KR101483401B1 - Eco-friendly Hybrid Paint Compositions - Google Patents

Abstract

The present invention relates to an eco-friendly hybrid paint composition, which uses an aqueous rubber modified epoxy resin and an additive as main ingredients, an aqueous acrylic resin and a curing accelerator as curing agents, and no chemical solvents, thereby becoming pollution free. The eco-friendly hybrid paint composition of the present invention has drastically improved physical properties such as adhesive strength, tensile strength, elongation, flexural strength, impact strength and water resistance.

Description

Eco-friendly Hybrid Paint Compositions

The present invention relates to an eco-friendly hybrid coating composition, specifically, an environmentally friendly hybrid coating composition having excellent physical properties such as pollution-free properties by using an aqueous rubber-modified epoxy resin and an additive as a subject and using an aqueous acrylic resin and a curing accelerator as a curing agent. The invention relates to.

Paints are materials that express color and appearance, which completely conceal the body and protect the body and decorate the exterior beautifully. Paint and water are used depending on whether water or solvent is used as a diluent. Separate by meteor. Acrylic paints, polystyrene resins, polyvinyl chloride resins, silicone resins, epoxy resins, asphalt, polyurethane resins, polyisobutylene resins are used for the oil paints, and polyvinyl chloride resins, epoxy resins, acrylic resins, and ethylene are used for the aqueous paints. Vinyl acetate resins, polyurethane resins, styrene-butadiene rubbers and the like are used.

Until now, oil paints, which have better adhesion, water resistance, and mechanical strength than water paints, have been preferred. In this regard, epoxy resins and acrylic resins used as paint resins have favored oil-based epoxy resins or oil-based acrylic resins rather than water-based resins. However, oil-based paints generally do not penetrate into the cement surface better than water-based paints, and organic solvents are commonly used to improve such disadvantages. The use of such organic solvents cause air pollution, causing enormous damage to the health of workers and those around them. These problems have encouraged the development of paints using aqueous epoxy resins or aqueous acrylic resins. Currently, the commonly used aqueous epoxy resin is a bisphenol A low molecular weight epoxy resin. However, water-based epoxy resins and water-based acrylic resins have some problems when used alone. That is, water-based epoxy resins generally have a thermosetting two-component type that is cured with an amine-based curing agent. It has high disadvantages of poor penetration into cement, lack of flexibility and low impact resistance.

On the other hand, aqueous acrylic resins are easier to use because the properties of the coating film appear when the water is dried in the form of thermoplastic resins, but the adhesive strength and strength are lower than those of the aqueous epoxy resins.

As a related art in this regard, Korean Patent No. 10-0937127 (registered on Jan. 14, 2010) discloses an aqueous epoxy coating composition comprising a main part containing a self-emulsifying epoxy resin and a curing agent part containing an aqueous epoxy resin curing agent. Wherein the curing agent portion comprises an aminoalkylpolydimethylsiloxane having a molecular weight of 5,000 to 10,000 at 3 to 10% by weight of the total curing agent portion composition. However, the present invention has a disadvantage in that the drying and curing speeds are high, and mechanical properties such as adhesive strength, tensile strength, flexural strength, and impact strength are insufficient.

In addition, Korean Patent No. 10-0938432 (registered on Jan. 15, 2010) discloses “30 to 95% by weight of an epoxy compound containing at least a bisphenol epoxy compound and 5 to 70% by weight of polyether glycol having a number average molecular weight of 200 to 3,000. An aqueous epoxy resin prepared by reacting and having an epoxy equivalent in the range of 300 to 2,000; Water-soluble amine curing agents; Sieving pigments; At least one additive selected from the group consisting of antifoaming agents, leveling agents, viscosity modifiers, plasticizers and antioxidants; And an aqueous epoxy coating composition comprising water ”is disclosed. However, the present invention is only to improve the adhesion and gloss, there is a disadvantage that the mechanical properties such as adhesive strength, tensile strength, bending strength and impact strength is insufficient.

Therefore, the situation is eagerly hope that the appearance of another type of paint to compensate for the above disadvantages.

The present invention has been made in order to solve the above problems, by curing the curing agent mixed with an additive to an aqueous rubber-modified epoxy resin and a curing accelerator mixed with an aqueous acrylic resin, pollution-free, adhesion, water resistance than conventional coating composition The object of the present invention is to provide an environmentally friendly hybrid coating composition having improved impact resistance.

The present invention is an aqueous rubber modified epoxy resin prepared by emulsifying a rubber-modified epoxy resin reacted with a polybutadiene rubber having a carboxyl group in an epoxy resin in water, a cryoprotectant, an antifoaming agent, a preservative, an anti-rusting agent, a dispersing agent, water, a repair thickener, 75-85% by weight of an additive containing an extender pigment and a thickener additive; It provides an environmentally friendly hybrid coating composition comprising 15 to 25% by weight of a curing agent prepared by mixing a curing accelerator with an aqueous acrylic resin.

In the present invention, the epoxy resin is a liquid equivalent of 300 or less, the polybutadiene rubber having a carboxyl group has a reactive carboxyl group at both ends of the molecular weight of 3000 ~ 7000, the rubber-modified epoxy resin is represented by the following formula It provides an environmentally friendly hybrid coating composition characterized in that.

(식1)

(Eq. 1)

(In Formula 1,

R is a polybutadiene chain,

R ': Bisphenol A epoxy resin chain)

In addition, the present invention, the rubber-modified epoxy resin of the subject matter is 22.0% by weight relative to the eco-friendly hybrid paint composition, the additive is 0.05 ~ 0.15% by weight antifreeze agent, 0.03 ~ 0.05% by weight antifoaming agent, 0.03 ~ preservatives 0.05% by weight, 0.11 to 0.13% by weight of anti-rust agent, 0.3-0.5% by weight of dispersant, 3.8 to 5.8% by weight of water, 0.18 to 0.22% by weight of thickener, 45.0-55.0% by weight of extender pigment, 3.2 to 3.4% by weight of thickener It is configured, the aqueous acrylic resin and the curing accelerator of the curing agent provides an environmentally friendly hybrid coating composition, characterized in that consisting of 19.4% by weight, 0.6% by weight relative to the environmentally friendly hybrid paint composition.

Finally, the present invention provides an eco-friendly hybrid coating composition, wherein the thickener is made by mixing 15 parts by weight of 20% ammonia water and 150 parts by weight of acrylic resin in 100 parts by weight of water.

Eco-friendly hybrid coating composition according to the present invention because the use of water-based rubber modified epoxy-acrylic resin is excellent in general properties such as pollution-free, adhesion, tensile strength, elongation, bending strength, impact strength, water resistance.

In addition, since the affinity for cement is greater than the conventional oil paint composition, the penetration power for fine pores is good, and since the solvent is water, the price is much cheaper than oil.

Eco-friendly hybrid coating composition according to the present invention will be described in detail below.

First, the eco-friendly hybrid coating composition according to the present invention is an antifreeze agent, antifoaming agent, antiseptic agent, anti-rusting agent on an aqueous rubber modified epoxy resin prepared by emulsifying rubber modified epoxy resin reacted with polybutadiene rubber having a carboxyl group in epoxy resin in water. 75-85 wt% of a main ingredient containing additives such as dispersants, water, water thickeners, extender pigments and thickeners; It is characterized by consisting of 15 to 25% by weight of a curing agent prepared by mixing a curing accelerator with an aqueous acrylic resin.

Hereinafter will be described in detail the subject and the curing agent constituting the environment-friendly hybrid coating composition of the present invention.

(1) subject

1) Rubber modified epoxy resin

The rubber-modified epoxy resin may be made by reacting a polybutadiene rubber having a carboxyl group with an epoxy resin, and the structural formula is as follows.

(식 1)

(Equation 1)

(In Formula 1,

R is a polybutadiene chain,

R ': Bisphenol A epoxy resin chain)

The rubber-modified epoxy resin may be obtained by adding polybutadiene rubber and a reaction catalyst to an epoxy resin and reacting at 140 to 160 ° C. for 3 to 5 hours to obtain an acid value of 0.1 to 0.5. In the reaction, the epoxy resin accounts for 50 to 60% by weight of the total reactants, the polybutadiene rubber accounts for 40 to 50% by weight, and the reaction catalyst is 0.1 to 0.5 parts by weight based on the total reactants.

The reaction is an addition reaction between the epoxide of the epoxy resin and the carboxyl group of the polybutadiene rubber. In order for the reaction to proceed safely, the equivalent ratio of the initial epoxide / carboxyl group must be 10 or more. Otherwise, the crosslinking reaction occurs in three dimensions and gelation occurs due to the molecular weight becoming too large.

It is preferable to use a liquid equivalent of 300 or less as the epoxy resin, and as polybutadiene rubber, one having a reactive carboxyl group at both ends of the molecule having an average molecular weight of 3000 to 7000 is used. Oxides (DBTO), triethylamine (TEA), triphenylphosphine (TPP), benzyldimethylamine (BDMA) and the like.

2) Water-based rubber modified epoxy resin

The aqueous rubber modified epoxy resin was made by mixing 50 parts by weight of the emulsifier with respect to 100 parts by weight of the rubber modified epoxy resin and then pouring hot water at 50 to 70 ° C. while stirring at a speed of 40 to 60 rpm. At this time, the water content is preferably 40 to 50% by weight of the total amount of the water-based rubber modified epoxy resin.

3) additive

Examples of the additives used in the subject include cryoprotectants, antifoams, preservatives, antirust agents, dispersants, water, water thickeners, extender pigments and thickeners.

The appropriate amount of the cryoprotectant is preferably 0.05 to 0.15% by weight based on the environment-friendly hybrid coating composition, and low molecular glycols may be used as the type thereof, and ethylene glycol, diethylene glycol, propylene glycol, and glycerin may be used. Etc. However, in the extremely cold -10 ℃ or less, even if more than 1% by weight of the subject is not effective because the product should be stored in a warm warehouse, the coating composition freezes and melts both the adhesion and strength problems occur.

The appropriate amount of the antifoaming agent is preferably from 0.03 to 0.05% by weight in the environment-friendly hybrid coating composition, the type is mainly used silicone or polyol, and can be used dispersed in an aqueous solvent or emulsified. .

The suitable amount of the preservative is preferably 0.03 to 0.05% by weight in the environment-friendly hybrid coating composition, benzoic acid, salicylic acid, formalin and the like may be used, but formalin should be avoided as much as possible due to severe human irritation. Since the coating composition uses a natural product such as cellulose for the purpose of thickening and adhesive strength, it is necessary to add an appropriate amount of preservative because the product may be deteriorated due to mold when the temperature and humidity are high, such as summer.

Suitable amount of the anti-bleach agent is preferably 0.11 to 0.13% by weight in the environment-friendly hybrid coating composition, mineral oil may be used as the kind. When the temperature rises in summer, moisture evaporates quickly, and moisture on the surface of the coating film evaporates faster than the inside, and a dry film is formed on the surface. If a dry film is formed in this way, cracks and wrinkles are formed in the whole coating later due to the undried components inside. Therefore, in order to solve the above-mentioned dryness, it is generally required to suppress evaporation of water by using mineral oil having low volatility. The use of low molecular weight glycols or plasticizers also slows down the evaporation of water and the fusion rate of solids, which helps to delay dryness.

The proper amount of water used as the diluting solvent is preferably 3.8 to 5.8% by weight in the environment-friendly hybrid coating composition, even if a small amount of water is increased or decreased significantly, the viscosity significantly affects the workability.

The extender pigment may be calcium carbonate, talc, silica, alumina, or the like, and an appropriate amount thereof is preferably 45-55 wt% in an environmentally friendly hybrid coating composition. At this time, when the amount of the extender pigment is less than 45% by weight, the viscosity is low and the adhesion is low due to the penetration into the micropores formed on the substrate.When the amount of the extender pigment is more than 55% by weight, the contact area is small due to the large amount of pores. This is done. The particle size usually used is 100 ~ 600mesh, but if the particle size is too small, the oil absorption is large, the viscosity is high, the flowability is poor, and the penetration is bad. do.

When the coating composition is applied to the floor, to obtain a coating film having a certain thickness, a water-reducing thickener must be added. The appropriate amount of the coating composition is preferably 0.18 to 0.22% by weight in an environmentally friendly hybrid coating composition, and cellulose may be used as the type. have. Cellulose is excellent in fresh water, and its water absorption capacity is 50 times its own weight, and it keeps in a swollen state with water, giving excellent workability and preventing the applied adhesive from flowing down. In addition, since cellulose is easily released in pure water but not easily in resin, it is preferable to disperse the cellulose in water in order to help absorb water, so that it does not form agglomerate in the mixer during swelling. On the other hand, when a small amount of ammonia is added, the cellulose can be more easily dissolved, and its amount of use has a great influence on the viscosity of the coating composition. Even if only 20% of the cellulose is increased, the viscosity of the mixture is increased by 10 times or more, and when the excessive amount of the cellulose is used, the fluidity of the coating composition is deteriorated and the penetration force is lowered. It also creates a film on the adhesive surface during drying, making it difficult for the resin liquid to penetrate into the pores of the body wall, leading to a decrease in adhesive strength.

The suitable amount of the dispersant is preferably 0.3 to 0.5% by weight in the environment-friendly hybrid coating composition, the range is an amount considering that the total amount is increased when the curing agent is mixed to reduce the concentration of the dispersant. The kind of anionic dispersant may be used as the kind, because most of the extender pigments mixed in the adhesive are anionic inorganic pigments.

The appropriate amount of the thickener is preferably 3.2 to 3.4% by weight in the environment-friendly hybrid coating composition, acrylic resin used as a thickener is generally synthesized using acrylic acid or methacrylic acid having a reactive carboxyl group as the main raw material. This is because they react with ammonia and become salts, resulting in high tackiness. The thickener is made by mixing 15 parts by weight of water with 20% ammonia and 150 parts by weight of acrylic resin for thickeners. They are highly viscous and when mixed, ammonia forms hydrogen bonds with the polar groups of the resin. When it shows high viscosity and receives an external force, it has the thixotropy property which shows flowability, and shows the outstanding workability. However, if the amount of the thickener exceeds 3.4% by weight, the water resistance of the ammonia becomes poor due to the water absorption of ammonia.

4) Manufacture of subject

The main theme of the eco-friendly hybrid coating composition can be made by mixing the antifreeze agent, antifoaming agent, preservative, anti-rusting agent, dispersing agent, water, water thickener, extender pigment, thickener as an additive to the aqueous rubber modified epoxy resin prepared above.

Specifically, the cryoprotectant, antifoaming agent, preservative, anti-rusting agent, dispersant, and water were added to the aqueous rubber-modified epoxy resin in order and mixed for 5-6 minutes, and then the water-reducing thickener was added to the water and mixed in the mixer, followed by stirring for 15-20 minutes. Let's do it. Subsequently, add the extender pigment and uniformly disperse for 30 minutes at a speed of 200 ~ 500rpm. Subsequently, after adding the thickener and mixing well, the subject of viscosity 70000-90000cp (25 degreeC) can be obtained by vacuum degassing in vacuum degree 3torr for 30 minutes, and removing a bubble.

(2) curing agent

 1) aqueous acrylic resin

The aqueous acrylic resin was added to the reactor, distilled water and emulsifier were mixed uniformly, the temperature was raised to 60-80 ° C, the mixture was mixed dropwise with the mixture of the catalyst and the acrylic monomer for 3-4 hours, and then cooled to 40 ° C or lower. . In the reaction, distilled water was used, but it is preferable to occupy 50 to 56% by weight of the total components of the aqueous acrylic resin.

At this time, if the amount of water is less than 50% by weight of micelles (micelle) by the emulsifier is not well formed, and if the amount of more than 56% by weight of the emulsifier is less than the strong micelles. As for the suitable usage amount of an emulsifier, 5-7 weight% is preferable in the total component of aqueous acrylic resin. As the emulsifier, anionic surfactants and nonionic surfactants can be used in combination.

The acrylic monomers account for 37 to 42% by weight of the total components of the aqueous acrylic resin, such as methyl methacrylate (MMA), 2-ethyl hexyl acrylate (2-EHA), 2-hydroxy ethyl methacryl Rate (2-HEMA), acrylic acid (AA), styrene (SM), methacrylic acid (MAA), butyl acrylate (BAM) and the like can be used.

It is preferable that the catalyst occupies 0.5-5% by weight of the total components of the aqueous acrylic resin, and examples thereof include potassium persulfate, ammonium persulfate, sodium persulfate, and the like.

The solid content of the aqueous acrylic resin prepared above is 45 to 50%, the average molecular weight is 20000 to 30000. In the aqueous acrylic resin, an amount corresponding to an acid value of 100 to 120 remains as a solid content of a reactive carboxyl group. When the solid content was too low, the molecular weight was small and the viscosity was low. On the contrary, when the solid content was formed high, the molecular weight was high, the viscosity was high, and the fluidity was poor. In addition, if too much acrylic acid or methacrylic acid is used in the manufacturing process, crystallization may occur at low temperatures, which may cause a solidification of the paint.

2) Preparation of Curing Agent

The curing agent was prepared by mixing a curing accelerator with an aqueous acrylic resin, wherein the amount of the aqueous acrylic resin in the curing agent is 97% by weight and the amount of the curing accelerator is preferably 3% by weight.

As the curing accelerator, it is preferable to use a tertiary amine in consideration of storage stability. The tertiary amines that can be used are diethylaminopropylamine, benzyldimethylamine, tolisdimethylaminomethylphenol, and ethylmethylimide. Sol, triethylamine and the like.

On the other hand, the eco-friendly hybrid coating composition according to the present invention is preferably composed of 75 to 85% by weight of the main agent and 15 to 25% by weight of the curing agent, when the content of the main body is less than 75% by weight, the content of the aqueous acrylic resin increases, so that Flexibility is improved, but a problem occurs that the adhesive strength is lowered, and when the content exceeds 85% by weight, the content of the water-based rubber modified epoxy resin is increased, so that the elongation and impact strength are lowered.

Finally, the curing reaction of the eco-friendly hybrid coating composition is by a three-dimensional complex reaction between the epoxide-epoxide, epoxide-hydroxyl group, epoxide-carboxyl group which is a reaction between the aqueous rubber modified epoxy resin and the aqueous acrylic resin.

Preparation Example 1 Preparation of Rubber Modified Epoxy Resin

110 g of epoxy resin (YD-128 of Kukdo Chemical Co., Ltd.), 90 g of polybutadiene rubber (CTBNx8 of Hypro), 0.4 g of dibutyltin oxide (DBTO) as a catalyst, reacted at 140 ° C. for 3 hours, and modified to a rubber having an acid value of 0.5. An epoxy resin was obtained. The acid value of the rubber-modified epoxy resin was measured by using an organic solvent as a solvent according to KSM ISO 276.

Preparation Example 2 Preparation of Aqueous Rubber-Modified Epoxy Resin

To 100 g of the rubber-modified epoxy resin prepared in Preparation Example 1, 4 g of Koremul-ESF-815 (Han Thickening Product) was well mixed as an emulsifier, followed by pouring 100 ml of water at 60 ° C. while stirring at 50 rpm to form an aqueous rubber-modified epoxy resin. Prepared.

Production Example 3 Preparation of Aqueous Acrylic Resin

54 g of distilled water and 6 g of an emulsifier (S-321 from Finecomtech) were added and mixed uniformly, while maintaining the temperature at 70 ° C., 1.0 g of ammonium persulfate and 10 g of methyl methacrylate (MMA) and methacrylic acid (MAA) Aqueous acrylic resins were prepared by reacting a mixture of 7 g, 7 g of 2-ethylhexyl acrylate (2-EHA) and 15 g of butyl acrylate (BAM) in a constant dropwise manner for 3.5 hours, followed by cooling to 40 ° C.

Preparation of Eco-friendly Hybrid Paint Composition

1) manufacture of subjects

First, 220 g of the aqueous rubber-modified epoxy resin obtained in Preparation Example 2, 1 g of ethylene glycol as a cryoprotectant, Nopco NxZ 0.4 g of antifoaming agent Nokco Korea Co., Ltd. 1.2 g of HV-1, 5 g of dispersant 44-S from Dispersant Korea Sanofko Co., Ltd., 38 g of water, were mixed well for 5 minutes, followed by hydroxyethyl methyl cellulose (HEMC) of Samsung Fine Chemicals Co., Ltd. ) 2g was dissolved in water and placed in the stirrer and stirred for 20 minutes. Subsequently, 500 g of calcium pigment carbonate was added and dispersed uniformly at 400 rpm for 30 minutes. Then, 32 g of thickener was added and mixed, followed by vacuum degassing for 30 minutes with a vacuum degree of 3 torr to remove bubbles. Thus, the subject of viscosity 70000-90000cp (25 degreeC) was obtained.

2) Preparation of Curing Agent

194 g of the aqueous acrylic resin obtained in Preparation Example 3 was mixed well with 6 g of triethylamine, a tertiary amine, as a curing accelerator to prepare a curing agent.

3) Preparation of Eco-friendly Hybrid Coating Composition

Eco-friendly hybrid coating composition was prepared by mixing and curing 80 g of the main ingredient obtained in 1) and 20 g of the curing agent obtained in 2) above.

Compared to 3) of Example 1, instead of the main 80g, 20g instead of 20g of the main agent 84g, 16g of the curing agent is mixed except that the rest was the same to prepare an environmentally friendly hybrid coating composition.

Compared to the 3) of Example 1, the environmentally friendly hybrid coating composition was prepared by mixing only the main 80g, the main 87g, and the curing agent 13g instead of 20g.

Compared to the 3 of Example 1, instead of the main 80g, 20g of the curing agent instead of 20g, 74g, 26g of the curing agent is mixed, the rest was the same to prepare an environmentally friendly hybrid coating composition.

(Comparative Example 1)

Compared to Example 1, KEM-128-70 from Kukdo Chemical Co., Ltd., an aqueous epoxy resin, was used instead of an aqueous rubber modified epoxy resin, and Kukdo Chemical Co., Ltd., an amine epoxy curing agent instead of an aqueous acrylic resin, was used. Only the point using KH-700 differs and the same was made the coating composition.

(Comparative Example 2)

39 g of water-soluble amine curing agent M2-0080 (manufactured by Deepia), leveling agent 0.5 g, antifoam 0.5 g, with active hydrogen equivalent weight (AHEW, 50%) of 220, solid content (NV%) of 50, and amine number (mg / KOH) 310 34g of the extender pigment and 20g of deionized water were sufficiently mixed at room temperature for 60 minutes. The mixture was aged at room temperature for 24 hours to prepare an aqueous precoating composition. BYK-348 (trade name of BYK Chemie) was used as a leveling agent, and white R-902 (trade name of DuPont) was used as a sieving pigment. . In addition, an aqueous prepaint composition was prepared using BYK-011 as an antifoaming agent.

570 g of a bisphenol A epoxy oligomer having an epoxy equivalent of 190 and a weight average molecular weight of 380, 500 g of polyethylene glycol having a number average molecular weight of 1,000, and 250 ppm of triethylammonium chloride as a catalyst were placed in a four-necked flask, and the temperature was increased to 130 ° C. under a nitrogen atmosphere. After the reaction was carried out after the reaction was carried out as the result of the reaction proceeds to measure the epoxy equivalent weight in the range of 500 ~ 530, the temperature was lowered to 60 ℃ and then 690 g of deionized water for 10 minutes to terminate the reaction. As a result, an aqueous epoxy resin in a transparent state having an epoxy equivalent of 870, a viscosity of Z3 and a solid content (NV%) of 60 was obtained.

100 g of the aforementioned preliminary coating composition, 148 g of aqueous epoxy resin, and about 50 g of deionized water were sufficiently mixed for 5 minutes to obtain an aqueous epoxy coating composition having a viscosity of 56 KU.

<Test method>

The coating compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were tested in various ways as follows, and the test results are shown in the following [Table 1].

1) Adhesive strength

According to ASTM D 1005, two pieces of aluminum test specimens were attached to the coating composition, and then completely cured and tested by tensile shear adhesion.

2) tensile strength

According to ASTM D 638, the coating composition was completely dry cured to prepare a test piece having a thickness of 3.2 mm, and then measured by a universal testing machine.

3) elongation

Elongation in the tensile test was measured according to ASTM D 638.

4) flexural strength

According to ASTM D 790, the coating composition was completely dried and cured to make a test piece having a thickness of 3.2 mm, and then measured by a universal testing machine.

5) Impact strength

The coating composition was completely dry cured according to ASTM D 256 to make a 3.2 mm thick specimen and then tested with an Izod impact tester.

6) water resistance

The coating composition was completely dried to prepare a test piece having a thickness of 3.2 mm, which was immersed in water for 10 days at room temperature, and then taken out, and the tensile strength was measured according to ASTM D 638.

(Test results analysis)

The eco-friendly hybrid coating composition of Examples 1 and 2 according to the present invention is superior in all items of adhesive strength, tensile strength, flexural strength, impact strength and water resistance than the coating compositions of Examples 3 and 4 and Comparative Examples 1 and 2. It can be seen that it is particularly flexible, tough, water resistant, has excellent adhesion, and shows excellent physical properties at various strengths.

The embodiments of the present invention only clearly show some of the technical idea included in the present invention, and modifications and specific implementations that can be easily inferred by those skilled in the art within the scope of the technical idea included in the specification of the present invention. It is obvious that all examples are included in the scope of the technical idea of the present invention.

Claims (4)

delete Rubber-modified epoxy resins prepared by emulsifying rubber-modified epoxy resins reacted with polybutadiene rubbers having a carboxyl group in epoxy resins in water are antifreeze agents, antifoaming agents, preservatives, antifreeze agents, dispersants, water, water thickeners, extender pigments, 75 to 85% by weight of an additive containing a thickener additive;
15 to 25% by weight of a curing agent prepared by mixing a curing accelerator with an aqueous acrylic resin,
The epoxy resin is a liquid equivalent of 300 or less equivalents,
The polybutadiene rubber having a carboxyl group is one having a reactive carboxyl group at both ends of the molecular weight of 3000 ~ 7000,
The rubber modified epoxy resin is an environmentally friendly hybrid coating composition, characterized in that represented by the following formula 1.

(Equation 1)
(In Formula 1,
R is a polybutadiene chain,
R ': Bisphenol A epoxy resin chain)
The method according to claim 2,
The rubber-modified epoxy resin of the subject matter is 22.0% by weight based on the environmentally friendly hybrid paint composition, the additive is 0.05 ~ 0.15% by weight cryoprotectant, 0.03 ~ 0.05% by weight antifoam, 0.03 ~ 0.05% by weight preservative, It consists of 0.11 to 0.13% by weight of anti-drying agent, 0.3 to 0.5% by weight of dispersant, 3.8 to 5.8% by weight of water, 0.18 to 0.22% by weight of water thickener, 45.0 to 55.0% by weight of extender pigment, and 3.2 to 3.4% by weight of thickener. The aqueous acrylic resin and the curing accelerator of the curing agent is an environmentally friendly hybrid coating composition, characterized in that consisting of 19.4% by weight, 0.6% by weight relative to the environmentally friendly hybrid paint composition.
The method according to claim 3,
The thickener is an environmentally friendly hybrid paint composition, characterized in that made by mixing 15 parts by weight of 20% ammonia water, 150 parts by weight of acrylic resin in 100 parts by weight of water.