JP2019059884A - Aqueous resin composition - Google Patents

Abstract

To provide an aqueous resin composition capable of providing a coating film excellent in storage stability and also excellent in durability and to provide a method for producing an aqueous resin composition.SOLUTION: There are provided: an aqueous resin composition which comprises an epoxysilane emulsion emulsified in water with one or two or more selected from a nonionic surfactant and an anionic surfactant and an aqueous dispersion of a resin having a carboxyl group; and a method for producing an aqueous resin composition which comprises: a step of emulsifying an epoxysilane in water with one or two or more selected from a nonionic surfactant and an anionic surfactant; and a step of mixing the epoxysilane emulsion and the aqueous dispersion of a resin having a carboxyl group.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous resin composition and a method for producing an aqueous resin composition.

  In recent years, environmental pollution, the influence on the human body, and the like have come to be considered, and in many cases, a water-based coating agent is used instead of a solvent-based coating agent as various surface coating agents.

  Such water-based coating agents include (a) aromatic-acrylic polymers, (b) epoxysilanes, (c) C10-C20 alkyl groups, and nonionics comprising polymerized units of 2 to 4 ethylene oxide An aqueous composition comprising a surfactant is disclosed (Patent Document 1).

Japanese Patent Publication No. 2016-532769

  However, in the case of an aqueous composition containing a polymer having a carboxyl group and an epoxysilane, the storage stability is insufficient because gelation progresses with the passage of time (Patent Document 1).

  The present invention has been made in view of the above problems, and provides an aqueous resin composition which is excellent in storage stability and further capable of donating a film excellent in durability, and a method of producing the aqueous resin composition. To be a task.

  In a first embodiment of the present invention, an epoxysilane emulsion emulsified in water with one or more selected from nonionic surfactants and anionic surfactants, and a resin having a carboxyl group It is an aqueous resin composition characterized by containing a water dispersion.

  In a preferred embodiment, the HLB of the nonionic surfactant is 10 or more and 20 or less.

  In a preferred embodiment, the nonionic surfactant is a polyoxyalkyl ether having one or more selected from an aliphatic hydrocarbon group having 10 to 30 carbon atoms and an aromatic hydrocarbon group, and It is one or more selected from polyoxyethylene sorbitan fatty acid ester having one or more selected from an aliphatic hydrocarbon group having 10 to 30 carbon atoms and an aromatic hydrocarbon group.

  In a preferred embodiment, the anionic surfactant is one or more selected from a sulfate ester salt having an aromatic hydrocarbon group, a sulfonate, a sulfosuccinate salt and a phosphate ester salt.

  In a preferred embodiment, the resin having a carboxyl group is a polyurethane having a carboxyl group.

  In another embodiment, the step of emulsifying epoxysilane in water with one or more selected from nonionic surfactants and anionic surfactants, epoxysilane emulsion and water of resin having a carboxyl group And a step of mixing the dispersion.

  In a preferred embodiment, after the step of mixing the epoxysilane emulsion and an aqueous dispersion of a resin having a carboxyl group, one or more selected from nonionic surfactants and anionic surfactants. 7. The method for producing an aqueous resin composition according to claim 6, further comprising the step of mixing the above.

  The aqueous resin composition of the present invention is excellent in storage stability and can provide a film excellent in durability.

  The aqueous resin composition of the present invention is an aqueous dispersion of an epoxysilane emulsion emulsified in water with one or more kinds selected from nonionic surfactants and anionic surfactants, and a resin having a carboxyl group. It contains the body.

  Although it does not specifically limit as said nonionic surfactant, Alkylene oxide addition type nonionic surfactant, polyhydric alcohol type nonionic surfactant, etc. are mentioned.

  The alkylene oxide addition type nonionic surfactant is a polyalkylene glycol obtained by directly adding an alkylene oxide to a higher alcohol, a higher fatty acid, an alkylamine or the like, or by adding an alkylene oxide to glycols. Or an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or adding an alkylene oxide to a higher fatty acid amide.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide.

  Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ether (for example, octyl alcohol ethylene oxide adduct, dodecyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide addition , Oleyl alcohol ethylene oxide adducts, lauryl alcohol ethylene oxide / propylene oxide block adducts etc .; polyoxyalkylene higher fatty acid esters (eg stearyl acid ethylene oxide adducts, lauric acid ethylene oxide adduct etc); polyoxyalkylenes Polyhydric alcohol higher fatty acid ester (eg, lauric acid diester of polyethylene glycol, polyethylene glycol Diester of oleic acid, stearic acid diester of polyethylene glycol, etc .; polyoxyalkylene phenyl ether (eg, nonylphenol ethylene oxide adduct, nonylphenol ethylene oxide / propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A. ethylene Oxide adducts, dinonylphenol ethylene oxide adducts, styrenated phenol ethylene oxide adducts, etc .; polyoxyalkylene alkyl amino ethers and (eg, laurylamine ethylene oxide adducts, stearylamine ethylene oxide adducts, etc.); poly Oxyalkylene alkyl alkanol amides (eg, ethylenic of hydroxyethyl lauric acid amide Oxide adducts, ethylene oxide adducts of hydroxypropyl oleic acid amide, ethylene oxide adducts of dihydroxy ethyl lauric acid amide, etc.) and the like.

  Among these, oxyalkylene alkyl ethers in which ethylene oxide is added to a higher alcohol having 10 to 30 carbon atoms, (lauryl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, oleyl alcohol ethylene oxide adduct) The polyoxyalkylene alkyl phenyl ether which ethylene oxide added to the C10-C30 alkyl phenol is preferable at the point of the storage stability of a water-based resin composition.

  As polyhydric alcohol type nonionic surfactant, polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester alkylene oxide adduct, polyhydric alcohol alkyl ether, polyhydric alcohol alkyl ether alkylene oxide adduct can be mentioned.

  Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan diolate, sucrose monostearate, etc. Can be mentioned.

  Specific examples of polyhydric alcohol fatty acid ester alkylene oxide adducts include ethylene glycol monooleate ethylene oxide adduct, ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide / propylene oxide random adduct, sorbitan Monolaurate ethylene oxide adducts, sorbitan monostearate ethylene oxide adducts, sorbitan distearate ethylene oxide adducts, sorbitan dilaurate ethylene oxide / propylene oxide random adducts and the like can be mentioned.

  Specific examples of polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, lauryl glycoside and the like.

Specific examples of polyhydric alcohol alkyl ether alkylene oxide adducts include sorbitan monostearyl ether ethylene oxide adduct, methyl glycoside ethylene oxide / propylene oxide random adduct, lauryl glycoside ethylene oxide adduct, stearyl glycoside ethylene oxide / propylene oxide random An additive etc. are mentioned.
The lower limit of the HLB of the nonionic surfactant is preferably 10, more preferably 11, and particularly preferably 12, and the upper limit is preferably 19, more preferably 18, and particularly preferably 17. If HLB is in the above-mentioned range, the storage stability of the aqueous resin composition becomes excellent, which is preferable.

  The HLB in the present invention is a value calculated by the following method of Griffin described in Takeshi Fujimoto "Introduction to New Surfactants" Sanyo Chemical Industries, Ltd. (1992), P128.

              HLB = (weight% of hydrophilic group) × (1/5)

  Examples of anionic surfactants include carboxylic acids or salts thereof, sulfates, salts of carboxymethylated products, sulfonates, sulfosuccinates and phosphates.

  Examples of carboxylic acids or salts thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof, and specific examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behen. Acids, oleic acid, linoleic acid, ricinoleic acid and coconut oil, palm kernel oil, rice bran oil, and mixtures of higher fatty acids obtained by saponifying beef tallow and the like. The salts include salts thereof such as sodium, potassium, ammonium and alkanolamines.

  As the sulfuric acid ester salt, higher alcohol sulfuric acid ester salt (sulfuric acid ester salt of aliphatic alcohol having 8 to 18 carbon atoms), higher alkyl ether sulfuric acid ester salt (ethylene oxide or propylene oxide of aliphatic alcohol having 8 to 18 carbon atoms) 1 10 to 10 mol adduct of sulfate ester), sulfated oil (natural unsaturated fat or oil or unsaturated wax as it is after being sulfated and neutralized), sulfated fatty acid ester (lower alcohol ester of unsaturated fatty acid) And neutralized) and sulfated olefins (sulfated and neutralized olefins having 12 to 18 carbon atoms). Examples of the salt include sodium salt, potassium salt, ammonium salt, alkanolamine salt and the like. Specific examples of the higher alcohol sulfate ester salt include octyl alcohol sulfate ester salt, decyl alcohol sulfate ester salt, lauryl alcohol sulfate ester salt, stearyl alcohol sulfate ester salt, alcohol synthesized using Ziegler catalyst (for example, ALFOL 1214: Sulfuric acid ester salt of CONDEA, alcohol synthesized by oxo method (for example, Dobanol 23, 25 and 45: manufactured by Mitsubishi Yuka, Tridecanol: manufactured by Kyowa Hakko, oxocol 1213, 1215, 1415: manufactured by Nissan Chemical, DIADOR 115 -L, 115 H, 135: manufactured by Mitsubishi Kasei Chemical Co., Ltd .; As a specific example of the higher alkyl ether sulfuric acid ester salt, lauryl alcohol ethylene oxide 2 molar adduct sulfuric acid ester salt, octyl alcohol ethylene Oxide 3 molar adduct sulfate ester salt; As specific examples of sulfated oil, sodium, potassium, ammonium, alkanolamine sulfate sulfated fatty acid such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, sheep oil and the like Specific examples of the ester include sodium, potassium, ammonium and alkanolamine salts of sulfates such as butyl oleate and butyl ricinoleate; and tepol (manufactured by Shell Co.) as a specific example of sulfated olefin.

  As salts of carboxymethylated compounds, salts of carboxymethylated aliphatic alcohols having 8 to 16 carbon atoms and salts of carboxymethylated aliphatic ethylene oxide adducts of 1 to 10 moles with 8 to 16 carbon atoms can be mentioned. Be Specific examples of salts of carboxymethylated fatty alcohols are octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dobanol 23 carboxymethylated sodium salt, tridecanol As a specific example of carboxymethylated sodium salt; carboxymethylated salt of 1 to 10 moles of ethylene oxide adduct of aliphatic alcohol, octyl alcohol ethylene oxide 3 mole adduct of carboxymethylated sodium salt, lauryl alcohol ethylene oxide 4 Molar adduct carboxymethylated sodium salt, dobanol 23 ethylene oxide 3 molar adduct carboxymethylated sodium salt, tridecanol ethylene oxide 5 mole adduct carboxymethylated sodium salt.

  Examples of the sulfonate include alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkane sulfonate, α-olefin sulfonate, igepon T type, and sulfonates of other aromatic ring-containing compounds. Specific examples of alkyl benzene sulfonates are dodecyl benzene sulfonic acid sodium salts; specific examples of alkyl naphthalene sulfonates are dodecyl naphthalene sulfonic acid sodium salts, dibutyl naphthalene sulfonates, alkane sulfonates, carbon number 8-18 alkanesulfonic acid sodium salt etc. are mentioned. Examples of sulfonates of aromatic ring-containing compounds include mono- or di-sulfonic acid sodium salts of alkylated diphenyl ethers and styrenated phenol sulfonic acid sodium salts.

  Examples of the sulfosuccinic acid salt include diesters and monoesters, and specific examples of the diesters include sulfosuccinic acid di-2-ethylhexyl ester sodium salt. Examples of the monoester type include sulfosuccinic acid monododecyl ester sodium salt and sulfosuccinic acid monopolyoxyethylene dodecyl ester sodium salt.

  Examples of phosphoric acid ester salts include higher alcohol phosphoric acid ester salts and higher alcohol ethylene oxide adduct phosphoric acid ester salts. Specific examples of higher alcohol phosphate ester salts include lauryl alcohol phosphate monoester disodium salt, lauryl alcohol phosphate diester sodium salt; and higher alcohol ethylene oxide adduct phosphate ester salts include oleyl alcohol ethylene oxide 5 mol adduct phosphoric acid monoester disodium salt etc. may be mentioned.

  Among them, it is preferable that the anionic surfactant is one or more selected from sulfuric acid ester salt having aromatic hydrocarbon group, sulfonic acid salt, sulfosuccinate salt and phosphoric acid ester salt. It is preferable in terms of the storage stability of the body. Particularly preferably, it is one or more selected from a sulfate ester salt having an aromatic hydrocarbon group and a phosphate ester salt.

  The epoxysilane is not particularly limited, and as the epoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexosyl) ethylmethyltrimethoxysilane, and β -(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane and the like. The said epoxysilane may be used individually by 1 type, and 2 or more types may be used together.

  As the above epoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane are used for the durability of the film obtained from the aqueous resin composition. It is preferable in point.

  A commercial item can also be used as said epoxysilane. For example, Shin-Etsu Silicone Co., Ltd. trade name "KBM-303", "KBM-402", "KBM-403", "KBE-402", and "KBE-403" etc. are mentioned.

  As the aqueous dispersion of the carboxyl group-containing resin of the present invention, resin particles of a carboxyl group-containing polyolefin resin, polyester resin, polyurethane resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, or epoxy resin are dispersed in water Resin emulsion.

  An acrylic resin emulsion and a polyurethane resin emulsion will be described below as one embodiment of the present invention.

The above acrylic resin is obtained by copolymerizing a polymerizable unsaturated monomer composition comprising a carboxyl group-containing unsaturated monomer and another unsaturated monomer.
Examples of the carboxyl group-containing unsaturated monomer include (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and the like.

  As other unsaturated monomers, (meth) acrylates having an alkyl group having 1 to 2 carbon atoms such as methyl (meth) acrylate and ethyl (meth) acrylate; n-propyl acrylate, i-propyl acrylate, n-butyl Acrylates, acrylates having an alkyl group having 3 to 4 carbon atoms such as i-butyl acrylate, tert-butyl acrylate, etc .; n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, "isostearyl acrylate" (trade name, manufactured by Osaka Organic Chemicals Co., Ltd.), cyclohexyl (meth) acrylate, methyl cyclo ene Alkyl or cycloalkyl (meth) acrylates having 6 or more carbon atoms such as sil (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate; isobornyl (meth) acrylate ) A polymerizable unsaturated monomer having an isobornyl group such as acrylate; a polymerizable unsaturated monomer having an adamantyl group such as adamantyl (meth) acrylate; a tricyclodecenyl group such as tricyclodecenyl (meth) acrylate Polymerizable unsaturated monomers; aromatic ring-containing polymerizable unsaturated monomers such as benzyl (meth) acrylate, styrene, α-methylstyrene, vinyl toluene, etc .; vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyl ester Childiethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloylyl Oxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltri-n-propoxysilane, γ- (meth) acryloyloxypropyltriisopropoxysilane, vinyltriacetoxy Polymerizable unsaturated monomers having a hydrolyzable silyl group such as silane, β- (meth) acryloyloxyethyl trimethoxysilane, etc .; perfluorobutylethyl (meth) acrylate, perfluorooctyl ester Perfluoroalkyl (meth) acrylates such as fluoro (meth) acrylate; polymerizable unsaturated monomers having a fluorinated alkyl group such as fluoroolefin; N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate etc Vinyl compounds; phosphoric acid group-containing polymerizable unsaturated monomers such as 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate; (meth) acrylonitrile , (Meth) acrylamide, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 2- (methacryloyloxy) ethyl trimethyl ammonium Nitrogen-containing polymerizable unsaturated monomers such as adducts of chlorides, glycidyl (meth) acrylates and amines; polymerizable unsaturated groups such as allyl (meth) acrylates and 1,6-hexanediol di (meth) acrylate Polymerizable unsaturated monomers having at least two in the molecule; 2-acrylamido-2-methylpropane sulfonic acid, 2-sulfoethyl (meth) acrylate, allyl sulfonic acid, 4-styrene sulfonic acid, etc .; sodium salts of these sulfonic acids and the like Polymerizable unsaturated monomers having a sulfonic acid group such as ammonium salt; and polymerizable unsaturated monomers having an acid anhydride group such as maleic anhydride, itaconic anhydride, citraconic anhydride and the like, which may be used alone or in combination It can be used in combination of species or more.

  The reaction temperature in polymerizing the carboxyl group-containing unsaturated monomer and the other unsaturated monomer is usually in the range of about 60 to about 200 ° C., preferably about 70 to about 160 ° C., and the reaction time is usually about 10 hours or less , Preferably about 0.5 to about 6 hours.

In the above reaction, it is preferable to add a polymerization initiator as appropriate. As such a polymerization initiator, for example, benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, di-tert-amyl peroxide, t-butyl Organic peroxides such as peroxy-2-ethyl hexanoate, tert-butyl peroxy laurate, tert-butyl peroxy isopropyl carbonate, tert-butyl peroxy acetate, diisopropyl benzene hydroperoxide; azobisisobutyro Nitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropiononitrile), azobis (2-methylbutyronitrile), 4,4'-azobis (4-cyanobutaπ) Acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis {2-methyl-N- [2- (1-hydroxy) Azo compounds such as butyl)]-propionamide}; and persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate and the like.
These polymerization catalysts may be used alone or in combination of two or more.

  The compounding amount of the polymerization initiator is 0.01 to 20 parts by mass, in particular 0.1 to 15 parts by mass, and particularly 0.3 to about 100 parts by mass of the polymerizable unsaturated monomer composition used in that stage. The range of 10 parts by mass is preferable from the viewpoint of the water dispersion stability of the resulting acrylic resin emulsion.

  The above polymerization is usually carried out in the presence of an organic solvent. The choice of the organic solvent can be made appropriately in consideration of the polymerization temperature, the ease of handling at the time of production of the emulsion and the long-term storage stability of the resulting aqueous dispersion.

  Moreover, it is possible to add an organic solvent also when dispersing an acrylic resin in water.

As the organic solvent, alcohol solvents, cellosolve solvents, carbitol solvents and the like are preferable. Specifically, for example, alcohol solvents such as n-butanol; ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol mono n-butyl ether, Examples include cellosolv solvents such as dipropylene glycol monomethyl ether and dipropylene glycol mono n-butyl ether; and carbitol solvents such as diethylene glycol monobutyl ether and diethylene glycol monoethyl ether.
In addition, as the organic solvent, inert organic solvents which are not mixed with water other than the above can also be used within a range that does not affect the water dispersion stability of the acrylic resin emulsion. And aromatic hydrocarbon solvents, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl ethyl ketone and cyclohexanone.

  The above-mentioned acrylic resin has a weight average molecular weight in the range of 5,000 to 100,000, particularly 10,000 to 50,000, and more particularly 10,000 to 30,000, the water dispersion stability of the acrylic emulsion And it is suitable from the viewpoints of finish, smoothness, polishability etc. of clear coating film.

In the present invention, the weight average molecular weight of the acrylic resin is “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) as a gel permeation chromatograph device, “TSKgel G4000HXL” as one column, “TSKgel as a column. A total of four G3000HXL "and one" TSKgel G2000HXL "(trade names, both manufactured by Tosoh Corporation) are used, and a differential refractometer is used as a detector; mobile phase: tetrahydrofuran, measurement The temperature can be measured under the conditions of 40 ° C., flow rate: 1 mL / min.
In the present invention, an acrylic resin emulsion can be obtained by dispersing the above acrylic resin in water.

As a method of water dispersion, an aqueous medium containing a basic compound or neutralizing a part or all of an anionic group such as a carboxyl group contained in the above-mentioned acrylic resin with a basic compound and dispersing it in water It is also possible to add and disperse the acrylic resin therein.
Examples of basic compounds for neutralization include ammonia, diethylamine, ethyl ethanolamine, diethanolamine, triethanolamine, monoethanolamine, monopropanolamine, isopropanolamine, ethylaminoethylamine, hydroxyethylamine, triethylamine, tributylamine, Organic amines such as dimethylethanolamine and diethylenetriamine; and alkali metal hydroxides such as caustic soda and caustic can be mentioned. The amount is 0.1 to 1.5 equivalents, preferably 0.5 to the carboxyl group in the acrylic resin. It is appropriate to use about 1.2 equivalents.

The acrylic resin emulsion obtained as described above can have an average particle size of 0.05 to 1.0 μm, preferably 0.08 to 0.8 μm.
In the present specification, as the average particle size, a sample is diluted with deionized water to a concentration suitable for measurement with a submicron particle analyzer N4 (trade name, manufactured by Beckman Coulter, Inc., particle size distribution measuring apparatus), It is a value measured at normal temperature (about 20 ° C.).

  Further, the hydroxyl value per solid content of the above acrylic resin emulsion is in the range of 70 to 170 mg KOH / g, particularly 100 to 120 mg KOH / g, the acid value per solid content is 5 to 50 mg KOH / g, 20 to 35 mg KOH / g, It is particularly preferable to be in the range of 20 to 30 mg KOH / g.

  The polyurethane resin emulsion is an emulsion of a polyurethane comprising a polyisocyanate, a compound having two or more active hydrogen groups, a compound having one or more active hydrogen groups and a carboxyl group, and a chain extender.

  The polyisocyanate is not particularly limited, and polyisocyanates commonly used in the art can be used. Specifically, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and araliphatic polyisocyanates can be mentioned. As aliphatic polyisocyanates, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 There may be mentioned 5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like. Examples of alicyclic polyisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane and the like. It can be mentioned. As aromatic polyisocyanate, tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5 Naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like can be mentioned. Examples of the aromatic aliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-α-tetramethyl xylylene diisocyanate and the like. Further, dimers or trimers of these organic polyisocyanates and modified products such as buretized isocyanate can be mentioned. In addition, these can also be used individually by 1 type and can also use 2 or more types together.

  The compound having two or more active hydrogen groups is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule, and examples thereof include polyhydric alcohols, polyether polyols, and polyester polyols. , Polyether ester polyols, polycarbonate polyols, polyolefin polyols, polyacrylic polyols, polyacetal polyols, polybutadiene polyols, polysiloxane polyols, fluorine polyols etc. And compounds having two or more hydroxyl groups at the molecular terminal or in the molecule. The polyhydric alcohol is not particularly limited. For example, ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, bisphenol A, bisphenol B, bisphenol S, hydrogenated bisphenol A, dibromo bisphenol A, 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerin, pentaerythritol And the like. The polyether polyol is not particularly limited, and examples thereof include an alkylene derivative of polyhydric alcohol, polytetramethylene glycol, polyetheretherol and the like. The polyester polyol and the polyether ester polyol are not particularly limited, and examples thereof include polyhydric alcohols, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, polyether polyols, and polyhydric carboxylic acid esters. Esterified products, castor oil polyols, polycaprolactone polyols and the like. The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene polyol, polyisoprene polyol and hydrogenated polyols thereof.

  Examples of the compound having one or more active hydrogen groups and a carboxyl group include: 2,2-dimethylol propionic acid, 2, 2-dimethylol butyric acid, 2, 2- dimethylol valeric acid, dioxymaleic acid, And carboxylic acid-containing compounds such as 6, 6-dioxybenzoic acid, 3,4-diaminobenzoic acid and the like, and derivatives thereof and salts thereof, and polyester polyols obtained using these. Furthermore, amino acids such as alanine butyric acid, aminocaproic acid, glycine, glutamic acid, aspartic acid and histidine etc., and carboxylic acids such as succinic acid, adipic acid, maleic anhydride, phthalic acid and trimellitic anhydride can also be mentioned.

  These carboxyl groups can be rendered water dispersible by finally neutralizing them into salts. In this case, examples of the neutralizing agent include nonvolatile bases such as sodium hydroxide and potassium hydroxide, trimethylamine, triethylamine, tertiary amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine, and volatilization of ammonia and the like. Sex bases etc. are mentioned. The neutralization can be carried out either before, during or after the urethanization reaction.

  The chain extender is not particularly limited, and specifically, diamines and polyamines can be used. Examples of diamines include ethylene diamine, trimethylene diamine, piperazine, isophorone diamine and the like, and examples of polyamines include diethylene triamine, dipropylene triamine, triethylene tetramine and the like.

  Although the manufacturing method of the said polyurethane resin emulsion of this invention is not specifically limited, For example, the following method is used. The stoichiometry is the sum of the compound having two or more active hydrogen groups, the compound having one or more active hydrogen groups, the compound having a hydrophilic group, and the active hydrogen group having reactivity with the isocyanate group contained in the chain extender. Theoretically terminated polyisocyanate (an equivalent ratio of isocyanate group to reactive functional group: 1: 0.85 to 1.1) is reacted without a solvent or in an organic solvent having no active hydrogen group for isocyanate termination After synthesis of the urethane prepolymer of (1), neutralization or quaternization of the anionic hydrophilic group or the cationic hydrophilic group of the component is carried out, if necessary, followed by dispersion emulsification in water. Thereafter, an equivalent amount of chain extender (equivalent ratio of isocyanate group to chain extender: 1: 0.5 to 0.9) less than the remaining isocyanate group is added, and the isocyanate group in the emulsion micelle and the chain extender And an interfacial polymerization reaction to form a urea bond. Thereby, the crosslink density in the emulsion micelles is improved, and a three-dimensional crosslink structure is formed. Thus, the formation of the three-dimensional crosslinked structure provides a coating film exhibiting excellent electrolytic solution resistance. Then, the polyurethane water dispersion can be obtained by removing the used solvent as needed. In addition, even if it does not use a polyamine etc. as said component, chain | strand elongation can also be performed by the water molecule which exists in water at the time of dispersion emulsification.

  In the synthesis of the urethane prepolymer, a solvent which is inert to the isocyanate group and which can dissolve the generated urethane prepolymer can also be used. These solvents include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2-pyrrolidone, toluene, propylene glycol monomethyl ether acetate and the like. It is preferable to finally remove these hydrophilic organic solvents used in the reaction.

  The aqueous resin composition of the present invention comprises a step of emulsifying epoxysilane in water with a nonionic surfactant and / or an anionic surfactant, and a step of mixing an aqueous dispersion of an epoxysilane emulsion and a resin having a carboxyl group. And.

  The step of emulsifying the epoxysilane in water with one or more selected from nonionic surfactants and anionic surfactants is selected from predetermined amounts of nonionic surfactants and anionic surfactants. It can carry out by mixing 1 type, or 2 or more types with a normal mixing method.

  The lower limit of the amount of the one or more selected from the nonionic surfactant and the anionic surfactant to the epoxysilane is preferably 25 parts by mass or more, and 50 parts by mass with respect to 100 parts by mass of the epoxysilane. The above is more preferable, and 75 parts by mass or more is more preferable. On the other hand, the upper limit is preferably 250 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less. Within the above range, the storage stability of the water-based resin composition becomes excellent, and a film excellent in physical properties and durability can be provided.

The step of mixing the epoxysilane emulsion and the aqueous dispersion of the resin having a carboxyl group is performed by mixing a predetermined amount of the epoxysilane emulsion and the aqueous dispersion of the resin having a carboxyl group according to a common mixing method. Can do.
The lower limit of the epoxysilane to 1 mol of carboxyl groups of the resin having a carboxyl group is 0.1 molar equivalent or more, and the blending amount of the epoxysilane emulsion to the aqueous dispersion of the resin having a carboxyl group is preferably 0 .3 molar equivalent or more, more preferably 0.5 molar equivalent or more. On the other hand, the upper limit is 2.0 molar equivalents or less, preferably 1.5 molar equivalents or less, and more preferably 1.0 molar equivalents or less. When the blending amount of the epoxysilane emulsion is in the above range, the storage stability of the aqueous resin composition is excellent, and a film excellent in durability can be provided.

  The aqueous resin composition of the present invention preferably further comprises the step of adding one or more selected from nonionic surfactants and anionic surfactants.

  One or more selected from the nonionic surfactant and the anionic surfactant in the above step may be one or more selected from the nonionic surfactant and the anionic surfactant described above. It can be used suitably.

  The lower limit of one or more selected from the nonionic surfactant and the anionic surfactant in the above step is 1 part by mass with respect to 100 parts by mass of the solid content of the aqueous dispersion of the resin having a carboxyl group. It is the above, Preferably it is 5 mass parts or more. On the other hand, the upper limit is 15 parts by mass or less, preferably 10 parts by mass or less. If the compounding amount is in the upper range, the storage stability of the water-based resin composition becomes more excellent, and a film having excellent durability can be provided.

  Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

Raw materials used in the examples and comparative examples are shown below.
(Nonionic surfactant)
・ Polyoxyethylene styrenated phenyl ether (HLB = 14.3, product name: Neugen EA-157, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
・ Polyoxyethylene tridecyl ether (HLB = 13.8, product name: Neugen TDS-100, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
・ Polyoxyethylene sorbitan monooleate (HLB = 15.0, product name: Solgen TW-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
・ Polyoxyalkylene branched decyl ether (HLB = 14.7, product name: Neugen XL-100, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(Anionic surfactant)
-Polyoxyethylene styrenated phenyl ether sulfate ammonium (product name: Hytenol NF-17, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
-Linear alkyl benzene sulfonate sodium (product name: Neogen S-20F, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(Epoxysilane)
・ Γ-Glycidoxypropyltriethoxysilane (Product name: KMB-403, Shin-Etsu Silicone Co., Ltd.)
(Water dispersion of resin having carboxyl group) · Polyurethane resin emulsion (Product name: Superflex 420, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

(Preparation of epoxysilane emulsion)
(Epoxysilane emulsion 1)
100 parts by mass of epoxysilane (γ-glycidoxypropyltriethoxysilane, product name: KMB-403, Shin-Etsu Silicone Co., Ltd.) and nonionic surfactant (polyoxyethylene styrenated phenyl ether, product name: Neugen EA- 157 parts by weight of Dai-ichi Kogyo Seiyaku Co., Ltd. was mixed by stirring with a homodisper (2.5 type, made by Prime Mix Co., Ltd.).

  While stirring the above mixture, 408 parts by mass of water was gradually added to prepare an epoxysilane emulsion 1.

(Epoxysilane emulsion 2 to 4)
It was prepared in the same manner as in the epoxysilane emulsion 1 except that the type and blending amount of the nonionic surfactant and the blending amount of water were changed as shown in Table 1.

(Preparation of aqueous resin composition)
Example 1
80 parts by mass of polyurethane resin emulsion (Product name: Superflex 420, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content 30% by mass) and 7 parts by mass of epoxysilane emulsion 1 (per 1 mol of carboxyl groups of polyurethane resin emulsion The epoxy resin 0.58 mole equivalent was mixed to obtain an aqueous resin composition 1.

(Examples 2 to 4)
An aqueous resin composition 2 to 5 was prepared in the same manner as in Example 1 except that the type and blending amount of the epoxysilane emulsion were changed as shown in Table 2.

(Example 5)
80 parts by mass of polyurethane resin emulsion (Product name: Superflex 420, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content 30% by mass) and 7 parts by mass of epoxysilane emulsion 1 (per 1 mol of carboxyl groups of polyurethane resin emulsion 0.58 molar equivalent of epoxysilane, 0.9 parts by mass of nonionic surfactant (polyoxyethylene styrenated phenyl ether, product name: Neugen EA-157, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and then aqueous resin Composition 5 was obtained.

(Examples 6 and 7)
The procedure of Example 5 was repeated, except that the nonionic surfactant was changed as shown in Table 2, to obtain aqueous resin compositions 6 and 7.

(Comparative example 1)
Polyurethane resin emulsion (Product name: Superflex 420, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content 30% by mass) 80 parts by mass and epoxysilane (3-glycidoxypropyltriethoxysilane, product name: KMB-403, Shin-Etsu Co., Ltd. An aqueous resin composition 8 was obtained by mixing 1.2 parts by mass (manufactured by Silicone Co., Ltd.) (0.58 molar equivalent of epoxysilane with respect to 1 mol of the carboxyl group of the polyurethane resin emulsion).

(Comparative example 2)
Polyurethane resin emulsion (Product name: Superflex 420, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content 30% by mass) 80 parts by mass and epoxysilane (3-glycidoxypropyltriethoxysilane, product name: KMB-403, Shin-Etsu Co., Ltd. 1.2 parts by mass (manufactured by Silicone Co., Ltd.) (0.58 molar equivalent of epoxysilane with respect to 1 mol of carboxyl group of polyurethane resin emulsion) and nonionic surfactant (polyoxyethylene styrenated phenyl ether, product name: Neugen An aqueous resin composition 9 was obtained by mixing 0.9 parts by mass of EA-157 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

  The aqueous resin composition was evaluated by the following evaluation method and evaluation criteria. Evaluation results are shown in Table 2

.
(Storage stability)
The viscosity of the aqueous resin composition was measured at 25 ° C. using a BM viscometer (single cylindrical rotational viscometer) according to JIS Z8803. At that time, (a) Measure the rotor rotational speed as 60 rpm, (b) Change the rotor rotational speed to 30 rpm and measure when the measured value in (a) is 8000 mPa · s or more, (c) When the measured value in the above (b) was 16000 mPa · s or more, the rotor rotational speed was changed to 12 rpm for measurement.

The viscosity measured above is V ₀ (mPa · s), and after 6 days at 50 ° C., the viscosity V _n (mPa · s) of the aqueous resin composition measured by the above method is calculated by the following formula (1) Calculation was done.

Viscosity change rate (%) = V _n (mPa · s) / V ₀ (mPa · s) × 100 (Equation 1)

(Formation of a film) Each aqueous resin composition is applied to a dry thickness of about 200 to 300 μm, dried at room temperature (25 ° C) for 24 hours, and then dried at 50 ° C for 3 hours and 120 ° C for 20 minutes. I made a film.

(Film durability) A test piece of 2 × 4 cm was cut out of this film, and this test piece was (1) ethyl acetate / toluene = 1/1 (mass ratio), (2) isopropyl alcohol, (3) ethanol (4) methyl ethyl ketone Immerse in, for 24 hours, measure the mass (W ₀ ) (g) before immersion and the mass (W _n ) (g) after immersion, and calculate the mass increase rate (%) according to the following formula (2) Calculation was done.

Mass increase rate (%) = (W _n (g) -W ₀ (g)) / W ₀ (g) × 100 (Equation 2)

表２より、エポキシシランを非イオン界面活性剤またはアニオン性界面活性剤で乳化したエポキシシラン乳化体とポリウレタン樹脂エマルジョンを含有する水系樹脂組成物（実施例１ないし４）、およびこれらに非イオン界面活性剤またはアニオン性界面活性剤を添加した水系樹脂組成物（実施例５ないし７）は、良好な保存安定性を示し、これらから作成された皮膜は優れた耐久性を有することがわかる。

From Table 2, aqueous resin compositions (Examples 1 to 4) containing an epoxysilane emulsion in which an epoxysilane is emulsified with a nonionic surfactant or an anionic surfactant and a polyurethane resin emulsion (Examples 1 to 4), and a nonionic interface thereto It can be seen that the aqueous resin compositions (Examples 5 to 7) to which an activator or an anionic surfactant is added show good storage stability, and the film prepared therefrom has excellent durability.

  On the other hand, a water-based resin composition (Comparative Example 1) in which epoxy silane and a polyurethane resin emulsion are simply mixed, a water-based resin composition in which epoxy silane, a polyurethane resin emulsion, and a nonionic surfactant are mixed (Comparative Example 2) The storage stability was found to be significantly deteriorated.

It can be used as paints and coatings for various industrial applications.

Claims (7)

  It is characterized by containing an epoxysilane emulsion emulsified in water with one or more selected from nonionic surfactants and anionic surfactants, and a water dispersion of a resin having a carboxyl group. Aqueous resin composition.   The aqueous resin composition according to claim 1, wherein HLB of the nonionic surfactant is 10 or more and 20 or less.   The polyoxyalkyl ether having one or two or more selected from the aliphatic hydrocarbon group having 10 to 30 carbon atoms and the aromatic hydrocarbon group, and the above nonionic surfactant having 10 to 30 carbon atoms Or one or more selected from polyoxyethylene sorbitan fatty acid esters having one or more selected from an aliphatic hydrocarbon group and an aromatic hydrocarbon group of The water-based resin composition as described in or 2.   The said anionic surfactant is 1 type, or 2 or more types selected from the sulfate ester salt which has an aromatic hydrocarbon group, a sulfonate, a sulfo succinate, and a phosphate ester salt, The aqueous resin composition according to any one of 1 to 3.   The aqueous resin composition according to any one of claims 1 to 4, wherein the resin having a carboxyl group is a polyurethane having a carboxyl group. Emulsifying epoxysilane in water with one or more selected from nonionic surfactants and anionic surfactants, mixing an epoxysilane emulsion and an aqueous dispersion of a resin having a carboxyl group, A method of producing a water-based resin composition characterized by comprising: After the step of mixing the epoxysilane emulsion and the aqueous dispersion of a resin having a carboxyl group, a step of further mixing one or more selected from nonionic surfactants and anionic surfactants The manufacturing method of the water-based resin composition of Claim 6 characterized by having.