JP2011122155A - Water-soluble acrylic modified epoxy ester resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble acrylic modified epoxy ester resin composition excellent in corrosion resistance, water resistance, drying property, water repellency, and water dispersibility; and a method of producing the water-soluble acrylic modified epoxy ester resin composition. <P>SOLUTION: The water-soluble acrylic modified epoxy ester resin composition comprises: a neutralization product which is prepared by adding a vinyl monomer and a second fatty acid having a double bond in the molecule to an epoxy ester compound prepared by an esterification reaction of an epoxy resin and a first fatty acid having an unsaturated bond in the molecule, polymerizing the mixture, and neutralizing the polymerization product with a basic neutralization agent; and water. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a water-soluble acrylic-modified epoxy ester resin composition contained in a paint and a method for producing the same.

  The paint is composed of a resin, a pigment, a solvent, an additive, and the like, and is used for the purpose of protecting the base material and improving the appearance of various products. Among them, since substrate protection is the most important application of paint, it is required that the paint can form a coating film having physical properties suitable for various uses. For example, paints applied to metal products such as automobile parts and ships are required to be able to form coatings with excellent water resistance, corrosion resistance, and drying properties in order to prevent corrosion of metal substrates due to water and the like. ing.

Resin has the greatest effect on the physical properties of paints, and various researches have been conducted to develop resin compositions with excellent water resistance, corrosion resistance, drying properties, and water dispersibility (properties that are dispersed in water). However, the development of water-soluble resin compositions and water-based paints having physical properties required by the industry compared to oil-soluble resin compositions is still in the initial stage.
That is, a water-based paint is one in which a resin is dissolved or dispersed in an aqueous medium. Examples of a method for dispersing a resin in an aqueous medium include a method using an emulsifier. There is a problem that the obtained coating film is inferior in water resistance and corrosion resistance. In addition, there is a method of introducing a large amount of hydrophilic groups into the resin to disperse the resin, but there is also a problem that a coating film having excellent corrosion resistance cannot be obtained.

  In order to improve such problems, a resin composition is produced by using a certain amount of an organic solvent in combination, and the water dispersion of the resin composition is suppressed while suppressing the introduction amount of hydrophilic groups and the use amount of an emulsifier. Has been proposed (see Patent Document 1), which can maintain the property and improve the water resistance and corrosion resistance of the paint. However, this technique has a problem that unless 10% by weight or more of an organic solvent is used, the dispersion stability of the pigment is greatly reduced, and particles are aggregated to cause sedimentation.

JP 2003-119245 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention is a water-soluble acrylic-modified epoxy ester resin composition excellent in physical properties required in the industry, specifically, corrosion resistance, water resistance, drying property, water repellency and water dispersibility. It is another object of the present invention to provide a method for producing a water-soluble acrylic-modified epoxy ester resin composition.

In order to achieve the above-mentioned object, the present invention provides an epoxy ester compound produced by esterifying an epoxy resin and a first fatty acid having an intramolecular unsaturated bond, into a second monomer having a vinyl monomer and an intramolecular double bond. A water-soluble acrylic-modified epoxy ester resin composition containing a neutralized product neutralized with a basic neutralizing agent and water after polymerizing the fatty acid of
The first fatty acid is selected from the group consisting of soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, tall oil fatty acid, tung oil fatty acid, bran oil fatty acid, sunflower oil fatty acid and safflower oil fatty acid ,
The second fatty acid is selected from the group consisting of oleic acid, ricinoleic acid, linoleic acid, elaeostearic acid and licanoic acid;
The vinyl monomer is styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, lauryl (meth) A water-soluble acrylic-modified epoxy ester resin composition characterized in that it is selected from the group consisting of acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.

The water-soluble acrylic-modified epoxy ester resin composition of the present invention can further contain a solid additive or a lipophilic additive.
The solid content of the water-soluble acrylic-modified epoxy ester resin composition according to the present invention is preferably 37 to 45 parts by weight, and 40 to 43 parts by weight based on 100 parts by weight of the resin composition. Is more preferable. At this time, the solid content is defined as a solid component excluding water and an organic solvent contained in the resin composition, and the solid content is defined as a content measured after being dispersed in water. .

Further, the present invention includes (a) an epoxy ester compound produced by esterifying an epoxy resin with a first fatty acid having an intramolecular unsaturated bond,
(B) A step of introducing a second fatty acid having a vinyl monomer and an intramolecular double bond into the epoxy ester compound produced in the above step (a) and polymerizing the compound.
(C) a step of neutralizing the polymer polymerized in the above step (b) with a basic neutralizing agent; and (d) dispersing the neutralized material neutralized in the above step (c) in water. Step,
A method for producing a water-soluble acrylic-modified epoxy ester resin composition comprising:
The first fatty acid is selected from the group consisting of soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, tall oil fatty acid, tung oil fatty acid, bran oil fatty acid, sunflower oil fatty acid and safflower oil fatty acid ,
The second fatty acid is selected from the group consisting of oleic acid, ricinoleic acid, linoleic acid, elaeostearic acid and licanoic acid;
The vinyl monomer is styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, lauryl (meth) ) Acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

  Furthermore, this invention can provide the coating material containing the resin composition manufactured with said manufacturing method.

According to the present invention, the above-mentioned problems can be solved and the object can be achieved, and a resin composition having a high solid content can be obtained by introducing the second fatty acid during the polymerization process of the epoxy ester compound and the vinyl monomer. When a resin composition having such a high solid content is used in a paint, the post-coating film is formed smoothly, which can improve the corrosion resistance and water resistance of the coating film. And the drying property of the paint can be increased.
Further, since the water-soluble acrylic-modified epoxy ester resin composition of the present invention can contain a solid additive or a lipophilic additive, when such a resin composition is used in a paint, Water repellency and dryness can be improved.

Hereinafter, the present invention will be described in detail.
<Water-soluble acrylic-modified epoxy ester resin composition and production method thereof>
A water-soluble acrylic-modified epoxy ester resin composition (hereinafter abbreviated as “resin composition”) according to the present invention includes an epoxy resin, a first fatty acid, a second fatty acid, a vinyl monomer, a basic neutralizing agent, and It contains water and further contains other components as necessary.

  Such a resin composition of the present invention is produced by first dissolving an epoxy resin in the absence of a solvent or in the presence of a small amount of an organic solvent, followed by esterification with a first fatty acid having an intramolecular unsaturated bond. The epoxy ester compound is copolymerized with a vinyl monomer and a second fatty acid to produce a polymer, and then the carboxyl group present at the terminal of the polymer is neutralized with a basic neutralizer, To disperse. This will be described in detail below.

(A) Formation of Epoxy Ester Compound The present invention includes a step of esterifying an epoxy resin and a first fatty acid in order to produce a resin composition.
At this time, the usable epoxy resin is not particularly limited and can be appropriately selected according to the purpose. Preferably, a bisphenol A type epoxy resin having a molecular weight of 350 to 2,000 (for example, manufactured by KUKDO Chemical Co., Ltd.). YD-128, YD-011, YD-012, and YD-014), a phenol novolac type epoxy resin having a molecular weight of 350 to 2,000 (for example, YDPN-631 manufactured by KUKDO Chemical Co., Ltd.), and a molecular weight of 350 to 2, 000 cresol novolac type epoxy resin (for example, YDCN-500-80P manufactured by KUKDO CHEMICAL CO., LTD.). Also, epoxy resin products of the same grade such as Kumho P & B products and Bakelite products can be applied.

In addition, when the molecular weight of the epoxy resin increases, the viscosity of the epoxy ester compound produced by the esterification reaction may increase and the water dispersibility may decrease. Conversely, when the molecular weight of the epoxy resin decreases. The water dispersibility is improved, but the water resistance, corrosion resistance and drying property of the final coating film may be lowered. Therefore, the molecular weight of the epoxy resin used is preferably 350 to 2,000.
Also, when the viscosity of the epoxy ester compound is high and the water dispersibility decreases, to increase the dispersibility, increase the amount of the organic solvent used to dissolve the epoxy resin and lower the viscosity of the resulting epoxy ester compound. However, as the amount of organic solvent used increases, the VOC (volatile organic compound) content of the final product increases and the negative impact on the environment increases. Therefore, the molecular weight of the epoxy resin is within the above range. Preferably there is.
Such an epoxy resin is preferably contained in an amount of 8 to 24 parts by weight based on 100 parts by weight of the resin composition. When the content of the epoxy resin is less than 8 parts by weight, the adhesion to the substrate may be reduced, and the corrosion resistance and water resistance of the coating film may be reduced. The viscosity of the resulting resin composition is increased, making it difficult to produce a solid resin composition. When applying a coating material, the adhesion and corrosion resistance may decrease due to increased flowability.

In the case of using a liquid epoxy resin (for example, YD-128 manufactured by KUKDO CHEMICAL CO., LTD.) In reacting the epoxy resin with the first fatty acid, the first step is performed without dissolving the epoxy resin. However, when a solid epoxy resin is used, it is preferably dissolved in an organic solvent and reacted with the first fatty acid.
At this time, the organic solvent used for dissolving the epoxy resin is not particularly limited and can be appropriately selected depending on the purpose. For example, hydrocarbon-based, alcohol-based, ketone-based, ester-based, ether-based Specifically, petroleum spirit, cyclohexane, toluene, xylene, methanol, ethanol, isopropyl alcohol, butyl alcohol, MEK, MIBK, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve, butyl cellosolve, butyl And carbitol.

Since the organic solvent is used in a small amount, there is no need to perform another removal process during the production of the resin composition. However, in order to adjust the VOC content of the final product, it is necessary to perform vacuum distillation before dispersing in water. A part can be removed by a method or the like. Specifically, the organic solvent is 2 to 8 parts by weight based on 100 parts by weight of the resin composition in consideration of water dispersibility, viscosity of the resin composition, pigment dispersibility and coating film forming ability when applied to a paint. It is preferable that a part by weight is contained.
The first fatty acid that undergoes esterification reaction with the epoxy resin is not particularly limited as long as it has an intramolecular unsaturated bond and can be appropriately selected according to the purpose. Preferably, it is a (semi) drying oil fatty acid having a value of 100 or more (specifically, those having an iodine value of 100 to 140 are regarded as semidrying oil fatty acids, and those having an iodine value exceeding 140 are regarded as drying oil fatty acids).
The first fatty acid is primarily formed by ester reaction of a carboxyl group present at the end of a molecule with an epoxy resin, and secondarily, an intramolecular unsaturated bond is later graft-polymerized with a vinyl monomer. Although it will act as the main chain of the polymer, the crosslink density of the resin composition is increased by reacting the first fatty acid with the epoxy resin in this way, and the water resistance and corrosion resistance of the coating film can be improved. it can.

Examples of the first fatty acid include a group consisting of soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, tall oil fatty acid, kiri oil fatty acid, bran oil fatty acid, sunflower oil fatty acid, and safflower oil fatty acid. And may be used alone or in combination of two or more as required.
The first fatty acid is preferably included in an amount of 12 to 28 parts by weight based on 100 parts by weight of the resin composition. When the content of the first fatty acid is less than 12 parts by weight, the crosslinking density of the resin composition is lowered, and the water resistance and corrosion resistance may be lowered at the time of forming the coating film, which exceeds 28 parts by weight. And the drying property of a coating film may fall.

(B) Production of Polymer The present invention includes a step of producing a polymer by introducing a vinyl monomer and a second fatty acid into the epoxy ester compound and causing a polymerization reaction in order to produce a resin composition.
In this case, the usable vinyl monomer is not particularly limited and may be appropriately selected depending on the purpose. For example, styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl It can be selected from the group consisting of (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.

The vinyl monomer can improve the drying property and hardness of the final coating film by the graft polymerization reaction of the double bond portion of the vinyl group present in the vinyl monomer with the unsaturated bond portion present in the epoxy ester compound. The carboxyl group derived from (meth) acrylic acid contained in the vinyl monomer can act as a hydrophilic group when the produced polymer is dispersed in water, thereby further improving the water dispersibility of the polymer. it can.
The vinyl monomer is preferably included in an amount of 6 to 22 parts by weight based on 100 parts by weight of the resin composition in consideration of water dispersibility, coating strength, drying property, water resistance, and the like.

  A polymerization initiator is used in the graft polymerization of the epoxy ester compound and the vinyl monomer. The polymerization initiator that can be used is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include azo compounds such as 2,2-azobisisobutyronitrile, benzoyl peroxide, and tert-butyl peroxybenzoate. , Peroxides such as di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, and these are used alone or in combination of two or more. be able to. In addition, the usage-amount of the said polymerization initiator is not specifically limited.

  Moreover, in this invention, in order to raise the solid content of a resin composition, a 2nd fatty acid is added in the case of the polymerization reaction of an epoxy ester compound and a vinyl monomer. That is, when a second fatty acid having an intramolecular double bond is added during graft polymerization of the epoxy ester compound and the vinyl monomer, the double bond of the second fatty acid is polymerized with the vinyl group of the vinyl monomer. By acting as an emulsifier that promotes mixing of a hydrophilic component (for example, water) and a lipophilic component (for example, an organic solvent) contained in the resin composition, the resin composition produced thereby Thus, a resin composition having a high solid content can be produced.

Usually, when a resin composition having a high solid content is used for a paint, a post-coating film is formed smoothly, and the corrosion resistance and water resistance of the coating film can be improved. In the production of the product, by including the second fatty acid, the resin composition having a high solid content, specifically, the solid content is 37 wt% to 45 wt%, preferably 40 wt% to 43 wt%. % Of the resin composition can be produced, thereby improving the corrosion resistance and water resistance of the coating film.
In addition, when a polymer is produced by adding a second fatty acid during graft polymerization, the carboxyl group present in the second fatty acid (however, the carboxyl group does not participate in the polymerization reaction and exists at the end of the polymer). ) Acts as a hydrophilic group, the water dispersibility can be further improved when the produced polymer is later dispersed in water.

The second fatty acid is not particularly limited as long as it is a monobasic acid composed of a substance having at least one double bond in the molecule, and can be appropriately selected according to the purpose, for example, oleic acid, It can be selected from the group consisting of ricinoleic acid, linoleic acid, elaeostearic acid and licanoic acid, and can be used alone or in admixture of two or more as required. In some cases, the same fatty acid as the first fatty acid can be used.
The second fatty acid is preferably contained in an amount of 0.8 to 3 parts by weight based on 100 parts by weight of the resin composition. When the content of the second fatty acid is less than 0.8 part by weight, the effect of reducing the viscosity of the resin composition may not be obtained. When the content exceeds 3 parts by weight, the stability of the resin composition is lowered. Can be.

(C) Production of Neutralized Product The present invention includes a step of neutralizing the polymer obtained as described above with a basic neutralizing agent in order to produce a resin composition. That is, the basic neutralizing agent serves to neutralize a carboxyl group present at the terminal of a polymer obtained by polymerizing the epoxy ester compound with the vinyl monomer and the second fatty acid. At this time, the neutralized carboxyl group is specifically a carboxyl group derived from (meth) acrylic acid contained in the vinyl monomer and a carboxyl group possessed by the second fatty acid.

At this time, the basic neutralizing agent is not particularly limited and can be appropriately selected according to the purpose. For example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylethanolamine, diethylethanolamine Ammonia, sodium hydroxide or potassium hydroxide can be used, and can be used alone or in admixture of two or more as required.
In addition, before neutralization with a basic neutralizing agent, the acid value of the polymer is about 20 mg KOH / g to 55 mg KOH / g, and thus the polymer is neutralized even if it has a low acid value. Can be stably dispersed in water, and can improve the dispersion stability of pigments later. When a resin composition containing a polymer having a low acid value is used in paint, water resistance and corrosion resistance are improved. A coated film is obtained.
The neutralized product produced as described above may have a number average molecular weight of 2,000 to 15,000.

(D) Dispersion in water The present invention includes a step of dispersing the neutralized product produced as described above in water in order to produce a resin composition.
In the present invention, in producing the resin composition, before the neutralized product is dispersed in water, a solid additive or a lipophilic additive (for example, wax or a lipophilic metal dryer) is further added and dispersed. Can be produced stably, and by including a solid additive or a lipophilic additive, it is possible to improve the drying property, water resistance, and water repellency of the final coating film. .
The resin composition of the present invention as described above can exhibit a viscosity in the range of 100 cps to 20,000 cps. However, the viscosity and solid content of the resin composition according to the present invention can be changed according to the acid value of the polymer, the type and amount of the organic solvent and the basic neutralizer contained in the resin composition. .

<Paint>
The present invention can provide a paint containing the above resin composition, specifically, an aqueous paint. In addition, the coating material of this invention can contain a pigment, a metal dryer, a leveling agent, a ultraviolet absorber, antioxidant, etc. other than the said resin composition.
The pigment contained in the paint of the present invention is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include metal oxides such as carbon black, titanium oxide, magnesium oxide, zinc oxide and iron oxide, aluminum Inorganic pigments such as flakes, mica, silicates, barium sulfate, and calcium carbonate, and organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, benzimidazolone, selenium, perylene, etc. Can be used as a mixture.

  The metal dryer plays a role of a catalyst for improving the drying property of the paint. By including such a metal dryer, a coating film with improved water resistance and corrosion resistance can be formed. The metal dryer that can be used is not particularly limited and can be appropriately selected depending on the purpose. For example, metal compounds such as tetraisopropyl titanate, dibutyltin laurate, dibutyltin acetate, dibutyltin dioctate, and cobalt naphthenate Etc.

  There is no restriction | limiting in particular as an ultraviolet absorber contained in the coating material of this invention, According to the objective, it can select suitably, For example, a benzotriazole type compound, an oxalic acid anilide type compound, a hydroxybenzophenone type compound etc. are mentioned. .

The coating material of this invention can form a coating film by coating a base material using a brush or a roller, and then naturally drying. Specifically, methods such as a spray method, an electrostatic method, and an electrodeposition method may be used as a method for applying a paint to a substrate.
In addition, there is no restriction | limiting in particular as a base material which can apply the coating material of this invention, According to the objective, it can select suitably, For example, a metal base material, a plastic base material, a wooden base material, a glass base material , Slate substrates, and substrates that can be generally used in various fields such as paper and rubber.

  Since such a coating material of the present invention contains the resin composition of the present invention, a coated material with the coating material of the present invention can provide a coating film excellent in corrosion resistance, water resistance, water repellency and the like. There is no restriction | limiting in particular as said coating material, According to the objective, it can select suitably, For example, a motor vehicle, a train, a bicycle, a ship, an airplane, a television, a radio, a refrigerator, a washing machine, a cooler, a cooler outdoor unit, a computer Or metal or plastic parts, tiles, roofing materials, wall materials, window frames, doors, roads, road signs, guardrails, bridges, tanks, chimneys, buildings, etc. used in these.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is explained in full detail, this invention is not limited to these.

[Example 1]
A four-necked flask equipped with a condenser, a thermometer, a reflux water separator, and a dropping funnel and capable of supplying nitrogen, adjusting the temperature and stirring, 6.0 parts by weight of linseed oil fatty acid and 6.0 parts by weight of sunflower oil fatty acid YD-128 (manufactured by KUKDO Chemical Co., bisphenol A type epoxy) 5.5 parts by weight, YD-014 (manufactured by KUKDO Chemical Co., bisphenol A type epoxy) 6.5 parts by weight, maleic anhydride 0.5 parts by weight, And 1.3 parts by weight of xylene were added in a constant amount, and then the mixture was heated to 180 ° C. with mixing and stirring. When the produced water began to flow out, xylene was refluxed, the temperature was raised to 230 ° C. while confirming the dehydrated state, and the esterification reaction was carried out while maintaining the reaction part temperature for 5 hours. When the acid value of the reaction product reaches 20 mg KOH / g to 23 mg KOH / g, the pressure is reduced and recovery of xylene used as the reflux solvent is started. After the recovery amount is 90% or more of the input amount, recovery is performed. , Cooled. At this time, the acid value of the reaction product was 15 mg KOH / g to 17 mg KOH / g, and diluted by further adding 3.5 parts by weight of butyl cellosolve at 150 ° C. or lower to obtain an epoxy ester compound.
Next, the temperature was maintained at 130 ° C., and 1.5 parts by weight of linoleic acid, 15.5 parts by weight of styrene, 1.5 parts by weight of acrylic acid, and 1.0 part by weight of DTBP were separately mixed in the reaction part. The mixture was poured over 3 hours and further reacted for 6 hours to obtain a polymer.
Next, the solution was cooled to 70 ° C., neutralized by adding 2.0 parts by weight of triethylamine (TEA) to the reaction part, and 49.2 parts by weight of ion-exchanged water was added little by little to disperse in water. A water-soluble acrylic-modified epoxy ester resin composition was produced.

[Example 2]
In Example 1, a water-soluble acrylic-modified epoxy ester resin composition was produced in the same manner as in Example 1 except that the contents shown in Table 1 below were applied.

[Example 3]
In Example 1, the contents shown in Table 1 below were applied, and the polymer obtained in Example 1 was added with MPP-620XF, a lipophilic additive, and then neutralized. In the same manner, a water-soluble acrylic-modified epoxy ester resin composition was produced.

[Comparative Example 1]
In Example 3, a water-soluble acrylic-modified epoxy ester resin composition was prepared in the same manner as in Example 3 except that linoleic acid corresponding to the second fatty acid was excluded and the contents shown in Table 1 below were applied. Manufactured.

[Comparative Example 2]
In Comparative Example 1, a water-soluble acrylic-modified epoxy ester resin composition was prepared in the same manner as in Comparative Example 1 except that the lipophilic additive MPP-620XF was excluded and the contents shown in Table 1 below were applied. Manufactured.

[Test Example 1]
The physical properties of the water-soluble acrylic-modified epoxy ester resin compositions produced in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are shown in Table 2.

1. Solid content (non-volatile content)
Each resin composition produced above is collected on a flat dish having an inner diameter of about 80 mm and spread uniformly so as to be dried smoothly, and then placed in a thermostatic chamber (105 ° C. ± 2 ° C.). After drying for a period of time, the solid content was measured by the following formula 1.
<Formula 1>
N = 100− (A−B) / C × 100
However, in formula, N shows solid content (%), A is the weight (g) of a plate and the resin composition before drying, B is the weight (B) of the plate and resin composition after a heating ( g) and C indicate the weight (g) of the collected resin composition.

2. Number average molecular weight The number average molecular weight was measured by gel permeation chromatography (GPC). The product name of the GPC equipment was Waters 410, the detector was RI, the column was Shodex KT-802, 803, 804, 805, and the eluent was tetrahydrofuran (THF).

3. Water dispersion stability After completion of water dispersion, the sample is placed in a transparent sample bottle and stored in a thermostat (60 ° C ± 2 ° C) for 14 days. Then, the state of each resin composition is visually determined, and the degree of change in viscosity is determined. Evaluation was made according to the following four criteria.
1) No change in the appearance of the resin composition was observed, and the viscosity change was less than 50% of the initial value:
2) No change in appearance of the resin composition was observed, and the viscosity change was 50% or more and less than 100% of the initial value: ○
3) Appearance change of resin composition is recognized or viscosity change is 100% or more of initial value: Δ
4) A precipitate is observed or the aqueous layer is separated: x

表２の結果から、本発明に係る樹脂組成物（実施例１〜３）は、固形分含量が高く、水分散安定性が比較例１〜２の樹脂組成物に比べて良好であることが確認された。

From the results of Table 2, the resin compositions (Examples 1 to 3) according to the present invention have a high solid content, and the water dispersion stability is better than that of Comparative Examples 1 and 2. confirmed.

[Production Example 1]
To the resin composition produced in Example 1, titanium oxide (Dupont, Ti-pure R-706), calcium carbonate (Korea Calcium), dispersant (BYK, BYK-190), and antifoaming agent (BYK, BYK- 021) was mixed with the contents shown in Table 3 below and softened with a sand mill for 1 hour. In the obtained softened product, a dryer (JINYANG CHEM., AMD-60), an anti-settling agent (Sud-Chemie, Optical LX), and a thickener (Rohm & haas, RM-825) were stirred with the contents shown in Table 3 below. And mixed to produce a water-based paint.

[Production Example 2]
In Production Example 1, an aqueous paint was produced in the same manner as in Production Example 1 except that the resin composition produced in Example 2 was used instead of the resin composition produced in Example 1.

[Production Example 3]
In Production Example 1, an aqueous paint was produced in the same manner as in Production Example 1 except that the resin composition produced in Example 3 was used instead of the resin composition produced in Example 1.

[Production Example 4]
In Production Example 1, a water-based paint was produced in the same manner as in Production Example 1 except that the resin composition produced in Comparative Example 1 was used instead of the resin composition produced in Example 1.

[Production Example 5]
In Production Example 1, a water-based paint was produced in the same manner as in Production Example 1 except that the resin composition produced in Comparative Example 2 was used instead of the resin composition produced in Example 1.

[Test Example 2]
The water-based paints produced in the above Production Examples 1 to 5 were evaluated by the following methods. The results are shown in Table 4.

1. Dryability (solidification)
A test piece similar to the finger-drying test was prepared, placed horizontally at room temperature, determined when the coating film did not peel off even when rubbed strongly with hand while drying, and evaluated according to the following four criteria.
1) Drying time is less than 8 hours: ◎
2) Drying time is 8 hours or more and less than 12 hours: ○
3) Drying time is 12 hours or more and less than 16 hours: Δ
4) Drying time is 16 hours or more: ×

2. 60 ° Glossiness KS M 5000-3312 paint, 60 ° specular gloss test method, using a gloss meter to measure the reflectance when the incident angle and horizontal angle are 60 °, respectively, the standard glass surface The specular glossiness was expressed as a percentage when the specular glossiness was taken as 100, and the average value measured five times was evaluated.

3. Water resistance After coating the coated plate obtained by coating the test piece with 80 μm and drying it at room temperature for 24 hours in water at room temperature for 3 days, the coating film is blistered, the adhesiveness is lowered, the coating film is softened or The degree of hardening and peeling was visually judged, and the following four criteria were evaluated according to the degree.
1) No abnormality is observed in the coating film: ◎
2) Fine blisters are observed in the coating film: ○
3) Swelling of the coating film is observed, but no peeling is observed: Δ
4) Swelling and peeling of the coating are observed: x

4). Corrosion resistance After applying a cross-cut so that the base material appears on the coating film of the test piece, and performing a test for 200 hours with a salt spray tester (35 ° C ± 2 ° C, 5% aqueous sodium chloride solution), peeling and corrosion of the coating film The degree was visually determined and evaluated according to the following four criteria according to the degree of rusting in the crosscut part.
1) No rusting is observed in the cross cut part: ◎
2) Less than 0.5 mm of rust is observed in the crosscut part: ○
3) Corrosion is observed at the crosscut part of 0.5 mm and less than 1 mm: Δ
4) At least 1 mm of rust is observed in the crosscut part: x

表４の結果から、本発明の樹脂組成物で製造された水性塗料（製造例１〜３）は、製造例４〜５で製造された水性塗料に比べて優れた乾燥性、耐水性、及び耐食性が得られることが分かった。

From the result of Table 4, the water-based paint (manufacture examples 1-3) manufactured with the resin composition of this invention was superior to the water-based paint manufactured in manufacture examples 4-5, and was excellent in drying property, water resistance, and It was found that corrosion resistance was obtained.

Claims (7)

An epoxy ester compound produced by esterifying a first fatty acid having an intramolecular unsaturated bond with an epoxy resin is charged with a second fatty acid having a vinyl monomer and an intramolecular double bond and polymerized. A neutralized product neutralized with a basic neutralizing agent, and a water-soluble acrylic-modified epoxy ester resin composition containing water,
The first fatty acid is selected from the group consisting of soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, tall oil fatty acid, tung oil fatty acid, bran oil fatty acid, sunflower oil fatty acid and safflower oil fatty acid ,
The second fatty acid is selected from the group consisting of oleic acid, ricinoleic acid, linoleic acid, elaeostearic acid and licanoic acid;
The vinyl monomer is styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, lauryl (meth) ) A water-soluble acrylic-modified epoxy ester resin composition selected from the group consisting of acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.   The water-soluble acrylic-modified epoxy according to claim 1, wherein the epoxy resin is selected from the group consisting of a bisphenol A type epoxy resin, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin each having a molecular weight of 350 to 2,000. Ester resin composition.   3. The water-soluble acrylic-modified epoxy ester resin composition according to claim 1, wherein the solid content of the resin composition is 37 to 45 parts by weight based on 100 parts by weight of the resin composition. . Based on 100 parts by weight of water-soluble acrylic-modified epoxy ester resin composition,
8 to 24 parts by weight of epoxy resin,
12 to 28 parts by weight of the first fatty acid,
0.8 to 3 parts by weight of a second fatty acid,
6 to 22 parts by weight of vinyl monomer,
The water-soluble acrylic-modified epoxy ester resin composition according to any one of claims 1 to 3, comprising 1 to 5 parts by weight of a basic neutralizer and a remaining amount of water. (A) a step of esterifying an epoxy resin with a first fatty acid having an intramolecular unsaturated bond to produce an epoxy ester compound;
(B) A step of introducing a second fatty acid having a vinyl monomer and an intramolecular double bond into the epoxy ester compound produced in the above step (a) and polymerizing the compound.
(C) a step of neutralizing the polymer polymerized in the above step (b) with a basic neutralizing agent; and (d) dispersing the neutralized material neutralized in the above step (c) in water. Step,
A method for producing a water-soluble acrylic-modified epoxy ester resin composition comprising:
The first fatty acid is selected from the group consisting of soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, tall oil fatty acid, tung oil fatty acid, bran oil fatty acid, sunflower oil fatty acid and safflower oil fatty acid ,
The second fatty acid is selected from the group consisting of oleic acid, ricinoleic acid, linoleic acid, elaeostearic acid and licanoic acid;
The vinyl monomer is styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, lauryl (meth) ) A production method characterized by being selected from the group consisting of acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.   6. The method for producing a water-soluble acrylic-modified epoxy ester resin composition according to claim 5, wherein the epoxy resin in step (a) is dissolved in an organic solvent and then reacted with the first fatty acid.   A paint comprising a resin composition produced by the production method according to claim 5 and forming a coating film.