WO2015015801A1 - Composition de revêtement - Google Patents

Composition de revêtement Download PDF

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Publication number
WO2015015801A1
WO2015015801A1 PCT/JP2014/003979 JP2014003979W WO2015015801A1 WO 2015015801 A1 WO2015015801 A1 WO 2015015801A1 JP 2014003979 W JP2014003979 W JP 2014003979W WO 2015015801 A1 WO2015015801 A1 WO 2015015801A1
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group
acid
metal
film
coating composition
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PCT/JP2014/003979
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English (en)
Japanese (ja)
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淳司 岩佐
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日本曹達株式会社
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Priority to JP2015529392A priority Critical patent/JP6077659B2/ja
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    • 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
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
    • 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
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates

Definitions

  • the present invention relates to a coating composition, and more particularly to a coating composition containing tetraalkoxysilane and / or a condensate thereof.
  • the alcoholic silica sol solution obtained by mixing this and alkoxysilanes with water using an inorganic strong acid or organic strong acid as a catalyst, followed by hydrolysis and polycondensation does not cause precipitation or gelation when mixed with the water glass.
  • a low-temperature curable composition characterized by mixing with a sol solution (B) diluted with water to an extent is known.
  • a coating composition for a metal material which is made of silicic acid or is formed by adding at least one selected from organic silicon compounds represented by the following general formulas (1) to (3) to silicic acid, are known.
  • R 1 is a hydrocarbon substituted with one or more of epoxy group, vinyl group, methacryl group, amino group, mercapto group, imidazole group, halogen, hydroxyl group, styryl group, acrylic group, and ether A bond or an ester bond may be included.
  • R 2 and R 3 are alkyl groups having 1 to 5 carbon atoms and may contain an ether bond.
  • n an integer of 1 to 3]
  • R 2 and R 3 have the same meaning as in the general formula (1), and R 4 represents m is 2 to 10, x and y are 0 or 1
  • R 5 is an alkyl group having 1 to 5 carbon atoms
  • R 6 is hydrogen, an alkyl group having 1 to 5 carbon atoms
  • Z is 0 or 1
  • R 7 is a hydrocarbon group that may contain —Si (OR 2 ) n R 3 3-n (R 2 , R 3 , n is as defined in the general formula (1)) ) (Wherein R 8 represents an alkyl group having 1 to 5 carbon atoms)
  • the base material to which the coating composition can be applied examples include wood, various metals, concrete, mortar, asbestos, slate, natural stone, gypsum and the like, but the resin base material is not exemplified and will be described later.
  • the present invention has been made in view of the above circumstances, and can be applied to a wide range of base materials including resins, and the surface of the base material can be made hydrophilic without surface modification treatment represented by UV / ozone treatment or plasma treatment.
  • An object of the present invention is to provide a coating composition which is modified to a surface having high reactivity and high reactivity and becomes a base film suitable for an inorganic film or a monomolecular film.
  • a coating composition containing tetraalkoxysilane and / or its condensate, silicate, and surfactant can be used to cure at low temperature and to be hydrophilic and highly reactive.
  • the inventors have found that a modified surface having a surface can be obtained, and have completed the invention.
  • the present invention (1) A coating composition containing tetraalkoxysilane and / or a condensate thereof, a silicate and a surfactant, and (2) the above (1), wherein the silicate is sodium metasilicate
  • the present invention relates to the coating composition described above, and further relates to (3) a thin film obtained by applying the coating composition described in (1) or (2) above on a substrate and curing it by room temperature and / or heat drying.
  • the thin film obtained by the coating composition of the present invention can be cured at a low temperature, a coating film can be formed on a base substrate having low heat resistance, for example, a resin substrate, and has excellent adhesion to the substrate. .
  • a transparent conductive film or a gas barrier film or the like is applied to the obtained thin film without performing high activation treatment such as UV / ozone treatment. It is possible to laminate an inorganic film or a monomolecular film.
  • FIG. 3 is a diagram obtained by measuring the distribution of each element component in the film thickness direction of the coated film (B-1) obtained in Example 1 by X-ray photoelectron spectroscopy.
  • the coating composition of the present invention is a liquid composition containing tetraalkoxysilane and / or its condensate, silicate, and surfactant. Usually, it contains water and / or an organic solvent.
  • each R 11 independently represents an alkyl group which may have a substituent.
  • An alkyl group having 1 to 6 carbon atoms is preferred.
  • Examples of the “alkyl group” of the “optionally substituted alkyl group” for R 11 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
  • N-pentyl group isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group, n-dodecyl group, n- An octadecyl group etc. are mentioned.
  • the “substituent” of the “optionally substituted alkyl group” include a halogen atom, an alkoxy group, a (meth) acryloxy group and the like.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms such as methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group and t-butyloxy group.
  • Examples of the compound represented by the formula (I) include, but are not limited to, the following compounds.
  • These tetraalkoxysilanes may be used alone or in combination of two or more.
  • the tetraalkoxysilane condensate of the present invention is an oligomer obtained by condensing tetraalkoxysilane.
  • water and silanol condensation catalyst are added to tetraalkoxysilane, and 5 to 100 ° C, preferably 20 to 60 ° C. It is obtained by reacting for 10 minutes to 10 days, preferably 30 minutes to 24 hours.
  • the mixing ratio of water is 0.1 to 2000 mol, preferably 0.5 to 1000 mol, per 1 mol of tetraalkoxysilane.
  • the mixing ratio of the silanol condensation catalyst to the tetraalkoxysilane is 0.1: 99.9 to 10: 1, preferably 1:10 to 1: 1 by mass ratio.
  • the silanol condensation catalyst is not particularly limited as long as it hydrolyzes the alkoxy group of tetraalkoxysilane and condenses silanol to form a siloxane bond, and organic metal, organic acid metal salt, acid, base, metal chelate compound , Their hydrolysates, or their condensates.
  • a silanol condensation catalyst can be used individually by 1 type or in combination of 2 or more types.
  • organic metal examples include alkyl metal compounds such as tetramethyl titanium and tetrapropyl zirconium, and metal alcoholates such as tetraisopropoxy titanium and tetrabutoxy zirconium.
  • organic acid metal salts include carboxylic acid metal salts, sulfonic acid metal salts, and phenol metal salts.
  • metal chelate compound examples include metal chelate compounds with ⁇ -ketocarbonyl compounds, ⁇ -ketoester compounds, ⁇ -hydroxyester compounds and the like.
  • Examples of the acid include organic acids and mineral acids. Specific examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like. Examples of the mineral acid include hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, and the like.
  • a photoacid generator that generates an acid by light irradiation, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like are also included in the acid.
  • the base include strong bases such as tetramethylguanidine and tetramethylguanidylpropyltrimethoxysilane; organic amines such as diethylenetriamine, carboxylic acid neutralized salts thereof, and carboxylic acids of imidazoles such as 2-methylimidazole acetate. Neutralized salts, quaternary ammonium salts and the like can be mentioned.
  • the average particle diameter of the tetraalkoxysilane condensate used in the present invention is preferably 1 to 100 nm, more preferably 1 to 10 nm, from the viewpoint of film hardness, coating unevenness during coating, and the like.
  • silicate examples of the silicate used in the present invention include metasilicate, orthosilicate, and sesquisilicate.
  • examples of the silicate salt include alkali metal salts such as sodium, potassium and lithium. These silicates may be used alone or in combination of two or more. From the viewpoint of the stability of the coating composition and the reactivity of the surface of the thin film obtained by coating, an alkali metal metasilicate is preferred, and sodium metasilicate is most preferred.
  • the surfactant used in the present invention is not particularly limited, and can be used as a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, or a combination thereof. .
  • Nonionic surfactants include acetylene glycol, oxyethylene adducts of acetylene glycol, acetylene polyoxyethylene oxide, alkyl alkanolamides, alkyl polyglycosides, oxyethylene dodecylamine, oleic acid diethanolamide, glycerin fatty acid esters, glycerol stearate , Sucrose fatty acid ester, sorbitan oleate, sorbitan stearate, sorbitan sesquioleate, sorbitan palmitate, sorbitan laurate, sorbitol, pentaerythritol fatty acid ester, polyether modified silicone, polyester modified silicone, polyoxyethylene alkylpropylenediamine, Polyoxyethylene glycol fatty acid ester; Polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate; Polyoxyethylene sorbitol fatty acid ester, polyoxyethylene
  • Cationic surfactants include 1-hydroxyethyl-2-alkylimidazoline quaternary salt, alkylammonium chloride, alkylisoquinolinium bromide, alkyldimethylbenzylammonium chloride, alkylpyridinium salt, alkylpropylenediamine acetate, octadecylamine Acetate, tetradecylamine acetate; Polyoxyethylene alkylamines such as dihydroxyethyl stearylamine; Fatty acid amidoamine salts such as stearamide ethyl diethylamine acetate; Fatty acid ester amine salts such as triethanolamine monostearate formate; Alkylamine salts such as laurylamine acetate; Alkylbenzyldimethylammonium salts such as benzalkonium chloride; Lauryl pyridinium chloride; Alkyltrimethylammonium halides such as octyltrimethylam
  • anionic surfactant examples include alkyl diphenyl ether disulfonic acid, dibutyl phenyl phenol disulfonic acid, alkyl sulfosuccinic acid ester di-salt, dialkyl sulfosuccinic acid ester salt, dioctyl sulfosuccinic acid sodium salt, diether hexyl sulfosuccinic acid sodium salt, alkyl sulfate ester salt, alkylbenzene Sulfonates, alkyl naphthalene sulfonates, isopropyl naphthalene sulfonates, alkyl phosphate esters, alkyl phosphates, dithiophosphate esters, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfosuccinates Salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl ether phosphat
  • amphoteric surfactants examples include dodecylbetaine, octadecylbetaine, dodecylcarboxymethylhydroxyethylimidazolinium betaine, dodecyldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine. These surfactants may be used alone or in combination of two or more. Among these surfactants, cationic or nonionic surfactants are preferable from the viewpoint of excellent coating properties and coating liquid stability.
  • Organic solvents include alcohols (methanol, ethanol, propyl alcohol, 2-propanol (isopropyl alcohol), n-butanol, s-butanol, t-butanol, n-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene Glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), ethers (tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc.), ketones (acetone, methyl ethyl ketone, acetylacetone, etc.), esters (Methyl acetate, ethylene glycol monoacetate, etc.), amides (forma De, N- methylformamide, pyrrolidone, N- methylpyrrolidone) and the like
  • a known compound as a component of the coating composition can be added to the coating composition of the present invention.
  • examples thereof include inorganic fine particles such as colloidal silica and colloidal alumina, dyes, pigments, dispersion materials, water repellent materials, thickeners, fragrances, and antibacterial components.
  • the coating composition of this invention does not have limitation in particular, For example, it can prepare by the following method. An aqueous solution in which a silicate and a surfactant are dissolved and an organic solvent are mixed, and tetramethoxysilane and / or a condensate thereof are added dropwise to the mixture.
  • the concentration of the tetraalkoxysilane and / or its condensate in the coating composition is 0.1 to 50% by mass, preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass.
  • the concentration of the silicate in the coating composition is 0.001 to 10% by mass, preferably 0.01 to 1% by mass, and more preferably 0.01 to 0.1% by mass.
  • the concentration of the surfactant in the coating composition is 0.0001 to 10% by mass, preferably 0.001 to 1% by mass, and more preferably 0.001 to 0.1% by mass.
  • the coating composition of the present invention can form a coating film on the surface of a substrate, which is an object, by a coating method such as brush, spray, dipping, spin coating, bar coating, or roll coating. Drying can be performed by room temperature drying and / or heating. Specifically, it is carried out at 20 to 250 ° C., preferably 20 to 60 ° C., for 1 minute to 1 hour, preferably 5 minutes to 30 minutes.
  • the thin film to be obtained is not particularly limited, but is preferably more than 1 nm and 5 ⁇ m or less.
  • the substrate to be coated with the coating composition of the present invention is not particularly limited as long as it can be coated.
  • iron, stainless steel, copper, aluminum and other metals; and ceramics, cement, glass; polycarbonate resin And resin base materials such as acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, and polyether sulfone, and the surface may be coated with another coating material.
  • the surface of the thin film is made of water and / or Or it is preferable to laminate
  • the organic solvent used is preferably an alcohol solvent, more preferably 2-propanol. Drying can be performed by the method described above.
  • a layer containing a hydrolytic condensate of a metal surfactant, an inorganic film, or the like can be further laminated on the thin film obtained from the coating composition of the present invention.
  • the layer containing the hydrolytic condensate of the metal surfactant is preferably a monomolecular film. Below, the preparation methods of the layer containing the hydrolysis-condensation product of a metal type surfactant are demonstrated.
  • the layer containing the hydrolytic condensate of the metal surfactant is, for example, “at least 1” as described in WO2003 / 076064, WO2004 / 091810, WO2006 / 009292, WO2009 / 104424, WO2008 / 059840, etc.
  • organic-inorganic composite film It is produced by bringing the organic-inorganic composite film into contact with an organic solvent solution containing the above-mentioned “metal-based surfactant having a hydrolyzable group”, “a compound capable of interacting with the metal-based surfactant” and water. be able to.
  • Examples of the “metallic surfactant having at least one hydrolyzable group” include the following general formula (II) [Wherein R 12 represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, a halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a linking group. Represents a hydrocarbon group having 1 to 30 carbon atoms or a halogenated hydrocarbon group having 1 to 30 carbon atoms including a linking group, and M represents a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom.
  • s represents any positive integer from 1 to (t ⁇ 1).
  • R 12 may be the same as or different from each other.
  • (ts) is 2 or more, X may be the same or different, but at least one of X is a hydrolyzable group.
  • the metal-type surfactant shown by these is preferable.
  • the hydrocarbon group of the hydrocarbon group having 1 to 30 carbon atoms which may have a substituent is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, alkyl groups such as n-decyl group and n-octadecyl group; alkenyl groups such as vinyl group, propenyl group, butenyl group, pentenyl group, n-decynyl group and n-octadecynyl group; phenyl group, 1-
  • Examples of the halogenated hydrocarbon group of the halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent include a halogenated alkyl group having 1 to 30 carbon atoms and a halogenated alkenyl group having 1 to 30 carbon atoms. And a halogenated aryl group having 1 to 30 carbon atoms.
  • a group in which two or more hydrogen atoms in an alkyl group having 1 to 30 carbon atoms are substituted with a halogen atom is preferable, and two or more hydrogen atoms in an alkyl group having 1 to 30 carbon atoms are fluorine atoms.
  • a fluorinated alkyl group substituted with is more preferable.
  • the branched portion is preferably a short chain having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.
  • hydrocarbon group of the hydrocarbon group containing a linking group and the halogenated hydrocarbon group of a halogenated hydrocarbon group containing a linking group may have 1 to Examples thereof are the same as those mentioned as the hydrocarbon group of 30 hydrocarbon groups and the halogenated hydrocarbon group of a halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
  • the linking group is preferably present between carbon-carbon bonds of a hydrocarbon group or a halogenated hydrocarbon group, or between carbon of the hydrocarbon group and a metal atom M described later.
  • linking group examples include —O—, —S—, —SO 2 —, —CO—, —C ( ⁇ O) O— or —C ( ⁇ O) NR 13 —
  • R 13 represents A hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group; Among these, from the viewpoint of water repellency and durability, an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group containing a linking group is preferable.
  • X represents a hydroxyl group or a hydrolyzable group.
  • the hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes.
  • an optionally substituted alkoxy group having 1 to 6 carbon atoms an optionally substituted acyloxy group; a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom; an isocyanate group Cyano group; amino group; or amide group.
  • alkoxy group having 1 to 6 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, and n-to.
  • a xyloxy group etc. are mentioned.
  • the acyloxy group include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group.
  • substituents include a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group.
  • a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an acyloxy group, a halogen atom, or an isocyanate group is preferable, and an alkoxy group or acyloxy group having 1 to 4 carbon atoms is more preferable.
  • M represents one kind of atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom.
  • a silicon atom is preferable from the viewpoint of availability of raw materials and reactivity.
  • Examples of the metal surfactant represented by the above formula (II) include the following silane coupling agents.
  • M is Si and R 12 is a hydrocarbon group, but the present invention is not limited thereto.
  • Examples of the “compound capable of interacting with a metal-based surfactant” include metal oxides; metal hydroxides; metal alkoxides; metal alkoxides partial hydrolysis products; metal alkoxides hydrolysis products; Coordinated metal compounds; silanol condensation catalysts such as acid catalysts are used.
  • metal oxides include methanol silica sol, IPA-ST, IPA-ST-UP, IPA-ST-ZL, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, and XBA-ST.
  • PMA-ST all of which represent the product names of organosilica sol manufactured by Nissan Chemical Industries, Ltd.
  • any metal hydroxide may be used as long as it is a metal hydroxide.
  • a manufacturing method of a metal hydroxide the method of hydrolyzing the below-mentioned metal alkoxide, the method of making a metal salt react with a metal hydroxide, etc. are mentioned.
  • what is marketed as a metal hydroxide can also be refine
  • metal alkoxides examples include silicon alkoxides such as Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7 -i) 4 , Si (OC 4 H 9 -t) 4 ; Ti ( Titanium alkoxides such as OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 -i) 4 , Ti (OC 4 H 9 ) 4 ; Ti [OSi (CH 3 ) 3 ] 4 , Ti Tetrakistrialkylsiloxytitanium such as [OSi (C 2 H 5 ) 3 ] 4 ; Zr (OCH 3 ) 4 , Zr (OC 2 H 5 ) 4 , Zr (OC 3 H 7 ) 4 , Zr (OC 4 H 9 ) 4 zirconium such alkoxide; Al (OCH 3) 3, Al (OC 2 H 5) 3, Al (OC 3 H 7 -i) 3, Al (OC 4 H 9) 3
  • indium alkoxides Sn Tin alkoxides such as (OCH 3 ) 4 , Sn (OC 2 H 5 ) 4 , Sn (OC 3 H 7 -i) 4 , Sn (OC 4 H 9 ) 4 ; Ta (OCH 3 ) 5 , Ta (OC 2 Tantalum alkoxides such as H 5 ) 5 , Ta (OC 3 H 7 -i) 5 , Ta (OC 4 H 9 ) 5 ; W (OCH 3 ) 6 , W (OC 2 H 5 ) 6 , W (OC 3 H 7- i) tungsten alkoxides such as 6 and W (OC 4 H 9 ) 6 ; zinc alkoxides such as Zn (OC 2 H 5 ) 2 ; lead alkoxides such as Pb (OC 4 H 9 ) 4 ; These metal alkoxides can be used alone or in combination of two or more.
  • the metal alkoxide partial hydrolysis product is obtained before the metal alkoxide is completely hydrolyzed, and examples thereof include a metal oxide sol precursor or an oligomer present in the state of oligomer. Can do.
  • the metal alkoxide partial hydrolysis product is stably dispersed without aggregation in an organic solvent in the absence of at least one selected from the group consisting of acids, bases and dispersion stabilizers.
  • Preferred examples include dispersoids having the above properties.
  • the dispersoid refers to fine particles dispersed in the dispersion system, and specific examples include colloidal particles.
  • the state of stable dispersion without agglomeration means that in the absence of acid, base and / or dispersion stabilizer in the organic solvent, the dispersoid of the hydrolysis product coagulates and becomes heterogeneous.
  • separated is said, Preferably the transparent and homogeneous state is said.
  • Transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the control sample is organic. This is a state in which the transmittance is preferably 80 to 100%, expressed as a spectral transmittance measured under the condition of using a solvent and a light wavelength of 550 nm.
  • the particle size of the dispersoid of the hydrolysis product is not particularly limited, but is preferably in the range of 1 to 100 nm and more preferably in the range of 1 to 50 nm in order to obtain a high visible light transmittance. More preferably, it is in the range of 1 to 10 nm.
  • an organic solvent is used in the absence of an acid, a base, and / or a dispersion stabilizer in an amount of 0.5 to 2.0 with respect to the metal alkoxide exemplified above.
  • a preferred example is a method of hydrolyzing in an organic solvent reflux temperature range from ⁇ 100 ° C. using less than double moles of water.
  • the metal alkoxide hydrolysis product used in the present invention is a product obtained by hydrolysis with water equal to or more than twice the metal alkoxides. Even if the hydrolysis product is obtained by hydrolyzing a metal alkoxide with water at least twice as much as the metal alkoxide, the metal alkoxide is less than twice the equivalent of the metal alkoxide.
  • the partial hydrolysis product of the metal alkoxides was obtained by partial hydrolysis with water, and the partial hydrolysis product was further mixed with a predetermined amount of water (the amount of water used in the previous partial hydrolysis and In a total amount of 2 times the equivalent of metal alkoxides).
  • the chelated or coordinated metal compound can be prepared by adding a chelating agent or a coordination compound capable of forming a complex with the metal of the metal compound to a solution of the metal compound.
  • a chelating agent or coordination compound a metal hydroxide, metal alkoxide, or metal alkoxide is chelated or coordinated to the metal of the hydrolysis product obtained by treating with water to form a complex. If it can do, it will not specifically limit.
  • Chelating agents or coordination compounds include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid; oxalic acid, malonic acid, succinic acid, glutaric acid Saturated aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, array acid, maleic acid; benzoic acid, toluic acid, Aromatic carboxylic acids such as phthalic acid; halogenocarboxylic acids such as chloroacetic acid and trifluoroacetic acid; ⁇ -diketones such as acetylacetone, benzoylacetone and hexafluoroacetylacetone; ⁇ -ketoesters such as methyl acetoacetate and
  • acid catalysts include mineral acids such as hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, etc.
  • a photoacid generator that generates an acid by light irradiation, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like can be exemplified.
  • silanol condensation catalysts include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates.
  • the content of water in the organic solvent solution containing a metal-based surfactant having at least one hydrolyzable group, a compound capable of interacting with the metal-based surfactant, and water is preferably 10 to 2000 ppm.
  • a method of adjusting or maintaining the water content to be within a predetermined amount range (i) a method of providing a water layer in contact with the organic solvent solution, and (ii) a water-retaining substance containing water
  • Examples of the coexisting method include (iii) a method of blowing a gas containing moisture.
  • the organic solvent solution is prepared by dipping, spin coating, spraying, roller coating, Mayer bar method. It can be carried out by contacting the thin film on the substrate by a method such as screen printing or brush coating, preferably by dipping.
  • the inorganic film examples include a transparent conductive film and a gas barrier film.
  • the material of the transparent conductive film is not particularly limited as long as it is conductive and transparent, but specifically, an indium oxide film doped with tin (ITO film), a tin oxide film doped with fluorine (FTO film), zinc oxide film doped with antimony, zinc oxide film doped with indium, and the like.
  • the gas barrier film is not particularly limited as long as it has gas barrier properties such as oxygen and water vapor, but is preferably a thin film of an inorganic compound, in particular, titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, A thin film of a metal oxide, metal nitride, metal carbide or a composite thereof having a metal element selected from the group consisting of tungsten and lead is preferred. Among these, silicon, titanium, zirconium, aluminum, and tin are preferable as the metal element. These may be used alone or in combination of two or more. The thickness of the layer is usually 10 to 100 nm.
  • a method of forming a transparent conductive film or gas barrier film made of an inorganic compound on the first layer can be formed by a known method, but physical methods such as sputtering, vacuum deposition, and ion plating are available. It can be performed by a method, a chemical method such as a spray method, a dip method, a thermal CVD method, a plasma CVD method, or the like.
  • a film made of silicon oxide can be formed by using, for example, a silicon compound sintered in the presence of oxygen gas as a target, and oxygen can be formed using metal silicon as a target.
  • a film can also be formed by reactive sputtering in the presence.
  • a film made of silicon oxynitride can be formed on a substrate by supplying silane gas together with oxygen gas and nitrogen gas into a chamber in which plasma is generated and reacting them.
  • a film made of silicon oxide can be formed by using, for example, an organic solvent solution containing a silicon compound as an evaporant. In the present invention, it is particularly preferable to form a film by sputtering, vacuum deposition, ion plating, or plasma CVD.
  • the coating composition of the present invention includes, for example, heat exchangers, fins for heat exchangers, building materials, roofs, window glasses, windshields, various mirrors, plastic lenses, lenses, tires, rubber, magnetic recording media, semiconductor material surfaces, etc. Processing to snowfall antennas, steel towers, telecommunication facilities, road traffic signs, traffic lights, etc .; Reduction of frictional resistance between ships and water, prevention of dirt on vehicles and aircraft bodies, surfaces of various metal materials It can be used for preventing corrosion of electrodes such as battery materials and the like, treating fish net surfaces, sealants, fireproof waterproof sealants, car wax, and the like.
  • Example 1 61.3 g of an aqueous solution in which 0.07 g of sodium metasilicate and 0.01 g of benzalkonium chloride were dissolved was mixed with 61.3 g of 2-propanol (IPA). 2.50 g of tetramethoxysilane (TMOS) was added dropwise to the resulting mixture to obtain a coating composition (A-1) having a solid content of 2%. The reaction solution after 5 minutes of mixing was sampled and 1 H NMR (D 2 O, 500 MHz) was measured. As a result, the signal derived from TMOS disappeared quantitatively, and the progress of hydrolysis and condensation was confirmed.
  • IPA 2-propanol
  • TMOS tetramethoxysilane
  • coating composition (A-1) is applied to a PET film (Cosmo Shine (registered trademark) A4300, manufactured by Toyobo Co., Ltd., film thickness: 188 ⁇ m) using a bar coater (bar # 3). Then, the film surface was dried by allowing to stand at room temperature for about 5 minutes. After ultrasonic cleaning with pure water for 5 minutes and IPA washing, heating drying was performed in a circulating oven at 60 ° C. for 10 minutes to obtain a coated film (B-1). The obtained coated film (B-1) was evaluated by a cross cut test (JIS K5400-8), and no peeling was observed.
  • JIS K5400-8 cross cut test
  • the obtained coated film (B-1) was immersed in a self-assembled monolayer (SAM) forming solution (SAMLAY (registered trademark), manufactured by Nippon Soda Co., Ltd.) for 10 minutes. After pulling up the film, it is washed with a cleaning solvent (NS Clean (registered trademark) 100, manufactured by JX Nippon Oil & Energy Corporation) and subjected to ultrasonic cleaning for 1 minute, and then dried in a circulation oven at 60 ° C. for 10 minutes. A SAM-forming film (C-1) was obtained. The static contact angle of the obtained SAM-forming film (C-1) was measured using a contact angle measuring device (Drop Master 700, manufactured by Kyowa Interface Science). The results are shown in Table 1. *
  • Example 2 to [Example 6] and [Comparative Example 1] 0.50 g of 0.10 M sodium metasilicate aqueous solution, 0.50 g of 0.01 M benzalkonium chloride aqueous solution, 10.8 g of water and 11.8 g of IPA were mixed. 0.50 g of TMOS was added dropwise to the obtained mixture, and the mixture was stirred at room temperature for 60 minutes to prepare a coating composition (A-2).
  • the obtained coating film was immersed in a self-assembled monolayer (SAM) forming solution (SAMLAY (registered trademark), manufactured by Nippon Soda Co., Ltd.) for 30 minutes. After the film is pulled up, the surface is washed with a hydrocarbon-based cleaning agent (NS Clean (registered trademark) 100, manufactured by JX Nippon Oil & Energy Corporation) and dried in a circulating oven at 60 ° C. for 10 minutes to form a SAM. Films (C-2) to (C-6) and (CC-1) were obtained. The static contact angles of (C-2) to (C-6) and (CC-1) were measured using a contact angle measuring device (Drop Master 700, manufactured by Kyowa Interface Science).
  • the coating film on the SAM-forming films (C-2) to (C-6) and (CC-1) is 1 mm ⁇
  • a cross cut was made in a 1 mm grid pattern, and a peel test was performed using a transparent adhesive tape.
  • the results are shown in Table 2. From the above results, the films (Examples 1 to 6) treated with the coating composition containing the surfactant can be laminated with a good SAM without performing UV / ozone treatment, and the obtained film is applied to the substrate. It was found that the adhesion was excellent.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement qui peut être durcie à faible température et qui forme un film mince hydrophile et de réactivité élevée. Cette composition de revêtement comprend un tétraalcoxysilane et/ou un condensat associé, un silicate et un agent tensioactif. Le film mince obtenu à partir de cette composition de revêtement présente une excellente adhérence à des substrats, et une couche contenant un condensat d'hydrolyse d'un tensioactif métallique, d'un film inorganique, etc. peut être stratifiée sur ledit film mince.
PCT/JP2014/003979 2013-08-01 2014-07-30 Composition de revêtement WO2015015801A1 (fr)

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KR102583115B1 (ko) * 2017-06-29 2023-09-27 스미또모 가가꾸 가부시키가이샤 조성물
KR102670627B1 (ko) * 2022-01-06 2024-06-04 유동현 표면 친수화 코팅용 조성물 및 그 제조 방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05294703A (ja) * 1991-01-19 1993-11-09 Suzuki Sangyo Kk 有機ケイ素基複合ケイ酸アルカリ組成物、その用途、 およびその製造法
JPH08188442A (ja) * 1995-01-12 1996-07-23 Agency Of Ind Science & Technol 低温度硬化性組成物とガラス質コーティング膜の形成法
JP2001294446A (ja) * 2000-04-07 2001-10-23 Mitsuboshi Belting Ltd 表面コート剤及び表面コートされた着色ガラスの製造方法

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JP4648667B2 (ja) * 2004-08-13 2011-03-09 日本ペイント株式会社 水性親水化処理剤
JP2009144088A (ja) * 2007-12-17 2009-07-02 Nippon Paint Co Ltd 親水化コーティング剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05294703A (ja) * 1991-01-19 1993-11-09 Suzuki Sangyo Kk 有機ケイ素基複合ケイ酸アルカリ組成物、その用途、 およびその製造法
JPH08188442A (ja) * 1995-01-12 1996-07-23 Agency Of Ind Science & Technol 低温度硬化性組成物とガラス質コーティング膜の形成法
JP2001294446A (ja) * 2000-04-07 2001-10-23 Mitsuboshi Belting Ltd 表面コート剤及び表面コートされた着色ガラスの製造方法

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