KR20000046304A - Heat hardenable water-system resin composition having excellent sagging and paint composition containing the same - Google Patents

Abstract

PURPOSE: A heat hardenable water-system resin composition is provided which exists as particle foam of safety in liquid phase and can foam uniform and transparent film at room temperature or rise temperature. A paint composition containing the resin composition is also provided which has excellent operation property, when we work by brush or roller. CONSTITUTION: A resin composition comprises; 5-40wt% of water-soluble polymer(I) comprised 0.1-30wt% of fattic acid or fattic acid denatured alkyd resin, 0.1-20wt% of radical polymeric monomer containing epoxy group, 3-3.5wt% of radical polymeric monomer containing carboxylic group, and 25-75 wt% of vinyl or acryl mononer having vinyl group; and 60-95wt% of emulsion polymer(II) comprised 0.1-10wt% of radical polymeric monomer containing carboxylic group, 0.1-10wt% of radical polymeric monomer having funtional group for increasing sticking, 0.1-15wt% of acryl amide compound, 0.1-30wt% of radical polymeric monomer containing amine group and 35-95wt% of vinyl or acryl monomer having vinyl group.

Description

Thermosetting resin composition with excellent flowability and coating composition containing the same

The present invention is an aqueous resin composition and paint composition designed to work well when brush or roller work, more specifically, in addition to fatty acid or fatty acid-modified alkyd resin, epoxy group-containing radical polymerizable monomer, carboxyl group-containing radical polymerizable monomer and other monomers. Water-soluble polymer (I) consisting of water, an organic solvent, a neutralizing agent and a radical initiator, a carboxyl group-containing radical polymerizable monomer, a radical polymerizable monomer having an adhesion promoting group, an acrylamide compound, an amine group-containing radical polymerizable monomer and other monomers In addition, it is composed of an emulsified polymer (II) composed of water, a radical initiator, an emulsifier and a neutralizing agent, and the water-soluble polymer (I) polymer and the emulsion polymer (II) polymer are connected by a chemical bond in the form of a grafting to be stable in an aqueous phase. Present in the form of particles and at room or elevated temperatures Capable of forming a uniform and transparent film relates to an aqueous resin composition.

Rheological properties of paints are very important factors for workability and performance of coating properties. That is, the viscosity behavior at high shear stress affects the coating thickness and concealment properties of a single coating, and the viscosity behavior at low shear stress affects leveling and sagging. In general, oil-soluble alkyd resins are known to have very good workability, and because they have a relatively high viscosity at high shear force and a relatively low viscosity at low shear force, they have a similar Newton viscosity behavior. Excellent coating film thickness and concealment properties, smoothness and vertical flow. However, since the aqueous coating uses a medium called water and is slower than the solvent in the evaporation rate, there is a problem in that vertical flowability is poor when the rheological properties are the same as the solvent type alkyd. For this reason, in aqueous coatings, the viscosity of the low shear force should be adjusted to a higher region than the solvent type alkyd.

Conventional emulsion polymers contain not only nonionic or ionic low molecular weight emulsifiers as dispersion stabilizers, but also polymers are polymerized in the form of particles in micelles, resulting in gloss and pigment dispersibility compared to water-soluble or water-dispersible resins. Poor Therefore, the coating composition containing the above-mentioned emulsion polymer has very poor rheology behavior such as one-time coating concealment properties and smoothness of the coating film, so that the coating composition must be coated several times for the concealment of the base or the old coating film when the brush or roller is coated. Brushes or roller marks remain on the paint-drying coating film to give a beautiful appearance. In order to solve this problem, a thickener capable of particle-particle interaction is used, but there is a limit in improving the workability of the aqueous paint.

In addition, in order to improve the rheological properties of the water-based paint, the method of mixing the emulsion polymer used as the main binder and the water-soluble resin having excellent pigment dispersibility greatly improves the viscosity behavior at low shear force, that is, smoothness. Viscosity behavior is not satisfactory, and there is a problem that delamination or gelation occurs during storage by the organic solvents and additives added during paint production.

In order to overcome the problems caused by mixing the above-mentioned emulsion polymer and water-soluble resin, that is, simple mixing between particles and polymer chains, a hybrid emulsion (hereinafter referred to as an 'emulsion') in which a water-soluble resin is mixed during the process of preparing an emulsion polymer polymer Manufacturing techniques are known. U.S. Patent No. 4,954,558 discloses a low molecular weight [support] resin during polymerization of emulsion polymer polymers to produce emulsions with pseudo-Newtonian viscosity behavior, excellent mechanical stability and cold-temperature repeatability, and excellent pigment dispersibility. resin)]. [Additional resin] used in this patent is solubilized in water or alkaline solution, prepared by continuous bulk polymerization or solution polymerization mentioned in US Pat. Nos. 4,410,673, 4,414,370, 4,628,071 and 4,921,934, and number averaged. It is a water-soluble resin having a molecular weight of about 500-2,000. U. S. Patent No. 5,227, 423 discloses a technique for improving the viscosity behavior by mixing an emulsion polymer prepared by emulsion polymerization method containing 15-35% of acid monomer in preparing vinyl acetate-ethylhexyl acrylate copolymer emulsion. Is mentioned.

However, the above two patented techniques improve the rheological behavior of the emulsion by mixing the water-soluble resin during the polymerization of the emulsion polymer, but the emulsion particles are still produced by simple mixing between the emulsion polymer particles and the water-soluble resin polymer chain or the emulsion polymer and the water-soluble resin polymer. Since is formed, it is still not satisfactory in terms of stability, and the viscosity at high shear force is still low, so that the concealment property in one coating is not satisfactory.

Accordingly, the present inventors prepared a water-soluble polymer (I) incorporating a fatty acid or fatty acid-modified alkyd resin and introducing an epoxy group in order to improve the viscosity of pigment dispersibility and high shear force, and prepared an emulsion polymer (II) incorporating an amine group. To prepare a stable aqueous resin composition by connecting the water-soluble polymer (I) and the emulsion polymer (II) to each other by chemical bonding in the form of grafting by the epoxy-amine reaction, the present invention was completed based on this.

Accordingly, it is an object of the present invention to provide a thermosetting resin composition having excellent flowability, which is designed to have excellent workability during brush or roller work.

Another object of the present invention to provide a coating composition containing the resin composition.

The aqueous resin composition of the present invention for achieving the above object is 0.1-30% by weight of fatty acid or fatty acid-modified alkyd resin, 0.1-20% by weight of epoxy group-containing radical polymerizable monomer, 3-35% by weight of carboxyl group-containing radical polymerizable 5-40% by weight of a water-soluble polymer (I) consisting of a monomer and a vinyl or acrylic monomer having 25-75% by weight of vinyl groups and 0.1-10% by weight of a carboxyl group-containing radically polymerizable monomer, for promoting adhesion of 0.1-10% by weight Emulsified polymer consisting of a radically polymerizable monomer having a functional group, 0.1-15% by weight of an acrylamide compound, 0.1-30% by weight of an amine group-containing radical polymerizable monomer and a vinyl or acrylic monomer having 35-95% by weight of a vinyl group ( II) consisting of 60-95% by weight.

Coating composition of the present invention for achieving the above another object is water, white pigment, sieving pigment and filler, dispersant, antifoaming agent, preservative, pH stabilizer, thickener and coating film based on 100 parts by weight of the resin composition 15-70 parts by weight It consists of mixing a preparation etc.

Another coating composition of the present invention for achieving the above another object is used as a self-leveling agent by mixing water, cement and other additives in 10-30 parts by weight of the resin composition of the present invention with respect to 100 parts by weight.

The present invention provides 0.1-30% by weight of fatty acid or fatty acid-modified alkyd resin, 0.1-20% by weight of epoxy group-containing radical polymerizable monomer, 3-35% by weight of carboxyl group-containing radical polymerizable monomer and 25-75% by weight of vinyl group. Water-soluble polymer (I) comprising a vinyl or acrylic monomer having, 0.1-10% by weight of a carboxyl group-containing radical polymerizable monomer, 0.1-10% by weight of radically polymerizable monomer having a functional group for promoting adhesion, 0.1-15% by weight An aqueous resin composition composed of an emulsified polymer (II) comprising an acrylamide compound of 1, an amine group-containing radical polymerizable monomer containing 0.1-30% by weight and a vinyl or an acrylic monomer having 35-95% by weight of a vinyl group. The resin composition is composed of 5-40% by weight of the water-soluble polymer (I) polymer and 60-95% by weight of the emulsion polymer (II) polymer, and the water-soluble polymer (I) polymer and the emulsion polymer (II). The polymers are connected by chemical bonds in the grafting form and are present in the form of particles stably in the water phase.

The carboxyl group-containing radically polymerizable monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, aconic acid, crotonic acid, citraconic acid, maleic acid, fumaric acid, cinnamic acid.

The epoxy group-containing radically polymerizable monomers are glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy cyclic hexyl methyl acrylate, 3,4-epoxy cyclic hexyl methyl methacrylate and aryl glycidyl esters. It is selected from the group consisting of, especially glycidyl methacrylate is preferred.

The fatty acid is one selected from the group consisting of dihydrolate caster fatty acid, coconut, lysinard, paulownia, olive, soybean, cottonseed, sourflower and deoiled fatty acid.

The fatty acid-modified alkyd resin may have an acid value of 20-70, a hydroxyl value (OH NUMBER) of 20-90, use the fatty acid, and use an existing fatty acid-modified alkyd resin having a whey of 40-55%.

The water-soluble polymer (I) of the present invention further comprises water, an organic solvent, a neutralizer, and a radical initiator, and the solid content is 40-50% by weight.

As the radical initiator of the present invention, an alkyl or aryl peroxide, a dialkyl peroxide, an azo compound, and the like are used. In particular, the half-life is selected in consideration of the polymerization temperature not to exceed 130 ° C. The amount used is 0.2 to 4% by weight based on the monomer mixture.

The content of water used in the water-soluble high polymer (I) is 35-70% by weight.

The organic solvent may be an alkylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether or diethylene glycol mono butyl ether, ethylene glycol, propylene glycol and the like. One or more of the same glycol compound, alcohol compound, ketone compound and aromatic compound may be used in combination, and the amount of the solution is 10-50% by weight based on the water.

The neutralizing agent is selected from the group consisting of primary, secondary, tertiary amines such as alkali metal hydroxide, dimethyl ethanolamine or diethanol amine and ammonia, and is at least 50%, preferably at least 80% relative to the molar equivalent of the carboxylic acid group. Using, the pH of the water-soluble polymer (I) is adjusted to 7-8.5.

The process for preparing the water-soluble polymer (I) of the present invention comprises copolymerizing radical copolymerizable monomers with an oil-soluble initiator in the organic solvent, neutralizing with a suitable base, solubilizing in water, and optionally removing the solvent. In the organic solvent, the step of copolymerizing the radical copolymerizable monomers with the oil-soluble initiator is carried out by a conventional solution polymerization method. Neutralization with the base may include neutralizing with an appropriate base in the presence of an organic solvent or neutralizing after removing the solvent.

The resin composition of the present invention consists of an emulsion polymer (II) and a water-soluble polymer (I) consisting of water, a radical initiator, a low molecular weight emulsifier and a neutralizer and a radical polymerizable monomer mixture.

The radically polymerizable monomer mixture included in the emulsion polymer (II) is 0.1-10% by weight of a carboxyl group-containing radically polymerizable monomer, 0.1-10% by weight of a radically polymerizable monomer having a functional group for adhesion promotion, 0.1-15% by weight Acrylamide compound, 0.1-30% by weight of an amine group-containing radical polymerizable monomer and 35-95% by weight of other monomers. At this time, the said carboxylic acid containing radically polymerizable monomer and other monomer use the monomer illustrated by water-soluble polymer (I).

The radically polymerizable monomer having an adhesion promoting functional group may be an acetoacetoxy group-containing radical polymerizable monomer such as acetoacetoxy ethyl methacrylate and vinyl acetoacetate or a ureido group-containing radical such as SIPOMER WAM and SIPOMER WAM II of Long France. One or more selected from the group consisting of polymerizable monomers, wherein the acrylamide compound is acrylamide, methacrylamide, ethacrylamide, N-methylol acrylamide, N-ethylol acrylamide, N-monoalkyl Or dialkyl acrylamide, N-aminomonoalkyl or dialkyl acrylamide and one or more from the group consisting of N-hydroxyalkyl or hydroxydialkyl acryl ± amide.

The amine group-containing radically polymerizable monomer uses one or more from the group consisting of monomers represented by the following formulas.

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are a linear or branched oxyalkyl group, a primary or secondary aminoalkyl group having 1 to 8 carbon atoms, and R ₄ and R ₅ are a hydrogen atom or 1 to C atoms It is an alkyl group of 4, R <_6> and R <_7> is a hydrogen atom or a C1-C8 alkyl group.

As the radical initiator, a water-soluble radical initiator such as persulfate is used alone or in combination of two or more, in addition to those exemplified in the water-soluble polymer (I), and 0.2 to 4% by weight based on the radically polymerizable monomer mixture.

The emulsifier used to promote the polymerization rate and to impart the stability of the polymer is used alone or mixed with each other, the amount is 0.2 to 2% by weight relative to the monomer mixture in the case of anionic emulsifier, nonionic In the case of 0 to 1% by weight.

The emulsion polymer (II) is prepared by a single or multistage emulsion polymerization method in the presence of a water-soluble polymer (I), and it is preferable to include a seed production step in order to uniformly control the particle diameter and particle size distribution of the final particles. desirable.

In addition, since the water-soluble polymer (I) is contained in the resin composition of this invention, in this invention, the low molecular weight emulsifier is mix | blended little or not. In this case, optimization of the manufacturing process for the emulsion polymer (II) should be realized in order to minimize the gel particles caused by the instability of the polymerization system.

In the present invention, since the process for producing the emulsion polymer (II) in the presence of the water-soluble polymer (I) takes place at 80-90 ° C. in the water phase, the amine group of the epoxy group and the radical polymerizable monomer contained in the water-soluble polymer (I). The base is used as a catalyst to promote chemical bonding of. The base to be used selects one or more of those used in preparing the water-soluble polymer (I).

The resin composition of the present invention is used in combination with various additives, that is, water, white pigments, extender pigments and fillers, pH stabilizers, dispersants, antifoaming agents, preservatives, thickeners and coating agents, etc. It is used for architectural and industrial coatings with excellent properties.

In addition, the resin composition of the present invention is mixed with water, cement, and additives to be used in self-leveling agents such as offices, buildings, underground parking lots and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Example

In the present invention, the resin physical properties are measured by the following method.

1. Solid content: Measured under the condition of 150 ° C / 30 minutes and calculated by gravimetric method.

2. pH value: Measured with a pH meter at 25 ℃.

3. Viscosity: Measure at 25 ° C using Brook Field viscometer.

4. Drop size: Measure with light scattering meter.

5. Degree of crosslinking: To 50 milliliters of tetrahydrofuran, 2 g of a dry solid component dried at room temperature was added, stirred for 1 hour, separated in a centrifuge (50000 rpm) for 1 hour, and the gel content was measured.

Preparation Example 1

Manufacture of Water-Soluble Polymer (I)

Into a four-necked flask equipped with a nitrogen inlet, a thermometer, a cooler, and a stirrer, 66.6 parts by weight of butyl carbitol was introduced, and nitrogen was introduced while the temperature was raised to 120 ° C. When the temperature is maintained at 120 ℃ to remove nitrogen, 4 parts by weight of benzoyl peroxide is mixed with the following monomer mixture to be injected for 3 hours, and maintained at the same temperature for 2 hours. If the resin acid value and solid content are 25 and 74% or more, respectively, the mixture is cooled to 80 ° C, 6.2 parts by weight of 25% ammonia water is added and maintained at the same temperature for 30 minutes, and then 172 parts by weight of ionized water is added.

Solid content of the prepared water-soluble polymer is 45% and the viscosity is 5124 cps.

Styrene 52 parts by weight Methyl methacrylate 30 parts by weight Deoiled Fatty Acid 20 parts by weight Butyl acrylate 70 parts by weight Methacrylic acid 8 parts by weight Glycidyl methacrylate 20 parts by weight

Preparation Example 2

Manufacture of Water-Soluble Polymer (I)

Into a four-necked flask equipped with a nitrogen inlet, a thermometer, a cooler, and a stirrer, 333 parts by weight of isopropyl alcohol is added, and nitrogen is added while raising the temperature. When isopropyl alcohol refluxed at a temperature near 85 ° C., nitrogen was removed and 15 parts by weight of azobisbunironitrile was 450 parts by weight of styrene, 120 parts by weight of methyl methacrylate, 200 parts by weight of butyl acrylate, 50 parts by weight of acrylic acid and It is dissolved in a monomer mixture of 120 parts by weight of 3,4-epoxy cyclic hexyl methyl methacrylate and 200 parts by weight of dihydrocaster fatty acid and injected for 4 hours and maintained at the same temperature for 2 hours. If the resin acid value and solid content are 38 and 74% or more, respectively, the mixture is cooled to 80 ° C., 62 parts by weight of dimethylethanolamine is added and maintained at the same temperature for 30 minutes, and then 805 parts by weight of ionized water is added.

Solid content of the prepared water-soluble polymer is 44.8%, the viscosity is 4537 cps.

Preparation Example 3

Manufacture of Water-Soluble Polymer (I)

Into a four-necked flask equipped with a nitrogen inlet, a thermometer, a cooler, and a stirrer, 166.5 parts by weight of butyl cellosolve are introduced, and nitrogen is introduced while the temperature is raised to 125 ° C. When the temperature is raised to 125 ℃, nitrogen is removed and 12.5 parts by weight of t-amyl peroxide 40 parts by weight of glycidyl methacrylate, 40 parts by weight of deoiled fatty acid, alkyd resin (isopropyl alcohol to adjust the solid content to 70% , Acid value 30, hydroxyl value 50, whey 42) 25 parts by weight, 185 parts by weight of styrene, 85 parts by weight of methyl methacrylate, 75 parts by weight of butyl acrylate and 50 parts by weight of acrylic acid were dissolved in the mixture for 3 hours, and the same temperature Keep 2 hours at. If the resin acid value and solid content are 90 and 74% or more, respectively, it cools to 80 degreeC, inserts 73 weight part of triethylamines, maintains it for 30 minutes, and adds 402.5 weight part of ionized water.

Solid content of the prepared water-soluble polymer is 45.5% and the viscosity is 6200 cps.

Comparative Production Example 1

Water soluble resin

In Preparation Example 1, 20 parts by weight of glycidyl methacrylate and 90 parts by weight of butyl acrylate were replaced with 110 parts by weight of butyl acrylate to prepare a water-soluble resin containing no epoxy group and fatty acid or fatty acid-modified alkyd resin.

Solid content of the prepared water-soluble polymer is 45.5% and the viscosity is 4300 cps.

Example 1

In a four-necked flask equipped with a nitrogen inlet, a thermometer, a cooler, and a stirrer, 240 parts by weight of ionized water and 2.0 parts by weight of anionic emulsifier are introduced, and nitrogen is introduced while the temperature is raised to 80 ° C. When the temperature is maintained at 80 ° C, 10% of 45 parts by weight of styrene, 54 parts by weight of 2-ethylhexyl acrylate, and 0.1 part by weight of methacrylic acid are added thereto, and 10 parts by weight of 1.0% by weight of sodium persulfate is added thereto for 10 minutes. . When the exotherm occurred, the temperature was adjusted to around 80 ± 2 ° C. and maintained for 40 minutes to prepare a seed. The particle diameter was 32 nm. When the temperature was maintained at 80 ℃, the monomer residue was injected for 60 minutes and maintained for 60 minutes to prepare a one-step emulsion polymer.

A solution obtained by dissolving 12 parts by weight of sodium persulfate was added to 30 parts by weight of ionized water at the same temperature for 10 minutes, followed by 225 parts by weight of ionized water, 89 parts by weight of the water-soluble polymer (I) prepared in Preparation Example 1, and 187 parts by weight of methyl methacrylate. 90 minutes by weight of butyl acrylate, 5 parts by weight of methacrylic acid, 5 parts by weight of N-methylol acrylamide N-methylethyl methacrylate, and 3 parts by weight of SIPOMER WAM II were added for 90 minutes and maintained for 90 minutes. . After the polymerization is completed, the mixture is cooled to around 50 ° C, 4 parts by weight of 25% ammonia is added and filtered / packed. The prepared resin composition had a solid content of 45%, a pH of 9, a viscosity of 78 cps, and a particle size of 100 nm.

Example 2

In Example 1, the water-soluble polymer (I) prepared in Preparation Example 2 was used instead of the water-soluble polymer (I) prepared in Preparation Example 1. The prepared emulsion polymer (II) had a solid content of 44.2%, a pH of 8.7, a viscosity of 100 cps, and a particle size of 110 nm.

Example 3

Instead of the water-soluble polymer (I) prepared in Preparation Example 1 and SIPOMER WAM II in Example 1, the water-soluble polymer (I) prepared in Preparation Example 3 and acetoacetoxy ethyl acrylate were used.

Example 4

Into a four-necked flask equipped with a nitrogen inlet, a thermometer, a cooler, and a stirrer, 295 parts by weight of ionized water and 6.0 parts by weight of anionic emulsifier are introduced, and nitrogen is introduced while the temperature is raised to 80 ° C. When the temperature is maintained at 80 ° C., 10% is added in 192 parts by weight of styrene and 103 parts by weight of 2-ethylhexyl acrylate, and 2.9 parts by weight of sodium persulfate is added in 29.5 parts by weight of ionized water for 10 minutes. When the exotherm occurred, the temperature was adjusted to around 80 ± 2 ° C. and maintained for 40 minutes to prepare a seed. The particle diameter was 35 nm. When the temperature was maintained at 80 ℃, the monomer residue was injected for 60 minutes, and maintained for 60 minutes to prepare a one-step emulsion polymer.

A solution obtained by dissolving 1.5 parts by weight of sodium persulfate was added to 29.4 parts by weight of ionized water at the same temperature for 10 minutes, followed by 204 parts by weight of ionized water, 68.7 parts by weight of water-soluble polymer (I) prepared in Preparation Example 1, and 59 parts by weight of methyl methacrylate. 90 minutes of a total emulsion containing 29.5 parts by weight of styrene, 46.3 parts by weight of butyl acrylate, 1.5 parts by weight of methacrylic acid, 6 parts by weight of N-methylethyl methacrylate, 1 part by weight of SOPOMER WAM II and 3 parts by weight of acrylamide And hold for 90 minutes. When the polymerization is complete, it is cooled to around 50 ° C., 2 parts by weight of 25% ammonia are injected and filtered / packed. The prepared resin composition had a solid content of 45%, a pH of 8.7, a viscosity of 110 cps, and a particle size of 97 nm.

Comparative Example 1

In preparing the one-stage emulsion polymer in Example 1 and preparing the second-stage emulsion polymer, a solution in which 12 parts by weight of sodium persulfate was dissolved in 30 parts by weight of ionized water was injected for 10 minutes, followed by 225 parts by weight of ionized water, and Comparative Preparation Example An emulsified polymer which does not occur in the epoxy-amine crosslinking reaction was prepared using a preemulsification solution consisting of 89 parts by weight of the water-soluble polymer prepared in 1, 187 parts by weight of methyl methacrylate, 108 parts by weight of butyl acrylate, and 5 parts by weight of methacrylic acid. . The prepared resin composition had a solid content of 45.4%, a pH of 9.5, a viscosity of 86 cps and a particle size of 110 nm.

The crosslinking degree of the emulsion polymer polymer prepared in Examples 1 to 4 and Comparative Example 1 was measured and shown in Table 2 below.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Degree of crosslinking (%) 74 78 76 73 2

Example 5-8 and Comparative Example 2

Paint production

Table 3 below is a white paint formulation applied to compare the physical properties of the resins prepared in Examples 1-4 and Comparative Example 1. In the production method, the raw material of the millbase step was sequentially inserted under stirring, and stirred with a high speed stirrer for 90 minutes to obtain a pigment dispersion having a particle size of 10 microns or less and a pH value of 10. The raw material of the finishing stage was continuously purchased under stirring, the pH value was adjusted to 8.5-9.5 with 25% ammonia water, and the preparation viscosity was adjusted to 80-85 KU.

White paint formulation Phase division Raw material Combination Mill base One Ionized water 8 2 silicon 0.2 3 antifreeze 2 4 HEC-Thickener 6.1 5 25% ammonia 0.08 6 Titanium dioxide 20 7 Talc 11 8 Calcium carbonate 11 deadline 9 Texanol 1.2 10 Resin composition 40 11 PARMETOL DF 35 0.2 12 HEUR type thickener 0.6 13 25% ammonia 0.08 14 Ionized water 4.34

Paint property comparison

Table 4 compares the physical properties of the paints prepared in Examples 5-8.

Paint Application Results division Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Paint property KU viscosity 84 83 81 82 84 pH value 8.7 8.8 8.6 9.0 9.0 Room Temperature Storage (ΔKU) 2 3 2 3 8 Heat storage (ΔKU) 2 3 4 3 13 Coating property Polish 45 50 54 50 39 Water resistance ○ ○ ○ ○ ○ Non-Pollution (ΔL) 0.4 0.5 0.3 0.3 0.9 Roller workability ○ ◎ ◎ ◎ △

Physical properties measurement method is as follows.

1. KU viscosity: The paint is kept at 25 ° C. and measured with a KU viscometer.

2. pH value: Measured at 25 ° C.

3. Store at room temperature (ΔKU): Store for 30 days at 25 ℃, measure the difference with the initial viscosity.

4. Heat storage (ΔKU): Store for 7 days at 60 ℃, measure the difference with the initial viscosity.

5. Gloss: After coating so that dry film thickness is 50 micron on glass plate, measure gloss at 60 degrees.

6. Water resistance: After coating twice with brush so that dry film thickness is 45 micron, slate plate is dried once a week and immersed in 40 ℃ hot water for 15 days. (Rank: × Bad △ Normal ○ Good ◎ Very good)

7. Non-pollution: After the specimen is made the same as the water resistance, the film is contaminated using a mixture of carbon black, silica, alumina, iron oxide and tar. Wash twice with a cotton soaked in water, dry and measure ΔL.

8. Roller workability: It is coated on the slate plate 2m long and 1m long to observe the concealment, gloss, roller rolling, smoothness and vertical flowability. (Rank: × Bad △ Normal ○ Good ◎ Very good)

As described above, the aqueous resin composition of the present invention stably exists in the form of particles in an aqueous phase, forms a uniform and transparent film at room temperature or at an elevated temperature, and the coating composition containing the same has excellent brush or roller workability. It is excellent in luster and heat storage and is very useful commercially.

Claims (12)

0.1-30 wt% fatty acid or fatty acid modified alkyd resin, 0.1-20 wt% epoxy group containing radical polymerizable monomer, 3-35 wt% carboxyl group containing radical polymerizable monomer and 25-75 wt% vinyl group or 5-40% by weight of water-soluble polymer (I) consisting of acrylic monomer, 0.1-10% by weight of carboxyl group-containing radical polymerizable monomer, 0.1-10% by weight of radically polymerizable monomer having functional group for adhesion promotion, 0.1-15% 60 to 95% by weight of an emulsified polymer (II) consisting of% acrylamide compound, 0.1-30% by weight of an amine group-containing radical polymerizable monomer and a vinyl or acrylic monomer having 35-95% by weight of vinyl groups. Thermosetting resin composition excellent in flowability. The method of claim 1, wherein the carboxylic acid-containing radically polymerizable monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, aconic acid, crotonic acid, citraconic acid, maleic acid, fumaric acid and cinnamic acid. Aqueous resin composition, characterized in that selected above. The method of claim 1, wherein the epoxy group-containing radical polymerizable monomer is glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy-cyclic-hexylmethyl acrylate, 3,4-epoxy-cyclic-hexylmethyl Aqueous resin composition, characterized in that it is selected from the group consisting of methacrylate and aryl glycidyl ester. 4. The aqueous resin composition according to claim 3, wherein glycidyl methacrylate is used as the epoxy-containing radically polymerizable monomer. The resin according to claim 1, wherein the fatty acid is selected from the group consisting of dihydrolate caster fatty acid, coconut, lysinard, paulownia, olive, soybean, cottonseed, saflower and deoiled fatty acid. Composition. The fatty acid-modified alkyd resin according to claim 1, wherein the fatty acid-modified alkyd resin has an acid value of 20-70 and a hydroxyl value of 20-90, uses the fatty acid of claim 5, and uses an existing fatty acid-modified alkyd resin having a whey of 40-55%. Aqueous resin composition, characterized in that. The resin composition of claim 1, wherein the amine group-containing radical polymerizable monomer is selected from the group consisting of monomers represented by the following formulas. Formula 1 Formula 2 Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are a linear or branched oxyalkyl group, a primary or secondary aminoalkyl group having 1 to 8 carbon atoms, and R ₄ and R ₅ are a hydrogen atom or 1 to C atoms It is an alkyl group of 4, R <_6> and R <_7> is a hydrogen atom or a C1-C8 alkyl group. The acrylamide compound of claim 1, wherein the acrylamide compound is acrylamide, methacrylamide, ethacrylamide, N-methylol acrylamide, N-ethylol acrylamide, N-monoalkyl or dialkyl acrylamide, N-aminomono. Aqueous resin composition, characterized in that one or more mixtures are used from the group consisting of alkyl or dialkyl acrylamides and N-hydroxyalkyl or hydroxydialkyl acrylamides. The radical polymerizable monomer having a functional group for promoting adhesion is acetoacetoxy group-containing radical polymerizable monomers such as acetoacetoxy ethyl methacrylate and vinyl acetoacetate and SIPOMER WAM and SIPOMER WAM II of Long France. The resin composition, characterized in that one or more selected from the group consisting of a ureido group-containing radical polymerizable monomer. The aqueous resin composition according to claim 1, wherein the water-soluble polymer (I) has a solid content of 40-50 wt%. 15, 70 parts by weight of the water-based resin composition of claim 1 is mixed with water, white pigments, extender pigments and fillers, dispersants, antifoaming agents, preservatives, pH stabilizers, thickeners and coating aids for stability, pigment dispersibility, workability and adhesion It is used for this excellent architectural and industrial top coat, water-based coating composition characterized by the above-mentioned. Water-based coating composition characterized in that it is used as a self-leveling agent by mixing water, cement and other additives in 10-30 parts by weight of the water-based resin composition of claim 1.