KR0151418B1 - Water Dispersed Urethane Resin Composition - Google Patents

Abstract

The present invention relates to a water-dispersed urethane resin composition for imparting high chipping resistance to a coating film, and more particularly, to a water-dispersed polyurethane polyester polyol main resin and a water-soluble block polyisocyanate cured resin for imparting hardness and softening. It relates to a resin composition for high chipping.

By using two kinds of water-dispersed polyurethane polyester polyol resins as main resins and water-soluble block polyisocyanate resins as curable resins, the carboxyl groups of the polymer chains were suppressed to the maximum, and during curing, isocyanates produced by dissociation of hydroxyl groups and blocking agents. The urethane bonds were formed by reaction with the groups to improve the acid resistance, chemical resistance, alkali resistance, water resistance, adhesion and chipping resistance of the coating film.

Description

Water Dispersed Urethane Resin Composition

The present invention relates to a water-dispersed urethane resin composition for imparting high chipping resistance to a coating film, and more particularly, to a water-dispersed polyurethane polyester polyol main resin and a water-soluble block polyisocyanate cured resin for imparting hardness and softening. It relates to a resin composition for high chipping.

Recently, due to serious environmental protection and environmental problems, the paint industry has been a lot of research on the powder and water-based coating as a substitute for useful paint. However, when applying water-soluble resins, which have been developed in the past and present, to paints, in terms of physical properties such as hiding power, gloss, water resistance, rust resistance, chemical resistance, adhesion, chipping properties, etc., they may be significantly inferior to the useful paints currently in use. In addition, in terms of workability, spray coating conditions, baking conditions, storage properties of the paint and the appearance of the coating could not meet the needs of consumers.

For example, US Pat. No. 4,673,753 relates to an unsaturated polyester resin having a water-soluble polyalkylene glycol, and has a problem in that yellowing occurs at high temperature curing with an amino resin (150 to 170 ° C.), US Pat. No. 3,870,684, 3,905,929, 4,028,313 and 4,764,553 are water-dispersed polyurethane ureas formed by chain-extending the remaining isocyanate groups of the polyurethane prepolymers with diaphine formed by urethane reaction of the main chain with polyester and urethane reaction of the side chain with polyethylene oxide. It's about Susie. This was found to be inadequate as a high chipping resin because the coating film was softened due to the lack of curing functional groups during the curing reaction with the amino resin. In the case of US Pat. No. 4,608,413, which has solved this problem and attempted to overcome the acid resistance problem of amino resins as a curing agent, a method of curing a water-soluble polyurethane resin containing a hydroxyl group with a water-soluble block polyisocyanate resin was adopted. The resins also greatly reduced the chipping properties of the coating film due to excessive increase in the hardness of the coating film, and also showed that the low temperature storage properties and pH control of the resins were very poor.

Therefore, in the present invention, in order to solve this problem, by using two kinds of water-dispersible polyurethane polyester polyol resin as the main resin, and water-soluble block polyisocyanate resin as the curable resin, the carboxyl group of the polymer chain is suppressed to the maximum, and cured At the time, the urethane bond is formed by reaction of the hydroxyl group and the isocyanate group generated by dissociation of the blocking agent, thereby improving acid resistance, chemical resistance, alkali resistance, water resistance, adhesion and chipping resistance of the coating film.

Therefore, in the present invention, as the main resin, polyethylene glycol containing a polyethylene oxide group for imparting hardness to the coating film is 0.3 to 10.0% in solid content, and dimethyl is 16 to 36 mgKOH / g before neutralization with propionic acid, and the acid value is 60. It is 0.3-10%, acid value 13-24 mgKOH / g, the acid value before -120 mgKOH / g, water-dispersed polyurethane polyester polyol resin of weight average molecular weights 3000-6000, and polyethylene glycol solid content for providing softening property to a coating film. A water-dispersed polyurethane polyester resin having a weight average molecular weight of 30 to 60 mg KOH / g and a weight average molecular weight of 10,000 to 25,000 is mixed at a solid ratio of 2: 1 to 4: 1, and as a curable resin, the acid value before neutralization by dimethylol propionic acid is used. A water-soluble block polyisocyanate having a content of 25-50 mgKOH / g, a content of blocked isocyanate (-NCO) of 4.0-15.0 wt% and a weight average molecular weight of 1,800-5,000 was prepared. The ratio of isocyanate group for a hydroxyl group fingers and cured resin 1: 1.4 to 1: 0.8, a solid content ratio of 50: 50 to 70: consists in that to prepare a water-based resin composition to be 30.

The present invention is described in more detail as follows.

A) Preparation of Water Dispersed Polyurethane Polyol Resin to Give Hardness to Coating Film

The resin has a molecular structure designed to simultaneously include a polyethylene oxide group in the side chain, an acid group and a hydroxyl group in the main chain, the introduction of the intramolecular polyethylene oxide group enhances the solubility of the polymer, and maintains a stable state against the electrolyte The carboxyl groups of dimethylol propionic acid, which form anionic urethane groups in the polymer, can be solubilized by the formation of salts by amine neutralization. The hydroxyl group of the polyester polyol, which acts as a functional group to prevent the gel from forming and also exists at the polymer end, is present as a functional group that forms a strong coating film by reacting with the remaining isocyanate group of the cured resin to form a urethane group upon curing.

The production method of the water-dispersed polyurethane polyester polyol resin is largely made by the following three-step reaction.

A. First Step Reaction: Polyester Polyol Synthesis, a polyester polyol is synthesized using a polyhydric alcohol and a polyvalent acid, as is generally known.

The polyhydric alcohols used in this step are mainly dihydric or trihydric alcohols. The trihydric alcohols used for maximizing the physical properties are 7 to 13% by weight and the total alcohol content is 40 to 60% by weight. . The secondary alcohols include 1,6-hexanediol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexanediol, and the like. And trihydric alcohols include trimethylolpropane, trimethylol ethane, and the like. In the present invention, two or more thereof are mixed and used.

In addition, the polyhydric acid used in this step is mainly divalent and trivalent acid, for example, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, maleic acid, fumaric acid, sebacic acid, cyclohexyl dicarboxylic acid, phthalic acid. And the like, and in the present invention, two or more thereof are mixed and used.

In the reaction, a tin-based catalyst is used, for example dibutyltin oxide.

After this reaction is made to react at the temperature of 180-220 degreeC by bulk polymerization using the said raw material, when an acid value reaches 1 or less, reaction is complete | finished.

The polyester polyols produced by this reaction generally have a hydroxyl value of 140-250 mgKOH / g, and preferably have a hydroxyl value of 160-200 mgKOH / g, which has a hydroxyl value of 4-8% by weight of the polyester polyol resin. Yes. When the hydroxyl value is 140 mgKOH / g or less, it is difficult to control the desired low molecular weight polyol prepolymer in the reaction with the polyhydric isocyanate which is the next step due to the increase in the molecular weight and degree of polyester polyol, and it is difficult to impart the desired hardness to the coating film, and 250 mgKOH When it is more than / g, the decrease of the molecular weight of the polyester polyol may cause gelation due to the rapid increase of the hard segment during the reaction with the polyvalent isocyanate which is the next step, and excessively increasing the hardness on the coating film has a significant adverse effect on the chipping property. Moreover, although the molecular weight of the polyester polyol of this invention uses a thing of 550-1,100, Preferably it is 600-900.

B. Second Step Reaction: Preparation of the polyurethane polyester polyol prepolymer, which is first mixing the polyester polyol prepared in the first step reaction with nonionic and anionic groups.

The nonionic and anionic groups are important reactive ingredients in ensuring the water dispersibility of the waterborne polyurethane polyols. In other words, the role of the nonionic group in the present invention is to enhance the water solubility of the prepolymer, to maintain a stable water dispersion polymer for the electrolytic material, and the amount of the nonionic group as a functional group to prevent the water dispersion from gelling at low temperature is It occupies 0.3-10.0 weight% of a polyurethane prepolymer solid content, Preferably it contains 1-3 weight%. Examples of the nonionic group include polyethylene glycol and polypropylene glycol containing a polyoxyethylene group (-O-CH ₂ -CH _2- ), with a molecular weight of preferably 300 to 500. In addition, the role of the anionic group of the present invention is a functional group that allows the carboxyl acid group to be neutralized by the amine after the prepolymer is formed to form a salt, so that the water is not gelled even at high temperatures, the anionic group. The amount of is preferably contained 3 to 10% by weight of the polyurethane prepolymer solid content, preferably 3 to 5% by weight, for example, dimethylol propionic acid. The three components are homogeneously mixed at 80 to 110 ° C. At this time, 3 to 6% by weight of a co-solvent, N-methyl-2pyrrolidone, is added to maximize the effect of homogeneous mixing in a short time.

If homogeneous mixing is found, the temperature is lowered to 70 ° C. and reacted with the polyvalent isocyanate. In order to suppress the viscosity increase during the reaction with the polyisocyanate and to give a smooth synthesis process, 25 to 45% by weight of the solvent is added to the prepolymer solids prior to the addition of the polyisocyanate. Typical solvents include acetone and methyl ethyl ketone. , Dimethylformamide, glycol ether esters, hydrogenated furan and the like. After adding a solvent, polyhydric isocyanate is added over 30 minutes, maintaining temperature at 60-65 degreeC.

As the polyvalent isocyanate which reacts with the three components to form a polyurethane polyol prepolymer, tetramethylene diisocyanate and hexamethylene diiocyaneti are dodecylmethylene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane -1,4-diisocyanate, isophordi isocyanate, 4,4-diisocyanate cyclohexylmethane, 2,4-diisocyanate toluene, 2,6-isocyanate toluene, 4,4-isocyanate naphthalene, 1,3- Bis (isocyanate methyl) cyclohexane, 1, 4- (isocyanate methyl) cyclohexane, etc. are preferable, The molecular weight is 150-400.

In particular, since the object of the present invention is in the production of a resin composition for imparting high chipping resistance and tough mechanical properties to a coating film, the present invention uses polyvalent aliphatic isocyanates having structural symmetry.

In the present invention, the polyhydric isocyanate is completely added, followed by sustaining for 3 hours or more while maintaining 60 to 65 ° C, and the end point is taken as the point where the isocyanate content becomes zero. The polyurethane polyol prepolymer formed in the reaction will include an acid group and a hydroxyl group at the same time, the acid value of the polyurethane polyol prepolymer is about 16 ~ 36mgKOH / g, the preferred acid value is 20 ~ 25mgKOH / g ,. In addition, the prepolymer of the present invention will have a hydroxyl value of 60 to 12-mgKOH / g, the preferred hydroxyl value is 70 to 100 mgKOH / g. As mentioned above, in the case of the acidic radical of the present invention, the water resistance and chemical property characteristics of the coating film are influenced, and in the case of the hydroxyl value, it acts as a factor influencing the mechanical properties of the coating film. It must not be under or exceeded.

C. Third Step: Water Disperse Polyurethane A polyol resin final reaction is the neutralization and solubilization step.

Since the carboxylic acid remaining in the main chain of the prepolymer prepared in the above step does not participate in the reaction, a salt is formed using an appropriate neutralizing agent to increase the water dispersibility of the present resin. Suitable neutralizing agents used here include amines, with tertiary amines being preferred, for example diethanolamine, diethylethanolamine, dimethylethanolamine, triethylamine, tributylamine, phenyldiethanolamine, methyl Diethanolamine, and the like, which are used alone, preferably an amine having low volatility. The neutralizing agent is used in an amount of about 0.7 to 2.5% by weight based on the present aqueous dispersion, and the degree of neutralization is in the range of about 55 to 80%.

In the reaction, 0.7 to 2.5% by weight of a neutralizing agent is added to the prepolymer maintained at 60 to 65 ° C. over 15 minutes, and then maintained for 10 minutes to terminate the neutralization reaction and to allow solubilization.

The water solubilization is performed by dispersing distilled water with a high speed (1000 to 2000pm) disperser in a state where the solid content of the prepared prepolymer is 45 to 50% by weight, and then dispersing for 30 to 60 minutes, thereby maintaining stable moisture. The body is formed. However, in the case of this aqueous dispersion, since a certain amount of solvent is contained, the pressure is reduced over 60 minutes at 10 to 50 cmHg while maintaining a stirring speed of 70 ° C. and 300 rpm. If the solvent is removed through this process, the final stable water dispersion can be obtained.

The water-dispersed polyurethane polyol resin prepared by the above method has a number average molecular weight of 1,000 to 3,000, a weight average molecular weight of 3,000 to 6,000, a final acid value of 3 to 16 mgKOH / g, a hydroxyl value of 60 to 120 mgKOH / g, 45 ~ 50% resin solids, pH 6.5 ~ 7.5, particle size 70 ~ 110 nanometers, surface tension 50 ~ 60dyne / cm, viscosity is bubble viscometer, it corresponds to D ~ G, and water dispersion with stability over 1 year at room temperature to be.

B) Preparation of Water Dispersed Polyurethane Polyol Resin That Gives Softness to Coating Film

The present invention uses a water-dispersed polyurethane polyester polyol resin for the purpose of preventing chipping defects due to excessive hardness enhancement of the coating film by imparting a certain amount of softening property to the coating film, this resin also has a polyethylene oxide group, Carboxylic acid groups were localized to form salts by neutralizing agents, and the molecular structure was designed so that hydroxyl groups are located at both ends of the main chain.

The reaction process of preparing the water-dispersed polyurethane polyester polyol resin is also subjected to the following three-step reaction as in the resin for imparting hardness. The raw material and the reaction process are also the same as described above.

A. First Step Reaction: Synthesis of polyester polyol, the polyester polyol prepared here has a hydroxyl value of 80-130 mgKOH / g, preferably a hydroxyl value of 90-110 mgKOH / g, molecular weight The 1,300-2,000 thing is used, Preferably, the thing of 1,600-1,700 is good.

B. Second Step Reaction: Synthesis of polyurethane polyol prepolymer, wherein the prepared prepolymer contains 0.2 to 7% by weight of nonionic groups as solids, preferably 0.8 to 2.4% by weight. In addition, the prepolymer contains 1 to 8% by weight of anionic groups in solid content, preferably 0.8 to 2.4% by weight. In addition, the present prepolymer has an acid value of 13 to 24 mgKOH / g, preferably an acid value of 17 to 20 mgKOH / g, a hydroxyl value of 30 to 60 mgKOH / g, and a preferable hydroxyl value of 40 to 50 mgKOH. / g is good

C. Third Step Reaction: The neutralization and solubilization step, wherein the amount of neutralizing agent used is about 0.7 to 2.3% by weight, and the degree of neutralization is about 75 to 95%.

The final water-dispersed polyurethane polyol thus formed has a number average molecular weight of 2000 to 4000, a weight average molecular weight of 10,000 to 25,000, a final acid value of 1 to 6 mgKOH / g, and a hydroxyl value of 30 to 60 mgKOH / g, 35 to 45% resin solids, pH of 7.0-8.0, particle size of 60-80 nanometers, surface tension of 55-65 dyne / cm, viscosity of M-Q with bubble viscosity and stability at room temperature for over 1 year To form an aqueous dispersion.

The two water-dispersed polyurethane polyols prepared by the method of the present invention are preferably combined in a ratio of 2: 1 to 4: 1 by solids ratio when the paint is applied, and when the ratio of the water-disperse resins is 2: 1 or less, Due to softening, the chemical resistance and mechanical properties are very poor, and if it is 4: 1 or more, the hardness of the coating film has a serious adverse effect on the chipping property and the adhesion to the top and top coats when the total system is applied.

C) Preparation of Water-Soluble Blocked Polyisocyanate Resin

Water-soluble block polyisocyanate resins are used to cause a curing reaction at a predetermined temperature with the water-dispersed polyurethane polyol resins prepared by the methods a) and b), which are localized by neutralizing agents by localizing carboxylic acid groups in the main chain. Formation was made to allow water solubility, and isocyanate groups were positioned at both ends of the main chain to block them with a blocking agent, thereby designing a stable molecular structure at room temperature.

The method for producing a water-soluble blocked polyisocyanate resin which is a cured resin of the present invention will be described in more detail as follows.

A. First Step Reaction: As in the first step reaction of the water-dispersed polyurethane polyester polyol resin, as the preparation step of the polyester polyol, the raw materials used and the reaction conditions are also the same as described above.

That is, the polyester polyol prepared in the first step reaction has a hydroxyl value of 100 to 180 mgKOH / g, preferably a hydroxyl value of 120 to 140 mgKOH / g, and has a molecular weight of 400 to 1200, preferably 700-900 is good.

B. Second stage reaction: forming a blocked polyisocyanate prepolymer, in which first the polyester polyol prepared in the first stage reaction and anionic groups, which are important reaction components in ensuring the water dispersibility of the prepolymer , And mix polyhydric alcohol.

At this time, the amount of the anionic group to be used is 6 to 12% by weight of the amount of the prepolymer as a solid, preferably 8 to 10% by weight, a typical example of this group is also dimethyl propionic acid.

The polyhydric alcohol is as mentioned above.

In order to homogeneously mix the three components at 80 to 110 ° C., N-methyl-2-piclidone, which is 2 to 5% by weight of cosolvent, is added. If homogeneous mixing is found, the polyhydric isocyanate (mentioned above) is added over 60 minutes while maintaining the temperature at 80 ° C. and then the reaction is continued for at least 4 hours. And when the residual isocyanate content reaches 4 to 16% by weight, a blocking agent is added dropwise, the reaction is an exothermic reaction, the temperature is raised to 110 ~ 120 ℃.

Blocking agents used in the reaction include caprolactam, acetone oxime, butan oxime, cyclohexynonone oxime, malonic acid-diethyl ester, acetoacetic ester, acetylacetone, etc. The present invention provides a method for blocking with oximes. Was adopted.

Thereafter, the reaction is terminated at 120 ° C. for at least 1 hour and the remaining isocyanate content is zero. Upon completion of all reactions of the prepolymer preparation, the blocked polyisocyanate prepolymers have 4-16% by weight of isocyanates blocked by oximes and contain 6-12% by weight of chlorinated groups and have a 25-50 mgKOH / g acid value. A preferable acid value is 30-40 mgKOH / g.

C. Third Step Reaction: The final step of the water soluble blocked polyisocyanate resin of the present invention is the neutralization and solubilization step.

In the present reaction, when the prepolymer production reaction is terminated, 3-7 wt% of a neutralizer corresponding to 85 to 100% of neutralization is added to the prepolymer over 10 minutes while maintaining the temperature at 90 ° C ondol. The neutralization reaction is then terminated and solubilization is possible. When the neutralization is completed, the water is maintained at 90 ℃ over 1 hour and the reaction is maintained for 1 hour to obtain a final water-soluble block polyisocyanate resin stable for 6 months or more at room temperature.

The final water-soluble blocked polyisocyanate resin formed as described above has a final acid value of 1 to 9 mgKOH / g, a weight average molecular weight of 1800 to 5000, a resin solid content of 35 to 45%, a pH of 7.5 to 9.5, and Z in a bubble viscosity meter. Has

D) Water Dispersed Urethane Resin Composition of the Present Invention

In the present invention, when the curable resin according to the above method c) and the water-dispersible polyurethane polyester polyol resin according to the methods a) and b) are applied to the paint, the blocking agent blocking the isocyanate of the cured resin at 150 to 170 ° C is volatilized. In addition, the molecular structure of the resins was designed such that the remaining isocyanate groups reacted with the hydroxyl groups of the water-dispersed polyurethane polyol resin to form new urethane groups, thereby completing the coating film formation.

Therefore, when applying the paint of the water-dispersed polyurethane polyester polyol resin and the water-soluble blocked polyisocyanate resin obtained by the above reaction process, the ratio of the hydroxyl group of the main resin and the isocyanate group of the cured resin is 1: 1.4 to 1: 0.8, that is, the resin. These solid secretions are combined in a range of 50:50 to 70:30 to enable formation of a highly chipping coating film for automobiles.

In the following preparation will be described in more detail the manufacturing process and components of the polyester polyol resin composition, the water-dispersed polyurethane pulley polyester polyol resin composition and the water-soluble block polyisocyanate resin composition which forms the basis of the main resin and the cured resin, It is not intended to limit the scope of the invention.

Production Examples 1 to 5 are methods for producing polyester polyols of main resins and cured resins, and Production Examples 6 to 8 are methods for producing water-dispersed polyurethane polyester polyols, which are main resins for the purpose of imparting hardness to coating films. 9 to 10 are methods for producing a water-dispersed polyurethane polyester polyol, which is a main resin for softening of the coating film, and Examples 11 to 12 are methods for producing a water-soluble blocked polyisocyanate, which are cured resins, and Examples 1 to 6, It relates to the formulation (Table 1) of the clear (CLEAR) coating film produced by varying the composition ratio using the main resin and the cured resin produced in the production example.

In addition, in order to simply evaluate the effects of the resin compositions of the present invention to prepare a comparative example (Table 2) with different components and ratios, after forming a clear (CLEAR) coating film and evaluated several conditions as shown in Table 3 The results were obtained, and in particular, it was confirmed that the present invention produced through the examples exhibited excellent effects in terms of all items.

[Production Example 1]

996.8 parts by weight of isophthalic acid, 710.4 parts by weight of adipic acid, 1374.8 parts by weight of neopentyl glycol, 241.8 parts by weight of trimethyl propane and 3.4 weights of tin-based catalyst as a catalyst in a reactor equipped with a stirrer, a thermometer, a nitrogen injection pipe, a separator and a cooler Buy wealth. The temperature is gradually raised while stirring at a rate of 200 rpm under nitrogen injection, and the temperature is raised to 200 ° C. and maintained. This reaction is a condensation reaction, the water is drawn out through the separator, and the reaction is controlled so that the refractive index of the dehydrated water is 1.3340 or less. When the acid value reaches 3 mgKOH / g during the reaction, the speed of the stirrer is increased to 350 rpm and the nitrogen is supplied with an excess of 75 mm Hg for 10 minutes. Thereafter, the reaction is terminated when the acid value falls below 1 mgKOH / g. The polyester polyol prepared by this reaction had a hydroxyl value of 193 mgKOH / g, a hydroxyl group of 5.84 wt%, and a molecular weight of 709. And the content of the trihydric alcohol included at this time is 7.3% by weight.

[Production Example 2]

498.4 parts by weight of isophthalic acid, 359.5 parts by weight of adipic acid, 593.7 parts by weight of neopentyl glycol, 161.0 parts by weight of trimethylolpropane, and 1.6 parts by weight of Passcat are used as a catalyst in a reactor installed as in Preparation Example 1. After the reaction process is the same as in Preparation Example 1. After the reaction was completed, the polyester polyol prepared by the present reaction had a hydroxyl value of 162 mgKOH / g, a hydroxyl group of 4.9% by weight, and a molecular weight of 980. And the content of the trihydric alcohol included at this time is 10.0% by weight.

[Manufacture example 3]

498.4 parts by weight of isophthalic acid, 350.7 parts by weight of adipic acid, 593.7 parts by weight of neopentyl glycol, 201.3 parts by weight of trimethylolpropane, and 1.7 parts by weight of Passcat as a catalyst are used in a reactor installed as in Preparation Example 1. After the reaction process is the same as in Preparation Example 1. When the reaction is completed, the polyester polyol prepared by the present reaction has a hydroxyl value of 174 mgKOH / g, 5.3 wt% of hydroxyl group, and a molecular weight of 919. And the content of the trihydric alcohol used at this time is 12.3% by weight.

[Production Example 4]

830.7 parts by weight of isophthalic acid, 241.0 parts by weight of adipic acid, 376.0 parts by weight of phthalic anhydride, 797.5 parts by weight of 1,6-hexanediol, 156.5 parts by weight of trimethylolpropane and 2.0 parts by weight of Passcat as a catalyst in a reactor installed as in Preparation Example 1. use. After the reaction process is the same as in Preparation Example 1. When the reaction is complete, the polyester polyol prepared by the present reaction has a hydroxyl value of 99 mgKOH / g, 3.0 wt% of hydroxyl group, and a molecular weight of 1787. And the content of the trihydric alcohol used at this time is 7.6% by weight.

Production Example 5

642.9 parts by weight of adipic acid and 709.1 parts by weight of 1,6-hexanediol were used in a reactor installed as in Preparation Example 1, 1.4 parts by weight of Passcat. After the reaction process is the same as in Preparation Example 1. When the reaction is complete, the polyester polyol prepared by the present reaction has a hydroxyl value of 134 mgKOH / g, 4.1 wt% of hydroxyl group, and a molecular weight of 840.

[Manufacture example 6]

In a newly installed reactor (stirrer, thermometer, nitrogen injection tube, cooler), 1465.0 parts by weight of polyester polyol 1, 20.0 parts by weight of polyethylene glycol (molecular weight 400), 94.0 parts by weight of dimethylolpropionic acid, N-methyl-2 -163.5 parts by weight of pyrrolidone and 1.8 parts by weight of dibutyltin dilaurate were injected with nitrogen under a nitrogen injection, and the temperature was raised to 100 ° C. such that the components were homogeneously mixed. When the components are completely mixed and transparent, the temperature is lowered to 70 ° C. and 644.0 parts by weight of acetone is added, and 280.0 parts by weight of hexamethylene diisocyanate is added while maintaining 65 ° C. The reaction is then continued for at least 3 hours under the same conditions. The end point of the reaction is set at the point where the isocyanate content becomes zero. Upon completion of the reaction, a prepolymer having a hydroxyl value of 68.0 mgKOH / g and an acid value of 21.2 mgKOH / g is prepared. In order to make the prepolymer into an aqueous dispersion, 44.0 parts by weight of ethanolamine in dimethyl was added to the prepolymer maintained at 65 ° C. over 15 minutes, and the reaction was carried out for 15 minutes. Thereafter, the neutralized prepolymer was added to the vessel containing 1889.0 parts by weight of 40 ° C. over 10 minutes, and dispersed at high speed (1000 to 2000 rpm) for 30 to 60 minutes to form a stable aqueous dispersion. However, since the hydrophobic dispersion contains a certain amount of acetone, if the pressure is reduced at 10 to 50 cmHg for 60 minutes while maintaining the temperature and the stirring speed of 300 rpm, the final product has stability of 1 year or more at room temperature. A water dispersion polyurethane polyester polyol resin of is obtained. The thus obtained water-dispersed polyurethane polyester polyol resin had a solid content of 47.0 wt%, a final acid value of 6.2 mgKOH / g, a hydroxyl value of 68.0 mgKOH / g, a pH of 7.1, a viscosity of G, a particle size of 85 nanometers, Stable water dispersion resin with a surface tension of 51 dyne / cm.

[Manufacture example 7]

1414.0 parts of polyester polyol of Preparation Example 2, 30.0 parts by weight of polyethylene glycol, 92.0 parts by weight of dimethylol propionic acid, 146.3 parts by weight of N-methyl-2-pyrrolidone and a catalyst in a newly installed reactor with dibutyltin dilaurate 1.7 weight part was injected under nitrogen injection and stirred in the same manner as in Preparation Example 6. When the reactants are homogeneously mixed, the mixture is cooled and charged with 601.6 parts by weight of acetone, and then 183.1 parts by weight of hexamethyl diisocyanate, and the reaction process is the same as in Preparation Example 6. Upon completion of the reaction, a prepolymer having a hydroxyl value of 70.3 mgKOH / g and an acid value of 22.4 mgKOH / g is formed. In order to make the present prepolymer into an aqueous dispersion, 48.9 parts by weight of dimethylethanolamine was added to the present prepolymer maintained at 65 ° C. over 15 minutes, and the reaction was carried out for 15 minutes. Thereafter, the neutralized prepolymer was added to a vessel containing 1743.2 parts by weight of distilled water at 40 ° C., and the procedure was the same as in Preparation Example 6. The water-dispersed polyurethane polyester polyol thus obtained had a solid content of 47.0 wt%, a final acid value of 4.4.mgKOH / g, a hydroxyl value of 70.3mgKOH / g, a pH of 7.3, a viscosity of bubble V, a particle size of 99 nanometers, and surface tension. It is a stable water dispersion resin of 53 dyne / cm.

[Manufacture example 8]

1448.0 parts by weight of polyester polyol of Preparation Example 3, 35.0 parts by weight of polyethylene glycol, 94.0 parts by weight of dimethylol propionic acid, 151.2 parts by weight of N-methyl-2-pyrrolidone and a catalyst in a newly installed reactor with dibutyltin dilaurate 1.8 parts by weight was added under nitrogen injection, followed by stirring in the same manner as in Preparation Example 6. When the reactants are homogeneously mixed, the mixture is cooled to 70 ° C., 662.0 parts by weight of acetone, and 200.0 parts by weight of hexamethyl diisocyanate are added over 30 minutes. Thereafter, the reaction process is the same as in Preparation Example 6. Upon completion of this reaction, a prepolymer having a hydroxyl value of 71.4 mgKOH / g and an acid value of 22.1 mgKOH / g is formed. In order to make the present prepolymer into an aqueous dispersion, 50.0 parts by weight of dimethylethanolamine was added to the present prepolymer over 15 minutes, and the reaction was carried out for 15 minutes. Thereafter, the neutralized prepolymer was added to a vessel containing 1802.7 parts by weight of distilled water at 40 ° C., and the procedure was the same as in Preparation Example 6. The water-dispersed polyurethane polyester polyol thus obtained had a solid content of 47.0 wt%, a final acid value of 4.4.mgKOH / g, a hydroxyl value of 71.4mgKOH / g, a pH of 7.3, a viscosity of F, a particle size of 108 nanometers, and a surface. It is a stable water-dispersible resin with a tension of 54 dyne / cm.

[Manufacture example 9]

600.0 parts by weight of polyester polyol of Preparation Example 4, 20.0 parts by weight of polyethylene glycol, 24.0 parts by weight of dimethylol propionic acid, 82.9 parts by weight of N-methyl-2-pyrrolidone and 0.7 weight of dibutyl tin dilaurate in the newly installed reactor The part is charged under nitrogen injection and stirred in the same manner as in Production Example 6. When the reactants are homogeneously mixed, 278.4 parts by weight of acetone is added, 52.0 parts by weight of hexamethyl diisocyanate is added, and the reaction process is the same as in Preparation Example 6. Upon completion of this reaction, a prepolymer having a hydroxyl value of 31.2 mgKOH / g and an acid value of 14.4 mgKOH / g is formed. In order to make the present prepolymer into an aqueous dispersion, 12.7 parts by weight of dimethylethanolamine was added to the present prepolymer over 15 minutes, and the reaction was carried out for 15 minutes. Thereafter, the neutralized prepolymer was added to a vessel containing 865.5 parts by weight of distilled water at 40 ° C., and the procedure was the same as in Preparation Example 6. The water-dispersed polyester polyol thus obtained had a solids content of 42.0 wt%, a final acid value of 2.9 mgKOH / g, a hydroxyl value of 37.2 mgKOH / g, a pH of 7.4, a viscosity of N, a particle size of 70 nanometers, and a surface tension of 61.0 dyne. It is a stable water dispersion resin that is / cm.

[Production Example 10]

640.0 parts by weight of polyester polyol of Preparation Example 4, 30.0 parts by weight of polyethylene glycol, 30.0 parts by weight of dimethylol propionic acid, 89.5 parts by weight of N-methyl-2-pyrrolidone and 0.8 weight of dibutyl tin dilaurate in the newly installed reactor The part was introduced under nitrogen injection and stirred in the same manner as in Preparation Example 6. When the reactants are homogeneously mixed, the mixture is cooled to 70 ° C., 300.8 parts by weight of acetone is added, and 52.0 parts by weight of hexamethyl diisocyanate are added thereto, and the reaction process is the same as in Preparation Example 6. Upon completion of this reaction, a prepolymer having a hydroxyl value of 46.3 mgKOH / g and an acid value of 16.7 mgKOH / g is formed. In order to make the prepolymer into an aqueous dispersion, 18.0 parts by weight of dimethylethanolamine was added to the prepolymer over 15 minutes and maintained for 15 minutes. Thereafter, the neutralized prepolymer was added to 931.0 parts by weight of distilled water at 40 ° C., and the procedure was the same as in Preparation Example 6. The water-dispersed polyurethane polyester polyol thus obtained had a solid content of 42.0 wt%, a final acid value of 1.7 mgKOH / g, a hydroxyl value of 46.3 mgKOH / g, a pH of 7.7, and a viscosity of 0 with a bubble viscosity meter, a particle size of 65 nanometers, and a surface tension of 63.0. It is a stable water-dispersible resin that is dyne / cm.

[Production Example 11]

670.0 parts by weight of the polyester polyol of Preparation Example 5, 67.0 parts by weight of trimethylolpropane, 201.0 parts by weight of dimethylol propionic acid, and 135.0 parts by weight of N-methyl-2-pyrrolidone were introduced into a newly installed reactor under nitrogen injection. Stirring in the same manner as in Preparation Example 6. When the reactants are homogeneously mixed, 840.7 parts by weight of hexamethylene diisocyanate is added over 1 hour while maintaining the reaction temperature at 70 ° C. to 80 ° C., and the reaction is maintained at 80 ° C. for at least 3 hours. Then, when the isocyanate content reaches 5.4% by weight, when 303.7 parts by weight of butanone oxime is added dropwise, an exothermic phenomenon occurs in which the temperature rises to 110 to 120 ° C. After all the exotherm has been removed, the reaction is continued for at least 2 hours while maintaining the temperature at 120 ° C., and the end point of the reaction is taken at the point where the isocyanate content becomes zero. Upon completion of this reaction, a prepolymer having an acid value of 40.4 mgKOH / g is formed. In order to neutralize this prepolymer, temperature was lowered below 90 degreeC, 131.0 weight part of dimethylethanolamine was put over 30 minutes, and it hold | maintained for 30 minutes. Thereafter, 2494.0 parts by weight of distilled water heated to 90 ° C. was added to the prepolymer maintained at 300 rpm over 1 hour, and maintained for 1 hour or more. The stable water-soluble blocked polyisocyanate resin had a solid content of 40.0% by weight and a final acid value of 1.0 mgKOH / g. , pH 8.7, Viscosity is a stable water-soluble resin of Z and a particle size of 40 nanometer or less in a bubble viscometer.

[Manufacture example 12]

840.0 parts by weight of the polyester polyol of Preparation Example 5, 67.0 parts by weight of trimethylolpropane, 201.0 parts by weight of dimethylolpropionic acid, and 350.0 parts by weight of N-methyl-2 pyrrolidone were added to a newly installed reactor under nitrogen injection. The reaction is carried out in the same manner as in Preparation Example 6. When the reactants are homogeneously mixed, 1110.0 parts by weight of isophorone diisocyanate is added and the reaction is carried out in the same manner as in Production Example 11. Then, when the isocyanate content reaches 6.0% by weight, 304.5 parts by weight of butanone oxime is added dropwise, and the reaction proceeds in the same manner as in Preparation Example 11, and when the reaction is terminated, a prepolymer having an acid value of 33.4 mgKOH / g is formed. Then 3302.3 parts by weight of distilled water is added to the prepolymer to obtain a stable water-soluble block polyisocyanate resin. The water-soluble blocked polyisocyanate resin thus obtained is a stable water-soluble resin having a solid content of 40.0% by weight, a final acid value of 1 mgKOH / g, a pH of 8.9, a viscosity of Z in a bubble viscosity meter, and a particle size of 40 nanometers or less.

Preparation Example 6,7,8 which is the water dispersion polyurethane polyol resin for hardness improvement prepared above, and Preparation Example 9,10 which is the water dispersion polyurethane polyol resin for softening provision are combined by 3: 1 solid ratio, When the main resins and Preparation Examples 11 and 12, which are water-soluble block polyisocyanate resins which are cured resins, are combined at a solid ratio of 50:50 to 60:40, that is, the hydroxyl group and the water-soluble block polyisocyanate resin of the water-dispersed polyurethane polyester polyol resins When the pigments and additives are added to the resin compositions of the present invention in which the equivalent ratio of isocyanate groups is 1: 1 to 1: 0.8, the optimum dispersion state of the paint is maintained, and during curing, the coating film is water resistant and chemically resistant. Properties and Mechanical Properties There are aqueous resin compositions that can improve patented chipping properties.

1) Use: 9 × 20cm electrodeposition specimen

2) Curing condition: 150 ℃ × 30 minutes

3) Coating thickness: Coating thickness after curing (um)

4) Acid resistance: 10% HSO, 50 ℃ × 3 hours, specimen 1/2 deposition

5) Basic resistance: 10% NaOH, 50 ℃ × 3 hours, 1/2 deposition of specimen

6) Water resistance: 40 hours × 240 hours after immersion, 1 hour left

7) Gasoline resistance: 1/2 of specimen, 1 hour deposition

8) chipping resistance: cold resistance chipping resistance, -40 ℃ × 3 hours

9) ⊙: Very good / ◎: Good / ▲: Normal / △: Poor

Claims (11)

Polyethylene glycol containing polyethylene oxide as the main resin is 0.3 to 10% in solid content, 16 to 36 mgKOH / g acid value before neutralization by dimethylol propionic acid, 60 to 120 mgKOH / g hydroxyl value, weight average molecular weight 3000 to 6000 Dispersed polyurethane polyester polyol resin and polyethylene glycol in a solid content of 0.3 to 10%, acid value before neutralization by dimethylol propionic acid, 13 to 24 mgKOH / g, hydroxyl value 30 to 60 mgKOH / g, weight average molecular weight 10,000 to 25,000 The dispersed polyurethane polyester polyol resin was mixed at a solid ratio of 2: 1 to 4: 1, and as a curable resin, the acid value was 25-50 mgKOH / g before neutralization by dimethylol propionic acid, and the content of blocked isocyanate (-NCO) The water-soluble block polyisocyanate having 4.0-15.5 weight% in solid content and the weight average molecular weights 1,800-5,000 is 1: 1.4-in ratio of the hydroxyl of a main resin and the isocyanate group of hardening resin. It mixes so that it may be 1: 0.8, The aqueous urethane resin composition characterized by the above-mentioned. The water-dispersed polyurethane polyester polyol resins according to claim 1, wherein the water-based polyurethane polyester polyol resins are prepared by reacting a polyhydric alcohol with a polyhydric acid at 180 to 220 ° C. to synthesize a polyester polyol, and then adding a co-solvent to prepare a non-ion at 80 to 110 ° C. And homogeneously mixed with the anionic group, a solvent and a polyvalent isocyanate were added at 70 ° C. to form a polyurethane polyester polyol prepolymer, and then dispersed in water with a neutralizing agent, followed by stirring at 70 ° C. and 300 rpm. Aqueous urethane resin composition obtained by removing a solvent by pressure-reducing at 50 cmHg for 60 minutes. 3. The polyester polyol resins according to claim 2, wherein the polyester polyol resins, which are the products of the first stage reaction of the water-dispersed polyurethane polyester polyol resins, have a trihydric alcohol content of 7 to 13% by weight and a total alcohol content in the polyester polyol resin solids. 40-60 weight%, and final hydroxyl group (-OH) content is 4-8 weight%, The aqueous urethane resin composition characterized by the above-mentioned. The nonionic group bonded to the side chains of the water-dispersed polyurethane polyester polyol resins includes polyethylene glycol having a molecular weight of 300 to 500 and polypropylene glycol, and is contained at 0.2 to 10.0% by weight of the present prepolymer solids. Aqueous urethane resin composition characterized by the above-mentioned. The water-based urethane resin according to claim 2, wherein the anionic group bonded to the main chain of the water-dispersed polyurethane polyester polyol resins is dimethylol propionic acid, and is used at 1 to 10% by weight of the present prepolymer solids. Composition. The aqueous urethane resin composition according to claim 2, wherein the neutralizing agent is an amine, and is used at 0.7 to 2.5% by weight based on the present aqueous dispersion. The method of claim 1, wherein the water-soluble blocked polyisocyanate resin reacts a polyhydric alcohol with a polyhydric acid at 180 to 220 ° C to synthesize a polyester polyol, and then adds an anionic group and a polyhydric alcohol coagent at 80 to 110 ° C. When the mixture is homogeneous and polyisocyanate is added, the residual isocyanate content becomes 4 to 16% by weight of the polyurethane prepolymer solid content, blocking with a blocking agent, neutralized by adding a neutralizing agent, and then water is added for 1 hour, 1 Aqueous urethane resin composition, which is prepared by maintaining the reaction for a time. 8. The aqueous urethane resin composition according to claim 7, wherein the anionic group is dimethylol as propionic acid, and 6 to 12% by weight of the present prepolymer solid content is used. 8. The aqueous urethane resin composition according to claim 7, wherein the neutralizing agent is an amine, and 3 to 7% by weight of the aqueous dispersion is used. The aqueous urethane resin composition according to claim 7, wherein the blocking agent is caprolactam, acetone oxime, butanone oxime, cyclohexynonone oxime, malonic acid-diethyl ester, acetoacetic ester, or acetylacetone. . A method of mixing the aqueous urethane resin composition according to claim 1 together with additives and pigments to use as a coating material for automobiles or automobile parts.