skeleton of the coating, thus improving scratch resistance and wear resistance.
  • the swelling and flexibility are lowered, the water absorption is lowered, the sufficient antifogging property cannot be maintained, the alkylsilyl isocyanate can be added only in a small amount, and the sufficient film hardness This is because no longer can be obtained.
  • a protective film having a water permeability and a water repellent layer are laminated as a protective layer, but it is necessary to increase the film thickness. As a result, the anti-fogging property is lost and the anti-fogging property, film hardness, and abrasion resistance cannot be combined in total.
  • Patent Document 5 it does not have film hardness or wear resistance that can be used for architectural or vehicle window glass or mirrors, and the surfactant is supported in the film.
  • the surface active agent flows out by wiping the poultice or repeatedly forming a water film on the surface, and the hydrophilicity is lowered in a short time.
  • the wear resistance is improved as compared with the prior art, it cannot be said that it is sufficient for architectural use or vehicle use.
  • the surfactant flows out, it is difficult to maintain excellent antifogging performance.
  • the present invention has been made under such circumstances, and has film hardness and abrasion resistance that can be used for construction, vehicles, or antifogging mirrors while maintaining sufficient antifogging properties.
  • the object of the present invention is to provide an antifogging film capable of maintaining excellent antifogging properties over a long period of time and an antifogging film-coated article having the antifogging film.
  • a water-absorbing composite film containing polyvinyl acetal resin, hydrolyzate or partial hydrolyzate of silicon alkoxide, and colloidal silica can have sufficient film hardness and wear resistance that can be used for construction and vehicles. I found out that I can do it. However, when the film has sufficient film hardness and wear resistance, the water absorption amount of the film decreases, and after the water absorption is saturated, the surface of the film becomes cloudy. On the other hand, it has been found that by imparting hydrophilicity to the surface of the coating, after water absorption is saturated, a water film is formed on the surface of the coating, so that no clouding occurs.
  • the surfactant flows out by wiping the coating surface with a compress or by repeatedly forming a water film on the coating surface.
  • the hydrophilicity of the coating surface is reduced in a short period of time.
  • the present inventors have found that wet cloth wear resistance and repeated anti-fogging properties can be greatly improved by high-density crosslinking on a porous composite film. The present invention has been completed based on such findings.
  • the present invention is as follows.
  • [1] A water-absorbing composite film containing a polyvinyl acetal resin, a hydrolyzate or partial hydrolyzate of silicon alkoxide, and colloidal silica, and a hydrophilic polymer brush fixed on the water-absorbing composite film.
  • Anti-fogging film [2] The antifogging film according to [1], including a primer layer between the water-absorbing composite film and the hydrophilic polymer brush.
  • the antifogging film according to [2] wherein the primer layer contains a hydrolyzate or partial hydrolyzate of ethyl silicate.
  • the water-absorbing composite film has 30 to 80 parts by mass of colloidal silica and 5 to 55 parts by mass of silica equivalent particles derived from a hydrolyzate or partial hydrolyzate of silicon alkoxide with respect to 100 parts by mass of the polyvinyl acetal resin.
  • the present invention while maintaining sufficient antifogging properties, it has film hardness and abrasion resistance that can be used for construction, vehicles, or antifogging mirrors, and has excellent antifoaming properties over a long period of time. It is possible to provide an antifogging film capable of maintaining the fogging property and an antifogging film-coated article having the antifogging film.
  • the antifogging film of the present invention comprises a water-absorbing composite film and a hydrophilic polymer brush fixed on the water-absorbing composite film.
  • a hydrophilic polymer brush fixed on the water-absorbing composite film.
  • the water-absorbing composite film contains a polyvinyl acetal resin, a hydrolyzate or partial hydrolyzate of silicon alkoxide, and colloidal silica.
  • the polyvinyl acetal resin used in the present invention can be obtained by subjecting polyvinyl alcohol to an acetalization reaction by condensing aldehyde with polyvinyl alcohol.
  • the degree of acetalization is usually set to 2 to 40 mol%, preferably 3 to 30%. It is set to mol%, more preferably 5 to 20 mol%.
  • the degree of acetalization can be measured based on, for example, 13 C nuclear magnetic resonance spectroscopy. If the degree of acetalization is in the range of 2 to 40 mol%, a water-absorbing composite film having good water absorption and water resistance and sufficiently exhibiting antifogging properties can be formed.
  • acetalization of polyvinyl alcohol a known method such as a precipitation method using an aqueous medium in the presence of an acid catalyst or a dissolution method using a solvent such as alcohol can be employed.
  • a polyvinyl acetal resin can also be obtained by using a polyvinyl acetate resin as a raw material and performing saponification and acetalization in parallel.
  • polyvinyl alcohol those having an average degree of polymerization of 200 to 4500, preferably 500 to 4500 are generally used.
  • the average degree of polymerization is 200 or more, it is possible to synthesize polyvinyl alcohol, and when the average degree of polymerization is 4500 or less, the solution viscosity does not become excessively high, and it is practically used as an antifogging film-coated article. From the viewpoint of sex. The higher the average degree of polymerization, the better the water resistance and water absorption.
  • the saponification degree of polyvinyl alcohol is generally 75 to 99.8 mol%.
  • the degree of saponification is 75 mol% or more, the solubility during the reaction is sufficient, and if it is 99.8 mol% or less, synthesis of polyvinyl alcohol becomes possible.
  • aldehyde to be subjected to condensation reaction with polyvinyl alcohol examples include aliphatic aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, hexyl carbaldehyde, octyl carbaldehyde, decyl carbaldehyde; benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde , Other aromatic aldehydes such as alkyl-substituted benzaldehyde, chlorbenzaldehyde, and other halogen-substituted benzaldehydes; aromatic aldehydes having a substituent such as hydroxy group, alkoxy group, amino group, cyano group on the aromatic ring; naphthaldehyde And aldehydes having a condensed aromatic ring such as anthraldehyde.
  • aromatic aldehyde is preferable in that a resin having good water absorption, water resistance, and transparency can be obtained.
  • Aromatic aldehydes have strong hydrophobicity and are excellent in water resistance even at a low degree of acetalization. Therefore, many hydroxyl groups remain and water absorption is excellent.
  • the content of the polyvinyl acetal resin in the water-absorbing composite film is usually 40 to 70% by mass, preferably 40 to 60% by mass, and more preferably 40 to 50% by mass from the viewpoints of film hardness, water absorption and antifogging properties. %.
  • Silicon alkoxide The water-absorbing composite film contains a hydrolyzate or partial hydrolyzate of silicon alkoxide as an essential component.
  • Silicon alkoxides include tetra acids that can be easily hydrolyzed with inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and organic acids such as p-toluenesulfonic acid, methanesulfonic acid, trichloroacetic acid, and trifluoroacetic acid to form silica.
  • Alkoxysilane is preferably used.
  • the four alkoxy groups of this tetraalkoxysilane may be the same or different, but from the viewpoint of availability, the same one is usually used.
  • the alkoxy group is preferably a lower alkoxy group having 1 to 4 carbon atoms from the viewpoint of hydrolyzability.
  • tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra- Examples thereof include tert-butoxysilane.
  • One of these tetraalkoxysilanes may be used alone, or two or more thereof may be used in combination.
  • the water-absorbing composite film preferably contains the silica-converted particles in an amount of 5 to 55 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin.
  • the content of the silica-converted particles is 5 parts by mass or more, the water-absorbing composite film has good antifogging properties and high pencil hardness.
  • the preferable content is in the range of 20 to 55 parts by mass, more preferably 30 to 55 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin.
  • Colloidal silica contained in the water-absorbing composite film is SiO 2 fine particles having an average particle diameter of about 5 to 50 nm.
  • the water-absorbing composite film has a certain degree of strength and flexibility.
  • the proportion of the inorganic component in the composite film can be increased, and the addition of this colloidal silica forms fine voids in the film, which makes it easier to incorporate moisture into the film. Therefore, the hardness of the coating can be improved while maintaining sufficient antifogging properties.
  • the proportion of the inorganic component in the film can be increased by adding colloidal silica, an antifogging film having sufficient film hardness and sufficient antifogging properties that does not cause scratches on the film even when the pencil hardness is 4H or higher.
  • the average particle size of the colloidal silica is too large, the haze value of the film becomes high and the film may become cloudy. If it is too small, aggregation tends to occur and the film cannot be uniformly dispersed. Therefore, the average particle size of colloidal silica is preferably in the range of 5 to 50 nm, more preferably in the range of 8 to 20 nm.
  • the average particle size of the colloidal silica can be measured by a laser diffraction light scattering method or the like.
  • the content of colloidal silica in the water-absorbing composite film is 30 to 80 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin described above.
  • the pencil hardness of the composite film can be 4H or more, and when it is 80 parts by mass or less, the hardness of the water-absorbing composite film is improved.
  • the preferred content of colloidal silica in the water-absorbing composite film is 50 to 80 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin from the viewpoint of pencil hardness.
  • a water-absorbing composite film-forming coating solution is prepared.
  • the water-absorbing composite film-forming coating solution can be prepared by the following method. Polyvinyl acetal resin, colloidal silica, and silicon alkoxide are added to the solvent at a predetermined ratio so that the content of these components in the resulting water-absorbing composite film satisfies the above-mentioned requirements. An appropriate amount of an inorganic acid or an organic acid as a decomposition catalyst is added, and various additives are added as necessary to prepare a coating solution for forming a composite film having a solid content concentration of 3 to 20% by mass.
  • an aqueous solvent that is a mixture of an organic solvent and water is preferable.
  • a polar solvent having miscibility with water such as alcohol, cellosolve, ketone, and ether can be used.
  • alcohol solvents examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, etc .; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and derivatives thereof; ketone solvents Are, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; examples of ether solvents include dioxane, tetrahydrofuran, and the like. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the water content is preferably 140 to 720 parts by mass, more preferably 400 to 600 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin.
  • a hydrolysis catalyst for the silicon alkoxide is added.
  • the hydrolysis catalyst it is preferable to use an acid catalyst, particularly an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, or an organic acid such as trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid or paratoluenesulfonic acid.
  • the concentration of the acid catalyst is preferably in the range of 0.001 to 2 mol / kg, expressed by the molar concentration of protons when it is assumed that the protons are completely dissociated from the acid.
  • the amount of water used for the hydrolysis is preferably 4 times or more, expressed by molar ratio with respect to the total amount of silicon alkoxide.
  • additives can be blended as necessary within a range that does not impair the object of the present invention.
  • additives include glycerin, ethylene glycol, polyethylene glycol, various other surfactants, leveling agents, ultraviolet absorbers, colorants, antifoaming agents, preservatives, silica for improving water absorption performance , Inorganic fillers such as talc, clay and alumina.
  • the water-absorbing composite film-forming coating solution prepared as described above is preferably stirred at room temperature for a predetermined time to allow the silicon alkoxide to hydrolyze to some extent, and then, on the hard substrate described above at room temperature. Apply.
  • the coating method is not particularly limited, but from the aspect of productivity, for example, flow coating method, spin coating method or dip coating method, reverse coating method, flexographic printing method, other roll coating method, curtain coating method, Further, a nozzle coating method, a spray coating method, a screen printing method, or the like can be used as appropriate.
  • the coating solution After applying the coating solution on the hard substrate, it is usually dried at room temperature for 5 to 20 minutes, and then subjected to heat treatment (prebaking) at a temperature of 50 to 130 ° C. for 5 to 60 minutes.
  • the thickness of the water-absorbing composite film thus formed is usually about 2 to 10 ⁇ m, preferably 2 to 6 ⁇ m.
  • the coating skeleton has a certain degree of strength and flexibility by adjusting the heating temperature and time, such as 10 minutes if the heating temperature is 120 ° C and 30 minutes to 60 minutes if the heating temperature is 60 ° C.
  • the coating film can be cured as it is, and the performance of the coating film such as hardness, abrasion resistance, and wet cloth abrasion resistance can be improved while maintaining sufficient antifogging properties. Further, since the proportion of colloidal silica and silicon alkoxide hydrolyzed or partially hydrolyzed in the film can be increased, the film hardness and sufficient anti-fogging property that the film is not scratched even when the pencil hardness is 4H or higher are provided. It can be set as an anti-fogging film.
  • the hydrophilic polymer brush immobilized on the water-absorbing composite membrane can be synthesized by, for example, the method described in JP 2010-57745 A. That is, a monomer composition having a hydrophilic group on the surface of a base material (for example, a hard substrate) is polymerized by an atom transfer radical polymerization method (ATRP) in the presence of a polymerization initiator to form a polymer brush on the surface of the base material. It can be manufactured through a step of forming. Since the hydrophilic polymer brush has a structure in which a large number of hydrophilic groups are bonded to the main chain in a brush shape, a surface having a large number of hydrophilic groups per unit area can be obtained.
  • a base material for example, a hard substrate
  • ATRP atom transfer radical polymerization method
  • the hydrophilic group is a hydrophilic group obtained by polymerizing N-methacryloyloxyethyl-N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine (hereinafter referred to as CMB) as a monomer. Highly suitable.
  • the polymerization initiator is preferably an organosilane compound.
  • organosilane compounds include (11- (2-bromo-2-methyl) propionyloxy) undecyltrichlorosilane, (4- (2-bromo-2-methyl) propionyloxy) butyltrichlorosilane, (6- ( And reactive silane-containing initiators such as 2-bromo-2-methyl) propionyloxy) hexyltrichlorosilane and (8- (2-bromo-2-methyl) propionyloxy) octyltrichlorosilane.
  • the amount of the polymerization initiator is preferably 0.001 to 10 mol, more preferably 0.01 to 5 mol, per 100 mol of the monomer.
  • the polymerization of the monomer composition can be performed, for example, by immersing the base material in a mixed solution of the monomer composition, the polymerization initiator, and the organic solvent.
  • a substrate having a hydroxyl group such as a glass plate as a substrate and using an organic silane compound as a polymerization initiator
  • the hydroxyl group on the substrate surface is not sufficient, it is preferable to provide a primer layer on the substrate surface in advance before attaching the organosilane compound so that the organosilane compound can be bonded at high density.
  • organic solvent for example, alcohol, such as water, methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, ketones, such as acetone and methyl ethyl ketone, alkyl ethers, such as diethyl ether and tetrahydrofuran, benzene
  • solvents used in usual solution polymerization such as aromatics such as toluene and xylene, hydrocarbons such as n-hexane and c-hexane, and acetates such as methyl acetate and ethyl acetate. It is preferable to use an organic solvent that has been deaerated beforehand using an inert gas or the like.
  • the amount of the organic solvent used is preferably adjusted so that the concentration of the monomer composition in the solution containing the monomer composition is 10 to 80% by mass.
  • a monovalent copper salt such as copper bromide or copper chloride
  • a polyvalent base such as bipyridyl or trisaminodiethylamine
  • a free initiator such as ethyl-2-bromoisobutyrate, or the like. You may coexist.
  • the polymerization conditions such as temperature and time for polymerizing the monomer composition are appropriately selected depending on the type of the polymerizable monomer and the polymerization initiator, and are not particularly limited.
  • the polymerization of the monomer composition is inactive. Although it proceeds even at room temperature in a gas atmosphere, the smaller the amount of unreacted monomer in the resulting polymer, the better.
  • the polymerization of the monomer composition is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • the weight average molecular weight of the polymer after polymerization of the monomer composition is preferably 1,000 to 1,000,000, more preferably 5000 to 100,000, from the viewpoint of the rheological properties of the polymer, hydrophilicity, and hydrophobic balance.
  • the weight average molecular weight of the polymer is measured by gel permeation chromatography.
  • the primer layer contains, for example, a hydrolyzate or partial hydrolyzate of silicon alkoxide, or colloidal silica together with them.
  • a hydrolyzate or partial hydrolyzate of silicon alkoxide, or colloidal silica together with them.
  • those having many silanol groups on the surface and water permeability to the underlying water-absorbing composite film are preferable, and hydrolyzate or partial hydrolyzate of silicon alkoxide or colloidal silica is added thereto. Those are preferred.
  • the amount of silicon alkoxide added to the primer layer forming coating solution is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.5% by mass in terms of silica solid content. If the amount of silicon alkoxide added is too small, a sufficient primer layer that can immobilize the polymer brush will not be formed, and if it is too large, the film thickness will be too thick and the water permeability to the water-absorbing composite film will be lost. There is a risk of cracks. By adding an acid catalyst to the coating solution, the hydrolysis of the silicon alkoxide can be promoted, and cracks in the primer layer can be suppressed. However, if the acid concentration becomes too high, handling becomes difficult and workability is reduced. .
  • a preferable addition amount is 0.1 to 4% by mass, and more preferably 0.5 to 2.0% by mass. Further, water may be added as appropriate in accordance with the hydrolysis of the silicon alkoxide, but when the primer layer is formed by drying at room temperature, it may be added without addition or in a small amount.
  • the coating solution is applied on a glass substrate or a water-absorbing composite film at room temperature.
  • the coating method is not particularly limited, but from the aspect of productivity, for example, flow coating method, spin coating method or dip coating method, reverse coating method, flexographic printing method, other roll coating method, curtain coating method, Further, a nozzle coating method, a spray coating method, a screen printing method, or the like can be used as appropriate.
  • the primer layer can be formed by drying at room temperature or drying by heating. When the coating liquid is absorbed by the water-absorbing composite film on the substrate, the primer layer is applied once and dried, and then the primer layer is applied again to the surface and dried to obtain the necessary primer layer. Can be formed on the water-absorbing composite membrane.
  • a hydrolyzed solution of ethyl silicate may be used, for example, Colcoat HAS series and Colcoat N-103X.
  • ethyl silicate hydrolyzate has a high binder property, so that a good primer layer can be formed only by adding a small amount.
  • the amount of ethyl silicate hydrolyzed solution added is preferably 0.005 to 0.5% by mass, more preferably 0.01 to 0.2% by mass, based on the primer layer forming coating solution. is there.
  • colloidal silica it is very effective to add colloidal silica to the primer layer to prevent the primer layer forming coating solution from being absorbed into the water-absorbing composite film and to improve water permeability and abrasion resistance.
  • colloidal silica By adding colloidal silica to the primer layer forming coating solution composed of the above silicon alkoxide, acid catalyst, and alcohol, the coating solution can be prevented from being absorbed into the water-absorbing composite film.
  • a primer layer capable of immobilizing the polymer brush can be formed with the coating.
  • the colloidal silica forms voids in the primer layer, which not only increases water permeability, but also forms irregularities on the surface, so that the polymer brush enters the dents to improve wear resistance and improve hydrophilicity for a long time. Will be maintained over time.
  • the average particle size of the colloidal silica is preferably in the range of 5 to 50 nm, more preferably in the range of 8 to 20 nm.
  • the amount of colloidal silica added is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass with respect to the primer layer forming coating solution. . If the amount of colloidal silica added is too small, the above-mentioned effects of water permeability and abrasion resistance cannot be obtained, and if too much, not only the primer layer becomes too thick and water permeability is lost, There is a risk of cracks.
  • the anti-fogging film of the present invention has a water absorption function (function to prevent water fog by adsorbing water droplets adhering to the film inside) and a hydrophilic function (function to prevent water fog from forming water drops adhering to the film).
  • a water absorption function function to prevent water fog by adsorbing water droplets adhering to the film inside
  • a hydrophilic function function to prevent water fog from forming water drops adhering to the film.
  • the antifogging film-coated article of the present invention has a hard substrate and the antifogging film of the present invention formed on the hard substrate.
  • the hard substrate used as the base material include various mirrors and a translucent hard substrate.
  • the translucent hard substrate for example, a polycarbonate substrate, a plastic substrate such as an acrylic resin substrate such as a polymethyl methacrylate substrate, or a glass substrate can be used depending on the situation, but in these, From the viewpoint of forming a water-absorbing composite film having high pencil hardness, a glass substrate is preferable.
  • the glass substrate is a plate glass commonly used for automobiles, buildings, industrial glasses, etc., so-called float glass, etc., various colored glasses such as clear, green, bronze, various functional glasses, tempered glass and the like.
  • various types of flat glass products such as multi-layer glass, flat plates and bent plates can be used.
  • the plate thickness is, for example, about 1 mm to 12 mm. Particularly, 3 mm to 10 mm is preferable for construction, and 2 mm to 5 mm is preferable for automobiles.
  • the plate thickness is usually about 2 to 8 mm, preferably 3 to 6 mm.
  • an oxidation method, a concavo-convex method, or the like may be applied to the surface on which the water-absorbing composite film is formed, if desired
  • the surface treatment can be performed.
  • the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
  • a processing method etc. are mentioned. These surface treatment methods are appropriately selected depending on the type of plastic substrate to be used. In general, corona discharge treatment is preferably used from the viewpoints of effects and operability.
  • the anti-fogging film-coated article of the present invention is an article in which a water-absorbing composite film having excellent anti-fogging property and high pencil hardness is provided on a hard substrate, in particular, a light-transmitting hard substrate. And antifogging mirrors for use in bathrooms, toilets, etc., antifogging window glass and antifogging mirrors for automobiles, etc., and antifogging window glass for buildings.
  • Appearance Appearance (presence of whitening and cracks) of the coating film of the obtained glass substrate with an antifogging film was visually observed and evaluated according to the following criteria.
  • Pencil hardness According to JIS K 5400 paint general test method, the surface of the film was scratched 5 times with a pencil to which a load of 1 kg (9.8 N) was applied, and the film was broken less than 2 times. The hardness was defined as pencil hardness.
  • Solmix AP-7 alcohol solvent (manufactured by Nippon Alcohol Industry)
  • -SREC KX-5 Polyvinyl acetal resin: (manufactured by Sekisui Chemical Co., Ltd., solid content 8%)
  • Snowtex OS colloidal silica (Nissan Chemical Industries, Amorphous silica 20%, particle size 8-11 nm)
  • TsOH p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Inc.)
  • TEOS Tetraethoxysilane (Shin-Etsu Silicone, KBE-04),
  • ⁇ KP-341 Leveling agent (Shin-Etsu Silicone)
  • HAS-6 ethyl silicate hydrolyzate (manufactured by Colcoat)
  • N-103X ethyl silicate hydrolyzate (manufactured by Colcoat)
  • HCl hydroochloric acid
  • Example 1 The coating solution for forming a water-absorbing composite film shown in Table 1 was applied by flow coating on a washed soda-lime silicate glass substrate (100 ⁇ 100 mm) in an environment of humidity 30% and room temperature 20 ° C. After drying for about 10 minutes under the same environment, the glass substrate with a water-absorbing composite film was obtained by heating and drying for 10 minutes in a clean oven set at 120 ° C. Next, the primer layer forming coating solution 1 shown in Table 2 was applied on the formed water-absorbing composite film by the flow coating method, dried for about 5 minutes, and then again the primer forming solution was applied by the flow coating method. After applying for about 5 minutes and drying for about 5 minutes, it was heated and dried in a clean oven set at 120 ° C. for 30 minutes to form a primer layer on the water-absorbing composite film.
  • Step 1 Silane coupling treatment to substrate surface
  • 18.1 g (40 mmol) of (11- (2-bromo-2-methyl) propionyloxy) undecyltrichlorosilane (Br-PUCS) was dissolved in 150 mL of toluene to prepare a coupling solution.
  • a glass substrate with a primer layer formed on a water-absorbing composite film is placed in a sample bottle, a coupling solution is added so that the glass substrate is completely immersed, the lid is covered, and the mixture is reacted at room temperature for 18 hours. Take out, wash with toluene, and dry with nitrogen gas, and bond Br-PUCS which is a polymerization initiator on the primer layer.
  • Step 2 Polymerization of CMB on primer layer
  • CuBr copper bromide
  • CMB N-methacryloyloxyethyl-N
  • CMB N-dimethylammonium- ⁇ -N-methylcarboxybetaine
  • a glass substrate was inserted, air was expelled with argon gas, the lid was closed, and atom transfer radical polymerization (ATRP) was started. Ethyl-2-bromoisobutyrate was used as a free initiator to obtain free CMB polymer. After 6 hours, the lid is opened and the reaction is terminated by contacting (deactivating) the air and the solution. The glass substrate is taken out, washed with ethanol and water, dried with nitrogen gas, and the CMB polymer chain on the outermost surface.
  • a CMB polymer was synthesized alone without using glass with Br-PUCS attached. Specifically, 30.9 mg (0.2143 mmol) of copper bromide (CuBr), 67.0 mg (0.4286 mmol) of 2,2′-bipyridyl and 1.007 g (4.317 mmol) of CMB were placed in a sample bottle, and ethyl-2 -32 ⁇ L (0.2143 mmol) of bromoisobutyrate and 10 mL of methanol degassed by argon gas bubbling were added, air was purged with argon gas, the lid was closed, and atom transfer radical polymerization (ATRP) was started.
  • CuBr copper bromide
  • 67.0 mg (0.4286 mmol) of 2,2′-bipyridyl and 1.007 g (4.317 mmol) of CMB were placed in a sample bottle, and ethyl-2 -32 ⁇ L (0.2143 mmol) of bromois
  • the obtained CMB polymer had a weight average molecular weight Mw of 15600 and an n number (degree of polymerization) of 43.52 on average. Therefore, it is presumed that polymer chains having an n number of CMB of 43.52 are also arranged on the glass substrate surface with the antifogging film.
  • Example 2 Antifogging in the same manner as in Example 1 except that the primer layer forming coating solutions 2 to 5 (corresponding to Examples 2 to 5 respectively) shown in Table 2 were applied on the water-absorbing composite film by the flow coating method. A glass substrate with a film was obtained.
  • Example 1 In the antifogging film obtained in Example 1, no irregularities, unevenness, whitening, cracks, etc. were observed in the appearance, and a good coating film free from fogging by breath was obtained.
  • a film hardness of 6H was obtained, and when a Taber abrasion test was performed, no film peeling occurred, and the difference in haze value before and after the test was 4% or less.
  • a coating film having excellent properties could be obtained.
  • Evaluation of anti-fogging properties after the compressive wear test showed that the surface hydrophilicity was maintained even though slight exhalation caused distortion due to cloudiness and water film non-uniformity, and formed on the water-absorbing composite film. It was confirmed that the polymer brush was crosslinked by the primer layer. Moreover, peeling, a crack, and a crack were not seen in the coating-film external appearance after a test.
  • Example 2 In the antifogging film obtained in Example 2, no irregularities, unevenness, whitening, cracks, etc. were observed in the appearance, and a good coating film free from fogging by exhalation was obtained.
  • a film hardness of 6H was obtained, and when a Taber abrasion test was performed, no film peeling occurred, and the difference in haze value before and after the test was 4% or less.
  • a coating film having excellent properties could be obtained.
  • the antifogging property after the compressive wear test was evaluated, the antifogging property was maintained even though slight exhalation caused distortion due to the non-uniformity of the water film.
  • colloidal silica the antifogging wear resistance was maintained. Improved. Moreover, peeling, a crack, and a crack were not seen in the coating-film external appearance after a test.
  • the coating film had no irregularities, unevenness, whitening or cracks in its appearance, and was a good coating film that was not fogged by exhalation. was gotten. Further, when the pencil hardness of the obtained coating film was measured, a film hardness of 9H was obtained, and in the Taber abrasion test, no film peeling occurred and the difference in haze value before and after the test was 4% or less. An excellent coating film could be obtained. Furthermore, when the antifogging property after the compressive wear test was evaluated, no fogging or distortion occurred, the excellent antifogging property was maintained, and no peeling, scratches or cracks were observed in the coating film appearance.
  • Comparative Example 1 has a film hardness of about 6H pencil hardness and abrasion resistance that can withstand the Taber abrasion test, but the hydrophilicity of the coating surface is due to the surfactant dispersed in the coating, The anti-fogging performance could not be maintained because the surfactant flowed out by the abrasion test.

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  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

La présente invention concerne : un film antibuée capable de conserver d'excellentes propriétés antibuée sur une longue période de temps, ledit film antibuée ayant une dureté de film et une résistance à l'abrasion suffisantes pour pouvoir être utilisé dans les domaines de la construction et de l'automobile ou dans un miroir antibuée tout en conservant des propriétés antibuée adéquates ; et un article revêtu d'un film antibuée utilisant le film antibuée selon l'invention. La présente invention est un film antibuée comprenant : un film composite absorbant l'humidité contenant une résine polyacétal de vinyle, un hydrolysat ou un hydrolysat partiel d'alcoxyde de silicium, et une silice colloïdale ; et une brosse polymère hydrophile fixée sur le film composite absorbant l'humidité. Un article revêtu d'un film antibuée utilisant le film antibuée selon l'invention est également décrit.
PCT/JP2012/071615 2011-08-29 2012-08-27 Film antibuée et article revêtu dudit film antibuée WO2013031738A1 (fr)

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WO2016129699A1 (fr) * 2015-02-13 2016-08-18 日本板硝子株式会社 Pare-brise
JPWO2018016452A1 (ja) * 2016-07-20 2019-05-16 日本板硝子株式会社 ウインドシールド及びウインドシールドの製造方法
CN111621240A (zh) * 2020-06-05 2020-09-04 中国科学院兰州化学物理研究所 一种聚合物刷修饰的透明防雾贴片及其制备方法
EP3692006A4 (fr) * 2017-10-04 2021-10-06 MCS Industries, Inc. Revêtement antibuée et procédé d'application
CN117227279A (zh) * 2022-06-14 2023-12-15 Ａｇｃ株式会社 带防雾层基板及带防雾层基板的制造方法

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JP2010057745A (ja) * 2008-09-04 2010-03-18 Osaka Organic Chem Ind Ltd 医療用材料
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JP2000129210A (ja) * 1998-10-28 2000-05-09 C I Kasei Co Ltd 農業用軟質塩化ビニル樹脂フイルム用べたつき防止剤およびその製造方法
JP2001152137A (ja) * 1999-11-26 2001-06-05 Central Glass Co Ltd 防曇性被膜形成基材およびその製造方法
JP2001316626A (ja) * 2000-05-02 2001-11-16 Seikoh Chem Co Ltd コーティング剤
JP2003321667A (ja) * 2002-05-01 2003-11-14 Showa Highpolymer Co Ltd 防曇剤組成物
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WO2016129699A1 (fr) * 2015-02-13 2016-08-18 日本板硝子株式会社 Pare-brise
JPWO2016129699A1 (ja) * 2015-02-13 2017-11-24 日本板硝子株式会社 ウインドシールド
JPWO2018016452A1 (ja) * 2016-07-20 2019-05-16 日本板硝子株式会社 ウインドシールド及びウインドシールドの製造方法
JP6998872B2 (ja) 2016-07-20 2022-01-18 日本板硝子株式会社 ウインドシールド及びウインドシールドの製造方法
EP3692006A4 (fr) * 2017-10-04 2021-10-06 MCS Industries, Inc. Revêtement antibuée et procédé d'application
US11673827B2 (en) 2017-10-04 2023-06-13 Mcs Industries, Inc. Anti-fogging coating and application process
CN111621240A (zh) * 2020-06-05 2020-09-04 中国科学院兰州化学物理研究所 一种聚合物刷修饰的透明防雾贴片及其制备方法
CN111621240B (zh) * 2020-06-05 2021-03-16 中国科学院兰州化学物理研究所 一种聚合物刷修饰的透明防雾贴片及其制备方法
CN117227279A (zh) * 2022-06-14 2023-12-15 Ａｇｃ株式会社 带防雾层基板及带防雾层基板的制造方法

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