KR101281344B1 - Method of water soluble epoxy ester modified vinyl resin composition for a ship and paint composition using the same - Google Patents

Abstract

The present invention relates to a method for preparing a water-soluble epoxy ester-modified vinyl resin composition for ships and to a coating composition using the same. The method for preparing a water-soluble epoxy ester-modified vinyl resin composition for ships is carried out by esterifying a fatty acid having an epoxy resin and an unsaturated bond in a molecule. A step of producing an epoxy ester compound; A step of neutralizing with a basic neutralizing agent after graft polymerization including a vinyl monomer and a phosphate ester compound having an intramolecular double bond in the epoxy ester compound produced in step A; And C step of dissolving the neutralized neutralized in step B in water; It is an object to provide a method for producing a resin composition comprising a, thereby improving the adhesion, excellent corrosion resistance, water resistance and excellent drying and storage stability.
According to the present invention, since the phosphate ester compound contained in the resin composition imparts a low viscosity effect at the time of solubilization and an adhesion promotion effect, it is possible to prepare a low viscosity water-soluble resin while having a low content of volatile organic compounds. Excellent adhesion to the steel surface and has the effect of improving the corrosion resistance and water resistance of the coating film.

Description

Manufacturing method of water-soluble epoxy ester-modified vinyl resin composition for ships and coating composition using the same TECHNICAL FIELD

The present invention relates to a method for producing a water-soluble epoxy ester modified vinyl resin composition for ships and a coating composition using the same.

Solvent-type paints of epoxy resins having excellent anticorrosive properties have been widely used for ships. However, due to the recent increase in awareness of environmental pollution, the demand for environmental regulation and reduction of volatile organic compounds and the consideration of work stability, the demand for substitution of aqueous or water-based paints instead of solvents is increasing. In the reduction of organic solvents, the content is continuously decreasing.

In the case of the paint used for the ship which is a large structure, it should be able to be dried at room temperature because it is difficult to heat and dry and maintain the beautiful appearance and gloss like the solvent type. However, water-based paints containing hydrophilic functional groups such as carboxyl groups and polyethylene oxides are generally inferior in water resistance, dryness and adhesion due to water properties having high surface tension and high latent heat of evaporation, and corrosion resistance is also inferior to solvent types. And the anionic hydrophilic group is neutralized and then water-soluble. If the neutralized salt is left in the coating, the compatibility may be insufficient and the gloss may be lowered. In the case of high temperature and high humidity, the appearance of the coating may be reduced.

Various studies have been conducted to develop an aqueous resin composition exhibiting properties similar to those of the solvent-type resin composition in water resistance, corrosion resistance, dryness, and adhesion, but having a level of physical properties required in the industry as compared to oil-based resin compositions. Development of a water-soluble resin composition and an aqueous coating is ongoing.

Initially, there is a method of using an emulsifier when dispersing the resin in an aqueous medium in order to make it aqueous, where an aqueous paint using a large amount of an emulsifier is insufficient in adhesion due to the emulsifier and weak in water resistance and corrosion resistance of the coating film. There was this. In addition, there is a method of dispersing the resin by introducing a large amount of hydrophilic groups in the resin, but this case also had a problem that the water resistance and corrosion resistance due to excessive hydrophilic groups are insufficient.

In order to improve such a problem, by using a certain amount of organic solvent in combination to produce a resin composition, while maintaining the water dispersibility of the resin composition and improving the water resistance and corrosion resistance of the paint while suppressing the introduction amount of the hydrophilic group or the amount of the emulsifier ( Japanese Patent Laid-Open No. 2003-119245) has been proposed. However, this technique has a problem in that the dispersion stability of the pigment is greatly reduced when the organic solvent is not used in an amount of 10% by weight or more, and the particles aggregate and cause sedimentation.

On the other hand, in the case of Republic of Korea Patent No. 10-1011337, in order to improve the corrosion resistance and water resistance of the coating film, a second fatty acid was added in the polymerization process of the epoxy ester compound and the vinyl monomer to prepare a resin composition having a higher solid content. However, when the second fatty acid is polymerized together with the acrylic monomer, there is a disadvantage in that it is difficult to completely polymerize due to the nature of the double bond of the fatty acid, and the remaining unreacted fatty acid has a problem in that it impairs the adhesion and water resistance of the paint.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is to provide a method for producing a resin composition having improved adhesion and excellent corrosion resistance, water resistance, and excellent dryness and storage stability.

In one aspect of the present invention, a method for producing a water-soluble epoxy ester-modified vinyl resin composition for marine use comprises a step of esterifying an epoxy resin and a fatty acid having an unsaturated bond in a molecule to produce an epoxy ester compound; A step of neutralizing with a basic neutralizing agent after graft polymerization including a vinyl monomer and a phosphate ester compound having an intramolecular double bond in the epoxy ester compound produced in step A; And C step of dissolving the neutralized neutralized in step B in water; Characterized in that it comprises a.

A step is A 'step of diluting the epoxy ester compound produced in the A step with a solvent; Characterized in that it comprises a.

The fatty acid in step A is at least one selected from the group consisting of soybean oil fatty acid, tall oil fatty acid, palm oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, tung oil fatty acid, rice bran oil fatty acid, sunflower fatty acid and cottonseed oil fatty acid It is done.

In step B, the vinyl monomers are styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl (meth). ) Acrylate, tertiary-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate It is characterized in that at least one selected from the group.

In step B, the phosphate ester compound is characterized by having the following formula.

(In the above formula, R1, R2 is H or CH ₃ ).

The epoxy resin is characterized in that the epoxy equivalent is selected from the group consisting of bisphenol A epoxy resin of 180 to 2100, respectively.

Solid content of the water-soluble epoxy ester modified vinyl resin composition for ships is 30 to 50 parts by weight based on 100 parts by weight of the resin composition, characterized in that the volatile organic compound is 10 parts by weight or less.

Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships is based on 100 parts by weight of a water-soluble epoxy ester modified vinyl resin composition for ships, 20 to 35 parts by weight of the epoxy ester resin; 8 to 20 parts by weight of the vinyl monomer; 3 to 10 parts by weight of the volatile organic compound; 0.01 to 2 parts by weight of the phosphate ester compound; And the water; characterized in that it comprises a residual amount.

In another aspect of the present invention to achieve this object, the coating composition is a resin composition prepared by the above-described manufacturing method; And additives mixed with the resin composition; And a control unit.

As described above, according to the present invention, in the polymerization process of the epoxy ester compound and the vinyl monomer, a phosphate ester compound is added together with the vinyl monomer to prepare a graft polymerized resin composition.

Therefore, when such a resin composition is used in paints, the phosphate ester compound contained in the resin composition gives a low viscosity effect and an adhesion promotion effect upon solubility, so that the water content of low viscosity and low viscosity is low. Resin can be manufactured, and it is excellent in adhesiveness with an iron surface, and has the effect of improving the corrosion resistance and water resistance of a coating film.

The preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings, in which the technical parts already known will be omitted or compressed for simplicity of explanation.

<Description of Method>

The water-soluble epoxy ester-modified vinyl resin composition for ships of the present invention (hereinafter referred to as a 'resin composition') includes an epoxy resin, a fatty acid, a vinyl monomer, a solvent, an amine neutralizer and water.

Solid content of the water-soluble epoxy ester modified vinyl resin composition for ships which concerns on this invention is 30-50 weight part with respect to 100 weight part of resin compositions, Preferably it is 35-45 weight part. In this case, the solid content may be defined as a nonvolatile component except water and an organic solvent included in the resin composition.

The resin composition first synthesizes an epoxy ester compound produced by esterifying a bisphenol A type epoxy resin with a fatty acid having an unsaturated bond in a molecule, and includes a vinyl monomer and a phosphate ester compound having a double bond in a molecule in the compound. After graft polymerization, the carboxyl group of the carboxyl group-containing monomer used in the vinyl monomer used in the polymerization product is neutralized with an amine neutralizer and then dissolved in water.

1.Step A

In this step, a process of generating an epoxy ester compound by esterifying a bisphenol A type epoxy resin and a fatty acid having an unsaturated bond in a molecule is performed.

At this time, the epoxy resin that can be used is not particularly limited, but preferably a bisphenol A epoxy resin having an epoxy equivalent of 180 to 2100 (for example, YD-128, YD-011, YD-014 and YD-017 of Kukdo Chemical Co., Ltd.). It can be selected from the group consisting of), and similar grade epoxy resins produced by other companies may be applied.

When using a resin having a large epoxy equivalent of the epoxy resin used in the above, the epoxy ester compound produced by the esterification reaction is improved in hardness, dryness, corrosion resistance and water resistance, but the viscosity may be increased, resulting in poor water dispersibility. When a resin having a small epoxy equivalent of the epoxy resin is used, the water dispersibility is improved, but the epoxy equivalent of the epoxy resin used is preferably 180 to 2100 because the hardness, water resistance, corrosion resistance and dryness of the final coating film may be lowered.

Such an epoxy resin is preferably included in 10 to 20 parts by weight based on 100 parts by weight of the water-soluble epoxy ester-modified vinyl resin composition. If the epoxy resin is included in less than 10 parts by weight, the adhesion to the substrate may be lowered, and the corrosion resistance and water resistance of the coating film may be lowered. When the epoxy resin is included in an amount exceeding 20 parts by weight, the viscosity of the resin composition to be produced is increased, and The content of solids is lowered at the time of fire, and the adhesion and corrosion resistance may be reduced due to the high viscosity even after the paint is manufactured.

On the other hand, the fatty acid having a carboxyl group present at the end of the molecule is esterified with the epoxy group present at both ends of the epoxy resin, and also reacted with the hydroxyl group generated by reacting with the epoxy group and the self-containing hydroxyl group of the epoxy resin to further esterify. In order to prepare an esterified compound of an epoxy resin and a fatty acid, the unsaturated bond in a molecule of a fatty acid is modified in a polymer formed by graft polymerization with a vinyl monomer and a phosphate ester compound having a double bond in a molecule in step B. It will act as water.

In this case, in order to perform the graft polymerization, the fatty acid which is esterified with the epoxy resin is not particularly limited as long as it has an unsaturated bond in the molecule, but the iodine value (numerical value indicating the degree of unsaturation in the molecule) is 100 to 160. Semi-drying oil fatty acids or dry oil fatty acids are preferred.

As the fatty acid is reacted with the epoxy resin in this way, the crosslinking density of the resin composition is increased to improve the water resistance, corrosion resistance, and drying property of the room temperature curing type of the coating film.

In an embodiment of the present invention, the fatty acid may be selected from the group consisting of soybean oil fatty acid, tall oil fatty acid, palm oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, tung oil fatty acid, rice bran oil fatty acid, sunflower fatty acid and cottonseed oil fatty acid have. In addition, the fatty acid may be used alone or in combination of two or more, if necessary, it is preferably included in 10 to 20 parts by weight based on 100 parts by weight of the water-soluble epoxy ester-modified vinyl resin composition. If the fatty acid is included in less than 10 parts by weight, the crosslinking density may be reduced due to the lack of unsaturated groups in the resin composition, thereby reducing the water resistance and corrosion resistance when forming the coating film, and when included in excess of 20 parts by weight, the hardness of the coating film may be reduced. Because there is.

In addition, the introduction of an unsaturated group in the epoxy ester resin compound may introduce not only fatty acids but also some organic acids including unsaturated groups such as maleic acid and fumaric acid. At this time, the amount used is preferably contained in 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition. Although there is no organic acid content, when it is 5 weight part or more, the hardness and hardenability of the resin composition manufactured are high, but since the viscosity of resin is high and water solubility is difficult, the content of the organic solvent may be increased.

In preparing the epoxy ester compound, the esterified compound of the epoxy resin and the fatty acid preferably contains 20 to 40 parts by weight based on 100 parts by weight of the water-soluble epoxy ester-modified vinyl resin composition. More preferably, it contains 20 to 35 parts by weight.

2. Step A '

In this step, a process of diluting the epoxy ester compound produced in step A with a solvent is performed. That is, depending on the epoxy resin used in step A, when the viscosity of the resulting epoxy ester compound is high, an organic solvent may be used to dissolve the resin compound.

The organic solvent used in the embodiment of the present invention is an alcohol-based, propylene glycol-based acetate that is compatible with water because the compatibility with the solvent should come out when the epoxy ester compound and the vinyl monomer are water-soluble after graft polymerization. Can be used.

In addition, the above-described organic solvent may be partially removed before and after the water solubilization in order to control the volatile organic solvent content. Specifically, the organic solvent is preferably included in 3 to 10 parts by weight based on 100 parts by weight of the resin composition in consideration of the water solubility, the viscosity of the resin composition, the storage stability ability.

3. Step B

In this step, the phosphate ester compound having a vinyl monomer and a double bond in the molecule is added to the epoxy ester compound produced in step A, graft polymerization, and neutralized with a basic neutralizing agent.

At this time, the vinyl monomer which can be used is not specifically limited, Styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, It may be selected from the group consisting of iso-butyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate and isobonyl (meth) acrylate.

Such a vinyl monomer may improve the dryness and hardness of the final coating film as the double bond portion of the vinyl group present in the monomer undergoes a graft polymerization reaction with the unsaturated bond portion present in the epoxy ester compound.

In addition, when the carboxyl group derived from (meth) acrylic acid contained in the vinyl monomer is dispersed in water at step C, the carboxyl group acts as a hydrophilic group, thereby increasing the water solubility of the polymer.

Such vinyl monomers are preferably included in an amount of 8 to 20 parts by weight based on 100 parts by weight of the resin composition in consideration of water solubility, strength of the coating film, dryness and water resistance.

Here, a polymerization initiator may be used in the graft polymerization of the epoxy ester compound with the vinyl monomer and the phosphate ester compound. In this case, the polymerization initiator that can be used is not particularly limited, but examples thereof include 2,2-azobisisobutylonitrile. Azo compounds, benzoyl peroxide, tert-butylperoxybenzoate, di-tert-butylperoxide, tert-butylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, etc. Peroxide can be used individually or in mixture of 2 or more types.

In addition, a phosphate ester compound having an intramolecular double bond is added to improve adhesion to the base of the resin composition. That is, when the phosphate ester compound is added during the graft polymerization of the epoxy ester compound and the vinyl monomer, the double bond of the phosphate ester compound is polymerized with the vinyl group of the vinyl monomer, so that the compound of the phosphate ester included in the resin composition is hydrophobic. A resin composition excellent in corrosion resistance and water resistance by performing the role of an emulsifier to mix well with the hydrophilicity, thereby lowering the viscosity of the resin composition to be prepared and improving adhesion of the base material by the effect of increasing adhesion, which is a characteristic of the phosphate ester compound. Can be prepared.

Here, the phosphate ester compound is represented by the following formula.

[Chemical Formula]

Where R 1 and R 2 are H or CH ₃ .

On the other hand, the phosphate ester compound is preferably included in 0.01 to 2 parts by weight, based on 100 parts by weight of the resin composition. If the phosphate ester compound is included in less than 0.01 parts by weight, it is difficult to expect the adhesive effect on the possession of the resin composition, if contained in more than 2 parts by weight may increase the viscosity of the resin composition during synthesis to reduce the reaction stability This is because the content of volatile organic solvent cannot be reduced because the content of organic solvent increases during the reaction.

In addition, in this step, the process of neutralizing the polymer produced by graft polymerization with an amine-based neutralizing agent is performed. That is, an amine neutralizing agent neutralizes the carboxyl group which exists in the side chain of the superposition | polymerization which polymerized the said vinyl monomer and the said phosphate ester compound to the said epoxy ester compound. In this case, the carboxyl group to be neutralized is specifically, a carboxyl group derived from (meth) acrylic acid contained in the vinyl monomer.

 Here, the material that can be used as the amine neutralizing agent is not particularly limited, but methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylethanolamine, diethylethanolamine, ammonia, etc. may be used. It can be used, it can be used individually or in mixture of 2 or more types as needed.

4. Step C

In this step, the neutralization neutralized in step B is dissolved in water. In other words, water is added to the polymer neutralized with the amine-based neutralizing agent in step B. At this time, the final acid value after solubilization is about 10-40 (mgKOH / g), and has a number average molecular weight of 3,000-15,000.

In addition, the water-soluble resin composition of the present invention may exhibit a viscosity in the range of 500 ~ 20,000cps. However, the viscosity and solid content of the resin composition of the present invention may vary depending on the acid value of the polymer, the type and amount of the organic solvent and the basic neutralizing agent included in the resin composition.

 <Description of Coating Composition>

 This invention can provide the coating material containing the resin composition demonstrated above. At this time, the water-based coating composition of the present invention, in addition to the water-soluble resin composition described above, additives suitable for various uses, for example, conventional additives such as metal dryers, leveling agents, ultraviolet absorbers, antioxidants, antifoaming agents, dispersants, etc. May be included.

The method for producing the water-soluble coating composition is not particularly limited, and for example, fillers such as calcium carbonate, pigments such as titanium oxide, additives, and the like are dispersed in the water-soluble resin composition to produce a mill base, and then various additives and the water-soluble resins. It can manufacture by adding and mixing a thickener and water for adjusting a viscosity to a composition.

Such coating material of this invention can form a coating film by airless coating, a base material, etc. using normal methods, such as a brush or a roller, and then drying naturally.

Although the base material which can be coated with the water-soluble coating composition of this invention is not specifically limited, For example, it can be generally used for the coating of large structures, such as metal base materials, such as iron, zinc, and aluminum, and wood.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Example 1

12 parts by weight of soybean oil fatty acid and 12 parts by weight of YD-011 (Kukdo Chemical, Bisphenol A epoxy) were weighed into a four-necked flask equipped with a stirrer, a thermometer, a water separation reflux device, a condenser, and an N2 gas supply. It heated up at ° C. The xylene was refluxed at 230 ° C. and the esterification reaction was maintained for 8 hours while dehydrating the water generated in the water separator. When the acid value of the reaction product became 1.0 (mgKOH / g) or less, the mixture was gradually depressurized and recovered and cooled until the xylene used as the reflux solvent was no longer recovered. 6 weight part of butyl cellosolves were added and diluted at 150 degrees C or less, and the epoxy ester compound was obtained.

Thereafter, the temperature was maintained at 150 ° C., and a mixed solution obtained by separately mixing 12.8 parts by weight of styrene, 2.8 parts by weight of acrylic acid, and 1.0 parts by weight of benzoyl peroxide was added dropwise over 2 hours, followed by further reaction for 5 hours to obtain a polymer.

Thereafter, the polymer was cooled to 80 ° C, neutralized by adding 3.2 parts by weight of triethylamine (TEA) to the reaction portion, and slowly added by 50 parts by weight of ion-exchanged water to prepare a water-soluble epoxy ester-modified vinyl resin composition.

[Example 2]

A water-soluble epoxy ester-modified vinyl resin composition was prepared in the same manner as in Example 1, except that the content shown in Table 1 was applied.

[Example 3]

A water-soluble epoxy ester-modified vinyl resin composition was prepared in the same manner as in Example 1, except that the content shown in Table 1 was applied.

Example 4

A water-soluble epoxy ester-modified vinyl resin composition was prepared in the same manner as in Example 1, except that the content shown in Table 1 was applied.

[Example 5]

A water-soluble epoxy ester-modified vinyl resin composition was prepared in the same manner as in Example 1, except that the content shown in Table 1 was applied.

[Example 6]

A water-soluble epoxy ester-modified vinyl resin composition was prepared in the same manner as in Example 1, except that the content shown in Table 1 was applied.

Comparative Example 1

A water-soluble epoxy ester-modified vinyl resin composition was prepared in the same manner as in Example 1, except that the phosphate ester compound was applied.

Comparative Example 2

A water-soluble epoxy ester-modified vinyl resin composition was prepared in the same manner as in Example 1, except that the phosphate ester compound was applied.

[Measurement method and evaluation result 1]

The physical properties of the water-soluble epoxy ester-modified vinyl resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated in the following manner, and the results are shown in Table 1 below.

1. Measurement of solid content (non-volatile content)

 Inner diameter of about 80mm, each of the resin composition prepared in the above on a flat plate, evenly divided to dry well, put in a thermostat (105 ± 2 ℃), dried for 3 hours and then measured the solid content It was.

2. Molecular Weight Measurement

Molecular weight and molecular weight distribution were measured by GPC (Gel Permeation Chromatography, Type R-410, Waters, USA), the detector connected RI, Shodex KF-802, KF-803, KF-804, KF-805 THF was used as the solvent.

3. Viscosity Measurement

Viscosity was measured using a Brookfield viscometer LVF as a rotational viscometer test method for non-Newtonian materials in ASTM D 2196 after maintaining the resin composition in a 25 ° C constant temperature water bath for 30 minutes. The unit was cps (mPa. s) units were used.

4. Storage stability after solubilization

After the synthetic resin composition was solubilized, it was placed in a transparent glass bottle for 10 days in a constant temperature bath (25 ± 2 ° C), and then visually observed the state of each resin composition. Evaluation was made based on the criteria.

 -No segregation of resin composition, little or no change in viscosity: Good (○)

 -There is no layer separation of the resin composition, and there are many viscosity changes: normal (△)

 -With layer separation: Bad (X)

Configuration Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Soybean oil fatty acid 12 14 16 7 7 7 14 7 Tall oil fatty acid - - - 7 7 7 - 7 YD-011 12 14 16 14 - 7 14 - YD-014 - - - - 14 7 - 14 BC 6 6 6 6 6 6 6 6 Styrene 12.8 8.8 4.8 8.8 8.8 8.8 9.2 9.2 Acrylic acid 2.8 2.8 2.8 2.8 2.8 2.8 2.8 2.8 Phosphate Ester 0.4 0.4 0.4 0.4 0.4 0.4 - - BPO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 TEA 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 Ion-exchange water 50 50 50 50 50 50 50 50 Sum 100 100 100 100 100 100 100 100 Non-volatile matter (%) 40.2 40.6 40.3 40.2 40.3 40.5 40.2 40.3 Molecular weight (Mn) 7500 7600 7200 7900 8300 8000 7100 7000 Viscosity (cps) 5800 3800 3000 4200 4700 4200 10000 12000 Storage stability ○ ○ ○ ○ ○ ○ △-○ △-○

As can be seen in Table 1, the resin composition according to the present invention Examples 1 to 6 can be confirmed that the viscosity is relatively low while the molecular weight is similar to or higher than Comparative Examples 1-2. Moreover, it was confirmed that water dispersion stability is also better than the resin composition of Comparative Examples 1-2.

[Production Example 1]

Titanium oxide (TiO ₂ ), calcium carbonate (CaCO ₃ ), and additives were mixed and dispersed in the resin composition prepared in Example 1 in the amounts shown in Table 2 below. A water-soluble paint was prepared by adding a desiccant, thickener and water to the prepared dispersion by stirring and mixing.

[Production Example 2]

 Except for using the resin composition prepared in Example 2, an aqueous paint was prepared in the same manner as in Preparation Example 1, shown in Table 2.

[Production Example 3]

Except for using the resin composition prepared in Example 3, an aqueous paint was prepared in the same manner as in Preparation Example 1, shown in Table 2.

[Production Example 4]

Except for using the resin composition prepared in Example 4, an aqueous paint was prepared in the same manner as in Preparation Example 1, shown in Table 2.

[Production Example 5]

Except for using the resin composition prepared in Example 5, an aqueous paint was prepared in the same manner as in Preparation Example 1, shown in Table 2.

Production Example 6

Except for using the resin composition prepared in Example 6, an aqueous coating was prepared in the same manner as in Preparation Example 1, shown in Table 2.

[Production Example 7]

Except for using the resin composition prepared in Comparative Example 1, an aqueous coating was prepared in the same manner as in Preparation Example 1, shown in Table 2.

[Production Example 8]

Except for using the resin composition prepared in Comparative Example 2, an aqueous paint was prepared in the same manner as in Preparation Example 1, shown in Table 2.

[Measurement method and evaluation result 2]

The water-soluble paints prepared using the water-soluble epoxy ester-modified vinyl resins prepared in Examples 1 to 8 and Comparative Examples were evaluated in the following physical properties, and the results are shown in Table 2 below.

1. Dryability (solidification drying)

Drying property is measured by drying time test method of paint of KSM 5000-2511 (the state that the film does not stretch or wrinkle when twisted at 90 degree angle while pressing with thumb with the arm perpendicular to the coating surface) Evaluated.

 -Less than 10 hours to dry

 10 hours to 15 hours

 -15 hours or more until solidification: X

2. 60 ° glossiness

60 ° glossiness is a test method of 60 ° mirror glossiness of paint of KSM 5000-3312 (as a percentage when the mirror surface glossiness of the standard glass surface is measured by measuring the reflectance when the incident angle and the horizontal angle are 60 ° respectively. 60 degree glossiness in the average value measured and displayed 5 times) was measured and evaluated.

3. Water resistance

After coating the coating film to 100 micrometers and drying it at room temperature for 24 hours, the test piece was immersed in water of normal temperature for 240 hours, and the peeling degree of the blister of a coating film, and the peeling degree of the coating film were visually evaluated and evaluated.

 -No abnormality in coating: ○

 -Slightly blister without peeling the coating: △

 -Peel off and blister: X

4. Anticorrosive

Crosscutting was carried out so that the test piece coating film was visible, and after 240 hours test in a salt spray test machine (35 ± 2 ° C., 5% aqueous sodium chloride solution), the degree of peeling and corrosion of the coating film was visually evaluated.

 -If there is no call out in the crosscut: ○

 -If rust is less than 1mm on cross cut part: △

 -If rust is more than 1㎜ on cross cut part: X

Configuration Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Suzy 50
(Example 1) 50
(Example 2) 50
(Example 3) 50
(Example 4) 50
Example 5 50
Example 6 50
(Comparative Example 1) 50
(Comparative Example 2) Titanium oxide 20 20 20 20 20 20 20 20 Calcium carbonate 20 20 20 20 20 20 20 20 Dispersant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Antifoam 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 drier 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Thickener 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 water 7.7 7.7 7.7 7.7 7.7 7.7 12.7 12.7 system 100 100 100 100 100 100 105 105 Drying ○ △ △ △ ○ △ △ ○ Glossy (60 °) 68 68 65 67 68 66 57 58 Water resistance ○ ○ ○ ○ ○ ○ X △ -X Improvisation ○-△ ○ ○ ○ ○ ○ X △ -X

As can be seen in Table 2, in the case of the water-soluble paints (Preparation Examples 1 to 6) prepared using the resin composition of the present invention, the adhesion with the base is increased by the influence of the phosphate ester compound, so that the water resistance and the corrosion resistance are manufactured. It was confirmed that it is better than the water-soluble paints prepared in 7 to 8, in the case of Preparation Examples 7 to 8 has a high viscosity to lower the solids during the production of paints, thereby lowering the gloss.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. And the scope of the present invention should be understood as the following claims and their equivalents.

Claims (9)

A step of esterifying the epoxy resin and the fatty acid having an unsaturated bond in the molecule to produce an epoxy ester compound;
A step of neutralizing with a basic neutralizing agent after graft polymerization including a vinyl monomer and a phosphate ester compound having an intramolecular double bond in the epoxy ester compound produced in step A; And
C step of dissolving the neutralized neutralized in the step B in water; Including but not limited to:
In the step B, the phosphate ester compound is characterized by having the following formula
Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships.

(In the above formula, R1, R2 is H or CH ₃ ). The method of claim 1,
Step A, A 'step of diluting the epoxy ester compound produced in step A with a volatile organic solvent; &Lt; RTI ID = 0.0 &gt;
Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships. The method of claim 1,
In step A above
The fatty acid is at least one selected from the group consisting of soybean oil fatty acid, tall oil fatty acid, palm oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, kerosene fatty acid, rice bran oil fatty acid, sunflower fatty acid and cottonseed oil fatty acid.
Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships. The method of claim 1,
In step B above
The vinyl monomers are styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate , Tertiary-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate Characterized in that at least one
Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships. delete The method of claim 1,
The epoxy resin is selected from the group consisting of bisphenol A epoxy resin having an epoxy equivalent of 180 to 2100, respectively.
Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships. The method of claim 2,
Solid content of the water-soluble epoxy ester modified vinyl resin composition for ships is 30 to 50 parts by weight based on 100 parts by weight of the resin composition, characterized in that the volatile organic solvent is 10 parts by weight or less
Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships. The method of claim 7, wherein
Based on 100 parts by weight of the water-soluble epoxy ester modified vinyl resin composition for ships,
20 to 35 parts by weight of the epoxy ester resin;
8 to 20 parts by weight of the vinyl monomer;
3 to 10 parts by weight of the volatile organic solvent;
0.01 to 2 parts by weight of the phosphate ester compound; And
The water; characterized in that it comprises a residual amount
Method for producing a water-soluble epoxy ester modified vinyl resin composition for ships. Claims 1 to 4 and 6 to 8 of the resin composition prepared by the method of any one of claims; And
An additive mixed with the resin composition; &Lt; RTI ID = 0.0 &gt;
Coating composition.