TW464680B - Aqueous polyurethane resin composition and aqueous metal surface-treatment composition containing same - Google Patents

Abstract

An aqueous metal surface-treatment composition having an excellent corrosion-prevention effect and a superior paint-adhesion, includes a polyurethane resin prepared by reacting (I) an urethane prepolymer prepared by a reaction of a polyol compound having an average molecular weight of 300 or more, with a dimethylol alkanoic acid, a compound having 3 or more active hydrogen atoms and an organic polyisocyanate compound, and having terminal isocyanate groups, with (II) a polyamine compound having 2 or more primary amino groups, in a such a proportion that the molar amount of the primary amino groups of the polyamine compound (II) exceeds the molar amount of the isocyanate groups of the urethane prepolymer (I), the polyurethane resin having terminal primary amino groups, and an aqueous medium for dispersing the polyurethane resins therein, wherein the polyol compound for the preparation of the urethane prepolymer (I) comprises (1) a polyester-polyol prepared from an aliphatic polyhydric alcohol and a polybasic carboxylic acid and having terminal hydroxyl groups and (2) a diol compound having a bisphenol skeleton and represented by the general formula (I), in which formula (I), R1 and R2 represent a hydrogen atom or a lower alkyl group, A represents a C2-C4 alkylene group and m and n represent an integer of 1 to 20.

Description

464680 Ministry of Economic Affairs_Central Bureau of Standards®; printed by the Industrial and Consumer Cooperatives A7 B7 V. Invention Description (i) [Technical Field of the Invention] The present invention relates to an aqueous polyurethane resin red product, and it contains the composition and has good properties. "Corrosion resistance and coating adhesion of metal surface treatment composition" [Past technology] So far, it has been widely used in household electrical products and building materials, or zinc-based alloy plated steel sheets. Due to the lack of sufficient money resistance and coating properties, steel plates such as these have been subjected to forming treatments such as die-casting and bending, and painting after applying complexation or phosphate treatment after treatment. However, it is not uncommon to apply it without painting based on the purpose and purpose. _v complex acid salt. Treated steel plate 'The surname resistance, color tone, and fingerprint applicability of the coated salt film on the steel plate are very important. Based on the use of the coating, the above performance requirements are added. The coating for surface coating is looking forward to a coating with high coating adhesion. Among such performance requirements, for example, the improvement of corrosion resistance There is a possibility of improvement based on the thickening of the chromate film, but the thick film obtained by this treatment. The chromate film has a problem of color tone due to the unique yellow color of the chromate film. In order to solve such problems, in recent years, JP-A-63-143265, JP-A-3-17189, JP-A4-71840, JP-A- Hei 5-161874, JP-A-Hei 6-145559, and JP-A-Hei 6_166735 Various methods have been mentioned in it. In Special Publication No. 63-143265, it was mentioned that Cr03 containing methanol and ethylene glycol is used on the zinc-based alloy plating layer formed on the surface of the steel plate (please read the precautions on the back before writing the 4 · Page) tr · —— ο.

464680 A7 B7 V. Description of the invention (2) Consumption cooperation between employees of the Central Standards Bureau of the Ministry of Economic Affairs, printing reconstitution agents, acid radicals such as phosphoric acid and boric acid, resins such as acrylic resins, colloidal silica, etc. The silicon chromate treatment solution is oxidized and subjected to chromate treatment. After that, the chromate film is subjected to a temperature of 0.5 to 3 at a baking temperature of 150 6C or lower. The temperature is acrylic acid, polyethylene, or ring. Oxygen and other resin baking methods. However, the effect of improving the corrosion resistance of the surface coating layer obtained by this method is still not satisfied. Japanese Patent Application Laid-Open No. 3-17189 mentioned that: Polyurethane-denatured polyolefin-based resins are made of resin sheaths containing fluorine-based resin particles and silica particles. However, since this resin film does not use a bridging agent, its corrosion resistance is still insufficient. The resin coating layer mentioned in Japanese Patent Application Laid-Open No. 4-71840 is based on zinc-plated or zinc-based alloy plated steel plate soil. It is a specific amount of chromic acid, salt coating, film layer, and Ni-containing powder. The organic resin film layer was coated and treated in this order. The resin skin layer "because it contains Ni powder with a thickness of 0.5 to 1.5 times the thickness of the resin film and a content of 10 to 80 vol%, which makes it have good adhesion", but the interface between the resin and the Ni powder Moisture easily penetrates, so the corrosion resistance and coating adhesion of the manufactured product still cannot satisfy β. In Japanese Patent Application Laid-Open No. 5-161874, it was mentioned that the contact surface of the steel sheet formed on the chromate film of the galvanized steel sheet. Solvent-based thermosetting resin 0.3 to 3.0 m thick steel plate. This solvent is a thermosetting resin. It is a polyurethane prepolymer containing a hydroxyl group produced by using polyhydric polyol, polyester polyol, and polyether polyester polyol. The resin used is a solvent system, and the composition is obviously different from the water-based metal surface treatment composition of the present invention, and there are some kinds of solvents accompanying the solvent. Please read the notes before the page ¢. Applicable to China National Standard (CNS) A4 specification (21〇297297) -6 Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs 464680 A7 B7 V. Description of the invention (3) Problems (such as environmental problems, drainage treatment Issues, cost issues, etc.). \ In kaiping 6-1 ’gas 4555, it was mentioned that the water-based polyurethane resin is

I Aqueous coating composition with main ingredients. The water-based polyurethane resin used in the water-based coating composition is a water-dispersed ether, ester-type polyurethane resin having a bisphenol-type bone lattice, an ester bone lattice, and a carboxyl group and having an average molecular weight of 3,000 or more, and a resin film formed therefrom. Corrosion resistance and resin adhesion are not always satisfactory. In Japanese Patent Application Laid-Open No. 6-166735, a water-based coating composition obtained by processing a polyurethane emulsion containing a primary amine group at the end by a water-soluble epoxy bridging agent is mentioned, but the coating composition is not formulated with Silicon dioxide used as a rust preventive pigment 'so the resin film resistance obtained is still generally' the corrosion resistance of the above-mentioned conventional surface-treated steel sheet is highly dependent on the water resistance and adhesion of the organic resin film, so The water resistance of the resin film is improved, and the content of the hydrophobic part in the resin is increased, or it is necessary to use a bridging agent to reduce the influence of the hydrophilic part as much as possible. However, when the hydrophobic part is increased, Resin tends to become gelled and cannot be used. On the one hand, when the bridging agent is used, since the baking time of the surface-treated steel sheet is less than 30 seconds, it is very difficult to fully display the properties that the resin originally has in such a short bridging process. of. [Problems to be Solved by the Present Invention] As shown in the foregoing general technical overview, in the short baking time of 30 seconds or less, it was not possible to obtain both good corrosion resistance and solvent resistance. Chinese National Standard (CNS) 8 4 threats (21〇χ297 mm)-; ~~: ~~ (Please read the precautions on the back before writing this page)

4 6 4 δ δ Γ. Α7 __, _ Β7 V. Description of the invention (4) Metal surface treatment composition on both sides. In addition, in order to improve the coating coating working environment, there is a very high expectation of a water-based treatment with a solvent-based treatment agent. The present invention solves such problems, and wants to provide a product with good financial properties and coating adhesion. An aqueous polyurethane resin composition and a metal surface treatment composition containing the composition. [Means for Solving the Problem] The result of intensive research by the present inventors, regarding the water-based polyurethane composition that satisfies both the performance of anti-corrosion and coating adhesion, and the metal surface treatment composition containing the composition, It was found that a composition mainly composed of a specific polyurethane resin skeleton can solve the above-mentioned problems, and then completed the present invention ◊ .......... In other words _'_ water system of the present invention ... poly.amine廉 树. 版 组 ._ 威 _ 物 '. 其. The ridge sign is printed on ... The Central Standards Bureau of the Ministry of Economic Affairs, Masonry Consumer Cooperative, is printed as an essential ingredient, containing polyalcohol compounds with an average molecular weight of 300 or more, two Hydroxymethylalkanoic acid, a compound containing three or more active hydrogens, and a polyurethane prepolymer obtained by reacting with an organic polyisocyanate compound and having an isocyanate group at the terminal, are reacted with (Π) containing two or more primary amine groups. The polyamine compound is obtained by reacting the polyamine compound (Π) with a higher amount of polyamino compound (in an excess ratio) relative to the isocyanate molar amount of the polyurethane prepolymer (I), and having a polyamine compound at the end. Primary amine polyamine A resin; and an aqueous medium containing the resin; and the polyol compound used in the preparation of the polyurethane prepolymer (I) is ① obtained from an aliphatic polyvalent alcohol and a polyvalent carboxylic acid and having argon at the end Based polyester polyols, and diol compounds containing bisphenol skeleton represented by the following general formula: This paper is applicable to the standard of China® National Standard (CNS) A4 (210X297 mm)

CD 484 68 C-A7 B7 V. Description of the Invention (5) Formula 2] R1 Η- ^ · 〇-A 知 〇CH§) -0 A-0 R * (However, R1 and R2 in the above formula (I) , Represents a hydrogen atom or a lower radical that is independent of each other, A represents a sulfinyl group having 2 to 4 carbon atoms, and m and η represent each other independently 1. to 20 < integers.) Also, the present invention A metal surface treatment composition having good corrosion resistance and coating adhesion, which is characterized by containing (a) the aforementioned water-based polyurethane resin composition of the present invention, (b) a hardener, and (c) silicon dioxide; Among them, the total solid content content of the aforementioned components (a) and (b) is 50-50: 9% of the total solid content weight and amount of the components (a), (_b) and (c) described above. %:,; '... And'-and;'-'+ The aforementioned-Cheng' 〃 The solid content of the component (c) is based on the total solid content of the components (a), (b), and (c). 3 to 50%. In addition, the water-based metal surface treatment composition of the present invention, and (d) the polyolefin wax having a silicidation value of 0 or 30 or less, may be 1 to 30% based on the total solid content of the components (a) to (d). Contains weight ratio. The constitution of the present invention is described in detail below. The water-based metal surface treatment composition of the present invention is characterized in that the base resin contained therein, in other words, the polyurethane resin in the water-based polyurethane resin composition of the present invention has a bone structure including side locks, and the bone structure is a specific A kind of reaction component is prepared by mixing it with a certain weight ratio. The resin component used in the water-based metal surface treatment composition of the present invention is applicable to the Chinese National Standard (CNS) A4 size (210X297 mm). First read the note on the back and then write this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

464680 A7 B7 Printed by the Central Bureau of the Ministry of Economic Affairs for the Industrial and Consumer Cooperatives. 5. Description of the invention (6) 'It is necessary to choose a water-based polyurethane resin that has achieved corrosion resistance, coating adhesion, solvent resistance, and drug resistance balance. Red adult ingredient (a). In order to satisfy these properties, it is necessary to use the water-based polyurethane resin composition (a) of the present invention in combination with other specific components and if necessary. In order to obtain a film with high corrosion resistance and high coating adhesion, it is necessary to have a good adhesion to the metal surface with a uniform coating film, and it is important to form a sufficient mesh structure in the obtained film. Therefore, it is necessary to use a resin with a specific structure in combination with a hardener. The water-based polyurethane resin composition that constitutes the base is a polyester polyol made from ① aliphatic polyhydric alcohol and polyvalent carboxylic acid and containing a hydroxyl group at the terminal, and ② substituted by general formula (I). The bisphenol bone-containing glycol compound is produced by using it as an essential component and containing a polyol compound having an average molecular weight of 300 or more, dimethylol alkanoic acid, a compound containing three or more active hydrogens, and an organic isocyanate compound. The water-based polyurethane resin composition is composed of a polyurethane prepolymer (I) containing an isocyanate group at the terminal and a polyamine compound (Π) containing at least two primary amine groups, with respect to the polyurethane prepolymer (I). The aforementioned polyamine compound (π) in the aforementioned amount of terminal isocyanate moles is prepared by reacting the amount of higher amino mols at a ratio of 剰 to obtain a polyurethane resin having a primary amine group at the terminal and used in an aqueous medium. Made by emulsifying and dispersing. The polyester polyol compound used in the present invention for producing an aqueous polyurethane composition ①'is selected from, for example, ethylene glycol, diethylene glycol, triethylene glycol: 1,2-propanediol, 1,3-propanediol ' Pentapentyl glycol, 1,2 butanediol, butanediol, 1,4-butanediol, 3-methylpentyl glycol, [l, 6] -ethylene glycol, water-based paper China National Standard (CNS) A4 specification (210X297 gong) (Please read the notes on the back before filling out this page) .0¾. .-. I order • 0: Α7 Β7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (7) Add low molecular weight polyalcohols such as bisphenol A, trihydroxymethylpropane, and glycerol, and for example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid Polybasic acids such as acids, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hydrazone tetrahydrophthalic acid, and hexahydrophthalic acid are reacted to obtain Its end contains the base. This type of polyester polyol compound ① contains 25 to 95% by weight relative to the total amount of the polyol compound component, and is particularly preferably formed in a ratio of 50 to 90% by weight. 'When the content ratio is outside the above range, However, the wealth and closeness of the obtained wax film are still insufficient. Also, the general formula (i) used in the present invention for producing a water-based polyurethane resin composition is ethylene glycol containing bisphenol bone, which is composed of, for example, methylenebisphenol, ethylene · bisphenol, butylene-bisvinyl- ·, Difference: Ya Liang, Ji Shuangpan_. Zun, Bianyu in the sound-Rl ... ··· .— 'and R2 are lower alkyl bisphenols, and epoxides (for example, ethylene oxide, propylene oxide, butylene oxide) having a breaking number of 2 to 4 are added by a known method. It is produced by the reaction, 'wherein the addition mol number of epoxide represented by m and η is 1 to 20 is necessary'. It is ideal to use 1 to 10 ^ When m and η exceed 20, the ring The content of the oxide component is too large, and the improvement effect of the corrosion resistance of the resin film obtained is insufficient, so it is not ideal. "Formula (I) contains two-dimensional ethylene glycol ②, which is 5% of the total amount of the dotalol compound component. ~ 75% by weight, and the ideal use ratio is 10 ~ 50% by weight. When the above ratio is out of the above range, the resistance and adhesion of the obtained resin film are still not sufficiently satisfied. 'Also, in the polyol compound component, the above-mentioned polyester polyol ① and bisphenol-containing polyol ② are combined with other polyol compounds (please read the precautions on the back before writing this page)- ο. One * it IJ ...... r This paper @size is applicable to Chinese National Standard (CNS) Α4 specification (210X297 mm) Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 64 68 "A7 ____B7_ V. Invention Explanation (8) It is also possible to use, and the adhesion and corrosion resistance of the resin film produced by the combined use of such other polyols according to the situation can be further improved. Other polyol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, pentaerythylene glycol, 1-butanediol, 1,3-butanediol Low molecular weight polyols, compounds such as diols, 1,4-butanediol, 3-methylpentanediol, hexanediol, water-added bisphenol A, trimethylolpropane, and glycerol, and these polymers Ethylene oxide compound of ethylene compounds and / or propylene oxide high adduct, polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, etc. polyester polyols' polycaprolactone polyols, polyolefin polyols And polybutadiene polyols. Other such polyol compounds account for 40% by weight relative to the combined amount of the components of the polyol compound, and can be used especially at less than 30% by weight. Polyurethane prepolymers for the preparation of polyurethane prepolymers (I), such as 2,2-Dimercaptopropionic acid, 2,2-Dimercaptomethyl, and 2,2-Dimercaptomethyl Glycyrrhizic acid and the like belong to it, and the self-emulsifying aqueous resin emulsion dispersion can be prepared by using these dimethylol alkanoic acid as a neutralizing agent through a neutralization reaction treatment. The amount of these dimethylol alkanoic acids' is used relative to 1 to 30% by weight of the solid content of the polyurethane prepolymer (j). When the content is less than 1% by weight, the self-emulsifying property of the polyurethane resin is insufficient. Also, when it exceeds 30% by weight, there are insufficient physical properties such as elongation of the resin film obtained by shellfish j. Also, the above-mentioned neutralizers for methyl disulfuric acid, such as trimethylamine and triethyl Organic amines such as amines, tripropylamines, tributylamines, N-methyldiethanolamine, and triethanolamine, as well as argon, sodium oxide, potassium hydroxide, and ammonia, etc. Chinese national standards (CHS ) Α4 size (210 × 297 mm) (Please read the precautions on the back before writing 4 · this page)

464680 A7 _____ B7 ___. V. Description of the invention (9) Organic salts are all ’and these orders must be used in sufficient amounts when reacting with carboxyl groups. In the present invention, 'the compound containing at least three active hydrogens used for preparing the polyurethane prepolymer (I) is used to have side locks of the polyurethane resin', and to make the strength, adhesion, and corrosion resistance of the coating film It can be used for improvement, such as melamine, diethylenetriamine, trimethylolpropane, quaternary erythritol, glycerol, or ethylene oxide and / or low addition of propylene oxide. And the molecular weight is less than 300, etc., especially when melamine is used, it has a significant improvement effect on the properties of the obtained resin film. Such a compound containing at least three active hydrogens is used in a proportion of 0.1 to 10% by weight based on the solid content of the polyurethane prepolymer (I). When it is less than 0.1% by weight, the performance of the obtained resin film will hardly improve the efficiency multiplier and it exceeds _ 1Q% by weight when used. When the financial institution _takes'— :, the stretchability of the resin film will be obtained. There are concerns about reduced physical properties. In the production of polyurethane prepolymer (I), it is of course possible to further add a low molecular weight compound containing two active hydrogens, which is usually used (printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs --- r-- --- ο—— (Please read the notes on the back before writing this page)

PB lock extender) 'Such lock extenders such as ethylene glycol, propylene glycol, pentaerythrylene glycol, hexanediol, or the like of ethylene oxide and / or propylene oxide low adducts, etc. ; Ethylenediamine, propylenediamine, hexamethylenediamine, toluenediamine, xylylenediamine, diaminodimethyl, diaminocyclohexylmethane, piperazine, 2-methylpiperazine Isophorone diamine, amines such as dihydrazine succinate, dihydrazone adipate, dihydrazine phthalate, etc., and their molecular weights are less than 300. The amount of such lock elongating agent used will vary depending on the molecular weight of the polyurethane resin that constitutes the object, and it is usually used relative to the prepolymer (Π weight is 10% by weight or less. 丨 This paper size 逋Wei Xuan X Tenghuan-13- 464680 Ministry of Economic Affairs t Central Prototype Bureau negative X Consumer Cooperative printed A7 B7 V. Description of the invention (10) Organic polyisocyanate compound used in the production of polyurethane prepolymer (I) in the present invention, Examples include aliphatic, alicyclic and aromatic polyisocyanates, such as tetramethylene diisocyanate, hexamethylene isocyanate, lysine diisocyanate, hydrogen-added xylylene Diisocyanate, 丨., 4_cyclohexyldiisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2s4, _ dicyclohexylmethane diisocyanate, isophorone diisocyanate, 3,3, _dimethoxy -4,4 '· bisphenylene diisocyanate, 1,5-naphthyl diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-toluene diisocyanate, 2,6_toluene di Isocyanate, 4,4-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate , Phenylene diisocyanate, xylylene diisocyanate ', tetramethylxylylene diisocyanate, etc. are all suitable. Among them, tetramethylene diisocyanate is used. Acid vinegar ·', Hexa- Methyl diisocyanate, lysine diisocyanate, added hydroxylylene diisocyanate, 4-cyclocyclohexylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, 2,4, _ In the case of dicyclohexyl methyl isocyanate, and isophoric I diisocyanate, etc., in the case of aliphatic or alicyclic polyisocyanate compounds, good chemical resistance, corrosion resistance, etc. cannot be obtained and have good weather resistance. The amount of such organic polyisocyanate compounds is a compound containing at least 3 active hydrogens via methyl alkanoic acid relative to the polyol compound used in the production of the polyurethane prepolymer (I). And if necessary, the total amount of active hydrogen contained in the elongation agent used is more than the equivalent, and it is suitable to adjust to 1: 1 to 2 times the equivalent to use. When the amount of organic isocyanate compound is less than 1 equivalent, Polyurethane prepolymers obtained in the (1) This paper points ^ ^ ^ applicable Chinese National Standard (CNS) (2I0X297 mm) -14 - Please note that first heard the matter again page

4 6 4 6 8 〇Α7 B7 V. Description of the invention (11) The subterminal has almost no residual isocyanate group, so the introduction of amine groups at the molecular terminal is impossible, and when it is more than 2 times the equivalent, the obtained In the molecule of the polyurethane prepolymer (I), because unreacted polyisocyanate groups remain, urea is excessively bonded to form when water is added, or due to the formation of a large amount of low molecular weight products, the resulting polyurethane is pre-prepared. The properties of the polymer (J) may be reduced. In the present invention, a poly saddle ester prepolymer (I) used in the production of an aqueous polyurethane resin composition is used. The above-mentioned raw material components are used in a solvent according to a known method. Reaction procedures can be made. It is also possible to appropriately change the order of input of these raw material components or to input them separately. The solvent used in the production of the polyurethane prepolymer (I) is: inactive to the reaction and has a high affinity for water. Organic solvents are suitable, such as acetone, methyl ethyl methyl alcohol I , Two-degree smoldering, four argonized n-flavor, N-methyl-2-o bicalanone, dimethylformamide 'dimethylacetamide, dimethyl subcode, and ethyl acetate, etc. The usage amount of these solvents is usually one weight relative to the above-mentioned raw material ingredients used in the production of the polyurethane prepolymer (I), and is used in a weight ratio of 10 to%, for example. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before writing this page) • tn-.ft- Furthermore, the polyurethane prepolymer (I) produced by the above method in the present invention It reacts with the polyamine compound (Π) to introduce a primary amine group into the terminal of the obtained polyurethane resin molecule. The polyamine compound ^, such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, xylylenediamine, diaminodibenzylmethanine, diamine Aminocyclohexylmethanine, n-diazine, 2-methylpiperazine, isophorone diamine, melamine, dihydrazine succinate, dihydrazine adipate, and dihydrazine phthalate, etc. are especially used Two paper sizes are applicable to China National Building Standard (CNS) A4 specifications (2〗 0X297 mm) -15 Printed by the Central Work Bureau of the Ministry of Economic Affairs and printed by the Bayer Consumer Cooperative 464 68 A7 B7 V. Description of the invention (12) In the case of rhenium compounds, resin films with good adhesion, corrosion resistance, and strength can be obtained. The above-mentioned polyamine compound (Π) has two effects of promoting the extension of the lock of the polyurethane prepolymer (I) and the introduction of amine groups. The amount of this polyamine compound (Π) is relative to that of the polyurethane prepolymer (I). ) Is more than the equivalent of the residual isonic acid ester group, and it is preferably used at a ratio of 1.05 to 2 times the equivalent. When the use is less than 1 equivalent, the obtained polyurethane does not introduce any free amine groups, and when it is used more than 2 times the equivalent, unreacted polyamine compounds remain, so it may be brought to Possibility of adverse effects on the properties of the obtained polyurethane. Also, the "method for reacting the polyurethane prepolymer (I) and the polyamine compound π" can be used by a known method for producing an aqueous polyurethane resin. For example, after dispersing the polyurethane prepolymer (I) in water, A method in which a polyamine compound is added for reaction, and a method in which a polyurethane prepolymer is added to an aqueous solution of the polyamine compound Π to disperse it and cause the two to react, any one method may be used; and, The polyamine compound (Π) may be added in a single amount, or it may be added in portions. Obtained through the above treatment. The water-based polyurethane resin emulsified dispersion ′ of the present invention usually has a solid content of 5 to 80% by weight, but is adjusted to 10 to 70%. The weight is suitable. When the solid content of the resin is less than 5% by weight, when the resin composition contains a large amount of water, the coating film obtained needs to be dried for a long time, and when it exceeds 80% by weight The obtained composition has a high viscosity and tends to be difficult to use. Also, in the aqueous polyurethane resin composition used in the present invention, according to the paper size, the Chinese National Standard (CNS) A4 specification (2K) χ 297 is applicable. (Please read the precautions on the back before writing this page. 4 · )

Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

46 4 6 8 C A7 ____ B7 V. Description of the invention (13) It is necessary to add thioether-based antioxidants and / or triazindene-based or benzophenone-based ultraviolet absorbers. The water-based polyurethane resin composition (a) used in the present invention generates several self-bridged reactions upon heating, but the corrosion resistance and solvent resistance of the obtained resin film are not ideal due to insufficient bridge reactions. Therefore, the water-based metal surface treatment composition in the present invention is blended with a hardener (b). The hardener (b) is selected from epoxy compounds, amines, polyvalent alcohols, polybasic acids, isocyanate compounds, and the like. However, in order to obtain a resin sheath having better corrosion resistance and solvent resistance, at least one of epoxy group, oxazoline group, alkoxysilyl group, isocyanate group, and aziridine group is selected as the hardener. A bridging compound containing one or more of these functional groups is more preferred. ~ Hardener compounds other than the above, such as amines, polyvalent alcohols, etc .. Polyalkaline acids, etc. are obtained from functional machines with strong hydrophilicity (amino groups, hydroxyl groups, carboxyl groups, etc.) The resin film is resistant; When an epoxy resin is used as a hardener, the chemical resistance and adhesion of the obtained film can be improved due to the chemical resistance and adhesiveness of the epoxy resin itself. In addition, when a hardener containing an oxalic acid 11-based system, a mahogany sintered system, an isocyanate-based system, and an aziridine-based compound is used, the same effect as that of an epoxy resin can be expected. The blending amount of the hardener (b), wherein the equivalent ratio between the functional groups of the polyurethane resin (amine, enemy, warp, etc.) and the functional groups of the hardener (functional groups of the hardener) in the polyurethane resin emulsion dispersion (3) Equivalent / functional group equivalent of polyurethane resin) is 1/10 to 1/1, and is based on the solid content ((a) + (b) + (c)) of the hardener (b) solid content by weight% system It is better to use 2 ~ 30%. When this paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) — Q—I (please read the precautions on the back before writing this page) Order ir. 464 68 (A7 B7 V. Description of the invention (14) The above equivalent ratio is less than 1/10, and the content of the hardener (b) is less than the total solid content ((a) + (b) + (c)) 2 ° /. When the hardener (b ) When the compounding effect exceeds the equivalent ratio of 1/1, and the content of the hardener (b) exceeds 30% of the total solid content ((a) + (b) + (c)), then the water-based polyurethane resin of the present invention The characteristics of the composition cannot be fully exerted, and the polyurethane resin and the residual unreacted excess hardener are responsible for the role of the plasticizer of the polyurethane resin. Insufficient adhesion. With respect to the total solid content weight of the water-based metal surface treatment composition (a) + (b) + (c) of the component (a) + (b), the total solid content content is preferably 50 to 97%. When the total content is less than 50%, the obtained resin film has insufficient financial properties and coating adhesion. Also, when it exceeds 97% soup form, it cannot be produced. High-corrosion-resistant tree film ..... Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling out this page), ιτ- in the water-based metal surface treatment composition of the present invention In order to improve the money-resistance of the obtained resin film, the content ratio of the dream dioxide (Si02) (c) is 3 to 50% of the total solid content ((a) + (b) + (c)). When Relative to the total solids weight ((a) + (b) + (c)) of silicon dioxide (c) solids weight less than 3%, the effect of improving the corrosion resistance of the resin film is insufficient, and it exceeds 50% In this case, the coupling effect of the resin component (a) and the hardener component (b). Is insufficient, so that the corrosion resistance of the obtained resin film is still unsatisfactory. ^ 'As for the particle size and type of the silica particles,' it is not particularly in the present invention. It is limited, and its particle size is preferably 2 to 5 nm, and this type is preferably selected from fumed silica, silicone, etc. The water-based metal surface treatment composition of the present invention is to obtain a coated surface. Uniform film, it can also contain the interface called wetting promoter

Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _____B7____ 5. Description of the invention (15). Active agents, tackifiers, conductive substances for improving the solubility, and coloring pigments for improving the pattern. In addition, since the water-based metal surface treatment composition of the present invention is added with a lubricating additive, the surface-treated metal material can be formed without using die-casting oil or the like. Such a treatment composition ′ can be suitably applied to a surface-treated steel sheet that does not require a degreasing process and a coating primer treatment. Lubricant additives that satisfy this effect include inorganic solid lubricants such as black lead and diluent, or organic lubricants such as natural paraffin and synthetic wax. The (d) as an additional component in the aforementioned components (a), (b) and (c) of the water-based metal surface treatment composition of the present invention is a polyolefin wax having a silicidation value of 0 or 30 or less and having a divergent structure, It may be contained in a proportion of 1 to 30% by weight based on the total solid content of the components (a) to (d). When the silicification value exceeds 30, the obtained polyolefin wax is easily miscible with the aforementioned polyurethane resin component due to its high polarity, and it becomes difficult to distribute it on the resin surface during film formation. Therefore, when a high level of processability is necessary, 'Often there is no way to achieve the desired performance. In addition, since the obtained resin film has insufficient water resistance and paint adhesion, it cannot be said to be appropriate for the above-mentioned applications. As a lubricating additive, it is preferred that it has a low compatibility with resin components and does not bind to esters, and the polyolefin wax having a silicidation value of 0. The blending amount of the above-mentioned polyolefin wax (d) is less than 1% by weight. Although the effect of improving the molding processability of the resin film is not great when it is added, and when it exceeds 30% by weight, the wax in the composition is scattered in the house casting device and its surroundings during the molding process, so the operating environment This has a bad effect, and the resistance of the obtained resin film is also insufficient. The average particle size of polyolefin soil (d) is 〇1 ～ 7 〇〇〇) 4 size (210 乂 297 cm) (Please read the precautions on the back before writing the page-) ο. 'Order Printed by Shelley Consumer Cooperative of the Central Bureau of Accreditation of the Ministry of Economic Affairs 464681 A7 ______B7_ V. Description of the invention (16) It is advisable "Under the condition that the average particle size is not more than 0 mm, the processability of the obtained resin film is insufficient. In the case of 7.0 · βηι, the distribution of the solidified polyolefin ants in the obtained resin film is not uniform, which is not ideal. It is preferable that the shape of the wax particles is spherical and does not require high processability. The metal material to which the salt of the water-based metal surface treatment group of the present invention is applied is a cold-rolled steel sheet, a bond zinc-based steel sheet, or an aluminum-based sheet. Furthermore, in order to improve the corrosion resistance, it is effective to perform a primer treatment on the surface of the metal slag. Such a primer is suitably treated with a known chromate treatment or phosphate treatment. On top of such a scalp film, a coating containing the water-based metal surface treatment composition of the present invention is subjected to a coating treatment to form a film of 0.3 to 6 g / m2, and properties such as corrosion resistance and solvent resistance are imparted. As ideal. As for the coating method of the coating material, there are a light coating method, a dipping method, an electrostatic coating method, and the like, but the invention is not particularly limited. The present invention will be further explained based on the following examples and comparative examples. The water-based polyurethane resin compositions used in the following examples and comparative examples are manufactured through the following processing steps. 1. Examples Production Examples of Waterborne Polyurethane Resin Compositions Production Example 1 uses an isophthalic acid / adipic acid (Molar ratio 1/1) mixture as a dibasic acid and uses 1 as an ethylene glycol component. 6-hexanediol to obtain 100 parts of a polyester polyol with a hydroxyl average molecular weight of 2000 at the terminal, 50 points of a bisphenol A propylene oxide adduct with an average molecular weight of 660, and 2,2-bis (hydroxymethyl) propane 15 parts of acid and 5 parts of melamine are mixed ', and then the mixture is heated to 90. This paper size applies to Chinese national standard (CNS > Λ4 specifications (210X297 mm ^: ~: ~ 2 ^ .: Please read the back Note § Item 4-Write this page again) Order 4 6 B ^ Γ · — A7 B7 V. Description of the invention (1 is a solution prepared by i ° C. Next, 110 1 part of dicyclohexylmethane diisocyanate, and N-methyl-2-pyrrolidone 110 was mixed into the solution, and then the mixture was heated to a maximum of 120 ° C and stirred for 5 hours to produce a prepolymer having an isocyanate group content of 2.6%. 14 parts of trimethylamine were neutralized therein. In addition, 5 parts of ethylene diamine and adipic acid di 20 parts were dissolved in 580 parts of deionized water, and then the solution was heated to .40 ° C. While maintaining the solution at the aforementioned temperature, the above-mentioned neutralization prepolymer was dropped, and a water system having a solid concentration of 31% was obtained. Polyurethane resin emulsion. Manufacturing Example 2 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Isophthalic acid / adipic acid (Mole ratio 1/1) as a dibasic acid component is used. 1,6-.Hex 'Difu as ethylene glycol component: To obtain 30 parts of a polyester polyol having an average molecular weight of 2,000 hydroxyl groups at the ends and 100 parts of a propylene oxide adduct of bisphenol A having an average molecular weight of 800 , 12 parts of 2,2-bis (hydroxymethyl) propionic acid, and 5 parts of melamine were mixed and heated to 90 ° C to form a solution. Next, 110 parts of dicyclohexylfluorane diisocyanate and N-methyl 100 parts of 2-pyrrolidone alkyl ketone was added to the solution, and then heated to a maximum of 120 ° C and stirred for 5 hours to produce a prepolymer having an isocyanate content of 3.0%. 10 parts of triethylamine was added Neutralization reaction is carried out there. Others include 5 parts of ethylenediamine, 2 parts of diethylenetriamine, and hexamethylene diamine. 17 parts of dihydrazine were dissolved in 620 parts of deionized water. The solution was further heated to 40 ° C, and the above-mentioned neutralized prepolymer / triethylamine mixed solution was dropped into the solution while maintaining its temperature. So we obtained water-based polyurethane-21 with a solid concentration of 29%-(Please read the precautions on the reverse side before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). Printed by the Industrial and Consumer Cooperatives 464680 A7 ___ B7 V. Description of the invention (1S) resin emulsion. Polyester polyol 1 obtained by using a dibasic acid isophthalic acid / adipic acid (mole ratio iH) mixture and 1,6-hexanediol as an ethylene glycol component and having an average molecular weight of 2000 at the end 70 points, 70 parts of propylene oxide adduct of bisphenol A with an average molecular weight of 1,000, 11 parts of 2,2-bis (via methyl) propionic acid, and 4 parts of melamine were mixed, and then the temperature was raised. To 900 ° C to dissolve β, and then '85 parts of isophorone diisocyanate and 10.0% of N-methyl-2-pyrrolidone were added to the solution 'through surface heating to the highest It was stirred for 5 hours to produce a prepolymer with an isocyanate content of 2.9%, and triethylamine was added for 10 minutes to perform a neutralization reaction treatment. In addition, 6 parts of ethylenediamine and 25 points of dihydrazine adipate were dissolved in 640 parts of deionized water. The solution was further heated to 40t, while maintaining the temperature. The above-mentioned mixture of Heng and prepolymer trimethylamine was dropped, and then a water-based polyurethane resin with a concentration of 30% was prepared and emulsified. liquid. Production Example 4 A polyester having an isophthalic acid / adipic acid (molar ratio 1/1) as a dibasic enzyme component and hexanediol as an ethylene glycol component was used to obtain a terminal polyester having an average molecular weight of 1,500 hydroxyl groups 100 parts of polyhydric alcohol, 50 parts by weight of bisphenol · α propylene oxide adduct with an average molecular weight of 5 80, 16 parts of 2,2-bis (via methyl) propionic acid, 4 parts of melamine are mixed, and the temperature is increased to 900c and allowed to dissolve. Next, 100 parts of isophora diisocyanate and 110 parts of N-methyl-D-pyrrolidone were added to the solution, and heated to the highest side and stirred for 5 hours to produce an isocyanate content of 3 4% of the prepolymer, and 13 parts of triethylamine were added thereto to perform a deka sum reaction. In addition, 3 parts of ethylene diamine and 20 parts of dihydrazine adipic acid are dissolved in deionized water. The paper is a universal T 囷 standard (CNS) A4 specification (2 丨 0X297). (Please read the notes on the back first 4 'write this page again)

-22- Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 46468 0 A7 B7 V. Description of Invention (19) 550 copies. The solution was further heated to 40 ° C while maintaining the temperature, and the above-mentioned prepolymer // diethylamine mixed liquid was dropped to prepare an aqueous polyurethane resin emulsion having a solid concentration of 31%. Production Example 5 An isougic acid / adipic acid (molar ratio 1/1) mixture as a dicarboxylic acid component and an ethylene glycol component were used. 6-hexanediol was obtained and the average molecular weight was contained at the end. 100 parts of polyester polyol in 2000, 60 parts of propylene oxide adduct of Shuangpan A with an average molecular weight of 580, 16 parts of 2,2-bis (via methyl) propionic acid, and 4 parts of melamine, The manhole temperature was 90 ° C to allow it to dissolve. Next, 100 parts of isophorone diisocyanate and 100 parts of N-methyl-pyrrolidone were added to the solution, and heated to a maximum of 120 ° C while climbing. The mixture was stirred for 22 hours to produce an isocyanate content of 2.4 % Of prepolymer ... Add another ^ factory. Π Add 13 parts of triethylamine to neutralize it. In addition, 3 parts of ethylenediamine, 1 part of diethylenetriamine, and 18 parts of dihydrazine adipate were dissolved in 500 parts of deionized water. The solution was further heated to 40 ° C, and while maintaining the temperature, the above-mentioned neutralized prepolymer / triethylamine mixed solution was dropped into the aforementioned solution, and an aqueous polyurethane resin having a solid content concentration of 34% was emulsified. liquid. Production Example 6 An isophthalic acid / adipic acid (molar ratio 1/1) mixture as a dibasic acid component and 1,6-hexanediol as an ethylene glycol component were used to obtain a terminal end and contain hydroxyl groups on average. 50 parts of polyester polyol having a molecular weight of 1,000, 50 parts of a propylene oxide adduct of bisphenol A with an average molecular weight of 660, 15 parts of 2,2 · bis (hydroxymethyl) propionic acid, and 5 parts of melamine were mixed, and the mixture was further mixed. Heating to 90 ° C applies the national standard of this paper (&^; ^ 8) 8 4 specifications (210 mm 297 mm) (please read the precautions on the back before writing the page 4) ο. Order Printed by S 4 6 8 0 a7 B7 from the Zhengong Consumer Cooperative of the Central Bureau of Quasi-Economics of the Ministry of Economic Affairs 5. Description of the invention (2 () to prepare such a solution. Next, 110 parts of dicyclohexylmethane diisocyanate and N-methyl- 110 parts of 2-pyrrolidone are added to the solution, and the mixture-the surface is heated to a maximum of 120 ° C-and stirred for 5 hours to produce a prepolymer with an isocyanate content of 2.8%, and then triethylamine 14 A portion was added to the mixture to perform a neutralization reaction. In addition, 5 parts of ethylenediamine and 20 parts of dihydrazine adipate were dissolved in 480 parts of deionized water. The solution was further heated to 40 ° C, and the aforementioned neutralized prepolymer / triethylamine mixed solution was dropped into the solution while maintaining the aforementioned temperature, thereby obtaining a water-based polyurethane resin having a solid concentration of 31% by weight. Emulsion 〇Production Example 7 ............ Isoeuronic acid / adipic acid (Mole ratio 8/2) mixture used as a di: alkanoic acid: component and used as ethylene glycol 1,6-hexanediol of the component is obtained, 100 parts of a polyester polyol having an average molecular weight of hydroxy group of 2000, 50 parts of a propylene oxide adduct of bisphenol A having an average molecular weight of 660, and 2,2-bis (hydroxymethyl) ) 15 parts of propionic acid and 5 parts of melamine were mixed, and the mixture was heated to 90 ° to prepare such a solution. Then, 110 parts of dicyclohexyl diisocyanate and N-methyl-2-pyrrolidone were mixed. 110 parts were added to the solution, and the mixture was heated to a maximum of 120 eC while stirring for 5 hours to produce a prepolymer with a content of 2.6%, and 14 points of triethylamine was added to neutralize In addition, 5 parts of ethylenediamine and 20 parts of dihydrazine adipate were dissolved in 580 parts of deionized water. The solution was heated to 40 ° C, and while maintaining the aforementioned temperature, the aforementioned neutralized prepolymer / triethylamine mixed solution was dropped into the solution. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 cm ^ ( (Please read the notes on the back before filling out this page)

Ay. -F'tT · 464680 A7 —______ B7________ V. Description of the invention (2l), an aqueous polyurethane resin emulsion with a solid content concentration of 3 1/0 weight was prepared. Production Example 8 The difference as a dibasic acid component will be used A mixture of phthalic acid / adipic acid (Molar ratio 1/1) and i, 6-hexanediol, which is an ethylene glycol component, was used to obtain 150 parts of a polyester polyol having an average molecular weight of hydroxy groups of 2000 and a molecular weight of 660 as the flat weight. 33 parts of propylene oxide adduct of bisphenol A, 15 parts of 2,2-bis (hydroxy ^) propionic acid, and 5 parts of melamine were mixed, and the mixture was heated to 90 ° C to prepare such a solution. Next, 110 parts of dicyclohexylmethane diisocyanate and 110 parts of each of N-methyl-2-propanone were mixed with the solution, and the mixture was heated to a maximum of 120 ° C while being stirred for 5 hours. In order to produce -prepolymer-τ with an isocyanic acid content ratio of 2: 4%, 4 parts of triethylamine was added, and a neutralization treatment was performed. In addition, 5 parts of ethylenediamine and 20 parts of dihydrazine adipate were dissolved in 580 parts of deionized water. The solution was further heated to 40 ° C, and the aforementioned neutralized prepolymer / triethylamine mixed solution was dropped onto the solution while maintaining the aforementioned temperature, thereby preparing an aqueous polyurethane resin having a solid content concentration of 32% by weight and emulsified. liquid. Manufacture example 9 Printed by the Central Bureau of Specimen, Ministry of Economic Affairs, Shelley Consumer Cooperative, using an isophthalic acid / adipic acid (Mole ratio 1/1) mixture as a dibasic acid component and using 1,6 as a glycol component -100 parts of hexamethylene glycol-terminated polyester polyol having an average molecular weight of 2000, 50 parts of a propylene oxide adduct of bisphenol A with an average molecular weight of 660, 2,2-bis (hydroxymethyl) propane 15 parts of acid and 5 parts of trimethylolpropane were mixed, and the mixture was heated to 90 ° C. to prepare such a solution. Next, apply the dicyclohexyl methane diisocyanate paper size to the Chinese National Standard (CNS) A4 specification (210X297 mm) -25- 464680 Printed on the A7 B7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (22 ) 110 parts of ester and 11 parts of N-fluorenyl_2 · pyrrolidone were mixed with the solution, while the mixture was heated to a maximum of 120 and stirred for 5 hours to prepare a pre-isocyanate content of 2.6%. A polymer was added with 14 parts of triethylamine to perform a neutralization reaction treatment. In addition, 5 parts of ethylenediamine and 20 parts of dihydrazine adipate were dissolved in 580 parts of deionized water. This solution was further heated to 40 ° C while maintaining the aforementioned temperature, and the aforementioned neutralized prepolymer / triethylamine mixed solution was dropped into the solution, thereby preparing an aqueous polyurethane resin having a solid concentration of 31% and emulsified. liquid. 2. Comparative Example Production of Water-Based Polyurethane Resin Composition Manufacturing Example 10 (Comparative) An isophthalic acid / adipic acid (molar ratio 1/1) mixture was used as a dibasic acid component and used as a glycol component The tenth, ^, hexahedron, and bismuth were mixed to obtain 229 parts of a polyester polyol having an average molecular weight of 1500 at the terminal, 16 parts of 2,2-bis (hydroxymethyl) propionic acid, and 4 parts of melamine, and mixed, and Warm to 90 ° C to dissolve. Next, '120 parts of isophorone diisocyanate and 110 parts of cold methyl-2-pyrrolidone were added to this solution, while heating to a maximum of 120 ° C and stirring for 5 hours to produce an isocyanate content of 3 8 % Prepolymer, and then added 13 parts of triethylamine to neutralization reaction treatment. In addition, 9 parts of ethylenediamine and 2 parts of diethylenetriamine were dissolved in 660 parts of deionized water. The solution was further warmed to 4 ° C, and while maintaining the temperature, the aforementioned Deca prepolymer / triethylamine mixed liquid was dropped into the aforementioned solution, thereby preparing an aqueous polyurethane resin emulsion having a solid content concentration of 33%. Manufacture Example 1 (Comparison) 150 parts of propylene oxide adduct of bisphenol A with an average molecular weight of 1000. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 cm) (Please read the note on the back first) Fill out this page again) Order ^ 6468 〇 Α7 Β7 V. Description of the invention (23), 16 parts of 2,2-bis (hydroxymethyl) propionic acid, 5 parts of trimethylolpropane are mixed, and the temperature is raised to 90 ° C so that Its dissolved. Next, 120 parts of isophorone diisocyanate and 100 parts of N-fluorenyl-2-pyrrolidone were added to the aforementioned solution, and one side was heated to a maximum of 120 ° C while stirring for 5 hours to produce an isocyanate content. 4.5% of the prepolymer, and then added 13 parts of triethylamine to the neutralization reaction treatment. In addition, 9 parts of ethylene diamine and 2 parts of diethylene triamine were dissolved in 500 parts of deionized water. The solution was further heated to 40 ° C, and while maintaining the temperature, the above-mentioned neutralized prepolymer / triethylamine mixed solution was dropped into the solution, so that an aqueous polyurethane resin having a solid content concentration of 33% was emulsified. liquid. Production Example 12 (comparative) 220 parts of a propylene oxide adduct of bisphenol A with an average molecular weight of 2000, 20 parts of 2,2-bis (hydroxymethyl) propionic acid, and 2 parts of melamine. It was heated to 90 ° C to dissolve. Next, 120 parts of isophorone diisocyanate and 130 parts of N-methyl-2-pyrrolidone were added to the solution, and heated to a maximum of 120 ° C while stirring for 5 hours to produce a pre-isocyanate content of 4.2%. The polymer was added with 18 parts of triethylamine to perform a neutralization reaction treatment. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In addition, 9 parts of ethylenediamine was dissolved in 640 parts of deionized water. The solution was further heated to 40 ° C, and while maintaining the temperature, the above-mentioned neutralized prepolymer / triethylamine mixed liquid was dropped on the solution, thereby preparing an aqueous polyurethane resin emulsion having a solid content concentration of 32%. . A polyester polyhydric polyester having an average molecular weight of 2,000 hydroxyl groups at the end was obtained by using an isophthalic acid / adipic acid (mol ratio 1/1) mixture as a dibasic acid component and 1,6-hexanediol as a glycol component. Alcohol 100 parts, average molecular -27- (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 46468 〇Α7 Β7 V. Description of the invention (Quantity 70 parts of propylene oxide adduct of 1000 propylene glycol, 11 parts of 2,2-bis (hydroxymethyl) propionic acid, and 4 parts of melamine were mixed and heated to 90 ° C to dissolve. Next, add 85 parts of isophorone diisocyanate and 100 parts of N-fluorenyl-2-pyrrolidone in this solution, one side was heated to a maximum of 120 ° C and the side was stirred for .5 hours to produce a pre-isocyanate content of 2.9%. Polymer, and then add triethylamine to neutralize the reaction. Dissolve 6 parts of ethylene diamine in deionized water. 483 wounds; neutral "and then warm the solution to 40 ° C, while maintaining the temperature On one side, the above-mentioned neutralized prepolymer / triethylamine mixed liquid was dropped into the solution, and thus obtained Water-based polyurethane resin emulsion with a concentration of 32%. Manufacturing Example 14 (Comparative) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Isophthalic acid / adipic acid will be used as the dibasic acid component. / 1) Mixture and use of 1,6-hexanediol as a glycol component to obtain 160 parts of a polyester polyol containing an average molecular weight of 2000 at the end of the hydroxyl group and 67 parts of a propylene oxide adduct of bisphenol A with an average molecular weight of 660 And 15 parts of 2,2-bis (hydroxymethyl) propionic acid were mixed and dissolved by heating to 90 ° C. Next, 93 parts of isophorone diisocyanate and N-methyl-2-pyrrolidone 130 were added. Part of this solution was heated up to 120 ° C while stirring for 5 hours to produce a prepolymer with an isocyanate content of 2.2%, and then triethylamine was added to neutralize the reaction. 5 parts of ethylene diamine and 1 part of diethylene triamine were dissolved in 587 parts of deionized water. The solution was heated to 40 ° C, and the prepolymer / triethylamine was maintained while maintaining the temperature. The mixed liquid was dropped into the solution, and an aqueous polyurethane resin emulsion having a solid content concentration of 32% was obtained. -28-(Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 size (2! 0X297 mm) 4 6 4 6 8 0 Central Labor Bureau of Ministry of Economic Affairs, Consumer Cooperatives Printed A7 B7 V. Description of the invention (25) Manufacturing example 15 (comparative) Isophthalic acid / adipic acid (Mole ratio 1/1) mixture as a single acid component will be used as the ethylene glycol component 丨Hexane / hexanediol to obtain 212 parts of polyester polyols with an average molecular weight of 2,000 hydroxyl groups at the ends, 87 parts of propylene oxide adducts with an average molecular weight of 660 double hope A, and 5 parts of trimeramine, and the mixture was heated to Dissolve at 90 ° C. Next, 110 parts of 4,4-dicyclohexylmethanine diisocyanate and 160 parts of N-fluorenyl-2- ° ratio were added to the solution. The solution 'side was heated to a maximum of 12 (TC-side and after 5 hours). Stir treatment to produce a prepolymer with an isocyanate content of 1.7%, and then add triethylamine to it for neutralization reaction treatment. In addition, 6 parts of ethylenediamine is dissolved in 720 parts of deionized water. The solution was warmed to 40 ° C, and while maintaining the temperature, the above-mentioned neutralized prepolymer / triethylamine solution was dropped into the falling liquid, and the aforementioned neutralized prepolymer / trimethylamine mixed solution was dropped. Not classified in water: no resin was produced. Production Example 16 (comparative) An isophthalic acid / adipic acid (letter ratio 1/1) mixture as a dibasic acid component and a glycol component were used 1,6-hexanediamine to obtain 100 parts of a polyester polyol with a hydroxyl average molecular weight of 2000 at the end, 50 parts of a propylene oxide adduct of bisphenol A with an average molecular weight of 660, and 2,2- (hydroxymethyl ) 15 parts of propionic acid, and 5 parts of melamine were mixed and dissolved by heating to 90 ° C. Next, 37 parts of isophorone diisocyanate was added. And 75 parts of N-fluorenyl-2-pyrrolidone in this solution. One side was heated to a maximum of 120 ° C and the surface was stirred for 5 hours to prepare a prepolymer with an isocyanate content of 0 ° /. 14 copies of base amines are used for neutralization reaction treatment. The size of this paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) -1 · " (Please read the precautions on the back before filling in this page )

464680 A7 B7 V. Description of the Invention (2δ). Manufacturing Example Π (Comparison) Please read the precautions of Λ before writing this page. Isophthalic acid / adipic acid (Molar ratio 1/1) will be used as the dibasic acid. ) Mixture using 1,6-hexanediol as a diol component to obtain 229 parts of a polyester polyol having a molecular weight of 1500 at the terminal, 16 parts of 2,2-bis (hydroxymethyl) propionic acid, and melamine 4 parts are mixed and heated to 90 ° to dissolve 11 Next, 120 parts of isophorone diisocyanate and 110 parts of N-methyl-2-pyrrolidone. Ketone are added to this solution, and heat is added to the highest side. 120 ° C surface and stirred for 5 hours to produce a prepolymer with an isocyanate content of 3.8%, and then added 13 parts of triylamine to it for neutralization reaction treatment. In addition, 9 parts of ethylenediamine and 12 parts of diethylenetriamine were dissolved in 693 parts of deionized water. The solution was further heated to 401 ° C while maintaining the temperature. The above neutralized prepolymer / triethylamine mixed solution was dropped into the solution, so that an aqueous polyurethane resin having a solid content concentration of 32% was emulsified. liquid. Examples 1 to 19 and Comparative Examples 1 to 5 1. Pretreatment (1-1) Co-test material The Ministry of Economic Affairs, Central Standards and Quarantine Bureau, Off-line Consumer Cooperative, printed the following materials, which are commercially available metal materials used as test materials ( ^) Galvanized zinc steel sheet on both sides. (EG): sheet thickness = 0.8mm (visual volume = 20/20 (g / m2)) (mouth) aluminum sheet (Al): JIS5052 material, sheet thickness = l_0mm (/,) cold Steel plate (SPCC): SPCC material, plate thickness = 0.8mm (1-2) Degreasing treatment for degreasing to supply materials, using micro-detergent-4336 (registered trademark / Yuebenli 7 彳 xi Co., Ltd.) ). (Concentration = 20g / l, temperature -30- This paper wave scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 46468 0 A7 B7 V. Description of the invention (27) Degree = 60 ° C '2 minutes spray) . Immediately after the degreasing treatment, the test materials were washed with water to provide the underlying chromate treatment or the underlying zinc phosphate treatment. (1-3-1) Under-layer chromate treatment For the formation of the chromate film of the EG material mentioned above, GIN CHOROME357 (registered trademark: Yoshimoto 'X-Li 歹 θ eve Co., Ltd.) or When the film of the aluminum plate was formed, a spray treatment (bath temperature = 50 ° C, time = 5 seconds) of ALCHOROME 712 (registered trademark: Yoshihisa Kiriichi 7th Co., Ltd.) was applied, and the formed film was formed. After the bottom film is washed with water, it is dried for 10 seconds at an ambient temperature of 220 ° C (to reach the steel plate temperature = 100 ° C). The amount of chromate was 10 mg / m2 ° (1-3-2). The underlying zinc phosphate treatment formed the zinc phosphate film. The test material was applied with .L 3020 (

V Registered trademark: immersion treatment (45 ° C, 2 minutes immersion) of 〆Ili 歹 4 p; manufactured by y〆 Co., Ltd., after washing with water and air-drying. The film weight was 2.0 g / m2. Printed by the Central Consumer Association of the Ministry of Economic Affairs #Associate Bureau 2. Additives (2-1) Hardeners The hardeners used in Examples 1 to 3 and Comparative Examples 1 to 15 are shown in Table 1. (2-2) The silicon dioxide used in the examples and comparative examples is shown in Table 2 -31-(Please read the precautions on the back before filling this page) This paper uses China as the standard Standard (CNS) A4 grid (210X297 mm) 464600 A7 B7 V. Description of the invention (28) (2-3) Polyolefin waxes used in the polyolefin wax examples and comparative examples are shown in Table 3. [Table 1] Please refer to the precautions of Sr for the hardener used in the examples and comparative examples. F This page &quot; fr Symbol type of functional group a Epoxy sorbitol needle polyglycidyl bond b oxazole Porphyrinyl oxazoline-styrene copolymer c Alkylsilyl 7-aminopropyltrimethoxysilane d Isocyanatomethylbenzyl diisocyanate oxime block e Azapropanetri-2,4, 6- (1-Ethyleneimine) -1,3,5-triazabenzene [Table 2] Silicon dioxide symbol type used in the examples and comparative examples, Si02 concentration, manufactured by Asahi Chemical Industry Co., Ltd., Bu AT-20N 20wt% manufactured by Gongkou 〇 Co., Ltd., Gongkou 0 # 200 water dispersion 10wt ° / 〇 [Table 3] Examples and comparison Types of polyolefin wax symbols used for remarks 1 Silication value of polyethylene waxes 02 Silication value of polyethylene waxes 40 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 3. Coating of tree film composition (3-1) Resin composition The composition system was prepared into 15 kinds of compositions for the examples (No. 1 to 15) and 13 kinds of resin compositions for the comparative examples (No. 16 to 28). Its composition is shown in Tables 4 and 5. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 〇A7 B7 V. Description of invention (29) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs [Table 4] Examples 1 to 19 Water-based metal surfaces The composition of the treatment composition The hydrazone composition of the water-based metal surface treatment composition * 1 Level No. (wt.%) Kind (wt.%) Kind (wt.%) Kind (wt.%) ) 1 Manufacturing Example 1 (7〇) a (10) 彳 (2〇)-2 Manufacturing Example 2 (60) a (10) Port (30) — 3 Manufacturing Example 3 (70) a (10) 彳 (2 〇) — Real 4 Manufacturing Example 4 (65) a (10) ρ (25)-5 Manufacturing Example 5 (70) a (10) ^ (2〇) — 6 Manufacturing Example 6 (70) a (10) Pair ( 20) .— Example 7 Manufacturing Example 7 (70) a (10) &gt; (2〇). 8 Manufacturing Example 8 (70) a (10) 彳 (20) — Example 9 Manufacturing Example 9 (70) a ( 10) xf (2〇) — 10 manufacturing example 1 (60) b (20) Π (20) — using 11 manufacturing example 1 (60) c (10) 彳 (30) — 12 manufacturing example 1 (70) d ( 10) cr (20) — 13 Manufacturing Example 1 (70) e (5) 4 (25) — 14 Manufacturing Example 2 (60) a (10) Port (30) — 15 Production Example 3 (55) a (10) 4 (20) 1 (15) [Table 5] Comparative Examples 1 to 15 Water-based. Composition of metal surface treatment composition Composition of water-based metal surface treatment composition 1 Quasi-polyurethane resin hardener Silicon dioxide wax Manufacturing Example No. (wt.%) Kind (wt.%) Kind (wt.%) Kind (wt.%) 16 Manufacturing Example 10 (60) a (10) 4 (3〇) — 17 Manufacturing Example 11 (60) a (1〇) P (30) — 18 Manufacturing Example 12 (65) a (10) 4 (25) — 19 Manufacturing Example 13 (60) a (10) Mouth (30)- 20 Manufacturing Example 14 (60) a. (10) 4 (3〇) — 21 Manufacturing Example 15 * 2 — — — 22 Manufacturing Example 16 (60) a (10) 4 (3〇) — 23 Manufacturing Example 17 ( 65) a (10) port (25) — 24 manufacturing example 1 (80) — 4 (2〇) — 25 manufacturing example 1 (30) d (40) port (30) — 26 manufacturing example 1 (40) d ( 5) 彳 (55)-27 Manufacturing Example 1 (90) d (10) — — 28 Manufacturing Example 3 (5 5) d (l〇) ^ (2〇) 2 (15) Table 4, Note to Table 5 * 1 ... The values in parentheses are relative to the full solid weight of the composition. The scale of the sheet is applicable to China National Standard (CNS) A4 (210X297 mm) -33- (Please read the notes on the back first Complete this page) Ministry of Economic Affairs Bureau of Standards HIGHLAND printed A7 B7 five consumer cooperative described (30) ratio (square / square) by weight of the partial amounts of solid ingredients invention. * 2… The polyurethane resin component is not dispersed in water, so the composition cannot be prepared. (3-2) Coating of resin composition Use the metal surface treatment composition shown in Table 4 and Table 5 to roll coater Coating treatment is performed on the surface of the test material, and the drying process is performed at an ambient temperature of 26 ° β (for reaching the test plate temperature = 160 °) for 30 seconds. (Patent amount = 1.0 g / cm2) 4 Coating performance test (4-1) Corrosion resistance The salt spray test was performed for 200 hours according to JS-Z-2731, and the occurrence of white rust was observed. <Evaluation Criteria> ◎ = The area where the rust occurs is less than full 3% of the area β 〇 = The area where rust occurs is 3% and less than 10% of the total area. △ = The area where the rust occurs is more than 10% and less than 30% of the total area. The area recorded by X is greater than the total area. (4-2) Soaked in silicate alkaline degreasing agent yN364S, made by Japan's Horiichi 7 Heart 2 Co., Ltd., concentration = 20 g / bu temperature = 60 ° Cy for 5 minutes After the treatment, the aforementioned evaluation test of the money resistance was performed. <Evaluation Criteria> ◎ = less than 3% of the total area where the rust occurred area. 〇 = 3% of the total area where the rust occurred was less than 10%. %. △ = The recording area accounts for more than 10% of the total area and the performance of this paper is applicable to China National Standards (CNS) A4 (21〇X2 * ^ i ^ y H.: * ---- m · ^ ^^ 1 l. J 0 J ^ i (Please read the notes on the back before writing this page) f _ _ '____. 1 ewmtf 1 ^ 1 ^^^ 1. -1 ^ 1 m »&gt; ^ ^^^ 1 ^^ 1 ---- ·-/ ij ^ 34- 4 6 4 6 8 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (31) Not deteriorated. X = Rust Occurrence area is more than 10% of the entire area and performance is degraded. (4-3) Coating Adhesion A melamine-based paint (T's evening # 1000, manufactured by Kansai vf Co., Ltd.) is applied and baked and dried 25 // ηι film thickness, baked at 125 ° C for 20 minutes, and then immersed in boiling water for 2 hours after 24 hours' and then performed a compensation test after 24 hours. Coating adhesion evaluation method According to JIS-5400, various tests such as square-shaped Exleyon test and impact were performed, and then evaluated based on such comprehensive evaluation. <Evaluation Criteria> ◎ = Coating film peeling area: 0% 〇 = Coating film peeling Area: less than 1% △ = coating film peeling area: less than 10% XF coating film Separation area: 10% or more (4-4) Machinability is a high-speed cylinder using a 115ππηφ diameter blank sheet with a penetration diameter of 50mm &lt; J &gt;, a crimping pressure of 1TON, and a deep drawing speed of 30.m / min Deep drawing test. In addition, during the test, the die-casting oil (made in Japan Working Oil, # 640) should be oiled at 2g / m2 as required. The shrinkage ratio at this time was 2.30. <Evaluation Criteria> ◎ = No oiling, shrinkage ratio = 2.40, shedding by extrusion 0 = No oiling, shrinkage ratio = 2.30, shedding by extrusion △ = Oiling, shrinkage ratio, 2.30 shedding by extrusion Oiled, shrinkage ratio = 2.30 and not extruded. The paper size is appropriate. Use Chinese National Standard (CNS) A4 size (210X297 mm) {Please read the precautions on the back before filling in this page) Order 4 6 4 6 8 A7 B7 V. Description of the invention (32) 5. Test results The test results are shown in Table 6 and Table 7. [Table 6]

The item is for the performance of the coating layer for the surface treatment composition of the ground film. The type of the coating amount The type of the coating amount is resistant to f plus \ Trial test 1 Engineering \ Properties 1 Properties \ Wood (g / m2) (g / tn2) Ϊ 1 EG chromate 0.01 1 1.0 ◎ ◎ ◎ Δ 2 EG chromate 0.01 2 1.0 ◎ ○ ◎ Δ 3 EG chromate 0.01 3 1.0 ◎ ◎ Δ 4 EG chromate 0.01 4 1.0 ◎ ◎ ◎ Δ 5 EG chromium Acid salt 0.01 5 1.0 ◎ ◎ ◎ Δ 6 EG Chromate 0.01 6 1.0 ◎ ◎ Δ 7 EG Chromate 0.01 7 1.0 ◎ ◎ ◎ Δ 8 EG Chromate 0.01 8 1.0 ◎ ◎ ◎ Δ 9 EG Chromate 0.01 9 1.0 ◎ ◎ ◎ △ 10 EG chromate 0.01 10 1.0 ◎ ◎ ◎ Δ 11 EG chromate 0.01 11 1.0 ◎ ◎ ◎ △ Δ 12 EG chromate 0.01 12 1.0 ◎ ◎ ◎ Δ 13 EG chromate 0.01 13 1.0 ◎ ◎ ◎ Δ 14 EG chromate 0.01 14 1.0 ◎ ◎ ◎ Δ 15 EG chromate 0.01. 15 1.0 ◎ ○ ◎ △ 16 EG chromate 0.01 1 0.5 〇 ◎ △ 17 EG chromate 0.01 1 3.0 ◎ ◎ ◎ Δ 18 EG phosphate 2.00 1 1.0 ◎ ◎ ◎ Δ 19 EG chromate 0.01 1 1.0 ◎ ◎ X (Please read the notes on the back before filling this page) The printed paper size of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -36- 464680 V. Invention Explanation (33) Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Sub-consumer Cooperative, A7, B7 [Table 7] Item for the following &lt; Film surface treatment composition coating board performance S Test type Pay amount Type Pay amount Resistance f Add \ Food 1 X \ Material (g / m2) (g / m2) Sex I Sex 1 bii chromate 0.01 16 1.0 XXX Λ 2 chromate 0.01 17 1.0 △ A Λ Λ i bii chromate 0.01 18 1.0 △ Λ Λ Λ 4 KG Chromate 0.01 19 1.0 Δ Λ Λ Λ b ϋϋ Chromate 0.01 20 1.0 XXX Λ 6 iiU Chromate 0.01 21 '1.0 Δ XX Λ Ί EG Chromate 0.01 22 1.0 XXXX 8 KG Chromium Acid salt 0.01 23 1.0 XXX Λ y EG chromate Γ o.oi 24 1.0 〇 η Λ 10 EG chromate 0.01 25 1.0 Δ XX Λ π EG k acid salt 0.01 26 1.0 XXXX 12 JbG chromate 0.01 27 1.0 XXX Λ li JbU Chromate 0.01 28 1.0 〇ο Γ) Λ 14 A1 Chromate 0.01 18 1.0 Δ Λ Λ X ih SPOJ Phosphate 2.00 18 1.0 Δ Δ Δ Δ As shown in Table 6 in Examples 1 to 19, when the zinc-based plated steel sheet, aluminum sheet, and cold-rolled steel sheet are formed with chromate or After the phosphate film is coated with the water-based surface treatment composition of the present invention and dried to form a film, the properties of corrosion resistance, durability, and coating adhesion are good. In addition, the good processability obtained by adding a lubricant has also been confirmed. On the one hand, in the cases of Comparative Examples 1 to 15 which are different from the present invention, the corrosion resistance, alkali resistance, and paint adhesion of the obtained film as shown in Table 7 are not sufficient. [Effects of the Invention] Based on the above description, the water-based surface treatment composition containing the water-based polyurethane resin composition of the present invention is applied to the surface of metal materials such as zinc-plated steel plates. (Cent) (please read ^ side note $ item before 4- write this page)

-37- 464680 A7 B7 V. Description of the invention (34) After coating treatment, it can form a film with good corrosion resistance, alkali resistance, and solvent properties. · (Please read the precautions on the back before filling out this page)-Ordered by the Central Ministry of Economic Affairs, Mabei Cooperative Consumption Seal &quot; This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) -38-

Claims (1)

ί '' φ- • η g | 6. Scope of Patent Application No. 87102042 Patent Application Amendment to Patent Scope Amendment Date: April 1989 1. A water-based polyurethane resin composition, characterized by: (1) a polyol compound with an average molecular weight of 300 or more, dimethylol Alkanoic acid, a compound containing three or more active hydrogens, and an amine ester prepolymer obtained by reacting with an organic polyisocyanate compound and having an isocyanate group at its terminal, are subjected to (Π) a polyamine containing two or more primary amine groups A compound obtained by reacting the aforementioned polyamine compound (Π) with an amount of isocyanate mol of the amine ester prepolymer (I) at an excess ratio to obtain a compound having a primary amine group at the terminal. Polyurethane resin; and an aqueous medium in which the resin is dispersed; and the polyol compound used in the preparation of the aforementioned amine ester prepolymer (I) contains the following components as essential components ① an aliphatic polyhydric alcohol and a polyvalent carboxylic acid A polyester polyol obtained from an acid and having a hydroxyl group at the terminal, and ② a diol compound containing a bisphenol skeleton represented by the following general formula (I); [Chem. 1]-( Read the notes on the back before filling this page), binding --- thread; printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs R: I R4 [but 'Ri and R2 in the above formula (I)' are mutually Each independently represents a hydrogen atom or a lower fluorene group, A is an alkylene group containing 2 to 4 carbon atoms, and m and η are each independently an integer of 1 to 20] -39 464 ^ 80 A8B8C8D8 / 2. Those who claim the scope of the patent and that the compound containing three or more active hydrogens used in the preparation of the aforementioned polyprepolymer (I) is a melamine. 2_ The water-based polyurethane resin composition according to item 1 of the scope of the patent application, wherein the content of the aforementioned poly-S-polyol contained in the polyol compound for the preparation of the amine brewing prepolymer (I) ① is relative to the amount of the aforementioned polyhydric alcohol. 25 to 95% by weight of the total amount of the alcohol compound β 3. For example, the water-based polyurethane resin composition of the first scope of the patent application, wherein the amine ester prepolymer (I) contains a bisphenol skeleton contained in a polyol compound for preparation The content of the glycol ② is 5 to 75% by weight based on the total amount of the polyol compound. 4. The aqueous polyurethane resin composition according to item 1 of the patent application range, wherein the aforementioned organic polyisocyanate for the preparation of the amine-vinegar prepolymer (I) is selected from aliphatic and alicyclic isocyanates. 5. The water-based polyurethane resin composition according to item 1 of the application, wherein the aforementioned polyamine compound (Π) is selected from a dibasic acid diacylhydrazone. 6. —A kind of water-based metal surface treatment composition, which has good corrosion resistance and coating adhesion, and is characterized in that it contains (a) an aqueous polyurethane resin such as any one of items 1 to 5 of the scope of patent application. Composition, (1 &gt;) hardener, and (c) silica; wherein the total solid content of the aforementioned components (a) and (b) is relative to the total of the aforementioned components (a), (b), and (c) 50 to 97% by weight of the solid content; and the content of the solid content of the aforementioned component (c) is 3 to 50% of the total solid content by weight of the aforementioned components (a), (b), and (c). 7. If the water-based metal surface treatment composition of item 6 of the patent application scope, the paper size of this paper applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the front side and then fill out this page ) i- · .: Install --- I ---- Order -------- * Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Online Economics 40- 4646if 〇 A8 B8 C8 D8 The hardener (b) contains an organic compound having an organic compound selected from the group consisting of an epoxy group, an oxyblocphyl group, a oxymethoxanyl group, an isoacid group, and an ethylimine group. Organic compounds with more than one functional group. 8. If the water-based metal surface treatment composition according to item 6 of the scope of the patent application, the additional component (d) is a polyolefin wax having a silicidation value of 0 to 30 or less, compared to the aforementioned components (a) to (d) in total solid form In terms of weight, it contains 1 to 30% by weight. (Please read the precautions on the reverse side before filling out this page) &lt; Packing --- 1 ----- Order ----- A Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy -41-This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm) ί '' φ- • η g | 6. Scope of Patent Application No. 87102042 Patent Application Amendment to Patent Scope Amendment Date: April 1989 1. A water-based polyurethane resin composition, characterized by: (1) a polyol compound with an average molecular weight of 300 or more, dimethylol Alkanoic acid, a compound containing three or more active hydrogens, and an amine ester prepolymer obtained by reacting with an organic polyisocyanate compound and having an isocyanate group at its terminal, are subjected to (Π) a polyamine containing two or more primary amine groups A compound obtained by reacting the aforementioned polyamine compound (Π) with an amount of isocyanate mol of the amine ester prepolymer (I) at an excess ratio to obtain a compound having a primary amine group at the terminal. Polyurethane resin; and an aqueous medium in which the resin is dispersed; and the polyol compound used in the preparation of the aforementioned amine ester prepolymer (I) contains the following components as essential components ① an aliphatic polyhydric alcohol and a polyvalent carboxylic acid A polyester polyol obtained from an acid and having a hydroxyl group at the terminal, and ② a diol compound containing a bisphenol skeleton represented by the following general formula (I); [Chem. 1]-( Read the notes on the back before filling this page), binding --- thread; printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs R: I R4 [but 'Ri and R2 in the above formula (I)' are mutually Each independently represents a hydrogen atom or a lower aryl group, A is an alkylene group containing 2 to 4 carbon atoms, and m and η are each independently an integer of 1 to 20] -39