KR20150025464A - Method of manufacturing water soluble modified epoxy ester resin composition and water soluble resin composition manufactured thereby - Google Patents

Abstract

The present invention relates to a method for manufacturing a water soluble resin composition, which comprises the steps of: a) generating an epoxy ester resin by estrifying one or more epoxy resin selected from a group consisting of bisphenol A and bisphenol F which have molecular weight of 350-1400 and epoxy equivalent of 180-1000 g/eq by using phosphate and unsaturated fatty acid; b) generating modified epoxy ester resin by modifying the epoxy ester resin with vinyl monomer; and c) dissolving the modified epoxy ester resin in water by neutrifying with a base material, and to a water soluble resin composition manufactured by the same. A pain including the resin composition of the present invention can from a coated film with excellent adhesion, anticorrosion, and anti-boiling.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble modified epoxy ester resin composition and a water-soluble resin composition prepared by the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a process for producing a water-soluble modified epoxy ester resin composition for use in paints and a water-soluble resin composition prepared thereby.

The paint is used for the purpose of protecting the base material of various products and improving the appearance of the various products. Various physical properties are required depending on the application. For example, paints applied to metal parts such as automobile parts and ships require adhesion, water resistance, corrosion resistance and dryness in order to prevent corrosion of metal substrates by water and the like.

Water-soluble paints are generally produced by using a water-dispersible resin by emulsifying with a surfactant or neutralizing a resin by introducing a large amount of a hydrophilic group into the resin, which has the greatest effect on the physical properties of such paints. However, the paint thus prepared is insufficient in chemical resistance such as corrosion resistance, water resistance and water resistance due to lack of adhesion with the material.

Therefore, there is a need for a new water-soluble resin capable of remarkably improving the chemical resistance such as corrosion resistance, water resistance and weather resistance by introducing an appropriate amount of hydrophilic groups into the chemical structure of the resin and improving the adhesion with the material.

The present invention relates to a process for producing a naturally drying water-soluble resin composition having excellent adhesion and corrosion resistance, which is used in industrial coatings for metals such as marine and automobile parts, and a water-soluble resin composition prepared by the method.

The present invention provides a resin composition comprising: a) at least one epoxy resin selected from the group consisting of bisphenol A-type epoxy resins and bisphenol F-FEP resins having a molecular weight of 350 to 1400 and an epoxy equivalent of 180 to 1000 g / eq by esterification using phosphoric acid and an unsaturated fatty acid, Producing a resin; b) modifying the epoxy ester resin with a vinyl monomer to produce a modified epoxy ester resin; And c) neutralizing the modified epoxy ester resin with a basic substance to obtain a water-soluble resin composition.

The production method of the present invention further comprises the step of adjusting the acid value of the above-mentioned water-soluble modified epoxy ester resin to 20-70.

The unsaturated fatty acid used for esterifying the epoxy resin is at least one selected from the group consisting of linseed fatty acid, safflower oil fatty acid, sunflower fatty acid, soybean fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, linoleic acid and ricinoleic acid, The molar ratio of the phosphoric acid and the unsaturated fatty acid is 4: 6 to 6: 4. The vinyl monomer used for modifying the epoxy ester resin is at least one selected from the group consisting of styrene, vinyl toluene, vinyl silane, acrylic acid, methacrylic acid, methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, iso Butyl methacrylate, isobutyl acrylate, ethyl methacrylate and ethylhexyl acrylate, and the weight ratio of the epoxy ester resin to the vinyl monomer is 3: 7 to 7: 3.

The basic substance neutralizing the modified epoxy ester resin is selected from the group consisting of diethylamine, triethylamine, diethanolamine, triethanolamine, aminomethylpropanol, dimethylethanolamine, aminoethylethanolamine, diisopropanolamine, and ammonia More than one.

The present invention also provides a water-soluble resin composition prepared by the above method.

Hereinafter, the present invention will be described in detail.

The method for producing a water-soluble resin composition according to the present invention is a method for producing a water-soluble resin composition by first preparing an epoxy ester resin produced by esterifying an epoxy resin with an unsaturated fatty acid having an unsaturated bond in a molecule with phosphoric acid and modifying the epoxy resin with a vinyl monomer to produce a modified epoxy ester resin Next, it is obtained by neutralizing the modified epoxy ester resin with a basic substance and dispersing it in water, which will be described in detail as follows.

a) Esterification  step

The present invention includes an esterification reaction of an epoxy resin with phosphoric acid and an unsaturated fatty acid to prepare a resin composition. At this time, the epoxy resin which can be used is not particularly limited, but one or more can be selected from the group consisting of bisphenol A type and bisphenol F type having a molecular weight of 350 to 1400 and an epoxy equivalent of 180 to 1000 g / eq.

When the molecular weight of the epoxy resin is more than 1400, the viscosity of the epoxy ester resin produced by the esterification reaction is increased to make it difficult to be water-dispersed and water-dispersible. When the molecular weight of the epoxy resin is less than 350, But it is difficult to be dried with a paint, the molecular weight of the epoxy resin used is preferably from 350 to 1400.

85% phosphoric acid (phosphoric acid) is phosphoric esterified in the epoxide functional group of the epoxy resin remaining after primary reaction of the epoxy resin with the unsaturated fatty acid, and the acid functional group of the phosphoric acid remaining after the phosphoric ester The adhesion to the steel material is improved and the corrosion resistance is improved in the physical properties of the final coating material.

On the other hand, the unsaturated fatty acid which undergoes esterification with the epoxy resin is not particularly limited as long as it has an unsaturated bond in the polymer, but an unsaturated fatty acid having a high iodine value, which is a numerical value indicating the degree of unsaturation in the molecule, May be selected from the group consisting of linseed oil fatty acid, safflower oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, linoleic acid and ricinoleic acid. Can be mixed and used.

The molar ratio of unsaturated fatty acid to phosphoric acid used in the esterification reaction of the epoxy resin is preferably 4: 6 to 6: 4. When the molar ratio thereof is less than 4: 6, adhesion with the material is insufficient, When the molar ratio exceeds 6: 4, the ratio of the unsaturated fatty acid is reduced and the Diels-Alder reaction becomes difficult.

b) Denaturing step

The present invention includes a step of producing a modified epoxy ester resin obtained by modifying an epoxy ester resin with a vinyl monomer in order to produce the resin composition. The vinyl monomers that may be used herein include styrene, vinyl toluene, vinyl silane, acrylic acid, methacrylic acid, methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl methacrylate, isobutyl Acrylate, ethyl methacrylate, and ethylhexyl acrylate.

The weight ratio of the epoxy ester resin to the vinyl monomer is preferably 3: 7 to 7: 3. When the weight ratio of these resins is less than 3: 7, the reaction between the epoxy esterified resin and the vinyl monomer is difficult, and when the weight ratio of these resins exceeds 7: 3, drying as a coating becomes difficult.

Such a modification reaction can improve the dryness and hardness of the final coating film as the double bond moieties present in the vinyl monomer react with the unsaturated bond moieties present in the epoxy ester resin, and the carboxyl groups contained in the vinyl monomers can be modified with the modified epoxy As the ester resin acts as a hydrophilic group when dispersed in water, the water-dispersibility of the modified epoxy ester resin can be increased.

An initiator can be used in the reaction of the epoxy ester resin and the vinyl monomer. The initiator that can be used is not particularly limited, but azo compounds such as 2,2-azobisisobutylonitrile, benzoyl peroxide, Butyl peroxide, tert-butyl peroxypivalate, and tert-butyl peroxy-2-ethylhexanoate. These peroxides may be used alone or in admixture of two or more. .

c) neutralization step

The present invention includes a step of neutralizing the modified epoxy ester resin prepared above with a basic material to prepare a resin composition. The basic substance neutralizes the carboxyl group present at the terminal of the modified epoxy ester resin obtained by polymerizing the epoxy ester compound and the vinyl monomer.

The material which can be used as the basic neutralizing agent is not particularly limited, but it is preferably at least one member selected from the group consisting of ethylamine, triethylamine, diethanolamine, triethanolamine, aminomethylpropanol, dimethylethanolamine, aminoethylethanolamine, diisopropanolamine and ammonia And may be used singly or in a mixture of two or more as necessary.

The present invention further includes a step of adjusting the final acid value of the neutralized water-soluble modified epoxy ester resin to 20 to 70. If the acid value is less than 20, the water-soluble is not achieved. If the acid value is more than 70, But the water resistance and the alkali resistance of the paint are remarkably deteriorated.

The modified epoxy ester resin composition produced by the present invention can improve the adhesion of metal base materials such as ships and automobile parts to industrial paints and improve chemical resistance including corrosion resistance.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

< Example  1>

A thermometer, a condenser, a stirrer, a condenser for removing water, and a heating device were attached to a 5 liter four-necked flask. 235 g of bisphenol epoxy resin EPIKOTE-1001 (manufactured by Kumho Shell, molecular weight: 900, epoxy equivalent: 450-500), 475 g of EPIKOTE-1004 (manufactured by Kumho Shell, molecular weight: 1,400, epoxy equivalent: 900-1,000) And 145 g of fatty acids were mixed and reacted at 150 캜 with gentle stirring to obtain an epoxy esterified resin having an acid value of 10 by mixing with 19.2 g of 85% phosphoric acid and cooling at a temperature of 70 캜. 348 g of methyl methacrylate, 146 g of butyl methacrylate, 86 g of methacrylic acid and 11.6 g of azobisisobutyronitrile as an initiator were mixed and the mixture was titrated at 140 DEG C for 2 hours to obtain an acrylate-modified epoxy ester resin. 95 g of aminomethyl propanol was added thereto and neutralized, followed by mixing with water to obtain a water-soluble resin having a nonvolatile content of 35%.

< Example  2>

A thermometer, a condenser, a stirrer, a condenser for removing water, and a heating device were attached to a 5 liter four-necked flask. 285 g of bisphenol epoxy resin EPIKOTE-1001 (manufactured by Kumho Shell, molecular weight: 900, epoxy equivalent: 450 to 500), 380 g of EPIKOTE-1004 (manufactured by Kumho Shell, molecular weight: 1,400, epoxy equivalent: 900 to 1,000) 140 g of castor oil fatty acid were mixed and reacted at 150 캜 with gentle stirring to obtain an epoxy esterified resin having an acid value of 10 by mixing with 19.2 g of 85% phosphoric acid. 385 g of styrene monomonomer, 99 g of butyl methacrylate, 66 g of methacrylic acid and 11 g of azobisisobutyronitrile as an initiator were mixed and the mixture was titrated at 140 DEG C for 2 hours to obtain an acrylate-modified epoxy ester resin. Thereto was added 90 g of dimethylethanolamine and neutralized, and water was mixed to obtain a water-soluble resin having a nonvolatile content of 35%.

< Example  3>

A thermometer, a condenser, a stirrer, a condenser for removing water, and a heating device were attached to a 5 liter four-necked flask. 237 g of bisphenol epoxy resin EPIKOTE-1001 (manufactured by Kumho Shell, molecular weight: 900, epoxy equivalent: 450-500), 475 g of EPIKOTE-1004 (manufactured by Kumho Shell, molecular weight: 1,400, epoxy equivalent: 900-1,000) And the mixture was reacted at 150 ° C with slow stirring to obtain an epoxy esterified resin having an acid value of 7 by mixing with 15.4 g of 85% phosphoric acid and cooling at a temperature of not more than 1, followed by reaction at 70 ° C. 150 g of methyl methacrylate, 150 g of styrene monomer, 66 g of methacrylic acid and 9.6 g of azobisisobutyronitrile as an initiator were mixed and the mixture was titrated at 140 DEG C for 2 hours to obtain an acrylate-modified epoxy ester resin. 95 g of aminomethyl propanol was added thereto and neutralized, followed by mixing with water to obtain a water-soluble resin having a nonvolatile content of 35%.

< Comparative Example  1>

A thermometer, a condenser, a stirrer, a condenser for removing water, and a heating device were attached to a 5 liter four-necked flask. 237 g of bisphenol epoxy resin EPIKOTE-1001 (manufactured by Kumho Shell, molecular weight: 900, epoxy equivalent: 450 to 500), 475 g of EPIKOTE-1004 (manufactured by Kumho Shell, molecular weight: 1,400, epoxy equivalent: 900 to 1,000) And 280 g of fatty acid were mixed and reacted at 200 DEG C under gentle stirring to cool the mixture in an acid value of 1 or less. To this mixture were added 500 g of a styrene monomer, 160 g of butyl acrylate and 13.2 g of azobisisobutyronitrile as an initiator, The mixture was stirred for 2 hours and then dissolved in xylene to obtain an oily acrylic ester-modified epoxy ester resin having a nonvolatile content of 40%.

< Manufacturing example  1>

Titanium oxide, calcium carbonate, a dispersant, a defoamer, a fume dryer, and a diluent were mixed with the resin composition prepared in Example 1 in the amounts shown in Table 1 to prepare a paint.

< Manufacturing example  2>

An aqueous paint was prepared in the same manner as in Preparation Example 1, except that the resin composition prepared in Example 2 was used instead of Example 1.

< Manufacturing example  3>

An aqueous paint was prepared in the same manner as in Preparation Example 1, except that the resin composition prepared in Example 3 was used instead of Example 1.

< Manufacturing example  4>

The resin composition prepared in Comparative Example 1 was used instead of Example 1, and a non-volatile oil content of 50% was prepared by using xylene as a diluent for preparing the paint.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 Example 1 45 - - - Example 2 - 45 - - Example 3 - - 45 - Comparative Example 1 - - - 43.1 TiO2 R-902 22.5 22.5 22.5 21.6 Calcium carbonate 10.8 10.8 10.8 10.3 Dispersant 0.9 0.9 0.9 0.8 Defoamer 0.5 0.5 0.5 0.4 Metal dryer 0.5 0.5 0.5 0.4 diluent 19.8 19.8 19.8 23.4 Sum 100 100 100 100

< Test Example >

The properties of the aqueous and oil-based paints prepared in Preparation Examples 1 to 4 were compared with those of the coating films after coating, and the results are shown in Table 2.

Each characteristic shown in Table 2 was evaluated by the following method.

One. Drying (Solidification)

First, the drying conditions were naturally dried, and the touching drying was checked to the extent that the hand stickiness remained within 30 to 60 minutes after coating. In the case of solidification drying, the same specimen as that of the tack-free drying test was prepared and placed horizontally at room temperature and dried, and then strongly rubbed with a hand to determine when the film was not pushed out. When the drying time was within 8 hours, it was very good. Within 12 hours, it was good. When it was 12 hours or more, it was normal.

2. The gloss, Acid resistance , Alkali resistance

The gloss is expressed as the intensity of the reflected light with respect to the intensity of the light incident at an angle of 60 °, measured according to ASTM-D-523 standard, and measured according to ASTM-D-1308 standard for acid resistance and alkali resistance.

3. Water resistance, Abdominal aquatic , Appearance state

The degree of change of the coating film was measured after immersing in water for one week and the degree of change of the coating film was determined after immersing in boiling water for 24 hours. , And peeling, cretering, change in hardness of the coating film, occurrence of dullness and the like were observed and evaluated.

4. Corrosion resistance

The coated film was scratched with a cross-cut, and after 200 hours of testing in a salt spray tester (35 ° C, 5% sodium chloride aqueous solution), the degree of adhesion to the material and the degree of corrosion of the material were visually determined.

5. Paint storage

Each of the paints of Preparation Examples 1 to 4 was diluted with each of the diluting agents twice and placed in a test tube, and the degree of separation of the pigment and the resin or the pigment and the diluting agent was evaluated by observation at room temperature for 30 days.

Paint composition Example 1 Example 2 Example 3 Example 4 dry Dry touch ○ ○ ○ ◎ Solidification drying ◎ ◎ ○ ◎ Glossiness (60.) 78 77 80 79 Water resistance ◎ ◎ ○ ◎ Alkali resistance ◎ ○ ○ ◎ Abdominal aquatic ◎ ◎ ◎ △ Corrosion resistance ◎ ○ ◎ △ Acid resistance ◎ ○ ◎ ◎ Paint Resistance ◎ ○ ◎ ◎

In the above Table 2, the evaluation items &amp; cir &amp;, &amp; cir &amp;, &amp; cir &amp;

As shown in Table 2, it was confirmed that the water repellency such as corrosion resistance and oil repellency including the adhesiveness of the water-based paints (Production Examples 1 to 3) prepared using the resin composition of the present invention was superior to the oil-based paints prepared in Production Example 4 there was.

Claims (8)

a) at least one epoxy resin selected from the group consisting of bisphenol A-type epoxy resins and bisphenol F-FEP-type epoxy resins having a molecular weight of 350 to 1400 and an epoxy equivalent of 180 to 1000 g / eq is esterified using phosphoric acid and an unsaturated fatty acid to produce an epoxy ester resin ;
b) modifying the epoxy ester resin with a vinyl monomer to produce a modified epoxy ester resin; And
c) neutralizing the modified epoxy ester resin with a basic substance to obtain a water-soluble resin composition.
The method according to claim 1,
Further comprising the step of adjusting the acid value of the water-soluble modified epoxy ester resin to 20 to 70. The method for producing a water-
The method according to claim 1,
Wherein the unsaturated fatty acid is at least one selected from the group consisting of linseed fatty acid, safflower oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, linoleic acid and ricinoleic acid.
The method according to claim 1,
Wherein the molar ratio of the phosphoric acid to the unsaturated fatty acid is 4: 6 to 6: 4.
The method according to claim 1,
The vinyl monomer may be at least one selected from the group consisting of styrene, vinyl toluene, vinyl silane, acrylic acid, methacrylic acid, methacrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl methacrylate, isobutyl acrylate, Ethyl methacrylate, and ethylhexyl acrylate. The method for producing a water-soluble resin composition according to claim 1,
The method according to claim 1,
Wherein the weight ratio of the epoxy ester resin to the vinyl monomer is 3: 7 to 7: 3.
The method of claim 1,
Wherein the basic substance is at least one selected from the group consisting of diethylamine, triethylamine, diethanolamine, triethanolamine, aminomethylpropanol, dimethylethanolamine, aminoethylethanolamine, diisopropanolamine and ammonia. A method for producing a resin composition.
A water-soluble resin composition produced by the method according to any one of claims 1 to 7.