KR100591802B1 - Water-soluble top coat composition for automobile repair - Google Patents

Abstract

The present invention relates to a water-soluble top coat composition for automobile repair, and more particularly, a blending resin of a urethane-modified acrylic polyol water dispersion resin and a polyurethane-urea water dispersion resin for use in water-soluble top coat for automobile repair. It relates to a coating composition. The composition of the present invention is 30 to 50% by weight of the blended resin of the urethane-modified acrylic polyol water-dispersion resin and polyurethane-urea water-dispersion resin, 1 to 30% by weight water-soluble pigment, 0.1 to 1.0% by weight antifoaming agent, thickener 0.1 It consists of -3.0 weight%, a neutralizing agent 0.01-5.0 weight%, and a smoothing agent 0.1-3.0 weight%, 5-10 weight% of hydrophilic organic solvents, and 30-60 weight% of deionized water, The coating composition which concerns on this invention is As well as the paint itself, it has superior physical properties than conventional paint compositions in physical properties after painting.

Description

Water-soluble top coat composition for automobile repair

The present invention relates to a water-soluble top coat composition for automobile repair, and more particularly, a blending resin of a urethane-modified acrylic polyol water dispersion resin and a polyurethane-urea water dispersion resin for use in water-soluble top coat for automobile repair. It relates to a coating composition.

In general, the painting of the car is made of a multi-layer coating, the process is electrodeposition, intermediate, colored top coat and transparent top coat. On the other hand, automotive repair coating is to coat the middle and top coat again on the existing coating film, in this case, the adhesion between the existing layer and the coating film of the repair coating may have a lot of influence on the mechanical properties. As such, the characteristics of the coating material for coating significantly affect the mechanical properties and physical properties of the coating film. For example, if the spreadability of the paint is not good, not only does the painter's work time take longer to achieve the desired level of concealment of the desired color, but also the maintenance paint to improve the interlayer adhesion, spreadability, and other mechanical properties. The polishing process must be carried out on the existing coating, which likewise leads to an increase in the working time of the operator.

In addition, the automotive repair paint is preferably a thermoplastic resin in a room temperature dry form rather than a thermosetting resin. However, in the manufacture of a thermoplastic resin in a room temperature dry form, if the crosslinking point of the polymer chains are increased in order to improve physical and mechanical properties, there is a risk of becoming a gel in the reaction process, the thermoplastic resin in a room temperature dry form with a high degree of crosslinking Has difficulty in its manufacture.

When thermosetting resin is applied to automotive refinish paints, the crosslinking in the polymer may be blocked with alcohols to be used for colored topcoats. However, since the curing temperature is 120 ℃ or higher, it is not directly applied to automotive refinish coating processes. it's difficult. In addition, in the case of the transparent top coat, there may be a two-component type in which the main component and the curing agent are separated in addition to the one-component paint as described above, but may cause high curing temperature and workability deterioration.

Therefore, the water-soluble paint that can be applied as an automobile repair paint should be able to dry naturally, and have excellent appearance such as gloss, sensibility, spreadability in paints, adaptability to transparent paints, and adhesion, hardness, and impact resistance. Physical properties such as storage stability of paints and stability of color separation.

In addition, the water-soluble paint can be improved by exhibiting properties other than the gloss than conventional oil-soluble paint. Since water is used instead of the organic solvent as the main solvent, the emission of volatile organic solvents can be greatly reduced, which is preferable for environmental preservation problems and a safe working environment for workers who perform painting work. In addition, water-soluble paints are known as excellent paints that can cope with future environmental regulations.

As water-soluble paints for automobile repairs, acrylic water-based resins or urethane water-based resins have been mainly used, or urethane-modified acrylic polyol-bonded water-based resins or polyurethane-urea water-dispersible resins in a more developed state have been used.

Republic of Korea Patent Application No. 95-69630 describes a specific method of manufacturing a polyacrylic water-dispersion resin and the raw material, the conventional acrylic water-dispersible resin is excellent in appearance, water resistance, adhesion and price, However, the chemical resistance and mechanical properties are relatively weak to be used as a repair paint for automobiles.

In addition, the Republic of Korea Patent Application No. 94-37415 describes a specific manufacturing method and raw materials of the urethane dispersion resin, which has excellent mechanical properties compared to acrylic dispersion resin, but impact resistance, water resistance, There was a disadvantage in that the competitiveness in adhesion and price is relatively low.

Therefore, a water-dispersible resin has been developed that complements the advantages of acrylic and urethane bonds and is competitive in terms of price. This resin polymerized the addition reaction of an acrylic bond and the condensation reaction of a urethane reaction from the manufacturing process, and produced the urethane modified acrylic polyol water dispersion resin which hybridizes two resins. The urethane-modified acrylic polyol water-dispersible resin has excellent mechanical properties by grafting acrylic having excellent weather resistance, adhesion to various resins, and compatibility with other binders to urethane having excellent abrasion resistance, elastic strength, solvent resistance, and the like. However, during the urethane reaction, it is possible to form at least one salt with a polyol containing active hydrogen for solubilization, and because the polyol containing active hydrogen is used, the amount of dimethylpropanoic acid is increased to increase the acid value. There is a problem that the impact resistance is lowered due to the hardness phenomenon of the coating film increases with the increase of. In addition, there is a problem that the elastic strength of the urethane is lowered and the reactivity is lowered when the urethane prepolymer is synthesized.

In addition, the polyurethane-urea water-dispersion resin was prepared to solve the disadvantages of the conventional water-dispersion resin, such as water resistance, solvent resistance, chemical resistance, coating hardness is reduced, but the instability and adhesion of the resin, Problems in storage and the like were shown, indicating a limitation as a resin.

In order to overcome the above problems, the present inventors have conducted extensive research. As a result, the urethane-modified acrylic polyol water-dispersible resin having excellent appearance and adhesion to other coating resins, such as gloss and lightness, and physical properties such as wear resistance and solvent resistance By preparing a resin composition obtained by blending a polyurethane-urea water-dispersible resin having physical and chemically stable physical properties, a water-soluble top coat composition for automobile repair was prepared, and the present invention was completed based on this.

Accordingly, it is an object of the present invention to provide a water-soluble top coat composition for automobile repair excellent in gloss, lightness, workability, adhesion, impact, hardness, wear resistance, and stability.

The composition of the present invention for achieving the above object is 30 to 50% by weight of the blending resin of the urethane-modified acrylic polyol water-dispersion resin and polyurethane-urea water-dispersion resin, 1 to 30% by weight of water-soluble pigment, 0.1 to 2 as the antifoaming agent It consists of 1.0 weight%, thickener 0.1-3.0 weight%, neutralizing agent 0.01-5.0 weight%, and leveling agent 0.1-3.0 weight%, 5-10 weight% of hydrophilic organic solvents, and 30-60 weight% of deionized water.

Hereinafter, the present invention will be described in more detail.

As described above, the present invention uses a resin obtained by blending a urethane-modified acrylic polyol water-dispersion resin and a polyurethane-urea water-dispersion resin, and the urethane-modified acrylic polyol water-dispersion resin and polyurethane-urea number used in the present invention. Let us look at each of the manufacturing method of the dispersion resin.

First, the production method of the urethane-modified acrylic polyol water dispersion resin can be divided into four stages;

end. Preparation of Polyester Polyols.

I. Preparation of Polyisocyanate End Polyurethane.

All. Preparation of acrylic water dispersion and urethane modified acrylic polyol.

la. Neutralization and preparation of urethane modified acrylic polyol water dispersion.

More specifically, a) In the synthesis of polyester polyols, dihydric alcohols and divalent acids are used. The dihydric alcohols include hydrogenated bisphenol, 1,6-hexanediol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, ethylene glycol, diethylene glycol, cyclohexane Diol, 1,4-cyclohexanedimethanol, and the like. In the present invention, two or more alcohols are used in combination. In addition, the dihydric acid includes phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, maleic acid, fumaric acid, sebaric acid, cyclohexyldicarboxylic acid, phthalic acid, and the like. use. In addition, when the dihydric alcohol and the divalent acid are reacted, a tin catalyst is used as the catalyst, for example, dibutyl tin oxide. Looking at the process, the dihydric alcohol and divalent acid is polymerized in a molten state, the polymerization temperature is 180 ~ 220 ℃, after the reaction when the acid value of the reactants reaches 1 or less to terminate the reaction to prepare a polyester polyol. The hydroxyl value of the polyester polyol thus prepared is generally 140-250 mgKOH / g. When the hydroxyl value is less than 140mgKOH / g, it is difficult to control the polyol prepolymer of the desired low molecular weight when reacting with the polyvalent isocyanate in the next step reaction by increasing the molecular weight and viscosity of the polyester polyol, and the molecular weight of the polyester polyol molecular weight of more than 250mgKOH / g The reduction may increase the hard segment when reacting with the polyvalent isocyanate in the next step, rather than reducing the flexibility on the coating. In this case, the molecular weight of the prepared polyester polyol is 500 to 3,000, preferably 700 to 2,000, as measured by GPC (Gel Permeation Chromatography).

B) preparing an isocyanate-terminated polyurethane, and mixing the polyester polyol prepared in step a) with a polyvalent diisocyanate, nonionic and anionic group. That is, it is a polymer of hydrophilic acrylic vinyl copolymer and relatively hydrophobic urethane. However, even in the case of relatively hydrophobic urethane moieties, a few hydrophilic groups can be obtained in the final step of water dispersion to obtain water products. Therefore, when reacting with diisocyanate, mixing with nonionic and anionic groups Conduct.

The method of water-oxidizing a polymer reacted in an organic solvent includes 1) forced dispersion by an emulsifier, 2) introduction of a hydrophilic nonionic group, and 3) dispersion by an ionic group. In the case of water dispersion by the emulsifier, the water resistance of the final dry coating film has a weak disadvantage, and when the ionic group is introduced into the polymer and water oxidized, it obtains a very stable water dispersion at room temperature and high temperature, excellent weather resistance and water resistance, high tensile Although capable of exhibiting strength and good elasticity, the water dispersion stabilized by ionic groups has the disadvantage of being sensitive to electrolytes and low temperatures. On the other hand, when water is oxidized polymer by introducing a non-ionic hydrophilic group such as polyethylene oxide, the non-ionic water dispersion has a stable advantage against the electrolyte and low temperature. In order to effectively disperse the final block copolymer, a nonionic hydrophilic group of polyethylene glycol having a molecular weight of 100 to 2,000 and a carboxylic acid in the range of 0.1 to 100 milliequivalents were used together. The carboxylic acid is then neutralized by the final amine to form salts. The amount of the anionic group preferably contains 1 to 10% by weight of the polyurethane oligomer solids in order to slightly hydrophobic the entire urethane and not to harm the overall water dispersion as compared to the acrylic portion to be blocked later. The amount of the nonionic hydrophilic group is 0.3 to 5% by weight of the polyurethane oligomer solids, preferably 0.5 to 2% by weight.

The polyester polyol, the nonionic hydrophilic group, and the ionic group are homogeneously mixed at 80 to 120 DEG C. At this time, in order to maximize the effect of homogeneous mixing in a short time, a co-solvent of N-methyl-2-pyrrolidine is 2 to 2 5 weight% is added. If homogeneous mixing is found, the temperature is lowered to 70 ° C. and reacted with the polyvalent isocyanate. In this case, since it is necessary to control the increase in viscosity due to the increase in molecular weight, in order to control the viscosity, 25 to 45 wt% of a co-solvent is added to the solid content of the polyurethane oligomer before the addition of the polyisocyanate. Acetone, methyl ethyl ketone, dimethylformamide, glycol ether ester, hydrogenated furan, etc. are mentioned.

After adding the solvent, polyvalent isocyanate is added over 30 minutes. Organic isocyanates used in the reaction are essentially diisocyanates such as paraphenylene diisocyanate, biphenyl 4,4-diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl acid-1,6-di Isocyanate, 1,4-tetramethylene diisocyanate, isopron diisocyanate, methylene-bis- (4-cyclohexyl isocyanate) and the like. In the present invention, the polyhydric isocyanate is completely added, and then the mixture is maintained for 3 hours or more while maintaining 50 to 100 ° C, preferably 60 to 65 ° C. At this time, the acid value of a polyurethane derivative is 3-20 mgKOH / g.

The urethane reaction is carried out under amine-based and tin-based catalysts. Preferred catalysts include triethylamine, dibutyldilaurate, steniusoctanoate, dioctyltin diacetate, red octanoate, spanius oleate, Dibutyl tin oxide and the like. At this time, the reaction monomer ratio between the isocyanate and the isocyanate reactive activator is about 1.1 to about 3.

The acrylic water dispersion of step c) is composed of a hydroxy group which provides a reaction site of an isocyanate with a carboxylic acid having an unsaturated double bond providing a neutralization place. Examples of the carboxylic acid having an unsaturated double bond include acrylic acid, methacrylic acid, methylmethacrylic acid, maleic acid, itaconic acid, fumaric acid and anhydrides thereof. In addition, the acrylic monomer containing a hydroxy group includes hydroxy ethyl methacrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy butyl acrylate.

In addition, other copolymerizable vinyl monomers may be added according to desired physical properties. For example, styrene, alphamethyl styrene, trivalent butyl styrene, vinyltoluene, vinyl xylene, or the like may be used. For the addition of such an aromatic monomer, an ester of methacryl having 1 to 3 carbon atoms in the alkyl group may be used. Suitable examples include methyl methacrylate. Alkyl esters of acrylic acid having 2 to 12 carbon atoms in the alkyl group and alkyl esters of 4 to 12 carbon atoms of methacrylic acid can be used as the polymerization monomer in at least one other part, which can provide flexibility of the film. Suitable vinyl monomers of this type include ethyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and the like.

The polyurethane resin prepared in steps a) and b) is subjected to radical polymerization by adding an acrylic monomer of step c) under a carboxylic acid and acetone solvent. The initiators of radical polymerization used at this time include azobis alpha, gamma-demethylvaleronitrile, trivalent butylperbenzoate, trivalent butylperacetate, and benzoyl peroxide which are completely dissolved in the final polymer. Heat is usually applied to circulate the solvent, and the acrylic monomer mixture and radical initiator are added simultaneously to circulate the solvent. Thereafter, the acetone, which is a solvent, is completely removed by reducing the pressure.

Step d) is a step of preparing the water dispersion, and since the previously prepared product has a carboxyl group for water dispersion, it must first be neutralized. Preferred bases as neutralizing agents are ammonia or triethylamine, diethylamine, N, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, N, N-diethylethanolamine, which are mainly soluble in water. , 2-dimethylamino-2-methyl-1-propanol, monoisopropanolamine, triisopropanolamine, tributylamine, monoethanolamine, triethanolamine, N-methyldiethanolamine, morpholine, and the like. The amount can be used at least up to 25% by weight of the total theoretical neutralization amount, up to 50 to 100% by weight relative to the acid value of the resin. The dispersion is then completely neutralized and the excess amine is used as solvent. The neutralized resin is added with deionized water while stirring at high speed to prepare an aqueous product, and the organic product is removed by vacuum distillation of the prepared aqueous product. Solid content of the final resin is about 40% by weight.

Secondly, the polyurethane-urea water-dispersion resin shares steps a) and b) in the preparation of the urethane-modified acrylic polyol water-dispersion resin. However, the amount of the ionic and nonionic groups which help dispersing is slightly higher. The amount of the anionic group is 4 to 12% by weight of the polyurethane oligomer at the isocyanate end, and preferably 6 to 10 It contains% by weight. And the amount of the nonionic group accounts for 0.5 to 8% by weight of the solids, preferably 1.5 to 3% by weight. The isocyanate-terminated polyurethane oligomer is neutralized with trivalent amine, deionized water is added while stirring at high speed, chain-extended with amine having two or more amino groups, and then vacuum distilled to remove the organic solvent. Dibutyl tin dilaurate, stenius octanoate, dioctyl tin diacetate, red octanoate, stenius oleate, dibutyl tin oxide and the like can be used as the catalyst used at this time. The amines having two or more amino groups used in this case are ethylenediamine, ditecei (2-methyl-1, 5-pentamethylenediamine), bisaminomethylcyclohexane, xylenediamine, diethylenetriamine, beshexamethylene Triamines and polyamines. At this time, the reaction temperature of the isocyanate-terminated polyurethane water dispersion and the chain extender is 5 to 90 ° C, preferably 20 to 60 ° C. Moreover, solid content of a final resin is about 40 weight%, the average particle diameter is 60-300 nm, and has an average molecular weight of 10,000-40,000.

In the coating composition of the present invention, a resin component, a water-soluble pigment, a dispersant as an additive, a thickener, an antifoaming agent, a leveling agent and a neutralizing agent, and a solvent as a component which evaporates after coating without participating in the film formation are specifically mentioned. The explanation is as follows.

The resin of the present invention is a coating composition prepared by blending the urethane-modified acrylic polyol water-dispersion resin and the polyurethane-urea water-dispersion resin prepared as described above, and occupies 30 to 50% by weight of the total paint. Within this range, the most desirable physical properties of the coating composition can be obtained. In addition, when blending the coating composition of the present invention, the appropriate ratio of the prepared urethane-modified acrylic polyol dispersion resin and polyurethane-urea dispersion resin is 8: 2 to 4: 6 by weight ratio. When the ratio of the urethane-modified acrylic polyol water-dispersion resin is 8 or more, the water resistance of the coating composition worsens, and when it is 4 or less, the hardness of the coating film becomes severe and the impact resistance thereof becomes weak.

In addition, the water-soluble pigment uses 1 to 30% by weight of the total paint, and examples thereof include colored pigments, water-soluble aluminum pastes, and mica pigments. The coloring pigment is different depending on the color of the base paint, the water-soluble aluminum paste used in the metallic paint is preferably used 1 to 15% by weight depending on the pure metallic and color metallic, mica pigment is a pearl paint is preferably 1 -10 weight% can be used.

As pigments, most of the pigments currently used for oil-based paints, but some pigments are poor in dispersion, coloration, storage stability, etc., in the case of the present invention, a pigment specially treated by water solubility is used, aluminum paste or In the case of mica pigments, it is preferable to use a pigment that has undergone an aqueous solubilization step due to its stability. Specific examples include Irgazin DPP Red BO, Irgazin A3R, Heliogen Maroon L39980HD, Heliogen L8730, and aluminum pastes include SSP524AR, SSP303AR, SSP504AR, and mica pigments include 9130WR, 9225W II, and 9504EWT1.

The solvent constituting the coating composition according to the present invention dissolves the resin during the preparation of the coating, improves the dispersion of the pigment, and imparts viscosity control and storage properties, the formation temperature of the minimum coating film, and the like. In addition, it creates the expected surface condition, imparts suitable properties to the coating equipment during painting, and contributes to the volatilization of the solvent. Specifically, deionized water is used as the main solvent, and hydrophilic organic solvents having usability and water of a hydrophilic system are used as the coarse solvent. In the present invention, deionized water occupies 30 to 60% by weight of the total coating material. The solvent accounts for 5 to 10% by weight. The hydrophilic organic solvent is acetone, methyl ethyl ketone, dimethylformamide, isopropyl alcohol, normal propyl alcohol, butyl cellosolve, butyl carbitol, butyl diglycol acetate, 2-ethyl hexanol, normal methyl 2-ferolidone , At least one selected from the group consisting of propylene glycol butyl ether, and ethanol, and a low boiling point solvent and a high boiling point solvent are mixed for the stability, workability and appearance of the paint. For example, the butyl carbitol is preferably 2 to 10% by weight of the total coating, preferably 1 to 8% by weight of hexanol and 3 to 10% by weight of isopropyl alcohol. When the hydrophilic organic solvent is less than 5% by weight, adhesion to the resin of the coating is poor, adhesion becomes unstable, bubbles of paint are generated a lot, cretaling occurs in the coating film, and it takes a long time to form the coating film, resulting in a long drying time. If it exceeds 10% by weight, the water resistance is lowered, and the coating film dries too quickly to generate fine bubbles.

Other additives include dispersants, antifoaming agents, thickeners, leveling agents and neutralizing agents. In the case of dispersants used to disperse pigmented pigments, 0.1 to 5.0% by weight of the total paint is used. And polymers such as aromatics, aliphatic ethoxylates, or polyacrylates having a nonionic group. Examples thereof include SER-AD FX-504 from Servodelden. If the amount of the dispersant is less than 0.1% by weight, it is difficult to disperse the pigment at a desired particle size (less than 5 microns) during dispersing. If the dispersant is more than 5.0% by weight, the dispersibility may be improved, but as a result of the increase in price, of course, the coating film There is a problem that inhibits sex.

In addition, the antifoaming agent used to suppress and remove the occurrence of micro foam, bubbles, pinholes, popping, etc. during dispersing or coating manufacturing is used 0.1 to 1.0% by weight of the total coating, for example, azitan 703N of Münjing Can be mentioned. If the amount of the antifoaming agent is less than 0.1% by weight, there is no defoaming effect, so many bubbles are generated during pigment dispersion and paint production, and there is a problem that it does not turn off easily. Of course, there is a problem of inhibiting the adhesion of the coating film.

In addition, as a rheology regulator of water-soluble paints, thickeners used to prevent flow during coating and storage stability of paints use 0.1 to 3.0% by weight of the entire paint, and anionic alkali swellable system and non-ionic urethane modified associative agent. Thieves thickeners are used in a ratio of 1: 1 to 1: 4, and examples thereof include taping gel PVC 60 of Münzing. If the amount of the thickener is less than 0.1% by weight, there is a problem in that it is difficult to control the sagging phenomenon during painting because there is no thickening effect of the paint and the tendency of the pseudo plastic. The hatching of the paint becomes difficult and there is a problem of inhibiting the smoothness of the coating film.

In addition, the leveling agent is used to improve the spreadability and appearance during painting work by reducing the difference in the interlayer surface tension between the paints, 0.1 to 3.0% by weight of the overall paint, for example, BYK-333, etc. have. If the amount of the leveling agent is less than 0.1% by weight, the wetting effect of the paint is poor, so that the paint does not stick well to the base material. When the amount exceeds 3.0% by weight, the surface tension of the paint as well as the increase in the paint price Sudden deterioration may cause cradling (cratering) phenomenon on the surface of the substrate during painting, and there is a problem of inhibiting the adhesion of the coating film.

Next, the neutralizing agent used for the storage stability and pH control of the dispersed coloring paste or the final paint is used so that the pH of the paint is 7-10 using 0.01 to 5.0% by weight of the total paint, for example, ammonia and triethylamine. Diethanolamine, N, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, N, N-diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, monoisopropanol, And at least one selected from the group consisting of triisopropanolamine, tributylamine, monoethanolamine, triethanolamine, N-methyldiethanolamine, N-methyldiethanolamine, and morpholine, wherein the amount of amine added is It is at least 25% by weight of the neutralization amount, and may be used up to 50 to 100% by weight with respect to the acid value of the resin. When the amount of the neutralizing agent is less than 0.01% by weight, the thermal storage stability of the coating is unstable after the final production of the paint, and when the amount is more than 5.0% by weight, a relatively large amount of amine reacts with the composition to precipitate small particles. have.

Preparation Example 1-Preparation of Acrylic Water Disperse Resin

80 parts by weight of xylene, 20 parts by weight of butanol, 150 parts by weight of styrene monomer, 80 parts by weight of butyl acrylate, 100 parts by weight of methyl methacrylate, 10 parts by weight of methacrylic acid, and hydroxyethyl meta 60 parts by weight of acrylate, 1.0 part by weight of azobisisobutyronitrile and 10 parts by weight of Kadura E10 were reacted at 140 ° C. for 180 minutes to copolymerize acryl, and then the prepared copolymer was decompressed to remove the solvent, followed by trivalent amine. It was neutralized and added to water to oxidize water.

Preparation Example 2-Preparation of Urethane Water Dispersible Resin

400 parts by weight of acetone, 150 parts by weight of hexadiethylene diisocyanate (HMDI), 450 parts by weight of Fomrez 55-1 (polyester polyol, Witco chemical) in a 2-liter three-necked flask reactor, and 100 parts by weight of dimethylpropionic acid at 180 ° C. After solution polymerization for 2 minutes, the diisocyanate content was about 2%, the temperature was maintained at 40 ° C, neutralized with trivalent amine, and water was slowly added to oxidize water.

Preparation Example 3-Preparation of Urethane-Modified Acrylic Polyol Water Dispersing Resin

150 parts by weight of 1,6-hexanediol, 100 parts by weight of 1,4-butanediol, 70 parts by weight of phthalic anhydride, 30 parts by weight of adipic acid, and 0.1 parts by weight of dibutyltin oxide in a 2-liter three-necked flask reactor for 6 hours at 200 ° C. After the reaction, the reaction was terminated when the acid value reached 1 or less, and 150 parts by weight of diisocyanate, 5 parts by weight of polyethylene glycol, 10 parts by weight of carboxylic acid and 10 parts by weight of N-methyl- 5 parts by weight of 2-pyrrolidine and 3 parts by weight of triethylamine were homogeneously mixed at 1000 ° C. When homogeneous mixing was found, the temperature was lowered to 70 ° C and 45 parts by weight of diisocyanate was added to 400 parts by weight of acetone for 30 minutes. 10 parts by weight of acrylic acid and 200 parts by weight of acetone, 80 parts by weight of hydroxyethyl methacrylate, and 0.1 parts by weight of benzoyl peroxide were added to the prepared urethane aqueous product. And then under reduced pressure to prepare a resin to completely remove acetone. 5 parts by weight of triethylamine is neutralized by adding 100 parts of the resin, and the neutralized resin is added with deionized water while stirring at high speed to prepare an aqueous dispersion, and vacuum distillation of the prepared aqueous dispersion removes an organic solvent. . Solid content of final resin was 40 weight%.)

Preparation Example 4-Preparation of Polyurethane-urea Water Dispersion Resin

150 parts by weight of 1,6-hexanediol, 100 parts by weight of 1,4-butanediol, 70 parts by weight of phthalic anhydride, 30 parts by weight of adipic acid, and 0.1 parts by weight of dibutyltin oxide in a 2-liter three-necked flask reactor for 6 hours at 200 ° C. After the reaction, the reaction was terminated when the acid value reached 1 or less, and 150 parts by weight of diisocyanate, 5 parts by weight of polyethylene glycol, 10 parts by weight of 100 milliliters of carboxylic acid and N-methyl-2 were added to the produced resin. 5 parts by weight of pyrrolidine and 3 parts by weight of triethylamine are homogeneously mixed at 1000 ° C. When homogeneous mixing is found, the temperature is lowered to 70 ° C and 45 parts by weight of diisocyanate is added to 400 parts by weight of acetone for 30 minutes. The resin was prepared by completely removing acetone by depressurizing the urethane aqueous product. 5 parts by weight of ethylenediamine was added to 100 parts by weight of the prepared resin, and the neutralized resin was added with deionized water while stirring at high speed to prepare an aqueous dispersion resin having a solid content of 40%. The solid content of the final resin was 40% by weight, the average particle diameter was 180nm, and had an average molecular weight of 22,000.)

Preparation Example 5-Blending Resin Preparation of Acrylic Water Dispersion Resin and Urethane Water Dispersion Resin

The resins prepared in Preparation Examples 1 and 2 were mixed at a weight ratio of 5: 5, and stirred while slowly adding 10 parts by weight of 10% diluted triethylamine to prevent shocking of the resin.

Preparation Example 6-Blending Resin Preparation of Urethane-Modified Acrylic Polyol Dispersed Resin and Polyurethane-urea Dispersed Resin

The resins prepared in Preparation Example 3 and Preparation Example 4 were mixed with 7: 3 in a weight ratio and stirred while adding 25 parts by weight of 10% diluted triethylamine.

Comparative Example 1

The coating composition was prepared by the following formulation, and the physical properties of the coating itself and the properties after coating are shown in Table 1 below.

38.9% by weight of deionized water

SER-AD FX-504 [7] 1.0 wt%

Azitan 703N [1] 1.0 wt%

Chronos 2190 [2] 12.0 wt%

Tapigel PUR 60 [3] 1.0 wt%

0.1% by weight of triethylamine

Butyl Carbitol [4] 4.0 wt%

Hexanol 1.0 wt%

Ethanol 1.0 wt%

Biwai-333 [5] 0.1 wt%

Acrylic Dispersion Resin [6] 39.0 wt%

(Density 1.3 g / cm ³ , solid content ratio 22% by weight, viscosity Ford Cup No.4: 32 seconds (25 ° C), pH: 8.20)

[1] antifoaming agents

[2] white pigments, chronos

[3] thickeners from Münzing

[4] solvents, union carbide

[5] smoothers, Biwai-Kisa

[6] acrylic water-soluble resin prepared in Preparation Example 1

[7] dispersants, Servodelden

Comparative Example 2

The coating composition was prepared by the following formulation, and the physical properties of the coating itself and the properties after coating are shown in Table 1 below.

Deionized Water 37.9 wt%

SER-AD FX-504 [7] 1.0 wt%

Azitan 703N [1] 1.0 wt%

Chronos 2190 [2] 12.0 wt%

1.0% by weight of oleate 430 [3]

Triethylamine 1.0 wt%

Butyl Carbitol [4] 4.0 wt%

Hexanol 1.0 wt%

Ethanol 6.0 wt%

Biwai-333 [5] 0.1 wt%

Urethane Water Dispersion Resin [6] 35.0 wt%

(Density 1.25 g / cm ³ , solid content ratio 20% by weight, viscosity Pod Cup No.4: 34 seconds (25 ° C), pH: 8.10)

[1] antifoaming agents

[2] white pigments, chronos

[3] thickeners

[4] solvents, union carbide

[5] smoothers, Biwai-Kisa

[6] urethane water dispersion resin prepared in Preparation Example 2

[7] dispersants, Servodelden

Comparative Example 3

The coating composition was prepared by the following formulation, and the physical properties of the coating itself and the properties after coating are shown in Table 1 below.

Deionized Water 36.9 wt%

SER-AD FX-504 [8] 1.0 wt%

Azitan 703N [1] 1.0 wt%

Chronos 2190 [2] 12.0 wt%

1.0% by weight of oleate 430 [3]

Tapigel PUR 60 [4] 1.0 wt%

Triethylamine 1.0 wt%

Butyl Carbitol [5] 4.0 wt%

Hexanol 1.0 wt%

Ethanol 6.0 wt%

Biwai-333 [6] 0.1 wt%

Urethane Modified Acrylic Polyol Water Dispersion Resin [7] 35.0 wt%

(Density 1.25 g / cm ³ , solid content ratio 21% by weight, viscosity Pod Cup No. 4:34 seconds (25 ° C), pH: 8.10)

[1] antifoaming agents

[2] white pigments, chronos

[3] thickeners

[4] thickeners from Münzing

[5] solvents, union carbide

[6] smoothers, Biwai-Kisa

[7] urethane-modified acrylic polyol aqueous dispersion resin prepared in Preparation Example 3

[8] dispersants from Servodelden

Comparative Example 4

The coating composition was prepared by the following formulation, and the physical properties of the coating itself and the properties after coating are shown in Table 1 below.

Deionized Water 36.9 wt%

SER-AD FX-504 [7] 1.0 wt%

Azitan 703N [1] 1.0 wt%

Chronos 2190 [2] 12.0 wt%

2.0% by weight of oleate 430 [3]

Triethylamine 1.0 wt%

Butyl Carbitol [4] 4.0 wt%

Hexanol 1.0 wt%

Ethanol 6.0 wt%

Biwai-333 [5] 0.1 wt%

Polyurethane-urea water dispersion resin [6] 35.0 wt%

(Density 1.25 g / cm ³ , solid content ratio 21% by weight, viscosity Pod Cup No. 4:34 seconds (25 ° C), pH: 8.10)

[1] antifoaming agents

[2] white pigments, chronos

[3] thickeners

[4] solvents, union carbide

[5] smoothers, Biwai-Kisa

[6] polyurethane-urea water-dispersion resin prepared in Preparation Example 4

[7] dispersants, Servodelden

Comparative Example 5

The coating composition was prepared by the following formulation, and the physical properties of the coating itself and the properties after coating are shown in Table 1 below.

38.4% by weight of deionized water

SER-AD FX-504 [8] 1.0 wt%

Azitan 703N [1] 1.0 wt%

Chronos 2190 [2] 12.0 wt%

0.5% by weight of oleate 430 [3]

Tapigel PUR 60 [4] 1.0 wt%

0.7% by weight of triethylamine

Butyl Carbitol [5] 5.0 wt%

Hexanol 2.0 wt%

Ethanol 3.0 wt%

Biwai-333 [6] 0.1 wt%

Resin [7] 35.3 wt%

(Density 1.25 g / cm ³ , solid content ratio 21% by weight, viscosity Pod Cup No. 4:34 seconds (25 ° C), pH: 8.10)

[1] antifoaming agents

[2] white pigments, chronos

[3] thickeners

[4] thickeners from Münzing

[5] solvents, union carbide

[6] smoothers, Biwai-Kisa

[7] Blending Resin of Acrylic Dispersion Resin and Urethane Dispersion Resin Prepared in Preparation Example 5

[8] dispersants, westbournedelden

Example 1

The coating composition was prepared by the following formulation, and the physical properties of the coating itself and the properties after coating are shown in Table 1 below.

37.5% by weight of deionized water

SER-AD FX-504 [8] 1.0 wt%

Azitan 703N [1] 1.0 wt%

Chronos 2190 [2] 12.0 wt%

0.5% by weight of oleate 430 [3]

Tapigel PUR 60 [4] 1.0 wt%

0.7% by weight of triethylamine

Butyl Carbitol [5] 5.0 wt%

Hexanol 2.0 wt%

Ethanol 3.0 wt%

Biwai-333 [6] 1.0 wt%

Resin [7] 35.3 wt%

(Density 1.25 g / cm ³ , Solid content ratio 22% by weight, Viscosity Pod Cup No. 4:28 sec (25 ° C.), H: 8.15)

[1] antifoaming agents

[2] white pigments, chronos

[3] thickeners

[4] thickeners from Münzing

[5] solvents, union carbide

[6] smoothers, Biwai-Kisa

[7] Blending Resin of Urethane Modified Acrylic Polyol Dispersion Resin and Polyurethane-urea Dispersion Resin Prepared in Preparation Example 6

[8] dispersants from Servodelden

Very good ◎ Good ○ Normal △ Bad ×

* Gloss: when measured at 60 degrees polisher

* Appearance: Determination of Zenity (Visually)

* Drying time: The time for the coating film to dry completely

* Workability: Good spraying condition when discharging paint, good wettability on resin

* Adhesiveness of coating film: cross cut 2mm 10 × 10

* Impact: When 500g weight is dropped from the height of 20cm, there should be no crack and peeling on the coating film.

* Pencil Hardness: Hardness Determination for HB

* Weatherability: Weatherproof QUV 100 days

* Water resistance: 40 ℃ 10 days immersion, cross cut 2mm

* Salt water spray resistance: No swelling 3mm away from cross cut after spraying for 240 hours

* Tensile strength: psi

* Stability: Precipitation of pigment in paint

* Heat Storage: Pod Cup No. after storage at 50 ℃ for 240 hours. 4, viscosity change ± 10% by weight

As can be seen in Table 1, Example 1 used by blending the urethane-modified acrylic polyol water-dispersion resin and polyurethane-urea water-dispersion resin of the present invention is an acrylic water-dispersion resin, urethane water-dispersion resin, acrylic-urethane blending resin It can be seen that the physical properties of the paint itself and the physical properties after coating are much better than those of Comparative Examples 1 to 5, each using a urethane-modified acrylic polyol water dispersion resin and a polyurethane-urea water dispersion resin.

Claims (1)

Antifoaming agent as 30-50% by weight of blending resin with a mixing ratio of urethane-modified acrylic polyol water-dispersion resin and polyurethane-urea water-dispersion resin in a weight ratio of 8: 2-4: 6, water-soluble pigment 1-30% 0.1 to 1.0% by weight, 0.1 to 3.0% by weight thickener, 0.01 to 5.0% by weight neutralizer, and 0.1 to 3.0% by weight leveling agent, and 5 to 10% by weight hydrophilic organic solvent and 30 to 60% by weight deionized water. A water-soluble top coat composition for automobile repair.