WO2018070297A1 - Composition de résine aqueuse, agent de revêtement et article - Google Patents

Composition de résine aqueuse, agent de revêtement et article Download PDF

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Publication number
WO2018070297A1
WO2018070297A1 PCT/JP2017/035923 JP2017035923W WO2018070297A1 WO 2018070297 A1 WO2018070297 A1 WO 2018070297A1 JP 2017035923 W JP2017035923 W JP 2017035923W WO 2018070297 A1 WO2018070297 A1 WO 2018070297A1
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Prior art keywords
mass
group
parts
resin composition
aqueous
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PCT/JP2017/035923
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English (en)
Japanese (ja)
Inventor
広義 神成
邦彦 小松崎
定 永浜
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Dic株式会社
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Priority to JP2018544966A priority Critical patent/JP6544612B2/ja
Priority to KR1020197009319A priority patent/KR102196220B1/ko
Priority to CN201780062408.3A priority patent/CN109790372B/zh
Publication of WO2018070297A1 publication Critical patent/WO2018070297A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to an aqueous resin composition, a coating agent, and an article having a coating film of the coating agent.
  • the coating agent is generally required to be capable of forming a coating film capable of preventing the deterioration of the surface of various base materials and to impart design properties to the surface of the base material.
  • a coating agent at a level that can prevent deterioration of the substrate surface caused by deterioration of hydrophilicity due to adhesion of chemicals such as water stains, oil stains, cleaning agents, and acid rain.
  • a coating agent capable of forming a coating film having excellent hydrophilic durability is demanded from the industrial world.
  • Demand for coating agents having the above-mentioned properties is increasing in the surface treatment application of metal base materials including steel plates, glass base materials including mirrors, and plastic base materials called hard-to-adhere base materials.
  • the coating agent is required to have a level of substrate follow-up that can prevent peeling and cracking of the coating film that occurs when processing metal substrates, and a high level of chemical resistance. It is done.
  • the chemical resistance is the peeling and dissolution of the coating film due to the influence of the cleaning agent in the steel industry where the coating surface formed on the surface of the metal substrate is frequently cleaned using an alkaline cleaning agent or the like. This is an important characteristic for preventing deterioration of the metal substrate.
  • the hydrophilic particles have low adhesion to the metal substrate, and tend to peel off easily under wet conditions, making it difficult to use for a long time.
  • the problem to be solved by the present invention is to provide an aqueous resin composition that is excellent in hydrophilic durability, chemical resistance, and substrate adhesion, and can form a coating film that can prevent deterioration of various substrates. .
  • a urethane resin having a silanol group and / or a hydrolyzable silyl group and a hydrophilic acrylic polymer having a silanol group and / or a hydrolyzable silyl group It has been found that a coating agent using an aqueous resin composition containing can form a coating film excellent in hydrophilic durability, chemical resistance and substrate adhesion, and has completed the present invention.
  • the present invention relates to a urethane resin (A) having a silanol group and / or a hydrolyzable silyl group, a hydrophilic acrylic polymer (B) having a silanol group and / or a hydrolyzable silyl group, and an aqueous medium ( C) and an article having an aqueous resin composition, a coating agent, and a coating film of the coating agent.
  • A urethane resin
  • B hydrophilic acrylic polymer
  • C aqueous medium
  • the aqueous resin composition of the present invention can form a coating film excellent in hydrophilic durability, chemical resistance and substrate adhesion as a coating agent, it can be used for surface protection of various substrates.
  • the substrate to which the coating agent of the present invention can be applied include metal substrates such as galvanized steel sheets, aluminum-galvanized steel sheets, aluminum sheets, aluminum alloy sheets, electromagnetic steel sheets, copper sheets, and stainless steel sheets, various plastics and their Examples include films, glass, paper, and wood.
  • the coating agent of the present invention can form a coating film excellent in hydrophilic durability and chemical resistance capable of preventing the deterioration of the surface of these base materials, aluminum fins, building members, home appliances, automotive exterior materials It can be used for various articles such as goggles, antifogging film sheets, antifogging glass, mirrors, and medical instruments.
  • the aqueous resin composition of the present invention comprises a urethane resin (A) having a silanol group and / or a hydrolyzable silyl group, a hydrophilic acrylic polymer (B) having a silanol group and / or a hydrolyzable silyl group, An aqueous medium (C) is contained.
  • Examples of the urethane resin (A) having a silanol group and / or a hydrolyzable silyl group include, for example, a urethane prepolymer having an isocyanate group at a terminal, at least one active hydrogen, and at least one silanol group and / or It can be obtained by reacting a compound having a hydrolyzable silyl group.
  • functional groups such as a hydroxyl group, a carboxyl group, an epoxy group, a (meth) acryloyl group, can be introduce
  • urethane prepolymer one obtained by reacting polyol (a1) and polyisocyanate (a2) is used.
  • polystyrene resin examples include polyether polyol, polyester polyol, polycarbonate polyol, and polyolefin polyol.
  • polyester polyol is preferable because a coating film excellent in substrate adhesion can be formed.
  • these polyols (a1) can be used alone or in combination of two or more. From the viewpoint of further improving the substrate adhesion, the polyol has a number average molecular weight of preferably 500 or more and 3,000 or less.
  • polyether polyol examples include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator. .
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6- Linear diols such as hexanediol; branched diols such as 1,3-butanediol and neopentylglycol; triols such as glycerin, trimethylolethane, trimethylolpropane and pyrogallol; sugar alcohols such as sorbitol; sucrose and aconite Sugars such as sugars; tricarboxylic acids such as aconitic acid, trimellitic acid and hemimellitic acid; phosphoric acid; polyamines of ethylenediamine and diethylenetriamine sugars; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; And 2,3-propane tri
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
  • polyether polyol it is preferable to use polyoxytetramethylene glycol formed by addition polymerization (ring-opening polymerization) of tetrahydrofuran.
  • polyether polyol it is preferable to use a polyether having a number average molecular weight of 500 to 3,000 because the adhesion to the substrate can be further improved.
  • polyester polyol examples include those obtained by esterification of low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ⁇ -caprolactone, and copolymers thereof. Examples include polyester.
  • Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butane having a molecular weight of about 50 to 300.
  • Examples thereof include aliphatic polyols such as diols, alicyclic structure-containing polyols such as cyclohexanedimethanol, bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof.
  • polycarboxylic acid examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and naphthalene.
  • Aromatic polycarboxylic acids such as dicarboxylic acids, and anhydrides or ester-forming derivatives thereof.
  • polyester polyol it is preferable to use a polyester polyol having a number average molecular weight of 500 to 3,000 because the adhesion to the substrate can be further improved.
  • polycarbonate polyol examples include those obtained by reacting a carbonate ester with a polyol, and those obtained by reacting phosgene with bisphenol A and the like.
  • Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate.
  • polyol that can react with the carbonate ester examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5.
  • -Relatively low molecular weight diols having a molecular weight of 50 to 2,000 such as pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polyhexamethylene adipate, etc.
  • a polyester polyol etc. are mentioned.
  • polycarbonate polyol it is preferable to use a polycarbonate polyol having a number average molecular weight of 500 to 3,000 because the adhesion to the substrate can be further improved.
  • polystyrene polyol examples include polyethylene polyol, polypropylene polyol, polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenated (hydrogenated) polyisoprene polyol.
  • a polyol having a hydrophilic group can be used in combination with the above-described one.
  • polyol having a hydrophilic group for example, a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group other than the above-described polyol (a1) can be used. Among these, it is preferable to use a polyol having an anionic group or a polyol having a cationic group.
  • polyol having an anionic group examples include a polyol having a carboxyl group and a polyol having a sulfonic acid group.
  • polyol having a carboxyl group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like. Of these, 2,2-dimethylolpropionic acid is preferred.
  • polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group react with various polycarboxylic acids can also be used.
  • the content thereof is preferably 1 part by mass or more, more preferably 2 parts by mass or more, preferably in a total of 100 parts by mass of the polyol (a1). Is 20 parts by mass or less, more preferably 10 parts by mass or less.
  • polyol having a sulfonic acid group examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof, and the aromatic
  • dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof, and the aromatic
  • the polyester polyol obtained by making it react with the low molecular weight polyol illustrated as what can be used for manufacture of the polyester polyol which has a structure is mentioned.
  • the polyol having a carboxyl group and the polyol having a sulfonic acid group are preferably used in the range where the acid value of the urethane resin (A) is 2 to 70 mgKOH / g, and used in the range of 10 to 50 mgKOH / g. More preferably.
  • the acid value as used in the field of this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a polyol which has the carboxyl group and sulfonic acid group which were used for manufacture of the said urethane resin (A).
  • the anionic groups are preferably partially or wholly neutralized with a basic compound or the like in order to develop good water dispersibility.
  • Examples of basic compounds that can be used when neutralizing the anionic group include organic amines such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine, sodium hydroxide, potassium hydroxide, and hydroxide. Examples thereof include metal hydroxides including lithium.
  • the basic compound is in a range where the basic group / anionic group of the basic compound is 0.5 to 3.0 (molar ratio). It is preferably used, and more preferably used in the range of 0.8 to 2.0 (molar ratio).
  • examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specific examples include N-methyl-diethanolamine, a polyol obtained by reacting a compound having two epoxies in one molecule with a secondary amine.
  • the tertiary amino group as the cationic group is partially or completely neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid, etc. Is preferred.
  • the tertiary amino group as the cationic group is preferably partly or entirely quaternized.
  • the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like. Among these, it is preferable to use dimethyl sulfate.
  • the polyol having a cationic group is preferably used in the range where the amine value of the urethane resin (A) is 2 to 50 mgKOH / g, and more preferably in the range of 5 to 30 mgKOH / g.
  • the amine value said by this invention is the theoretical value computed based on the usage-amount of tertiary amino group containing compounds, such as a polyol which has the tertiary amino group used for manufacture of the said urethane resin (A).
  • examples of the polyol having a nonionic group include a polyol having a polyoxyethylene structure.
  • the polyol having a hydrophilic group is preferably used in the range of 0.3 to 10% by mass in the total amount of the polyol (a1) used in the production of the urethane resin (A).
  • polyol (a1) in addition to the above-described polyol, other polyols can be used as necessary.
  • Examples of the other polyols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 1,4-butanediol.
  • relatively low molecular weight polyols such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, and cyclohexanedimethanol.
  • polyisocyanate (a2) that can react with the polyol (a1) examples include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, triene diisocyanate, Aromatic polyisocyanates such as naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate; Fats such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate Cyclic structure Such polyisocyanates having
  • the urethane prepolymer (A) having an isocyanate group can be produced, for example, by mixing and reacting the polyol (a1) and the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent. it can.
  • the reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1). It is preferably performed in the range of 0.9 to 3, and more preferably in the range of 0.95 to 2.
  • the reaction of the polyol (a1) and the polyisocyanate (a2) can be usually performed in a temperature range of 50 to 150 ° C.
  • the isocyanate group equivalent of the urethane prepolymer (A) obtained by the above reaction is 3,500 to 100,000 g / eq. Is preferably 10,000 to 60,000 g / eq. Is more preferable.
  • Examples of the organic solvent that can be used in producing the urethane prepolymer (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; acetonitrile Nitrile solvents such as amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
  • the organic solvent removes part or all of the organic solvent by, for example, distilling under reduced pressure during or after the production of the urethane resin (A). May be.
  • Examples of the compound having a silanol group and / or a hydrolyzable silyl group include ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, and ⁇ -amino.
  • Amino group-containing alkoxysilane compounds such as propyltrimethoxysilane and ⁇ -aminopropyltriethoxysilane, hydroxyl group-containing alkoxysilane compounds such as ⁇ -hydroxypropyltrimethoxysilane and ⁇ -hydroxypropyltriethoxysilane, and ⁇ -mercaptopropyltrimethoxy Examples include mercapto group-containing alkoxysilane compounds such as silane and ⁇ -mercaptopropylmethyldimethoxysilane.
  • the urethane prepolymer having no isocyanate group for example, the hydroxyl group of the polyol (a1) is excessively designed relative to the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate (a2).
  • examples thereof include a urethane prepolymer having a hydroxyl group remaining after the reaction and a urethane prepolymer obtained by adding a chain extender to the urethane prepolymer (A).
  • chain extender polyamines, hydrazine compounds, other active hydrogen atom-containing compounds and the like can be used.
  • polyamine one or more kinds can be used.
  • hydrazine compound one or more kinds can be used.
  • hydrazine N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine
  • succinic acid dihydrazide adipic acid dihydrazide, glutaric acid dihydrazide
  • Sebacic acid dihydrazide isophthalic acid dihydrazide
  • ⁇ -semicarbazide propionic acid hydrazide and the like.
  • one or more kinds can be used, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, , 4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol and other glycols; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, Examples thereof include phenols such as hydrogenated bisphenol A and hydroquinone, water, and the like, and they can be used within the range in which the storage stability of the aqueous resin composition of the present invention does not deteriorate.
  • an alkoxysilyl group is preferably used because of its high crosslinkability and improved solvent resistance.
  • a trimethoxysilyl group and a triethoxysilyl group are preferable because of excellent crosslinkability and improved solvent resistance.
  • silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ -glycidoxypropylmethyldiethoxysilane.
  • ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other epoxy group-containing alkoxysilane compounds ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane Contains isocyanato groups such as ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylethyldimethoxysilane, ⁇ -isocyanatopropylethyldiethoxysilane, ⁇ -isocyanatopropyltrichlorosilane Amino groups such as alkoxysilane compounds, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane
  • the urethane resin (A) it is preferable to use a resin having an alicyclic structure because a coating film excellent in chemical resistance can be formed.
  • Examples of the alicyclic structure include a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, a cyclooctyl ring, a propylcyclohexyl ring, a tricyclo [5.2.1.2.6] decyl skeleton, and a bicyclo [ 4.3.0] -nonyl skeleton, tricyclo [5.3.1.1] dodecyl skeleton, propyltricyclo [5.3.1.1] dodecyl skeleton, norbornene skeleton, isobornyl skeleton, dicyclopentanyl skeleton, Examples thereof include an adamantyl skeleton. Among these, a cyclohexyl ring structure is preferable.
  • the alicyclic structure is preferably present in the range of 10 to 5000 mmol / kg with respect to the whole of the urethane resin (A) from the viewpoint of forming a coating film excellent in chemical resistance, and preferably 1000 to 3000 mmol / kg.
  • the range of is more preferable.
  • the alicyclic structure is a polyisocyanate-derived alicyclic structure having an alicyclic structure that can be used as the polyisocyanate (a2) used when the urethane resin (A) is produced.
  • a2 polyisocyanate
  • A urethane resin
  • the ratio of the alicyclic structure contained in the said urethane resin (A) with respect to the whole said urethane resin (A) said by this invention is the polyol (a1) used for manufacture of the said urethane resin (A). And the total mass of all raw materials such as polyisocyanate (a2) and the amount of the alicyclic structure contained in the alicyclic structure-containing compound used in the production of the urethane resin (A).
  • the urethane resin (A) has a silanol group and / or hydrolyzable silyl group content in the range of 0.1 to 5% by mass in the urethane resin (A). In view of the ability to form a coating film having excellent properties and substrate adhesion, a range of 1 to 3% by mass is more preferable.
  • hydrophilic acrylic polymer (B) having a silanol group and / or a hydrolyzable silyl group examples include an acrylic monomer (b1-1) having an amide group, an acrylic monomer (b1-2) having an oxyethylene group, and A polymer of a hydrophilic acrylic monomer (b1) containing an acrylic monomer (b1-3) having a silanol group and / or a hydrolyzable silyl group can be used.
  • hydrophilicity of the hydrophilic acrylic polymer (B) indicates affinity with water, and specifically, the solubility in 100 g of water (20 ° C.) is preferable. Indicates 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more.
  • hydrophilicity of the hydrophilic acrylic monomer (b1) indicates affinity with water, specifically, the solubility in 100 g of water (20 ° C.) is as follows: The content is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more.
  • the hydrophilic acrylic monomer (b1) if necessary, the acrylic monomer (b1-1) having the amide group, the acrylic monomer (b1-2) having the oxyethylene group, the silanol group and In addition to the acrylic monomer (b1-3) having a group having a hydrolyzable silyl group, other acrylic monomers can be used.
  • acrylic monomer (b1-1) having an amide group for example, a compound represented by the following general formula (1) can be used.
  • R 1 in the general formula (1) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 2 represents an alkyl group having 1 to 3 carbon atoms, — (CH 2 ) 3 — N (CH 3 ) 2 or (CH 2 ) 3 —N (CH 3 ) 2 represents a methyl chloride salt.
  • Examples of the compound represented by the general formula (1) include N-hydroxyethylacrylamide, N-methylolacrylamide, N-methoxyethylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N, N. -Dimethylaminopropylacrylamide, N, N-dimethylaminopropylacrylamide, methyl chloride salt of N, N-dimethylaminopropylacrylamide, N-isopropylacrylamide and the like. These monomers can be used alone or in combination of two or more.
  • acrylic monomer (b1-1) having an amide group for example, a compound represented by the following general formula (2) can be used.
  • R 3 and R 4 in the general formula (2) represent an alkylene group having 1 to 3 carbon atoms.
  • Examples of the compound represented by the general formula (2) include N-acryloylmorpholine.
  • acrylic monomer (b1-2) having an oxyethylene group examples include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol copolymer (meth) acrylate, and methoxypolyethylene glycol polypropylene glycol copolymer.
  • acrylic monomer (b1-3) having a silanol group and / or a hydrolyzable silyl group examples include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, ⁇ -(Meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane, etc. It is done. These monomers can be used alone or in combination of two or more.
  • the total content of the units derived from the acrylic monomers (b1-1), (b1-2) and (b1-3) is preferably 100% by mass or more in 100% by mass of the hydrophilic acrylic polymer (B). More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
  • the ratio ((b1-1) / (b1-2)) of the unit derived from the acrylic monomer having the amide group (b1-1) and the unit derived from the acrylic monomer having the oxyethylene group (b1-2) is From the viewpoint of maintaining a high level of hydrophilicity and hydrophilic sustainability, it is preferably 99/1 or more and 50/50 or less on a molar basis, and more preferably 90/10 from the viewpoint of obtaining even better hydrophilic sustainability. It is 70/30 or more.
  • acrylic monomer having a sulfonic acid group examples include an acrylic monomer having a quaternary ammonium group, an acrylic monomer having a carboxyl group, an acrylic monomer having an amino group, an acrylic monomer having a cyano group, and a hydroxyl group.
  • acrylic monomer having an imide group an acrylic monomer having a methoxy group, and the like.
  • acrylic monomer having a sulfonic acid group examples include sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate, sodium 2-acrylamido-2-methylpropanesulfonate, and the like. These monomers can be used alone or in combination of two or more.
  • acrylic monomer having a quaternary ammonium group examples include tetrabutylammonium (meth) acrylate and trimethylbenzylammonium (meth) acrylate. These monomers can be used alone or in combination of two or more.
  • acrylic monomer having a carboxyl group examples include (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, crotonic acid, fumaric acid and the like. These monomers can be used alone or in combination of two or more.
  • acrylic monomer having an amino group examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, (meth) acryloxyethyltrimethylammonium chloride, and the like. Can be mentioned. These monomers can be used alone or in combination of two or more.
  • acrylic monomer having a cyano group examples include acrylonitrile, cyanomethyl acrylate, 2-cyanoethyl acrylate, cyanopropyl acrylate, 1-cyanomethylethyl acrylate, 2-cyanopropyl acrylate, 1-cyanocyclopropyl acrylate, 1-cyano.
  • examples include cycloheptyl acrylate, 1,1-dicyanoethyl acrylate, 2-cyanophenyl acrylate, 3-cyanophenyl acrylate, 4-cyanophenyl acrylate, 3-cyanobenzyl acrylate, and 4-cyanobenzyl acrylate. These monomers can be used alone or in combination of two or more.
  • acrylic monomer having a hydroxyl group examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono ( And (meth) acrylate. These monomers can be used alone or in combination of two or more.
  • acrylic monomer having an imide group examples include (meth) acrylimide, N-methylol maleimide, N-hydroxyethyl maleimide, N-glycidyl maleimide, N-4-chloromethylphenyl maleimide, N-acetoxyethyl maleimide and the like. Can be mentioned. These monomers can be used alone or in combination of two or more.
  • acrylic monomer having a methoxy group examples include 3-methoxybutyl (meth) acrylate), 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, and the like. Can be mentioned. These monomers can be used alone or in combination of two or more.
  • Acrylic monomer (b1-1) having amide group, acrylic monomer (b1-2) having oxyethylene group, and acrylic monomer (b1-3) having silanol group and / or hydrolyzable silyl group The amount is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the hydrophilic acrylic monomer (b1).
  • hydrophilicity and hydrophilic sustainability can be maintained at a high level.
  • the range of 99/1 to 50/50 is preferable, and the range of 90/10 to 70/30 is more preferable from the viewpoint of obtaining even more excellent hydrophilic sustainability.
  • the average addition mole number of the oxyethylene group of the acrylic monomer having the oxyethylene group (b1-2) is preferably in the range of 5 to 13 moles, from 8 to 10 moles, from the viewpoint of hydrophilic sustainability. More preferably, it is the range.
  • radical polymerizable monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, 2-ethylbutyl (meth) acrylate, n-pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, nonyl ( (Meth) acrylate, dodecyl (meth) acrylate, 3-methylbutyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl
  • the hydrophilic acrylic resin (B) has a silanol group and / or a hydrolyzable silyl group content within the range of 0.1 to 10% by mass in the acrylic resin (B), It is preferable because a coating film having excellent substrate adhesion can be formed, more preferably in the range of 0.2 to 5% by mass, and still more preferably in the range of 0.5 to 3% by mass.
  • the method for producing the hydrophilic acrylic polymer (B) known radical polymerization can be used.
  • the hydrophilic acrylic monomer (b1), a polymerization initiator, water and / or an organic solvent examples include a method in which the radically polymerizable monomer is mixed and stirred at a temperature in the range of 40 to 90 ° C., for example, and the radical polymerization proceeds in 1 to 10 hours, if necessary.
  • polymerization initiator examples include peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, cumene hydroperoxide Organic peroxides such as 2,2′-azobis- (2-aminodipropane) dihydrochloride, 2,2′-azobis- (N, N′-dimethyleneisobutylamidine) dihydrochloride, azobisiso And azo compounds such as butyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleric acid nitrile), and the like.
  • peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate
  • benzoyl peroxide t-butylperoxy-2-ethy
  • polymerization initiators can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is, for example, in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the monomer that is a raw material for the hydrophilic acrylic polymer (B).
  • organic solvent examples include methanol, ethanol, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, hexane, acetone, cyclohexanone, 3-pentanone, acetonitrile, isopropyl alcohol, 1, Examples include 2-propanediol and 1,3-butanediol. These organic solvents can be used alone or in combination of two or more.
  • the amount of the organic solvent used is, for example, in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the monomer that is a raw material for the hydrophilic acrylic polymer (B).
  • the weight average molecular weight of the hydrophilic acrylic polymer (B) is preferably in the range of 10,000 to 100,000, preferably in the range of 15,000 to 50,000, from the viewpoint of affinity with the polyurethane (A). It is more preferable that In addition, the weight average molecular weight of the said hydrophilic acrylic polymer (B) shows the value obtained by measuring on condition of the following by gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • Examples of the aqueous medium (C) include water, organic solvents miscible with water, and mixtures thereof.
  • organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, 1,2-propylene glycol, and 1,3-butylene glycol; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol— n-butyl ether, diethylene glycol-n-butyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol methyl ether, etc.
  • Glycol ether solvent N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone Lactam solvent; N, an amide solvent such as N- dimethylformamide.
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone Lactam solvent
  • N an amide solvent such as N- dimethylformamide.
  • the aqueous medium (C) is preferably water alone or a mixture of water and an organic solvent miscible with water, more preferably water alone, in consideration of safety and environmental load reduction.
  • the aqueous medium (C) is preferably contained in the range of 30 to 80% by mass and more preferably in the range of 50 to 70% by mass in the total amount of the aqueous resin composition of the present invention.
  • the aqueous resin composition of the present invention includes a crosslinking agent, a plasticizer, an antistatic agent, a wax, a surfactant, a light stabilizer, a flow regulator, a dye, a leveling agent, a rheology control agent, if necessary.
  • Various additives such as ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments can be used.
  • the durability of the coating film of the aqueous resin composition of the present invention can be further improved.
  • the 1 or more types chosen from the group which consists of an amino resin, an aziridine compound, a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and an isocyanate compound can be used, for example.
  • the dispersion stability of the aqueous resin composition of the present invention can be further improved by using the surfactant.
  • a surfactant it is possible to maintain the substrate adhesion and water resistance of the resulting coating film, so that it can be used within a range of 20 parts by mass or less with respect to 100 parts by mass of the urethane resin (A). It is preferable not to use as much as possible.
  • a curing agent or a curing catalyst may be used in combination as necessary within a range not impairing the effects of the present invention.
  • the curing agent examples include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, and a polyisocyanate.
  • the curing agent it is preferable to use a compound having a silanol group and / or a hydrolyzable silyl group in order to form a coating film excellent in corrosion resistance, water resistance and substrate adhesion.
  • the hydrolyzable silyl group or silanol group of the compound improves the adhesion to the substrate, and as a result, the coating film excellent in corrosion resistance. Can be formed.
  • Examples of the compound having a silanol group and / or a hydrolyzable silyl group include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -Epoxysilane compounds such as glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and ⁇ -aminopropyl Aminosilanes such as trimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropylmethyldiethoxysilane can be used.
  • At least one selected from the group consisting of ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is used. It is preferable because the crosslink density of the coating film is improved and the corrosion resistance, water resistance and substrate adhesion are improved.
  • the compound having a silanol group and / or a hydrolyzable silyl group forms a coating film excellent in chemical resistance and is used for obtaining the aqueous urethane resin composition of the present invention excellent in storage stability. It is preferably used in the range of 0.01% by mass to 10% by mass with respect to the total amount of (A).
  • Examples of the curing catalyst that can be used in the aqueous resin composition of the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, and tin octylate.
  • the aqueous resin composition of the present invention may contain an emulsifier, a dispersion stabilizer and a leveling agent as necessary, but from the viewpoint of suppressing a decrease in water resistance of the crosslinked coating film, it may not contain as much as possible. Preferably, it is 0.5% by mass or less based on the solid content of the aqueous resin composition.
  • the aqueous resin composition of the present invention can be used as a coating agent for the purpose of protecting the surface of various substrates and imparting design properties to various substrates.
  • Examples of the base material include metals, various plastics and films thereof, glass, paper, and wood.
  • Examples of the metal substrate include galvanized steel sheets, aluminum-galvanized steel sheets, aluminum sheets, aluminum alloy sheets, electromagnetic steel sheets, copper sheets, and stainless steel sheets used for automobiles, home appliances, building materials, and the like.
  • ABS resin acrylonitrile-butadiene-styrene resin
  • PC resin polycarbonate resin
  • plastic film base materials include polyethylene terephthalate film, polyester film, A polyethylene film, a polypropylene film, a TAC (triacetyl cellulose) film, a polycarbonate film, a polyvinyl chloride film and the like can be used.
  • the aqueous resin composition of the present invention can form a coating film excellent in chemical resistance including acid resistance and alkali resistance even if the crosslinked coating film has a thickness of about 5 ⁇ m. Moreover, even if the crosslinked coating film has a thickness of about 1 ⁇ m, a coating film excellent in chemical resistance including acid resistance and alkali resistance can be formed.
  • the aqueous resin composition of the present invention can be coated on a substrate, dried and cured to form a coating film.
  • the organic solvent volatilizes after the water in the aqueous resin composition volatilizes. After volatilization of water, it consists of an organic solvent, a urethane resin (A), and a hydrophilic acrylic resin (B), and the organic solvent promotes the fusion of the urethane resin (A) and the hydrophilic acrylic resin (B). Thus, a good coating film having no coating film defect is formed.
  • Examples of the coating method include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
  • the drying may be natural drying at normal temperature, but may be heat-dried. Heat drying is preferably carried out usually at 40 to 250 ° C. for a time of about 1 to 600 seconds.
  • a base material is a thing which is easy to deform
  • an article having a coating film of a coating agent using the aqueous resin composition of the present invention for example, aluminum fins, building members, home appliances, automobile exterior materials, goggles, antifogging film sheets, antifogging glass, mirrors, medical An instrument etc. are mentioned.
  • aqueous dispersion was distilled under reduced pressure to obtain a urethane resin (A-1) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the ratio of the alicyclic structure per solid content of the urethane resin (A-1) aqueous dispersion is 1436 mmol / kg, and the content of alkoxysilyl groups in the urethane resin (A-1) is 2.34. It was mass%.
  • aqueous dispersion was distilled under reduced pressure to obtain a urethane resin (A-2) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the proportion of the alicyclic structure per solid content of this urethane resin (A-2) aqueous dispersion is 0 mmol / kg, and the content of alkoxysilyl groups in the urethane resin (A-2) is 2.52. It was mass%.
  • aqueous dispersion 6 parts by mass of an 89% by mass phosphoric acid aqueous solution was added and held at 45 ° C. for 1 hour, then cooled to 40 ° C., and 1134 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion.
  • This aqueous dispersion was distilled under reduced pressure to obtain a urethane resin (A-3) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the ratio of the alicyclic structure to the solid content of the urethane resin (A-3) aqueous dispersion is 1376 mmol / kg, and the content of alkoxysilyl groups in the urethane resin (A-3) is 5.63. It was mass%.
  • aqueous dispersion 14 parts by mass of an 89% by mass phosphoric acid aqueous solution was added and held at 45 ° C. for 1 hour, then cooled to 40 ° C., and 2795 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion.
  • This aqueous dispersion was distilled under reduced pressure to obtain a urethane resin (A-4) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the proportion of the alicyclic structure per solid content of this urethane resin (A-4) aqueous dispersion is 4442 mmol / kg, and the content of alkoxysilyl groups in the urethane resin (A-4) is 2.39. It was mass%.
  • aqueous dispersion 22 parts by mass of an 89% by mass phosphoric acid aqueous solution was added and held at 45 ° C. for 1 hour, then cooled to 40 ° C., and 4518 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion.
  • This aqueous dispersion was distilled under reduced pressure to obtain a urethane resin (A-5) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the proportion of the alicyclic structure per solid content of this urethane resin (A-5) aqueous dispersion is 5150 mmol / kg, and the content of alkoxysilyl groups in the urethane resin (A-5) is 2.74. It was mass%.
  • aqueous dispersion 6 parts by mass of an 89% by mass phosphoric acid aqueous solution was added and held at 45 ° C. for 1 hour, then cooled to 40 ° C., and 1061 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion.
  • This aqueous dispersion was distilled under reduced pressure to obtain a urethane resin (A-6) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the proportion of the alicyclic structure per solid content of this urethane resin (A-6) aqueous dispersion is 1474 mmol / kg, and the content of alkoxysilyl groups in the urethane resin (A-6) is 0.12. It was mass%.
  • aqueous dispersion 6 parts by mass of an 89% by mass phosphoric acid aqueous solution was added and maintained at 45 ° C. for 1 hour, then cooled to 40 ° C., and 1059 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion.
  • This aqueous dispersion was distilled under reduced pressure to obtain a urethane resin (A′-1) aqueous dispersion having a nonvolatile content of 30% by mass.
  • the proportion of the alicyclic structure per solid content of this urethane resin (A′-1) aqueous dispersion is 1476 mmol / kg, and the content of alkoxysilyl groups in the urethane resin (A′-1) is 0 It was mass%.
  • Table 1 shows the ratio of the alicyclic structure per solid content of the urethane resin aqueous dispersions obtained in Preparation Examples 1 to 6 and Comparative Preparation Example 1 and the content of alkoxysilyl groups.
  • hydrophilic acrylic polymer (B-1) had a weight average molecular weight of 20,000 and a nonvolatile content of 50% by mass.
  • the content of alkoxysilyl group in the hydrophilic acrylic polymer (B-1) was 1.1% by mass.
  • hydrophilic acrylic polymer (B-2) had a weight average molecular weight of 20,000 and a nonvolatile content of 50% by mass.
  • the content of alkoxysilyl group in the hydrophilic acrylic polymer (B-2) was 1.1% by mass.
  • hydrophilic acrylic polymer (B-3) had a weight average molecular weight of 20,000 and a nonvolatile content of 50% by mass.
  • the content of alkoxysilyl groups in the hydrophilic acrylic polymer (B-3) was 11.24% by mass.
  • hydrophilic acrylic polymer (B-4) had a weight average molecular weight of 20,000 and a nonvolatile content of 50% by mass.
  • the content of alkoxysilyl group in the hydrophilic acrylic polymer (B-4) was 8.16% by mass.
  • hydrophilic acrylic polymer (B-5) had a weight average molecular weight of 20,000 and a nonvolatile content of 50% by mass.
  • the content of alkoxysilyl group in the hydrophilic acrylic polymer (B-5) was 1.1% by mass.
  • hydrophilic acrylic polymer (B′- 1) 20 parts by mass of a 0.5% by mass isopropyl alcohol solution of the azo polymerization initiator “V-59” was dropped into a reaction apparatus at 80 ° C. for 4 hours to carry out radical polymerization, whereby a hydrophilic acrylic polymer (B′- 1) was obtained.
  • the obtained hydrophilic acrylic polymer (B′-1) had a weight average molecular weight of 20,000 and a non-volatile content of 50% by mass.
  • the content of alkoxysilyl group in the hydrophilic acrylic polymer (B′-1) was 0% by mass.
  • Example 1 Preparation of aqueous resin composition (1)
  • aqueous dispersion having a non-volatile content of 30% by mass obtained in Preparation Example 1 (non-volatile content: 72 parts by mass), hydrophilic acrylic polymer (B-1) having a non-volatile content of 50% by mass obtained in Preparation Example 7 (B-1) 60 parts by mass (non-volatile content: 30 parts by mass), 1,2-propylene glycol 30 parts by mass and 1 , 3-Butylene glycol 30 parts by mass and ion-exchanged water 30 parts by mass were added to obtain an aqueous dispersion.
  • the aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (1) having a nonvolatile content of 30% by mass.
  • Example 2 Preparation of aqueous resin composition (2)
  • aqueous dispersion having a non-volatile content of 30% by mass obtained in Preparation Example 1 (non-volatile content: 72 parts by mass) and a hydrophilic acrylic polymer (B-2) having a nonvolatile content of 50% by mass obtained in Preparation Example 8 (B-2) 60 parts by mass (non-volatile content: 30 parts by mass), 1,2-propylene glycol 30 parts by mass and 1 , 3-Butylene glycol 30 parts by mass and ion-exchanged water 30 parts by mass were added to obtain an aqueous dispersion.
  • the aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (2) having a nonvolatile content of 30% by mass.
  • Example 3 Preparation of aqueous resin composition (3)
  • a thermometer thermometer
  • a stirrer stirrer
  • a reflux condenser a reflux condenser
  • a dropping device 240 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Preparation Example 1 (nonvolatile content: 72 parts by mass) was prepared.
  • nonvolatile content 30 parts by mass
  • a hydrophilic acrylic polymer (B-3) having a nonvolatile content of 50% by mass obtained in Example 9
  • An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water.
  • the aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (3) having a nonvolatile content of 30% by mass.
  • Example 4 Preparation of aqueous resin composition (4)
  • aqueous dispersion obtained in Preparation Example 1 nonvolatile content: 72 parts by mass
  • nonvolatile content 30 parts by mass
  • hydrophilic acrylic polymer (B-4) having a nonvolatile content of 50% by mass obtained in Example 10
  • An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (4) having a nonvolatile content of 30% by mass.
  • Example 5 Preparation of aqueous resin composition (5)
  • aqueous dispersion obtained in Preparation Example 1 nonvolatile content: 72 parts by mass
  • nonvolatile content 30 parts by mass
  • a hydrophilic acrylic polymer (B-5) having a nonvolatile content of 50% by mass obtained in Example 11
  • An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water.
  • the aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (5) having a nonvolatile content of 30% by mass.
  • Example 6 Preparation of aqueous resin composition (6)
  • a urethane resin A-2
  • A-2 aqueous dispersion having a non-volatile content of 30% by mass obtained in Preparation Example 2
  • hydrophilic acrylic polymer B-1 having a non-volatile content of 50% by mass obtained in Preparation Example 7
  • B-1 60 parts by mass (non-volatile content: 30 parts by mass)
  • 1,2-propylene glycol 30 parts by mass and 1 3-Butylene glycol 30 parts by mass and ion-exchanged water 30 parts by mass were added to obtain an aqueous dispersion.
  • the aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (6) having a nonvolatile content of 30% by mass
  • Example 7 Preparation of aqueous resin composition (7)
  • aqueous dispersion obtained in Preparation Example 3 nonvolatile content: 72 parts by mass
  • hydrophilic acrylic polymer (B-1) having a non-volatile content of 50% by mass obtained in Preparation Example 7 B-1) 60 parts by mass (non-volatile content: 30 parts by mass)
  • 1,2-propylene glycol 30 parts by mass and 1 3-Butylene glycol 30 parts by mass and ion-exchanged water 30 parts by mass were added to obtain an aqueous dispersion.
  • the aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (7) having a nonvolatile content of 30% by mass.
  • Example 8 Preparation of aqueous resin composition (8)
  • aqueous dispersion obtained in Preparation Example 4 was prepared.
  • nonvolatile content 30 parts by mass
  • a hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass obtained in Example 7 30 parts by mass of 1,2-propylene glycol, and 1,3-butylene glycol 30
  • An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (8) having a nonvolatile content of 30% by mass.
  • Example 9 Preparation of aqueous resin composition (9)
  • aqueous dispersion obtained in Preparation Example 5 were prepared.
  • nonvolatile content 30 parts by mass
  • a hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass obtained in Example 7 30 parts by mass of 1,2-propylene glycol, and 1,3-butylene glycol 30
  • An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (9) having a nonvolatile content of 30% by mass.
  • Example 10 Preparation of aqueous resin composition (10)
  • aqueous resin composition (10) In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 240 parts by mass (nonvolatile content: 72 parts by mass) of the urethane resin (A-6) aqueous dispersion obtained in Preparation Example 6 were prepared.
  • nonvolatile content 30 parts by mass
  • a hydrophilic acrylic polymer (B-1) having a nonvolatile content of 50% by mass obtained in Example 7 30 parts by mass of 1,2-propylene glycol, and 1,3-butylene glycol 30
  • An aqueous dispersion was obtained by adding parts by mass and 30 parts by mass of ion-exchanged water. The aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (10) having a nonvolatile content of 30% by mass.
  • aqueous dispersion 30 parts by mass of 1,3-butylene glycol and 30 parts by mass of ion-exchanged water were added to obtain an aqueous dispersion.
  • the aqueous dispersion was distilled under reduced pressure to obtain an aqueous resin composition (C2) having a nonvolatile content of 30% by mass.
  • the metal base used was a phosphoric acid chromate treated aluminum plate, 55 mass% aluminum-zinc alloy plated steel plate (GL steel plate), and the plastic base used was acrylonitrile-butadiene-styrene resin (ABS). Resin) and a substrate made of polycarbonate resin (PC resin).
  • C The number of grids not peeled was 40 or more and less than 60.
  • D The number of grids not peeled was less than 40.
  • Table 3 shows the evaluation results of the aqueous resin compositions (1) to (10) prepared in Examples 1 to 10 and the evaluation results of the aqueous resin compositions (C1) to (C4) prepared in Comparative Examples 1 to 4. Shown in
  • Examples 1 to 10 shown in Table 3 are examples using the aqueous resin composition of the present invention. From the evaluation results of Examples 1 to 10, the coating film obtained using the aqueous resin composition of the present invention has excellent hydrophilic durability and chemical resistance, and excellent adhesion to various substrates. It has been confirmed that it has sex.
  • Comparative Example 1 is an example using a hydrophilic acrylic polymer having neither a silanol group nor a hydrolyzable silyl group. It was confirmed that the coating film obtained using the aqueous resin composition of Comparative Example 1 was remarkably insufficient in hydrophilic durability, chemical resistance and substrate adhesion.
  • Comparative Example 2 is an example using a urethane resin having neither silanol groups nor hydrolyzable silyl groups. It was confirmed that the coating film obtained using the aqueous resin composition of Comparative Example 2 was remarkably insufficient in hydrophilic durability, chemical resistance and substrate adhesion.
  • Comparative Example 3 is an example in which a hydrophilic acrylic polymer having a silanol group and / or a hydrolyzable silyl group was not used. Although the coating film obtained using the aqueous resin composition of Comparative Example 3 was excellent in chemical resistance and substrate adhesion, it was confirmed that the hydrophilic durability was extremely insufficient.
  • Comparative Example 4 is an example in which a urethane resin having a silanol group and / or a hydrolyzable silyl group was not used. It was confirmed that the coating film obtained using the aqueous resin composition of Comparative Example 4 was remarkably insufficient in hydrophilic durability, chemical resistance and substrate adhesion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention vise à fournir une composition de résine aqueuse qui est capable de former un film de revêtement qui a une excellente persistance d'hydrophilie, une excellente résistance chimique et une adhérence au substrat et qui peut empêcher la détérioration de divers substrats. Une composition de résine aqueuse selon la présente invention est caractérisée en ce qu'elle comprend (A) une résine uréthane ayant un groupe silanol et/ou un groupe silyle hydrolysable, (B) un polymère acrylique hydrophile ayant un groupe silanol et/ou un groupe silyle hydrolysable, et (C) un milieu aqueux. La présente invention comprend un agent de revêtement contenant la composition de résine aqueuse et un article ayant un film de revêtement de l'agent de revêtement.
PCT/JP2017/035923 2016-10-11 2017-10-03 Composition de résine aqueuse, agent de revêtement et article WO2018070297A1 (fr)

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KR1020197009319A KR102196220B1 (ko) 2016-10-11 2017-10-03 수성 수지 조성물, 코팅제 및 물품
CN201780062408.3A CN109790372B (zh) 2016-10-11 2017-10-03 水性树脂组合物、涂布剂和物品

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WO2021205834A1 (fr) * 2020-04-07 2021-10-14 Dic株式会社 Composition de résine aqueuse et agent de revêtement

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WO2020129672A1 (fr) * 2018-12-21 2020-06-25 Dic株式会社 Composition de résine d'uréthane, agent de traitement de surface et article
JP7413771B2 (ja) * 2019-12-25 2024-01-16 日清紡ケミカル株式会社 水性樹脂用架橋剤組成物および水性樹脂組成物

Citations (3)

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JP2000265053A (ja) * 1999-03-18 2000-09-26 Nippon Nsc Ltd 水性樹脂組成物
JP2004300196A (ja) * 2003-03-28 2004-10-28 Sk Kaken Co Ltd 水性塗料組成物
JP2009143969A (ja) * 2006-08-11 2009-07-02 Nippon Nsc Ltd 水系反応性樹脂及びその製造方法

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EP1961790A4 (fr) * 2005-12-12 2009-09-02 Dainippon Ink & Chemicals Composition aqueuse de revêtement, film de revêtement composite organique/inorganique et procédé servant à produire ceux-ci
JP5885029B2 (ja) * 2012-03-29 2016-03-15 Dic株式会社 水性複合樹脂組成物及びそれを用いたコーティング剤

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2000265053A (ja) * 1999-03-18 2000-09-26 Nippon Nsc Ltd 水性樹脂組成物
JP2004300196A (ja) * 2003-03-28 2004-10-28 Sk Kaken Co Ltd 水性塗料組成物
JP2009143969A (ja) * 2006-08-11 2009-07-02 Nippon Nsc Ltd 水系反応性樹脂及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021205834A1 (fr) * 2020-04-07 2021-10-14 Dic株式会社 Composition de résine aqueuse et agent de revêtement

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KR102196220B1 (ko) 2020-12-30
CN109790372A (zh) 2019-05-21
TWI743217B (zh) 2021-10-21
JPWO2018070297A1 (ja) 2019-06-24
JP6544612B2 (ja) 2019-07-17
TW201823389A (zh) 2018-07-01
CN109790372B (zh) 2022-03-11

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