JP5770505B2 - Urethane prepolymer composition for water-based polyurethane resin and water-based polyurethane resin composition containing the same - Google Patents

Description

The present invention relates to aqueous polyurethane resin composition capable of forming a film excellent in corrosion resistance, in particular relates to a urethane prepolymer composition and the water-based polyurethane resin composition containing organosilica sol.

  Polyurethane resin can form coatings and molded articles with wear resistance, adhesiveness, non-stickiness, rubber elasticity, so from the viewpoint of safety against environmental pollution and occupational health, paints, adhesives Water-based polyurethane resin compositions are widely used as binders and coating agents.

  On the other hand, materials used for automobiles, home appliances, and building materials include zinc-based plated steel sheets such as electrogalvanized steel sheets and hot-dip galvanized steel sheets, and galvanized steel sheets for the purpose of further improving corrosion resistance and paintability. Inorganic surface-treated steel sheets subjected to chemical conversion treatment such as chromate treatment and phosphate treatment are often used. Further, for the purpose of further improving corrosion resistance and the like, a resin-coated steel sheet in which an organic resin film is formed on a surface-treated steel sheet that has been subjected to chromate treatment has been proposed.

  However, the surface treatment method using chromate not only has the problem that the chromate fume is scattered in the treatment process, but also has the problem that the wastewater treatment equipment requires a large amount of money, and further the chemical conversion. There is a problem that chromic acid is eluted from the treated film. As for hexavalent chromium compounds, many public institutions such as the International Agency for Research on Cancer Review (IARC) have certified it as a carcinogen for the human body, so they do not use chromate treatment or hexavalent chromium. A chromium-free technique replaced with another crosslinkable metal has been put to practical use, but in this case, there is a problem that the corrosion resistance is inferior compared with the conventional chromate treatment.

  Furthermore, as a resin system applied to the organic resin film as described above, polyurethane resin is partly used because it has excellent hardness and elongation, but polyurethane resin has many polar groups. Therefore, there is a problem that many of them are inferior in corrosion resistance compared to other resin systems.

  For the purpose of improving the corrosion resistance of such water-based polyurethane resins, techniques for blending silica such as water-soluble silica (Patent Documents 1 to 3) and silica particles (Patent Documents 4 to 6) have been proposed. Furthermore, scaly silica (Patent Documents 7 and 8), scaly silica treated with a cationic surfactant or an amine-based alkaline substance (Patent Document 9), or Ca ion exchange silica (Patent Documents 10 and 11) is used. It has also been proposed.

  However, none of the above conventional methods of blending silica can still satisfy the point of corrosion resistance because water-dispersed colloidal silica and silica particles are added later to water-based resins such as water-based urethane resins. It is not done.

JP 2005-133173 A JP 2006-114891 A JP 2007-162098 A JP 2005-043913 A JP 2006-043913 A JP 2008-255466 A JP 2004-322573 A JP 2007-076005 A JP 2002-348538 A JP 2007-204770 A JP 2009-287078 A

As a result of intensive studies to improve the corrosion resistance of the water-based polyurethane resin, the present inventors dispersed organosilica (silica whose surface was treated with an organic substance) in advance in the urethane prepolymer, and then the water-based polyurethane resin. The inventors have found that good results can be obtained by manufacturing, and reached the present invention.
Accordingly, a first object of the present invention is to provide a urethane prepolymer composition suitable for an aqueous polyurethane resin composition capable of forming a film excellent in corrosion resistance.
The second object of the present invention is to provide an aqueous polyurethane resin composition capable of forming a film excellent in corrosion resistance.
A third object of the present invention is to provide a paint or a water-based metal surface treating agent containing a water-based polyurethane resin composition capable of forming a film having excellent corrosion resistance.

但し、上式中のR^１は、エチレンオキシド構造化合物の末端水酸基とジ-又はトリイソシアネート化合物とのウレタン化反応の残基、又は、ジ-若しくはトリオール化合物とのエチレンオキシド付加反応の残基を表し、R^２はメチル基又はエチル基、ｎは５〜１００の数を表す。
本発明の水酸基を有する水系ポリウレタン樹脂組成物には、更にアミン系の鎖伸長剤を反応させても良い。特に前記ウレタンプレポリマーとして、末端ＮＣＯのプレポリマーの該イソシアネート基１当量に対し、第１級又は第２級アミノ基を有するアルカノールアミン化合物を、アミノ基の当量比で０．１〜１．０の割合で反応させてなる、末端に水酸基を有するウレタンプレポリマーを使用することが好ましく、該水酸基１当量に対して、水分散ポリイソシアネート化合物をイソシアネート基の当量比で０．５〜２．５配合してなる一液硬化型水系ポリウレタン樹脂組成物とすることが特に好ましい。
本発明の水系ポリウレタン樹脂組成物は、特に、塗料用及び水系金属表面処理剤用として好適である。 That is, the present invention is a urethane prepolymer composition for an aqueous polyurethane resin composition containing an organosilica sol having an inert organic solvent containing no hydroxyl group as a dispersion solvent, wherein the silica content introduced by the organosilica sol is The urethane prepolymer composition is contained in a solid content of the urethane prepolymer composition, and the urethane prepolymer has a hydroxyl group at the terminal, and the urethane prepolymer composition is water. In a urethane prepolymer composition having an NCO group at the end, which contains an organosilica sol having an inert organic solvent not containing a hydroxyl group as a dispersion solvent, the silica content introduced by the organosilica sol is 5 to 40 mass in the solid content of the urethane prepolymer composition An aqueous polyurethane resin composition obtained by dispersing the contained composition in water, wherein an alkanolamine compound having a primary or secondary amino group with respect to 1 equivalent of the isocyanate group of the resin composition An aqueous polyurethane resin composition having a hydroxyl group, which is obtained by reacting such that the equivalent ratio of amino groups is 0.1 to 1.0, and the aqueous polyurethane resin composition. It is a paint or water-based metal surface treatment agent to be contained. However, the solid content of the urethane prepolymer composition means “all raw material components”.
The aqueous polyurethane resin composition having a hydroxyl group of the present invention may contain 5 to 40% by mass of the hydrophilic compound represented by the following general formula (1) in the total solid content of the urethane prepolymer composition. preferable.

However, R ¹ in the above formula represents a residue of a urethanation reaction between a terminal hydroxyl group of an ethylene oxide structural compound and a di- or triisocyanate compound, or a residue of an ethylene oxide addition reaction with a di- or triol compound, R ² represents a methyl group or an ethyl group, and n represents a number of 5 to 100 .
The aqueous polyurethane resin composition having a hydroxyl group of the present invention may be further reacted with an amine chain extender. Particularly the urethane prepolymer, relative to the isocyanate group equivalent of the prepolymer ends NCO, an alkanolamine compound having primary or secondary amino groups, an equivalent ratio of amino groups 0.1 to 1.0 It is preferable to use a urethane prepolymer having a hydroxyl group at the terminal, which is reacted at a ratio of 0.5 to 2.5 by an equivalent ratio of an isocyanate group with respect to 1 equivalent of the hydroxyl group. It is particularly preferable to prepare a one-component curable aqueous polyurethane resin composition.
The aqueous polyurethane resin composition of the present invention is particularly suitable for paints and aqueous metal surface treatment agents.

  The water-based polyurethane resin composition of the present invention is excellent in corrosion resistance and can form a coating film or a molded article of polyurethane resin having abrasion resistance, adhesiveness, non-adhesiveness, and rubber elasticity. It is also excellent in terms of safety such as occupational health, and is suitable for paints, adhesives, binders, coating agents and the like.

Hereinafter, the urethane prepolymer composition for an aqueous polyurethane resin composition and the aqueous polyurethane resin composition of the present invention will be described in detail.
The urethane prepolymer composition for an aqueous polyurethane resin composition of the present invention is prepared by adding an organosilica sol having an organic solvent containing no hydroxyl group, which is inert to the urethane prepolymer, as a dispersion solvent. Has the biggest feature.

  The urethane prepolymer used in the present invention contains known raw materials (polyisocyanate component (a), polyol component (b), ionic group introduction component (c), ionic group neutralizer component (d), emulsifier component ( e) and the chain extender component (f) and the like) and the method.

  The inert organic solvent not containing a hydroxyl group used as a dispersion solvent for the organosilica sol used in the present invention is not particularly limited as long as it is inert to the urethanization reaction. For example, ketone-based, ester-based, Ether-based, hydrocarbon-based, and other inert organic solvents can be used.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone.

  Examples of the ester solvent include ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and methyl methacrylate. Hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, tripropylene glycol diarylate and the like.

  Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like.

  Examples of the hydrocarbon solvent include n-hexane, cyclohexane, benzene, toluene, xylene, solvent naphtha, styrene, and halogenated hydrocarbons such as dichloromethane and trichloroethylene.

  Examples of the other inert organic solvent include acetonitrile, acetamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

  In the present invention, N-methyl-2-pyrrolidone is preferably used as the inert organic solvent from the viewpoint of ease of production of the organosilica sol, and a ketone solvent is preferably used from the viewpoint of reaction temperature and solvent removal. Particularly preferred. In the present invention, N-methyl-2-pyrrolidone, methyl ethyl ketone and methyl isobutyl ketone are particularly preferably used.

  The production method of the organosilica sol using the inert organic solvent used in the present invention as a dispersion solvent is not particularly limited, and any known method may be used. For example, it can be produced by a method of mixing water-dispersed colloidal silica or a silica-sol solvent having a hydroxyl group and an inert organic solvent, and then removing water or an alcohol solvent by azeotropic or ultrafiltration.

The water-dispersed colloidal silica is not particularly limited, and commercially available products can be used. Examples of commercially available products include Snowtex C, Snowtex O, Snowtex N, Snowtex NXS, Snowtex OS, Snowtex OUP, Snowtex OL, Snowtex PS-MO, Snowtex PS-S, and Snowtex S. , Snowtex UP, Snowtex PS-M, Snowtex PS-L, Snowtex 20, Snowtex 30, Snowtex 40 (all are trade names manufactured by Nissan Chemical Industries, Ltd.), Silica Doll-20, Silica Doll -30, silica doll-40, silica doll-30S, silica doll-20AL, silica doll-20A, silica doll-30S, silica doll-20G, silica doll-20GA, silica doll-40G-80, silica doll-20P, Silica Doll-12S-4 ( These are trade names manufactured by Nippon Chemical Industry Co., Ltd.), AT-20, AT-30, AT-40, AT-50, AT-20A, AT-300 (all trade names manufactured by ADEKA Corporation), etc. Is mentioned.
Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil MOX80, Aerosil MOX170 (all are trade names manufactured by Nippon Aerosil Co., Ltd.), Aerodisp VP W7622 and Aerodisp W7520N (all degussa) Product name), CAB-O-SPERSE 2017A, CAB-O-SPERSE GP32 / 12, CAB-O-SIL M5 (trade name of CABOT CORPORATION), NIPGEL AY200, NIPGEL AY220, NIPGEL AY420, NIPGELAY NIPGEL AY460, NIPGEL AY401, NIPGEL AY601, NIPGEL AY603, NIPGEL AZ200, N PGEL AZ201, NIPGEL AZ204, NIPGEL AZ260, NIPGEL AZ360, NIPGEL AZ400, NIPGEL AZ410, NIPGEL AZ600, NIPGEL BY200, NIPGEL BY200 (all trade names made by Nippon Silica Industries, Ltd.), etc. It can also be used.

  Examples of the silica sol of the solvent having a hydroxyl group include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, ethylene glycol, glycerin, propylene glycol, triethylene glycol, and polyethylene glycol. Alcohol solvents such as benzyl alcohol, 1,5-pentanediol and diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Organosilica sol dispersed in ether, diethylene glycol monobutyl ether, etc. I can get lost. Examples of commercially available products include organosilica sol IPA-ST, NPC-ST-30, EG-ST, BA-ST, and PGM-ST (all are trade names manufactured by Nissan Chemical Co., Ltd.).

  The organosilica sol having an inert organic solvent as a dispersion solvent used in the present invention may be blended into the urethane prepolymer at any timing before or after the urethanization reaction, but the boiling point of the inert organic solvent is higher than the urethanization reaction temperature. When it is low (less than about 80 ° C.), it is preferable to blend after the urethanization reaction. Moreover, it is preferable to mix at 50-80 degreeC for 1-3 hours from a viewpoint of the dispersibility mixing property of the silica to urethane.

  The compounding amount of the organosilica sol used in the present invention is an amount of 5 to 40% by mass, preferably 10 to 30% by mass as a silica equivalent in the total solid content (total raw material components) of the urethane prepolymer composition. More preferably, it is 15-25 mass%. When the content of the silica solid content is less than 5% by mass, the effect of improving the corrosion resistance of the coating film obtained from the composition of the present invention cannot be sufficiently obtained, and the amount exceeds 40% by mass. In addition to the above-mentioned improvement in the corrosion resistance improvement effect, physical properties such as the strength of the coating film and the adhesion to the substrate become insufficient, which is not preferable.

但し、上式中のR^１は、エチレンオキシド構造化合物の末端水酸基とジ-又はトリイソシアネート化合物とのウレタン化反応の残基、又は、ジ-若しくはトリオール化合物とのエチレンオキシド付加反応の残基を表し、R^２はメチル基又はエチル基を表す。 The urethane prepolymer composition according to the present invention preferably contains a hydrophilic compound represented by the following general formula (1) in an amount of 5 to 40% by mass in the total solid content of the composition. It is preferable to contain -30 mass%. If it is less than 5% by mass, the dispersion stability of the urethane prepolymer composition of the present invention tends to decrease, and if it is contained in an amount exceeding 40% by mass, water resistance and mechanical properties when a coating film is formed, etc. May get worse.

However, R ¹ in the above formula represents a residue of a urethanation reaction between a terminal hydroxyl group of an ethylene oxide structural compound and a di- or triisocyanate compound, or a residue of an ethylene oxide addition reaction with a di- or triol compound, R ² represents a methyl group or an ethyl group .

In the present invention, as the hydrophilic compound represented by the general formula (1), in particular, one having a linear polyoxyethylene chain having one end at a methoxy group or an ethoxy group and a number average molecular weight of 200 to 5,000. Urethane reaction product of 1 mol of all compound and 1 mol of di- or triisocyanate compound, or polyether compound by dehydration condensation reaction of 1 mol of monool compound and 1 mol of di- or triol compound, urethane prepolymer It is preferable to contain 5-40 mass% in the total solid of a composition. Therefore, the hydrophilic compound represented by the general formula (1) is preferably a compound in which n is a number from 5 to 100.

  Examples of the di- or triisocyanate compound include divalent or trivalent isocyanate compounds of the polyisocyanate component (a) described later. Among these, it is preferable to use triisocyanate from the viewpoint that the isocyanate group in the compound represented by the general formula (1) becomes divalent and can be incorporated into the urethane prepolymer main chain. In the present invention, it is more preferable to use a trimerized diisocyanate. In particular, 2,4- and / or 2,6-tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or It is preferable to use a trimer of dicyclohexylmethane-4,4′-diisocyanate.

  Examples of the di- or triol compound include the low-molecular polyol compounds described later. Among these, the hydroxyl group of the compound represented by the general formula (1) is divalent, and the urethane prepolymer main chain. It is preferable to use triol because it can be incorporated into the inside, and it is particularly preferable to use trimethylolethane, trimethylolpropane or glycerin.

The reason why R ² in the general formula (1) is limited to a methyl group or an ethyl group is that the hydrophilicity is inhibited when the alkyl group has 3 or more carbon atoms, and the dispersion stability and storage stability of the water-based polyurethane resin are reduced. This is because is inferior.

  N in the general formula (1) is a number of 5 to 100, preferably a number of 10 to 50, more preferably a number of 15 to 35. If n is less than 5, the hydrophilicity is insufficient, so that the water dispersion stability of the urethane prepolymer or silica in the case of water-based polyurethane is inferior. The strength and adhesion to the substrate are inferior, which is not preferable.

Moreover, in this invention, nonionic group introduction | transduction compounds other than the said hydrophilic compound can also be used. Such compounds include, for example, ethylene oxide polyadducts of low molecular weight amine compounds having two or more active hydrogens, such as ammonia and methylamine, ethylamine, aniline, phenylenediamine, isophoronediamine, or ethylene oxide / propylene oxide copolymer. Adducts: Polyethylene glycol monoalkyl esters which are isocyanurate bodies (trimers) of diisocyanate compounds.

In the water-based polyurethane resin composition of the present invention , in particular, a prepolymer having NCO at the end is used as the urethane prepolymer, and an alkanolamine compound having a primary or secondary amine group is used as the chain extender. It is preferable to make it react so that it may become 0.1-1.0 by the equivalent ratio of the amino group with respect to 1 equivalent of isocyanate groups of a prepolymer, and it is preferable to make it the aqueous polyurethane resin composition which has a hydroxyl group.
The amount of the alkanolamine compound used is 0.1 to 1.0 in terms of the equivalent ratio of amino groups to 1 equivalent of isocyanate groups in the urethane prepolymer as described above. 9 is more preferable. If it is out of the range of 0.1 to 1.0, the polyurethane coating film to be formed tends to cause whitening, deterioration of physical properties, etc., which is not preferable.

Examples of the alkanolamine compound having a primary or secondary amine group include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, N- (β-aminoethyl) ethanolamine, N -(Β-aminoethyl) isopropanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine and 2-amino-2-methylpropanol (2-amino) Isobutanol) and the like. In order to carry out a chain extension reaction of the urethane prepolymer, it is preferred to use those having two amino groups, further, from the standpoint of crosslinking with the later-described water-dispersible polyisocyanate, a hydroxyl group is one Those are preferred. From the viewpoint of the reactivity with such a water-dispersed polyisocyanate and the balance with the chain extension reaction, it is preferable to use N- (β-aminoethyl) ethanolamine in the present invention. It is more preferable to use other alkanolamine in combination.

The water-dispersed polyisocyanate is a cross-linking agent for making the water-based polyurethane resin composition of the present invention into a one-part curable water-based polyurethane resin composition, and the blending amount thereof is the hydroxyl group 1 of the water-based polyurethane resin having the hydroxyl group. It is preferable that the equivalent ratio of isocyanate groups of the water-dispersed isocyanate compound is 0.5 to 2.5, more preferably 0.8 to 2.0, particularly 1.2 to It is preferably 1.8. If the equivalent ratio is less than 0.5, the hydroxyl group in the water-based polyurethane resin remains, so that there is a problem that the coating film to be formed has a tack (stickiness). Since the polyisocyanate compound remains in a large excess, the curability is inferior and the physical properties of the coating film tend to become brittle.

As the water-dispersed polyisocyanate used as a crosslinking agent in the present invention, a diisocyanate compound, polyisocyanate compound of a polyisocyanate component (a) to be described later, a polyisocyanate compound, or a modified or blocked product thereof used in water is used. Can do. As a dispersion method of these water-dispersed polyisocyanates, for example, a forced emulsification method using a nonionic emulsifier, the above polyisocyanate is copolymerized with a hydrophilic group-containing compound having a hydrophilic group such as an ethylene oxide chain, Examples thereof include a self-emulsification method for introducing a hydrophilic group such as an ethylene oxide chain into the molecule, and a method using these in combination.
Commercially available self-emulsifiable polyisocyanate compounds include CR-60N (trade name, manufactured by DIC Corporation), Disojoule DA, Sumijoule (trade name, manufactured by Sumika Bayer Urethane Co., Ltd.), Takenate WD series. (Trade names manufactured by Mitsui Chemicals Co., Ltd.), Coronate C3062, Coronate C3053, Aquanate series (trade names manufactured by Nippon Polyurethane Industry Co., Ltd.), Bihijoule 3100, Bihijoule VPLS2150BA, Bihijoule VPLS2306, Bihijoule VPLS2319, Bihijoule VPLS2336 (Bayer Corporation) Product name) and the like.

  As said polyisocyanate component (a), 1 type, or 2 or more types, such as diisocyanate and the polyisocyanate compound which has three or more isocyanate groups in 1 molecule, can be mixed and used.

Examples of the diisocyanate compound include 2,4- and / or 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, and diphenyldimethylmethane. -4,4'-diisocyanate, 2,5,2 ', 5'-tetramethyldiphenylmethane-4,4'-diisocyanate, cyclohexylbis (4-isocyanatetriphenyl) methane, 3,3'-dimethoxydiphenylmethane-4, 4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,3'-diisocyanate, 2,2'-dimethyl-5,5'-dimethoxydiphenylmethane -4,4'-diiso Anate, 3,3′-dichlorodiphenyldimethylmethane-4,4′-diisocyanate, benzophenone-3,3′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′- Aromatic diisocyanates such as dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate; isophorone diisocyanate, dicyclohexyl Alicyclic rings such as methane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate, norbornene diisocyanate Diisocyanate; methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2, 2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, tetramethyloxy Examples include aliphatic diisocyanates such as lylene diisocyanate.

The above diisocyanate may be used in the form of a modified product such as carbodiimide modification, isocyanurate modification, biuret modification or the like, or may be used in the form of a blocked isocyanate blocked with various blocking agents.

  Examples of the polyisocyanate compound having three or more isocyanate groups in one molecule include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6- Triisocyanate, 1,3,7-naphthalene triisocyanate, biphenyl-2,4,4′-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, 3-methyldiphenylmethane-4,6,4′-triisocyanate Isocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, Bicycloheptane triisocyanate, tris (isocyanate Triphenylol thiophosphate and dimethyltriphenylmethane tetraisocyanate, and isocyanurate trimerization, burette trimerization, and trimethylolpropane adducts of the above-mentioned diisocyanates. These isocyanate compounds may be used in the form of modified products such as carbodiimide modification, isocyanurate modification, biuret modification, etc., or may be used in the form of blocked isocyanates blocked with various blocking agents.

  The polyisocyanate compound component (a) is particularly preferably hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate from the viewpoints of yellowing resistance, availability, and ease of production.

  Examples of the polyol component (b) used in the aqueous polyurethane resin composition of the present invention include a diol compound and a polyol compound having three or more hydroxyl groups. These can be used alone or in combination of two or more.

Examples of the diol compound and the polyol compound having three or more hydroxyl groups include low molecular weight polyols, polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline or non-crystalline polycarbonate polyols, polybutadiene polyols, Examples include silicone polyols. In the present invention, particularly, polyether polyols, polyester polyols, and polycarbonate polyols can be preferably used.

  Examples of the low molecular polyols 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, 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-octane Diols, 2-methyl-1,8-octanediol, 1,9-nonanediol and 1,10-decanediol, and ethylene Aliphatic diols such as ether diols such as glycol, triethylene glycol, dipropylene glycol and tripropylene glycol; Cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; Trimethylolethane, trimethylolpropane, hexitols, pliers Examples thereof include trivalent or higher polyols such as tolls, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, and tetramethylolpropane.

  Examples of the polyether polyols include ethylene oxide and / or propylene oxide adducts of the above low molecular polyols, polytetramethylene glycol, and the like. The number average molecular weight of the polyether polyols used in the present invention is preferably 500 to 7000, more preferably 1000 to 5000.

  Examples of the polyester polyols include polyols such as the above-described low molecular weight polyols, polycarboxylic acids having an amount less than the stoichiometric amount, or ester-forming derivatives such as esters, anhydrides and halides, and / or lactones. And those obtained by direct esterification reaction with hydroxycarboxylic acid obtained by hydrolytic ring-opening and / or transesterification reaction. Examples of the polyvalent carboxylic acid or its ester-forming derivative include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, Aliphatic dicarboxylic acids such as dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, trimesic acid, castor oil fatty acid Polycarboxylic acids such as tetracarboxylic acids such as pyromellitic acid It is below. The ester-forming derivatives include acid anhydrides of these polyvalent carboxylic acids; halides such as the polyvalent carboxylic acid chlorides and bromides; methyl esters, ethyl esters, propyl esters, and isopropyls of the polyvalent carboxylic acids. 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. The number average molecular weight of the polyester polyols used in the present invention is preferably 500 to 7000, more preferably 1000 to 5000.

  Examples of the ionic group-introducing component (c) include those that introduce an anionic group and those that introduce a cationic group. Examples of those that introduce an anionic group include polyols containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, 1,4-butanediol-2-sulfonic acid, etc. Polyols containing a sulfonic acid group of, for example, N, N-dialkylalkanolamines, N-methyl-N, N-diethanolamine, N-butyl-N, N-alkyl-N, N-dialkanolamines and trialkanolamines such as N-diethanolamine can be mentioned.

  The amount of the ionic group-introducing component (c) used depends on the type of polyol and polyisocyanate used and the use of an emulsifier, but in a self-emulsifying system using an ionic group-introducing component, usually an aqueous polyurethane It is 0.5-50 mass% with respect to all the reaction components which comprise resin, Preferably it is 1-30 mass%. If it is less than 0.5% by mass, the storage stability is poor, and if it exceeds 50% by mass, the water dispersibility of the urethane prepolymer and the physical properties of the urethane coating may be adversely affected.

  As the ionic group neutralizer component (d), as an anionic group neutralizer, trialkylamines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylethanolamine, N, N-dimethylpropanol N, N-dialkylalkanolamines such as amine, N, N-dipropylethanolamine, 1-dimethylamino-2-methyl-2-propanol, N-alkyl-N, N-dialkanolamines, triethanolamine And tertiary amine compounds such as trialkanolamines; basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. As neutralizing agents for cationic groups, organic carboxylic acids such as formic acid, acetic acid, lactic acid, succinic acid, glutaric acid and citric acid, organic sulfonic acids such as paratoluenesulfonic acid and alkyl sulfonate, hydrochloric acid, phosphoric acid and nitric acid In addition to inorganic acids such as sulfonic acid and epoxy compounds such as epihalohydrin, quaternizing agents such as dialkyl sulfuric acid and alkyl halides may be mentioned. The amount of these neutralizing agents used is usually excessive and insufficient with respect to 1 equivalent of ionic group, and the physical properties such as water resistance, strength and elongation of the coating film obtained from the aqueous polyurethane resin may be lowered. Since it is, it is preferable that it is 0.5-2.0 equivalent, and it is more preferable that it is 0.8-1.5 equivalent.

  Examples of the emulsifier component (e) include fatty acid salts, sulfates of higher alcohols, sulfates of liquid fatty oils, sulfates of aliphatic amines and aliphatic amides, phosphates of aliphatic alcohols, dibasic Anionic surfactants such as acid fatty acid ester sulfonate, fatty acid amide sulfonate, alkylallyl sulfonic acid, formalin condensed naphthalene sulfonate, primary amine salt, secondary amine salt, tertiary amine salt, Examples include cationic surfactants such as quaternary amine salts and pyridinium salts, amphoteric surfactants such as betaine type, sulfate ester type, and sulfonic acid type, and nonionic surfactants.

  As the chain extender component (f), a known chain extender used in an aqueous polyurethane resin composition can be used singly or as a mixture of two or more kinds. An amine compound and a polyvalent primary alcohol compound are preferred, and a polyvalent amine compound is more preferred.

  Examples of the polyvalent amine compound include low molecular diamines in which the alcoholic hydroxyl group of the low molecular diol described above is substituted with an amino group, such as ethylene diamine and propylene diamine; polyoxypropylene diamine, polyoxyethylene diamine and the like Ether diamines; mensendiamine, isophoronediamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) 2 , 4,8,10-tetraoxaspiro (5,5) undecane, etc .; m-xylenediamine, α- (m / paminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodi Aromatic diamines such as phenyl sulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α, α′-bis (4-aminophenyl) -p-diisopropylbenzene; hydrazine; The dicarboxylic acid dihydrazide compound which is a compound of the dicarboxylic acid illustrated in the polyhydric carboxylic acid used for a polyol and hydrazine is mentioned.

  The amount of the chain extender component (f) used is not particularly limited and can be appropriately used. For example, when the prepolymer method is selected, the equivalent amount of the isocyanate group in the prepolymer is 1 equivalent. On the other hand, the equivalence ratio of the primary and secondary amino groups of the chain extender is preferably in the range of 0.1 to 1.5, since the dispersibility of the obtained water-based polyurethane resin is good. More preferably, it is 0.5 to 1.0.

  Moreover, you may use the well-known crosslinking agent which gives a crosslinked structure to a polyurethane molecule as needed for the urethane prepolymer composition or water-based polyurethane resin composition of this invention. Suitable crosslinking agents for the aqueous polyurethane resin include melamine, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylated methylol melamine, butylated methylol melamine, melamine resin. Etc. In the present invention, it is particularly preferable to use melamine which is excellent in dispersibility of polyurethane and is inexpensive.

  In the production of the urethane prepolymer composition of the present invention, a solvent inert to the reaction can be used as necessary. Examples of the solvent include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone and the like. These solvents are generally 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. In the present invention, among these solvents, it is particularly preferable to use a solvent having a boiling point of 100 ° C. or lower because the urethane prepolymer can be distilled off under reduced pressure after water dispersion.

  The equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component (a) and the alcoholic hydroxyl group of the polyol component (b) used in the urethane prepolymer composition of the present invention is 1.0 to 5.0. It is preferable that it is in the range of 1.05-3.0. The urethane prepolymer comprising (a) and (b) preferably has an isocyanate group at the end in order to react the ionic group introduction component (c) used as necessary. Therefore, an equivalent ratio (NCO / OH) of less than 1.0 is not preferable because a urethane prepolymer having a terminal hydroxyl group is obtained. Moreover, when it exceeds 5.0, since it may affect the storage stability of the water-based polyurethane resin composition obtained by disperse | distributing a urethane prepolymer in water, it is unpreferable.

Moreover, in the water-based polyurethane resin composition of this invention, it is preferable that water is 30-900 mass parts with respect to 100 mass parts of urethane resins, Preferably 80-400 mass parts is mix | blended. When the blending amount of water is less than 30 parts by mass, the viscosity of the water-based polyurethane resin composition is high and handling becomes difficult, and when it is more than 900 parts by mass, the curability when forming a coating film decreases. Since the physical properties of the coating film are lowered, it is not preferable.

  The water-based polyurethane resin composition of the present invention can be used not only as a one-component type but also as a two-component type using a curing agent such as water-dispersed isocyanate. By using a crosslinking agent such as a water-based epoxy resin, a water-based amino resin, and a blocked isocyanate in combination with the water-based polyurethane resin composition of the present invention, the anticorrosion property and the like can be further improved.

  Various known additives may be further used in the aqueous polyurethane resin composition of the present invention as necessary. Examples of the additive include a light stabilizer, an antioxidant, an ultraviolet absorber, a pigment, a dye, a film forming aid, a curing agent, an antiblocking agent, a leveling agent, an antigelling agent, a dispersion stabilizer, and a radical scavenger. Agent, heat resistance imparting agent, inorganic and organic filler, plasticizer, lubricant, antistatic agent, reinforcing agent, catalyst, thixotropic agent, antibacterial agent, antifungal agent, anticorrosive agent, antifoaming agent, non-associative increase Examples thereof include a viscosity agent, an organic solvent, a surface conditioner, and an anti-settling agent.

  In addition, 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, a polycondensate thereof, a chelate, which gives particularly strong adhesion to a substrate, and the like. You may further use an agent, an epoxy compound, etc.

  Among the above-mentioned various additives, when the water-based polyurethane resin composition of the present invention is used for coatings and coatings, hindered amine light stabilizers, ultraviolet absorbers, antioxidants (phosphorous, phenolic or sulfur-based antioxidants). It is preferable to use an oxidizing agent).

  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-tertiary 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] benzo Triazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole 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-C 12 ~C ₁₃ 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-tert 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 phosphorus antioxidant 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 , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol di Phosphite, bis (2,5-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicine (Milphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4′-isopropylidene diphenyl phosphite, bis [2,2′-methylenebis (4 6-Diamylphenyl)] Isopropylidene 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] dioxaphospin-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, etc. .

  Examples of the phenol-based antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditertiarybutyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditertiarybutyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(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- (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-di-tert-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-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] 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) propyl Pioneto], tocopherol and the like.

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

  When the amount of each of the hindered amine light stabilizer, ultraviolet absorber, and antioxidant used is less than 0.001 part by mass with respect to 100 parts by mass of the solid content of the aqueous polyurethane resin composition of the present invention, sufficient addition effect is obtained. If it is larger than 10 parts by mass, it may affect the dispersibility and the physical properties of the coating, so 0.001 to 10 parts by mass is preferable, and 0.01 to 5 parts by mass Is more preferable. In addition, these hindered amine light stabilizers, ultraviolet absorbers and antioxidants can be added by adding to the polyol component, adding to the urethane prepolymer, adding to the aqueous phase during water dispersion, Although the method of adding etc. is mentioned, From a viewpoint that operation is easy, the method of adding to a polyol component or the method of adding to a urethane prepolymer is preferable.

  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 recording paper coating agent, printing ink binder agent, steel plate coating agent, agricultural film coating agent, glass, slate, concrete and other inorganic structures Material paints, woodwork paints, fiber treatment agents, sponges, puffs, gloves, condoms and the like. Among these, it is preferable to use it as a coating material application for paints, wood, paper, fibers, glass, electronic material parts and steel plates, and it is particularly preferable to use them as paints for surface-treated steel plates.

  Further, the aqueous polyurethane resin composition of the present invention includes other aqueous resin emulsions such as synthetic resin emulsions such as polyvinyl acetate, ethylene vinyl acetate copolymer, acrylic resin, and rubber latexes such as natural rubber, SBR, and NBR. Therefore, it is also useful as these modifiers.

Hereinafter, although a reference example and a comparative example explain the present invention still in detail, the present invention is not restricted by these. In the reference examples and comparative examples, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

[Synthesis Example 1]
<Manufacture of organosilica sol: N-methyl-2-pyrrolidone (hereinafter NMP) sol>
NMP was mixed with water-dispersed silica (manufactured by ADEKA, Adelite AT-30A: average particle size 12.5 nm, solid content 30%), and dehydration operation was performed at 65 to 80 ° C. to obtain a solid content of 30.5. % NMP sol was obtained. The obtained NMP sol had a water content of 0.05%.

[ Reference Production Examples 1-1 to 1-4]
<Manufacture of urethane prepolymer>
Based on the formulation described in Table 1 below, (a) a polyisocyanate component, (b) a polyol component, (c) an ionic group-introducing component, a compound represented by the general formula (1) and a solvent are blended, The reaction was carried out at 100 ° C. for 2 to 3 hours. After confirming the arrival at the predetermined isocyanate content, silica (organosilica sol) described in Table 1 below was blended and stirred at 70 to 80 ° C. for 1 to 2 hours to obtain the urethane prepolymer of the present invention.

[Comparative Production Examples 1-1 and 1-2]
Based on the formulation described in Table 1 below, (a) a polyisocyanate component, (b) a polyol component, (c) an ionic group-introducing component, a compound represented by the general formula (1) and a solvent are blended, The reaction was carried out at 100 ° C. for 2 to 3 hours. After confirming the arrival at the predetermined isocyanate content, a urethane prepolymer was obtained.

[Comparative Production Example 1-3]
Based on the formulation described in Table 1 below, (a) a polyisocyanate component, (b) a polyol component, (c) an ionic group-introducing component, a compound represented by the general formula (1) and a solvent are blended, The reaction was carried out at 100 ° C. for 2 to 3 hours. After confirming the arrival at a predetermined isocyanate content, silica powder was added and stirred at 70 to 80 ° C. for 1 to 2 hours to obtain a urethane prepolymer.

＊１：ジシクロヘキシルメタン−４，４’−ジイソシアネート
＊２：イソホロンジイソシアネート
＊３：ポリオキシプロピレングリコールMw１０００（(株)ADEKA製）
＊４：メチルペンタンジオール／アジピン酸ポリエステルジオールMw１０００（(株)クラレ製）
＊５：ポリカーボネートジオールＭｗ１０００（(株)クラレ製）
＊６：ポリテトラメチレングリコールMw１０００（(株)保土ヶ谷化学製）
＊７：トリメチロールプロパン
＊８：ジメチロールプロピオン酸
＊９： Perstorp社製、製品名Ymer N１２０、OH官能基数２、Mｗ１０００
＊１０：HDI（ヘキサメチレンジイソシアネート）のイソシアヌレート体とメトキシPEG-１０００の、１／１（モル）反応化合物
＊１１：前記合成例１によって得られたＮＭＰゾル
＊１２：日産化学工業(株)製MEK（メチルエチルケトンシリカゾル）、製品名：MEK-ST（SiO₂ 30%、水分0.5%≧）
＊１３：アエロジル２００（(株)アエロジル化学工業製の商品名）

* 1: Dicyclohexylmethane-4,4'-diisocyanate * 2: Isophorone diisocyanate * 3: Polyoxypropylene glycol Mw1000 (manufactured by ADEKA)
* 4: Methylpentanediol / adipic acid polyester diol Mw1000 (manufactured by Kuraray Co., Ltd.)
* 5: Polycarbonate diol Mw1000 (manufactured by Kuraray Co., Ltd.)
* 6: Polytetramethylene glycol Mw1000 (Hodogaya Chemical Co., Ltd.)
* 7: Trimethylolpropane * 8: Dimethylolpropionic acid * 9: Perstorp, product name Ymer N120, OH functional group number 2, Mw1000
* 10: 1/1 ( mol) reaction compound of isocyanurate of HDI (hexamethylene diisocyanate) and methoxy PEG-1000 * 11: NMP sol obtained in Synthesis Example 1 * 12: Nissan Chemical Industries, Ltd. MEK (methyl ethyl ketone silica sol), product name: MEK-ST (SiO ₂ 30%, moisture 0.5% ≧)
* 13: Aerosil 200 (trade name, manufactured by Aerosil Chemical Co., Ltd.)

[ Reference Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2]
<Manufacture of water-based polyurethane resin>
Based on the formulation described in Table 2 below, ion-exchanged water, to which (d) an ionic group neutralizing agent component has been added in advance, is poured into a urethane prepolymer at 60 to 70 ° C. with stirring, at 30 to 40 ° C. for 30 minutes. After the dispersion, (f) a chain extender is added, and the mixture is stirred for 1 to 2 hours until the isocyanate group disappears by IR (infrared spectrophotometer), and the solvent (MEK) is removed to remove the aqueous polyurethane resin composition. The following storage stability was evaluated. Moreover, the following corrosion resistance was evaluated about the coating film formed using the obtained water-based polyurethane resin composition. The results are also shown in Table 2.

[Comparative Example 1-3]
Based on the formulation described in Table 2 below, an aqueous polyurethane resin was produced under the same conditions as in Reference Example 1, and water-dispersed silica (manufactured by ADEKA, product name Adelite AT-30A, solid content 30%) was prepared. Was stirred and mixed at room temperature for 1 hour to obtain a test solution. The results of evaluating the corrosion resistance and storage stability in the same manner as in the Reference Example are also shown in Table 2.

[ Reference Examples 2-1 to 2-3 and Comparative Example 2-1]
Based on the formulation described in Table 3 below, an aqueous polyurethane resin was produced under the same conditions as in Reference Example 1, and the storage stability was evaluated. Moreover, according to the mixing | blending described in Table 3 with respect to the hydroxyl equivalent of water-based polyurethane resin, 1.0-2.0 times equivalent (NCO Index 1.0-2.0) of water-dispersed isocyanate (Mitsui Chemicals ( Co., Ltd., product name Takenate WD-725, NCO% 15.8) was mixed to obtain a test solution, and then the corrosion resistance was evaluated in the same manner as in Reference Example 1-1. The results are also shown in Table 3.

[Comparative Examples 2-2 and 2-3]
Based on the formulation described in Table 3 below, an aqueous polyurethane resin blended with water-dispersed silica was produced under the same conditions as in Comparative Example 1-3, and the storage stability was evaluated. Moreover, after mix | blending water-dispersed isocyanate on the conditions similar to the said reference example 2-1, a test liquid was obtained, and corrosion resistance was evaluated similarly to the reference example 2-1. The results are also shown in Table 3.

<Corrosion resistance evaluation>
After applying a water-based urethane resin composition obtained in Reference Examples and Comparative Examples to a galvanized steel sheet that has not been surface-treated so that the dry film has a thickness of 60 μm, a coating film is formed. The film was subjected to a corrosion resistance test as follows.

<Corrosion resistance test>
A salt spray test was performed based on JIS Z 2371, and the occurrence of rust after 96 hours was observed.
Evaluation criteria A: Less than 10% of the total area of rust
○: Rust generation is 10% to less than 40% of the total area
Δ: Rust generation is 40% to less than 70% of the total area
X: Rust generation is 70% or more of the total area

<Storage stability evaluation of water-based polyurethane resin>
The storage stability when the aqueous polyurethane resins obtained by the above Reference Examples and Comparative Examples were stored at 25 ° C. for 30 days was visually evaluated based on the following criteria.
A: There is no increase in viscosity, separation or sedimentation.
○: Slight increase in viscosity, separation or sedimentation is observed.
Δ: Increase in viscosity, separation or sedimentation is observed, but usable.
X: Viscosity increase, separation or sedimentation is remarkable, and cannot be used.

＊１：トリエチルアミン
＊２：エチレンジアミン
＊３：アジピン酸ジヒドラジド
＊４： (株)ＡＤＥＫＡ製、ＡＴ−３０Ａ、固形分３０％
＊５：ウレタンプレポリマーのイソシアネート１当量に対するアミノ基の当量比

* 1: Triethylamine * 2: Ethylenediamine * 3: Adipic acid dihydrazide * 4: ADEKA, AT-30A, solid content 30%
* 5: Equivalent ratio of amino group to 1 equivalent of isocyanate in urethane prepolymer

＊１：ジエタノールアミン
＊２：Ｎ−（β−アミノエチル）エタノールアミン
＊３：三井化学（株)製、タケネートＷＤ-７２５、ＮＣＯ％１５．８％
表中の数値は、水系ポリウレタン樹脂１００質量部に対する質量部
＊４：（水分散イソシアネート配合前の）水系ポリウレタン樹脂の保存安定性
＊５：ウレタンプレポリマーのイソシアネート１当量に対するアミノ基の当量比
＊６：水系ポリウレタン樹脂の水酸基当量に対する水分散ポリイソシアネートのイソシアネート基の当量比（イソシアネート基／水酸基）

* 1: Diethanolamine * 2: N- (β-aminoethyl) ethanolamine * 3: Takenate WD-725 manufactured by Mitsui Chemicals, NCO% 15.8%
The numerical values in the table are parts by mass with respect to 100 parts by mass of the water-based polyurethane resin. * 4: Storage stability of the water-based polyurethane resin (before blending the water-dispersed isocyanate) * 5: Equivalent ratio of amino groups to 1 equivalent of isocyanate in the urethane prepolymer * 6: Equivalent ratio of isocyanate group of water-dispersed polyisocyanate to hydroxyl group equivalent of water-based polyurethane resin (isocyanate group / hydroxyl group)

The coating film obtained from the aqueous polyurethane resin composition of the reference example produced by blending the organosilica sol with the urethane prepolymer is blended with silica powder (Comparative Example 1-2) or water-dispersed silica (Comparison) It was confirmed that the coating film obtained from Example 1-3) had a remarkable effect on corrosion resistance. Further, it was confirmed that the reference invention ( Reference Example 2-1) in which the alkanolamine compound was used as a chain extender and the water-dispersed isocyanate was blended as a two-component curing agent had a further remarkable effect. .

  The water-based polyurethane resin composition of the present invention is excellent in corrosion resistance and can form a coating film or a molded article of polyurethane resin having abrasion resistance, adhesiveness, non-adhesiveness, and rubber elasticity. In addition, it is suitable for paints, adhesives, binders, coating agents, etc., which are excellent in terms of safety such as occupational health, and are extremely useful in industry.

Claims (9)

  A urethane prepolymer composition for an aqueous polyurethane resin composition containing an organosilica sol containing an inert organic solvent not containing a hydroxyl group as a dispersion solvent, wherein the silica content introduced by the organosilica sol is the urethane prepolymer composition 5 to 40% by mass in the solid content of the urethane prepolymer, wherein the urethane prepolymer has a hydroxyl group at the terminal.   An aqueous polyurethane resin composition obtained by dispersing the urethane prepolymer composition according to claim 1 in water.   In the urethane prepolymer composition containing an organosilica sol having an inert organic solvent not containing a hydroxyl group as a dispersion solvent and having an NCO group at the end, the silica content introduced by the organosilica sol is the same as that of the urethane prepolymer composition. A water-based polyurethane resin composition obtained by dispersing the composition contained in a solid content in an amount of 5 to 40% by mass in water, wherein the primary or second is based on 1 equivalent of the isocyanate group of the resin composition. A water-based polyurethane resin composition having a hydroxyl group, which is obtained by reacting an alkanolamine compound having a secondary amino group with an amino group equivalent ratio of 0.1 to 1.0. The hydrophilic compound represented by the following general formula (1) has a hydroxyl group according to claim 2 or 3 which is contained in an amount of 5 to 40% by mass based on the total solid content of the urethane prepolymer composition. Water-based polyurethane resin composition;

However, R ¹ in the above formula represents a residue of a urethanation reaction between a terminal hydroxyl group of an ethylene oxide structural compound and a di- or triisocyanate compound, or a residue of an ethylene oxide addition reaction with a di- or triol compound, R ² represents a methyl group or an ethyl group, and n represents a number of 5 to 100. The water-based polyurethane resin composition having a hydroxyl group according to claim 3 , wherein the alkanolamine compound is an alkanolamine having two amino groups and one hydroxyl group . The alkanolamine Amin is, N-(beta-aminoethyl) ethanolamine or an alkanolamine mixture including the compound, water-based polyurethane resin composition having a hydroxyl group as claimed in claim 5. The water-dispersed polyisocyanate compound is blended in an equivalent ratio of isocyanate groups of 0.5 to 2.5 with respect to 1 equivalent of the hydroxyl group of the aqueous polyurethane resin composition having a hydroxyl group described in any one of claims 2 to 6. A one-part curable water-based polyurethane resin composition characterized by comprising: A paint comprising the water-based polyurethane resin composition according to any one of claims 2 to 6 or the one-part curable water-based polyurethane resin composition according to claim 7 . A water-based metal surface treatment agent comprising the water- based polyurethane resin composition according to any one of claims 2 to 6 or the one-component curable water-based polyurethane resin composition according to claim 7 .