JP2012102210A - Aqueous polyurethane resin composition, coating material using the composition and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin composition which excels in water resistance, chemical resistance, adhesion to a base material and the like and coating material stability as well, and can be suitably used in the surface treated steel plate coating material application, a coating material containing the aqueous polyurethane resin composition, and a plate-coated product coated with the coating material.SOLUTION: The aqueous polyurethane resin composition is obtained by dispersing an isocyanate group-terminated urethane prepolymer obtained by reacting a polyol (A), an isocyanate (B), and an anion group-introduced polyol (C) having a carboxyl group or a sulfonic acid group into water with the use of an anionic group neutralizing agent (D) to perform water extension. The component (A) has a 10-32C long-chain alkylene diol compound (a) as an essential component and the amount of the component (a) incorporated is 1-20 mass% of the total amount of the components (A), (B), and (C) and the equivalent ratio (NCO/OH) of isocyanate groups (NCO) in the component (B) to all hydroxyl groups (OH) of the components (A) and (C) is 1.3-1.9.

Description

  The present invention relates to a water-based polyurethane resin composition, in particular, a water-based polyurethane resin composition excellent in chemical resistance such as water resistance and acid resistance and alkali resistance and paint stability, a paint containing the water-based polyurethane resin composition, and The present invention relates to a coated product obtained by applying the aqueous polyurethane resin composition to the surface of a plate-like material.

Polyurethane resins are widely used as paints, adhesives, binders, coating agents, etc. because of their wear resistance, adhesiveness, non-stickiness, and rubber elasticity. Many reports of water-based polyurethane resin compositions have been made from the viewpoint of safety such as hygiene.
However, water-based polyurethane resin compositions have a problem that they are inferior in physical properties such as water resistance, chemical resistance, heat resistance, and tensile properties as compared with solvent-based or solvent-free ones.
For example, a paint used for coating a surface-treated steel sheet is required to have chemical resistance such as water resistance, acid resistance, and alkali resistance, but the present water-based polyurethane resin composition is still indispensable. Nothing is known that can satisfy the physical properties.

  In addition, a fluorinated polymer obtained by reacting a polyoxyalkylene-containing substance with a reaction product of a polyfunctional isocyanate and a fluorinated alcohol has been proposed as an improved water repellency and oil repellency of a fiber substrate (patent) Document 1) shows that this fluorinated polymer is not suitable for use as a paint for steel sheets because of its poor adhesion to steel sheets.

In addition, as a water-based polyurethane resin having improved water resistance, chemical resistance, heat resistance, and the like, a water-based polyurethane resin containing a long-chain alkyl group in the side chain is disclosed. However, when this water-based polyurethane resin is urethanized using a short branched diol as the main chain (Patent Documents 2 to 4), urethane bonds having high cohesive energy are close to each other, and the generated urethane prepolymer is aggregated. Since the viscosity increases, water dispersion becomes difficult.
Furthermore, water-dispersed polyurethane resin compositions comprising an isocyanurate compound having a long-chain alkyl group, a polyol and water are disclosed (Patent Documents 5 and 6). In this case, although improvement in water resistance, chemical resistance, and heat resistance was observed, there was a problem in the stability of the paint.

Japanese National Patent Publication No. 11-511814 JP 2000-007909 A JP 2005-510600 Gazette JP-A-2005-068228 WO06 / 038466 JP 2009-203316 A

  As a result of intensive studies in order to solve the above-mentioned conventional drawbacks, the present inventors, as a result, water-elongated a urethane prepolymer in which a certain amount of a long-chain alkylene diol compound is incorporated in the urethane resin skeleton, It was found that a water-based urethane resin composition excellent in chemical resistance such as water resistance, acid resistance and alkali resistance, adhesion to a substrate, etc. and excellent in paint stability can be obtained, and the present invention has been achieved. .

  Therefore, the object of the present invention is to be suitably used for surface-treated steel sheet paint applications that are excellent in water resistance, chemical resistance (acid resistance, alkali resistance), adhesion to the base material, etc. and excellent in paint stability. An object of the present invention is to provide a water-based urethane resin composition that can be used, a paint containing the water-based polyurethane resin, and a plate-like coated product obtained by applying the paint.

That is, the present invention relates to a terminal isocyanate group urethane prepolymer obtained by reacting a polyol (A), an isocyanate (B), and an anionic group-introduced polyol (C) containing a carboxyl group or a sulfonic acid group. A water-based polyurethane resin composition obtained by dispersing in water using a functional group neutralizing agent (D) and extending the water, wherein the component (A) is a long-chain alkylene diol compound having 10 to 32 carbon atoms ( When a) is an essential component, the amount of the component (a) is 1 to 20% by mass of the total amount of the components (A), (B) and (C), and the isocyanate in the component (B) An aqueous polyurethane characterized in that the equivalent ratio (NCO / OH) of the group (NCO) to the total hydroxyl groups (OH) of the component (A) and the component (C) is 1.3 to 1.9 Resin composition , Paint characterized by containing a water-based polyurethane resin composition, and a coated product characterized by comprising applying a paint to a sheet material.
The compound (a) is preferably a long chain alkylene diol compound having 12 to 18 carbon atoms, and the compounding amount of the anionic group-introduced polyol (C) is (A), (B), and ( It is preferable that it is 0.1-30 mass% of the total amount of C) component.
Moreover, the coating material of this invention is suitable for the coating of a surface-treated steel plate.

  With the water-based polyurethane resin composition of the present invention, a paint having excellent stability can be obtained. Moreover, the coated product which has the coating film excellent in water resistance, chemical resistance, etc. can be obtained by coating the coating material of this invention on a surface-treated steel plate.

  The aqueous polyurethane resin composition of the present invention is obtained by reacting a polyol (A), an isocyanate (B), and an anionic group-introduced polyol (C) containing an anionic group selected from a carboxyl group and a sulfonic acid group. This is a water-based polyurethane resin composition obtained by dispersing the terminal isocyanate group-containing urethane prepolymer in water using (D) an anionic group neutralizing agent component and extending the water.

The component (A) comprises a long-chain alkylene diol compound (a) having 10 to 32 carbon atoms as an essential component, and the blending amount of the component (a) is that of the components (A), (B) and (C). It is 1-20 mass% of a total amount, it is preferable that it is 1.5-15 mass%, and it is more preferable that it is 2-10 mass%.
When the content is less than 1% by mass, the water-based polyurethane resin composition has low water resistance and chemical resistance. When the content exceeds 20% by mass, the dispersibility of the urethane prepolymer in water decreases, thereby producing a water-based polyurethane resin. Is not preferable, and the stability of the paint is lowered.

  Examples of the long-chain alkylene diol compound having 10 to 32 carbon atoms include decane diol, undecane diol, dodecane diol, tridecane diol, tetradecane diol, pentadecane diol, hexadecane diol, heptadecane diol, octadecane diol, nonadecane diol, Icosandiol, Hencicosandiol, Docosandiol, Tricosandiol, Tetracosandiol, Pentacosandiol, Hexacosandiol, Heptacosandiol, Octacosandiol, Nonacosanediol, Triacontanediol, Hentriacontandiol And linear or branched diols such as dotriacontanediol.

  Among these, since a water-based polyurethane resin composition excellent in water resistance and chemical resistance is obtained, the component (a) is preferably a long-chain alkylene diol having 12 to 18 carbon atoms. -Dodecanediol or 1,12-octadecanediol is particularly preferred.

  The polyol (A) other than the component (a) is not particularly limited. For example, polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline or non-crystalline polycarbonate polyols, number average Low molecular polyols having a molecular weight of less than 200 can be used.

  Examples of the polyether polyols include 1,2-propanediol, 1,3-propanediol; trimethylolpropane, glycerin, polyglycerin, pentaerythritol, and other low molecular polyols, as well as bisphenol A and ethylenediamine. Examples include ethylene oxide and / or propylene oxide adducts to amine compounds and the like; polytetramethylene ether glycol and the like.

  Examples of the polyester polyols include polyols such as the above-described low-molecular polyols, polyvalent carboxylic acids in an amount less than the stoichiometric amount, or ester-forming derivatives thereof such as esters, acid anhydrides, and carboxylic acid halides. Polyester polyols obtained by direct esterification reaction or transesterification reaction; and polyester polyols obtained by direct esterification reaction of the polyol with a lactone or a hydroxycarboxylic acid obtained by hydrolysis ring-opening reaction thereof. .

  Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, and 2-methyladipine. Fats such as acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid and castor oil fatty acid trimer A tetravalent or higher carboxylic acid such as pyromellitic acid.

  Examples of the ester-forming derivative of the polyvalent carboxylic acid include anhydrides of the above-mentioned polyvalent carboxylic acid, or carboxylic acid halides such as chloride and bromide; methyl ester, ethyl ester, propyl ester, isopropyl of the polyvalent carboxylic acid. Examples include lower aliphatic esters such as esters, butyl esters, isobutyl esters, and amyl esters.

  Examples of the lactones include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

  Examples of the polyester polycarbonate polyols include, for example, a reaction product of a polyester glycol such as polycaprolactone polyol and an alkylene carbonate, and a reaction product obtained by reacting a reaction product of ethylene carbonate and a polyhydric alcohol with an organic dicarboxylic acid. Is mentioned.

  Examples of the crystalline or non-crystalline polycarbonate polyol include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polypropylene glycol, and / or polytetramethylene glycol. The reaction product of diol and phosgene, diallyl carbonate (for example, diphenyl carbonate) or cyclic carbonate (for example, propylene carbonate), and the like.

  The polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline or non-crystalline polycarbonate polyols preferably have a number average molecular weight of 300 to 5,000, more preferably 500 to 3,000.

  Examples of the low molecular polyols having a number average molecular weight of less than 200 include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanedioe Aliphatic diols such as 1,9-nonanediol, cyclohexanedimethanol, cyclohexanediol and other alicyclic diols; trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, polyglycerin, pentaerythritol, dipenta Trivalent or higher polyols such as erythritol and tetramethylolpropane are exemplified.

Isocyanate (B) is not particularly limited, and diisocyanate and polyisocyanate having three or more isocyanate groups in one molecule can be used.
Examples of the diisocyanate include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate. , Aromatic diisocyanates such as dianisidine diisocyanate and tetramethylxylylene diisocyanate; cycloaliphatic such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans and / or cis-1,4-cyclohexane diisocyanate, norbornene diisocyanate Diisocyanates; 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) -trimethylhexamethylene diisocyanate And aliphatic diisocyanates such as lysine and lysine diisocyanate; and mixtures thereof.

  Examples of the polyisocyanate include triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, trifunctional or higher isocyanate such as a mixture thereof, and trifunctional thereof. Examples of the above-mentioned modified products such as carbodiimide modification, isocyanurate modification, and biuret modification, blocked isocyanates obtained by blocking these with various blocking agents, isocyanurates (trimers) of diisocyanates, and biuret trimers described above. .

  Among these, it is preferable to use an aliphatic diisocyanate or an alicyclic diisocyanate because it is easy to obtain and an aqueous polyurethane resin composition excellent in weather resistance and strength is obtained. 1,6-hexamethylene diisocyanate It is particularly preferable to use dicyclohexylmethane-4,4′-diisocyanate or isophorone diisocyanate.

(C) An anionic group-introduced polyol is a polyol containing a carboxyl group and / or a sulfonic acid group, for example, a carboxyl group such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, etc. Examples thereof include polyols containing, and polyols containing a sulfonic acid group such as 1,4-butanediol-2-sulfonic acid.
Among them, it is preferable to use a polyol containing a carboxylic acid group from the viewpoint of easy availability, and it is particularly preferable to use dimethylolpropionic acid.

  Moreover, the compounding quantity of (C) anionic group introduction | transduction polyol should be the quantity used as the range of 0.1-30 mass% with respect to the total amount of said (A), (B), and (C) component. Is more preferable, and it is more preferable that it is the quantity used as 0.5-20 mass%, and it is especially preferable that it is the quantity used as 1.0-10 mass%. When the blending amount of the component (C) is less than 0.1% by mass, the water dispersibility of the polyurethane is inferior, so that the storage stability of the water-based polyurethane resin and the stability of the paint may be lowered, and the content exceeds 30% by mass. As the cohesive energy of the urethane bond increases, the viscosity of the urethane prepolymer increases, causing problems such as difficulty in water dispersion.

The blending amount of the polyol (A), polyisocyanate (B), and (C) anionic group-introduced polyol is the total amount of the polyol (A) and anionic group-introduced polyol (C) at the stage of reacting them. The equivalent ratio (NCO / OH) of the isocyanate group of the isocyanate (B) to 1 equivalent of the hydroxyl group is an amount that is 1.3 to 1.9, and is preferably an amount that is 1.4 to 1.8. It is preferable that it is the quantity used as 1.5-1.7.
When the NCO / OH ratio is less than 1.3, since the urethane prepolymer has a relatively high molecular weight, the water dispersibility of the urethane prepolymer tends to decrease, and the storage stability of the water-based polyurethane resin and the stability of the paint May get worse. In addition, when the NCO / OH ratio exceeds 1.9, carbon dioxide generated by the reaction between the isocyanate group and water rapidly foams when the prepolymer is dispersed in water, which may hinder the production of the resin composition. , Effects such as water resistance and acid resistance of the resin may be reduced.

  In order to produce the water-based polyurethane resin composition of the present invention, first, a polyol (A), an isocyanate (B), and a solvent that is inert to the reaction and that has a high affinity for water are used as necessary. An anionic group polyol (C) is reacted to synthesize a terminal isocyanate urethane prepolymer.

  Suitable solvents that are inert to the reaction and have a high affinity with water include, for example, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, and the like. These solvents are usually used in an amount of 3 to 100 parts by mass with respect to 100 parts by mass of the total amount of the raw materials used for producing the prepolymer. When using a solvent having a boiling point of 100 ° C. or lower as these solvents, it is preferable to synthesize the aqueous polyurethane resin and then remove the solvent by distillation under reduced pressure or the like.

Examples of the method of dispersing the terminal isocyanate urethane prepolymer with water include (1) a prepolymer mixing method in which the prepolymer is added and dispersed in water, and (2) a phase inversion method in which water is added to the prepolymer and dispersed. . The anionic group neutralizing agent (D) used for water dispersion may be added to either the prepolymer or water.
Thus, after carrying out water dispersion of the terminal isocyanate urethane prepolymer, the water-based polyurethane resin composition of this invention is synthesize | combined by carrying out water extension in water.

  Examples of the anionic group neutralizing agent (D) include trialkylamines such as trimethylamine, triethylamine, and tributylamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, and N, N-dipropylethanolamine. N-N-dialkylalkanolamines such as 1-dimethylamino-2-methyl-2-propanol, tertiary-alkanolamines such as N-alkyl-N, N-dialkanolamines, triethanolamine, etc. Amine compounds; basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like.

  The amount of these neutralizing agents used is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the anionic group of the component (C), and 0.8 to 1.5 equivalents. More preferably, the amount is If the amount of the neutralizing agent used is excessive or insufficient, physical properties such as water resistance, strength and elongation of the coating film obtained from the water-based polyurethane resin may be lowered.

When performing the said water extension, it is preferable to make it water-elongate, stirring at a temperature of 30-75 degreeC, and it is more preferable that a temperature shall be 40-65 degreeC.
When the temperature is lower than 30 ° C., the reaction takes a long time, resulting in a decrease in production efficiency. When the temperature exceeds 75 ° C., a foaming phenomenon may occur due to rapid carbon dioxide generation due to a water elongation reaction. When it contains, a manufacturing problem arises.
As a method for determining the end point of the reaction in water elongation, a method of confirming disappearance of an isocyanate group using IR (infrared spectrophotometer) is simple and preferable.

  In the production of the water-based polyurethane resin composition of the present invention, an emulsifier may be used when the polyurethane is dispersed in water. Emulsifiers include ordinary anionic surfactants and nonionic surfactants, and cationic interfaces such as primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts and pyridinium salts. Activators and further known ones such as amphoteric surfactants such as betaine type, sulfate type and sulfonic acid type can be mentioned.

  Examples of the anionic surfactant include sodium sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate; polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate; sodium Sulfolicinolate; Alkyl sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; Fatty acid salts such as sodium laurate, triethanolamine oleate and tolethanolamine abiates; Sodium benzene sulfonate, Alkaline phenol hydroxyethylene Alkyl aryl sulfonates such as alkali metal sulfate High alkyl naphthalene sulfonate; naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate; polyoxyethylene alkyl sulfate salt; polyoxyethylene alkyl aryl sulfate salt; polyoxyethylene ether phosphate; polyoxyethylene alkyl ether acetate N-acyl amino acid salt; N-acyl methyl taurine salt and the like.

  Examples of the nonionic surfactant include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerin fatty acid esters; and alcohols having 1 to 18 carbon atoms. Examples include ethylene oxide and / or propylene oxide adduct; ethylene oxide and / or propylene oxide adduct of alkylphenol; ethylene glycol and / or propylene oxide adduct of alkylene glycol and / or alkylene diamine. Examples of the alcohol having 1 to 18 carbon atoms constituting these nonionic surfactants include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol, and tertiary amyl alcohol. Hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like.

  Examples of the alkylphenol include phenol, methylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 3,5-di-tert-butylphenol, 4- (1,3-tetramethylbutyl) phenol, 4-isooctylphenol, 4-nonylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, bisphenol F etc. are mentioned.

  Examples of the alkylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1 , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, etc. Examples of the alkylene diamine include those in which the alcoholic hydroxyl group of these alkylene glycols is substituted with an amino group. Further, the ethylene oxide and propylene oxide adducts may be random adducts or block adducts.

  Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkylpyridinium bromide and imidazolinium. Examples thereof include laurate.

  Examples of the amphoteric surfactant include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethyl Examples include betaine types such as metal salts of carboxymethyl betaine and hydroxypropyl phosphate, amino acid types such as metal salts of β-laurylaminopropionic acid, sulfate ester types, and sulfonic acid types.

  The amount of the emulsifier is not particularly limited, but from the viewpoint of physical properties such as water resistance, strength, elongation and the like of the coating film obtained by applying the aqueous polyurethane resin composition, the above (A) to (C) It is preferable that it is 1-30 mass parts with respect to 100 mass parts of total amounts of a component, and it is more preferable that it is 5-20 mass parts. If the amount is less than 1 part by mass, the effect of improving dispersibility may not be obtained. If the amount exceeds 30 parts by mass, the physical properties of the coating film described above may be reduced.

  Moreover, in the water-based polyurethane resin composition of this invention, in order to give a crosslinked structure to a polyurethane molecule, you may further mix | blend the crosslinking agent normally used for a urethane prepolymer as needed.

  Examples of the crosslinking agent include melamine, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylated methylol melamine, butylated methylol melamine, and melamine resin. . In the present invention, it is preferable to select and use an inexpensive melamine excellent in dispersibility in polyurethane from among these.

  When using the water-based polyurethane resin composition of this invention as a coating material etc., it can dilute and use it suitably. The solid content concentration at the time of dilution is not particularly limited, but from the viewpoints of dispersibility, coating film, operability for obtaining a molded article, etc., the total amount of the components (A) to (C) is 100 parts by mass. It is preferable that it is 1-65 mass% with respect to it, and it is more preferable that it is 5-50 mass%.

  Moreover, you may add the various additives normally used to the water-based polyurethane resin composition of this invention as needed. Examples of such additives include pigments; dyes; film-forming aids; curing agents; external cross-linking agents; viscosity modifiers; leveling agents; antifoaming agents; anti-gelling agents; and light stabilizers such as hindered amines; -Based compounds, phosphorus compounds, sulfur compounds and other antioxidants; triazine compounds, benzoate compounds, UV absorbers comprising 2- (2-hydroxyphenyl) benzotriazole compounds; radical scavengers; heat resistance imparting agents Inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing agents, catalysts, thixotropic agents, antibacterial agents, antifungal agents, antiseptic agents, and rust inhibitors.

  Further, when the aqueous polyurethane resin composition of the present invention is used for a paint or a coating agent, a silane coupling agent, colloidal silica, tetraalkoxysilane and its condensation polymer that give particularly strong adhesion to the substrate, Chelating agents and epoxy compounds may be used.

  Among the various additives, when the aqueous polyurethane resin composition of the present invention is used for a coating film or coating exposed outdoors, it is possible to use a hindered amine light stabilizer, an ultraviolet absorber, and an antioxidant. preferable.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6- Tetramethyl-4-piperidylmethyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracar Xylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) .Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2,3 4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidi Amino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8 , 12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8 , 12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s -Triazin-6-yl] -1,5,8,1 2-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy] ) Butyl Ruboniruokishi] ethyl] -2,4,8,10-spiro [5.5] undecane.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzene Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxypheny) such as phenyl] benzotriazole B) benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12-C13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylpheny ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 1,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5 Di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5 -Di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-di) Benzoates such as 3 butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyl Substituted oxanilides such as oxanilide; Cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metals Examples include salts or metal chelates, particularly nickel or chromium salts or chelates.

Examples of the antioxidant include phosphorus-based, phenol-based, and sulfur-based antioxidants.
Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,5-di-tert-butylphenyl) phosphite, and tris (nonylphenyl). Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) octyl phosphite, Diphenyl decyl phosphite, diphenyl octyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, di Butyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4′-isopropylidene diphenyl phosphite, bis [2,2′-methylenebis (4,6-dia) Milphenyl)], isop Pyridene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert 3-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis-tert-butyldibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy Ethyl) amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-trakis (1,1-dimethylethyl) dibenzo [d, f] [ 1,3,2] dioxaphosphepin-6-yl] oxy] propyl] phenol 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite and the like.

  Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylene bis [(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl- 4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis 4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-3- Methylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2 Tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4 -Tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris ( , 5-Ditertiarybutyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-) 3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propio Over the door], tocopherols, and the like.

  Examples of sulfur-based antioxidants include polyols such as dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropionate). [Beta] -alkyl mercaptopropionic acid esters.

  Each usage-amount of the said hindered amine light stabilizer, a ultraviolet absorber, and antioxidant shall be 0.001-10 mass parts with respect to 100 mass parts of total amounts of the said (A)-(C) component. Particularly preferred is 0.01 to 5 parts by mass. When the amount is less than 0.001 part by mass, a sufficient addition effect may not be obtained. When the amount is more than 10 parts by mass, the dispersibility and the physical properties of the coating may be adversely affected.

  As a method of adding these hindered amine light stabilizers, ultraviolet absorbers and antioxidants, a method of adding to a polyol, a method of adding to a prepolymer, a method of adding to a water phase at the time of water dispersion, and adding after water dispersion Any method may be used, but from the viewpoint of easy operation, a method of adding to a polyol and a method of adding to a prepolymer are preferred.

Applications of the water-based polyurethane resin composition of the present invention include paints, adhesives, surface modifiers, organic and / or inorganic powder binders, molded articles, and the like.
Specifically, glass fiber sizing agent, thermal paper coating agent, inkjet paper coating agent, printing ink binder agent, steel plate coating agent, agricultural film coating agent, glass, slate, concrete and other inorganic structural material coatings Wood paint, fiber treatment agent, sponge, puff, gloves, condom and the like. Among these, it is preferable to use it as a coating material for paint, wood, paper, fiber, glass, electronic material parts, and steel plates, and it is particularly preferable to use it as a paint for surface-treated steel plates.

  When the aqueous polyurethane resin composition of the present invention is used as a paint, for example, brush coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, curtain roll coating, dip coating, rod coating, It can apply | coat to a base material by the method selected suitably, such as a doctor blade coat.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

As the long-chain alkylene diol compound (a) in the polyol (A), 1,12-octadecanediol 6.0 g (0.0209 mol), and as the other component (A), 1,6-hexanediol and adipic acid and 65.7 g (0.0375 mol) of a polyester polyol (number average molecular weight 1750) obtained from isophthalic acid (mass ratio of adipic acid / isophthalic acid is 50/50), and dicyclohexylmethane-4,4 ′ as isocyanate (B) -42.5 g (0.1620 mol) of diisocyanate (hereinafter referred to as hydrogenated MDI) and 5.74 g (0.0428 mol) of dimethylolpropionic acid as an anionic group-introduced polyol (C) were charged into a reaction flask.
The ratio of the component (a) in the total amount of the components (A) to (C) at this time is 5% by mass, the ratio of the component (C) is 4.8% by mass, and the equivalent ratio of NCO / OH is 1. 6.

  Furthermore, 25.7 g of N-methyl-2-pyrrolidone was added as a solvent, and the reaction was carried out at 100 to 110 ° C. under a nitrogen stream for 2 to 3 hours, so that the NCO content percentage was 3.4% or less. After confirmation, 4.33 g (0.0428 mol) of triethylamine was added as an anionic group neutralizing agent (D) so that the neutralization rate was 1.0, and a urethane prepolymer having a solid content of 80% by mass was added. Obtained.

  Antifoaming agent (manufactured by ADEKA, B1016) 0.1 g in 110 g of water, and 1.18 g (0.0117 mol) of triethylamine so that the neutralization ratio with the urethane prepolymer is 0.2. In an aqueous solution obtained by stirring, 109 g of the urethane prepolymer was added and dispersed by stirring at 20 to 40 ° C. for 15 minutes. The obtained urethane prepolymer dispersion is subjected to a water extension reaction at 30 to 40 ° C. for 12 hours and at 50 to 55 ° C. until the NCO group disappears in the measurement by IR (infrared spectrophotometer). An aqueous polyurethane resin composition having a solid content of 40% was obtained.

As the long-chain alkylene diol compound (a) in the polyol (A), 12.0 g (0.0593 mol) of 1,12-dodecane diol, and as the other component (A), a polycarbonate diol of 1,6-hexanediol ( Number average molecular weight 2000) 49.0 g (0.0245 mol), 51.9 g (0.234 mol) of isophorone diisocyanate (hereinafter referred to as IPDI) as isocyanate (B), and dimethylol as an anionic group-introduced polyol (C) 7.17 g (0.0535 mol) of propionic acid was charged into the reaction flask.
The ratio of the component (a) in the total amount of the components (A) to (C) at this time is 10% by mass, the ratio of the (C) component is 6.0% by mass, and the equivalent ratio of NCO / OH is 1. 7.

  Further, after adding 24.6 g of N-methyl-2-pyrrolidone as a solvent and reacting at 100 to 110 ° C. for 2 to 3 hours under a nitrogen stream, it was confirmed that NCO% was 5.4% or less. Then, 5.41 g (0.0535 mol) of triethylamine was added as an anionic group neutralizing agent (D) so that the neutralization rate was 1.0, and a urethane prepolymer having a solid content of 80% by mass was obtained.

  Antifoaming agent (manufactured by ADEKA, B1016) 0.1 g in 110 g of water, and 1.47 g (0.0145 mol) of triethylamine so that the neutralization ratio with the urethane prepolymer is 0.2. In an aqueous solution obtained by stirring, 108 g of the urethane prepolymer was added and dispersed by stirring at 20 to 40 ° C. for 15 minutes. The obtained urethane prepolymer dispersion is subjected to a water extension reaction for 12 hours at 30 to 40 ° C. and for the time until the NCO group disappears in measurement by IR (infrared spectrophotometer) at 40 to 45 ° C. An aqueous polyurethane resin composition having a solid content of 40% was obtained.

As the long-chain alkylene diol compound (a) in the polyol (A), 2.4 g (0.0084 mol) of 1,12-octadecanediol, and as the other component (A), polytetramethylene ether glycol (number average molecular weight 2000) ) 81.4 g (0.0407 mol), 31.9 g (0.1216 mol) of hydrogenated MDI as isocyanate (B), and 4.30 g (0.0321) of dimethylolpropionic acid as an anionic group-introducing polyol (C). Mol) was charged to the reaction flask.
The ratio of the component (a) in the total amount of the components (A) to (C) at this time is 2% by mass, the ratio of the component (C) is 3.6% by mass, and the equivalent ratio of NCO / OH is 1. It was 5.

  Furthermore, after adding 26.8 g of N-methyl-2-pyrrolidone as a solvent and reacting at 100 to 110 ° C. under a nitrogen stream for 2 to 3 hours, it was confirmed that NCO% was 2.3% or less. (D) 3.24 g (0.0320 mol) of triethylamine was added as an anionic group neutralizing agent component so that the neutralization rate was 1.0, and a urethane prepolymer having a solid content of 80% by mass was obtained. .

  0.18 g of defoaming agent (manufactured by ADEKA, B1016) in 110 g of water, and 0.88 g (0.0087 mol) of triethylamine so that the neutralization ratio with the urethane prepolymer is 0.2. In an aqueous solution obtained by stirring, 109 g of the urethane prepolymer was added and dispersed by stirring at 20 to 40 ° C. for 15 minutes. The obtained urethane prepolymer dispersion is subjected to a water extension reaction at 30 to 40 ° C. for 12 hours and at 60 to 65 ° C. until the NCO group disappears in IR (infrared spectrophotometer) measurement. An aqueous polyurethane resin composition having a solid content of 40% was obtained.

[Comparative Example 1]
As component (A), 77.7 g (0.0444 mol) of the polyester polyol used in Example 1 was used, and as a component (B), 36.6 g (0.140 mol) of hydrogenated MDI was used. The components (A) to (C) were reacted in the same manner as in Example 1 except that NCO was not used, and after confirming that the NCO content% was 2.9% or less, As the anionic group neutralizing agent (D), triethylamine was added in an amount of 4.33 g (0.0428 mol) so that the neutralization rate was 1.0, to obtain a urethane prepolymer having a solid content of 80% by mass.
The ratio of component (C) in the total amount of components (A) to (C) at the time of preparation was 4.8% by mass, and the equivalent ratio of NCO / OH was 1.6.
The obtained urethane prepolymer was subjected to water dispersion and water elongation reaction in the same manner as in Example 1 to obtain an aqueous polyurethane resin composition having a solid content of 40%.

[Comparative Example 2]
As component (a), 30.0 g (0.105 mol) of 1,12-octadecanediol, 18.0 g (0.0103 mol) of the polyester polyol used in Example 1 as the other component (A), and ( B) Components (A) to (C) were reacted in the same manner as in Example 1 except that 66.2 g (0.252 mol) of hydrogenated MDI was used as the component, and the NCO content% was After confirming that it was 5.3% or less, 4.33 g (0.0428 mol) of triethylamine was added as an anionic group neutralizing agent (D) so that the neutralization rate was 1.0, A urethane prepolymer having a content of 80% by mass was obtained.
The proportion of component (a) in the total amount of components (A) to (C) at the time of preparation is 25% by mass, the proportion of component (C) is 4.8% by mass, and the equivalent ratio of NCO / OH is 1. 6.
Using the obtained urethane prepolymer, an attempt was made to produce an aqueous polyurethane resin composition by the same method as in Example 1. As a result, an aqueous polyurethane resin composition with poor water dispersion and good dispersibility was obtained. Couldn't get.

[Comparative Example 3]
The polyester polyol used in Example 1 as component (A) other than component (a) 77.1 g (0.0441 mol) of polyester polyol, and 31.1 g (0.119 mol) of hydrogenated MDI as component (B) ) Was used, the components (A) to (C) were reacted in the same manner as in Example 1, and it was confirmed that the NCO content% was 0.6% or less. As a group neutralizing agent (D), triethylamine was added in an amount of 4.33 g (0.0428 mol) so that the neutralization rate was 1.0 to obtain a urethane prepolymer having a solid content of 80% by mass.
The proportion of component (a) in the total amount of components (A) to (C) at the time of preparation is 5% by mass, the proportion of component (C) is 4.8% by mass, and the equivalent ratio of NCO / OH is 1. 1
When an attempt was made to produce an aqueous polyurethane resin composition by the same method as in Example 1 for the obtained urethane prepolymer, the urethane prepolymer was not dispersed in water, and an aqueous polyurethane resin composition could not be obtained.

[Comparative Example 4]
The polyester polyol used in Example 1 as component (A) other than component (a) 53.8 g (0.0307 mol) of polyester polyol, and 54.5 g (0.208 mol) of hydrogenated MDI as component (B) The components (A) to (C) were reacted in the same manner as in Example 1 except that they were used, and after confirming that the NCO content% was 6.3% or less, Triethylamine as a compatibilizer (D) was added in an amount of 4.33 g (0.0428 mol) so that the neutralization rate was 1.0, to obtain a urethane prepolymer having a solid content of 80% by mass.
The proportion of component (a) in the total amount of components (A) to (C) at the time of preparation is 5% by mass, the proportion of component (C) is 4.8% by mass, and the equivalent ratio of NCO / OH is 2. 2.
Using the obtained urethane prepolymer, an attempt was made to produce an aqueous polyurethane resin composition in the same manner as in Example 1. As a result, foaming accompanying carbon dioxide generation was marked when the urethane prepolymer was dispersed in water. I couldn't get anything.

[Comparative Example 5]
(A) Instead of the long-chain alkylene diol compound, 6.0 g (0.041 mol) of 1,8-octanediol and 58.9 g of the polyester polyol polyester polyol used in Example 1 as the other component (A) ( 0.0337 mol), and the components (A) to (C) were reacted in the same manner as in Example 1 except that 49.3 g (0.188 mol) of hydrogenated MDI was used as the component (B). After confirming that the% content of NCO was 4.0% or less, triethylamine was used as the anionic group neutralizing agent (D), and 4.33 g (0.3%) so that the neutralization rate was 1.0. 0428 mol) and a urethane prepolymer having a solid content of 80% by mass was obtained.
The ratio of 1,8-octanediol in the total amount of components (A) to (C) at the time of preparation was 5% by mass, the ratio of component (C) was 4.8% by mass, and the NCO / OH equivalent ratio was 1 .6.
The obtained urethane prepolymer was subjected to water dispersion and water elongation reaction in the same manner as in Example 1 to obtain an aqueous polyurethane resin composition having a solid content of 40%.

[Comparative Example 6]
A urethane prepolymer similar to that used in Example 1 was dispersed in water under the same conditions, and then the molecular weight was increased using 3.57 g (0.119 mol) of ethylenediamine as a chain extender, thereby producing an aqueous polyurethane resin. A composition was obtained.

[Comparative Example 7]
The emulsifier used in Comparative Example 6 (manufactured by ADEKA, product name Adeka Pluronic F-108: ethylene glycol adduct of polypropylene glycol, average molecular weight 15500, ethylene oxide content 80 mass%) Comparative examples of NCO / OH equivalent ratio, neutralization rate, solid content, etc., except that 10 parts by weight and 100 parts by weight of the total amount of components (B) and (C) were added and dispersed in water. The water-based polyurethane resin composition was obtained under the same production conditions as in Comparative Example 6 with the same settings as in Example 6.

<Performance evaluation>
Evaluation of coating stability, water resistance, acid resistance, alkali resistance and adhesion of the water-based polyurethane resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 5 to 7 was performed as follows. It was.
These results are shown in Table 1.

[Paint stability]
15 parts by mass of Cymel 325 (manufactured by Nippon Cytec Industries, Ltd., methylated melamine resin, solid content 80%) is mixed and stirred with respect to 100 parts by mass of the aqueous polyurethane resin composition obtained in the examples and comparative examples. Dimethylethanolamine was added to adjust the pH to 8.5 to obtain a test solution. The viscosity of the obtained test solution before and after being allowed to stand at 40 ° C. for 10 days was measured, and the stability of the paint was evaluated based on the increased viscosity.
○: No increase in viscosity and good stability.
Δ: An increase in viscosity was observed.
X: Significant increase in viscosity was observed.

[Test specimen preparation]
Examples 1 to 5 and Comparative Examples were used on electrogalvanized steel sheets that were degreased after using an electrogalvanized steel sheet as a base material and degreasing at 60 ° C. for 5 minutes using a degreasing agent having a pH of 11 to 13. The aqueous polyurethane resin composition obtained by 1-4 was apply | coated to 1 micrometer thickness. A test specimen was prepared by heating and drying in an atmosphere of 300 ° C. for 4 seconds so that the plate temperature of the steel plate was 75 ° C.

[Water resistance test]
About the obtained test body, the water-resistant spot test for 24 hours was performed under 65 degreeC / 95% relative humidity, and the state of the coating film after a test was visually evaluated on the following reference | standard.
5: No abnormality in the coating film.
4: The float of the coating film was 5% or less of the total area.
3: The float of the coating film was 6 to 20% of the total area.
2: The float of the coating film was 21% or more of the total area.
1: The coating film was completely peeled off.

[Acid resistance test]
The specimen was immersed in a 1% H ₂ SO ₄ aqueous solution (25 ° C.) for 24 hours, and the state of the coating film after immersion was visually evaluated according to the following criteria.
5: No abnormality in the coating film.
4: The float of the coating film was 5% or less of the total area.
3: The float of the coating film was 6 to 20% of the total area.
2: The float of the coating film was 21% or more of the total area.
1: The coating film was completely peeled off.

[Alkali resistance test]
The test specimen was used and immersed in a 1% NaOH aqueous solution (25 ° C.) for 1 hour, and the state of the coated film after immersion was visually evaluated according to the following criteria.
5: No abnormality in the coating film.
4: The float of the coating film was 5% or less of the total area.
3: The float of the coating film was 6 to 20% of the total area.
2: The float of the coating film was 21% or more of the total area.
1: The coating film was completely peeled off.

[Adhesion]
A water-based polyurethane resin composition was applied to an untreated electrogalvanized steel sheet to a thickness of 1 μm, and then heat-dried in an atmosphere of 300 ° C. for 15 seconds and a steel sheet temperature of 150 ° C. to obtain a test piece. It was.
According to JIS K5600-5-6 (cross cut method), the degree of peeling of the coating film of the test piece was evaluated according to the following criteria.
5: No abnormality in the coating film.
4: Slight lift (area of 5% or less) was observed in the coating film.
3: A slight float (over 5%, area of 20% or less) was observed in the coating film.
2: Many floats (area over 20%) were observed in the coating film.
1: The coating film was completely peeled off.

  From the results of the Examples and Comparative Examples, it was confirmed that only the water-based polyurethane composition of the present invention had good results in all of paint stability, water resistance, chemical resistance and adhesion.

  Since the water-based polyurethane resin composition of the present invention is water-based, it not only destroys the environment, but also has good workability and excellent chemical resistance such as paint stability, water resistance, acid resistance, and alkali resistance. Since it forms a coating film, it is suitable for producing materials and molded products with excellent water resistance and chemical resistance by painting on the surface of wood, paper, fiber, glass, electronic material parts, steel plates, etc. .

Claims (6)

  The terminal isocyanate group urethane prepolymer obtained by reacting the polyol (A), the isocyanate (B), and the anionic group-introducing polyol (C) containing a carboxyl group or a sulfonic acid group is converted into an anionic group neutralizing agent. (D) is a water-based polyurethane resin composition that is dispersed in water and elongated with water, wherein the component (A) is an essential component of a long-chain alkylene diol compound (a) having 10 to 32 carbon atoms. Then, the blending amount of the component (a) is 1 to 20% by mass of the total amount of the components (A), (B) and (C), and the isocyanate group (NCO) in the component (B) An aqueous polyurethane resin composition, wherein the equivalent ratio (NCO / OH) of the component (A) and the component (C) to the total hydroxyl groups (OH) is 1.3 to 1.9.   The aqueous polyurethane resin composition according to claim 1, wherein the compound (a) is a long-chain alkylene diol compound having 12 to 18 carbon atoms.   The compounding quantity of the said anionic group introduction | transduction polyol (C) is 0.1-30 mass% of the total amount of said (A), (B), and (C) component, It was described in Claim 1 or 2 An aqueous polyurethane resin composition.   A paint comprising the aqueous polyurethane resin composition according to any one of claims 1 to 3.   A coated product obtained by applying the coating material according to claim 4 to a plate-like material.   The coated product according to claim 5, wherein the plate-like material is a surface-treated steel plate.