KR101643653B1 - Method of water soluble epoxy ester modified vinyl resin composition with anti fire for a ship and paint composition using the same - Google Patents

Abstract

The present invention relates to a method for producing a water-soluble epoxy ester-modified vinyl resin composition for a ship to which a flame retardant property is imparted, comprising the steps of: A) producing an epoxy ester-containing flame retardant compound by esterification reaction of an epoxy resin and a fatty acid having an unsaturated bond in a molecule; (B) a step of adding a vinyl monomer and a phosphoric ester compound having an intramolecular double bond to the flame retardant-containing epoxy ester compound produced in the step (A), graft-polymerizing the resultant and then neutralizing with a basic neutralizing agent; And (C) dissolving the neutralized neutralized product in step (B) in water; And a control unit.
The present invention also relates to a water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant property, comprising 20 to 35 parts by weight of an epoxy ester resin; 8 to 20 parts by weight of a vinyl-based monomer; 3 to 10 parts by weight of a volatile organic compound; 0.01 to 2 parts by weight of a phosphoric acid ester compound; And water as a remaining amount.
As a result, the phosphoric acid ester compound contained in the resin composition gives an effect of adhesion improvement as well as a low viscosity effect at the time of water-soluble, so that it is possible to produce a water-soluble resin having a low viscosity and a low content of volatile organic compounds, It is possible to impart flame retardancy to an epoxy resin having halogen (or bromine), as well as an effect of improving adhesion to a surface and improving corrosion resistance and water resistance of a coating film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble epoxy ester-modified vinyl resin composition for ships and to a coating composition using the same,

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

A solvent type paint of an epoxy resin excellent in corrosion resistance has been widely used for marine use.

In recent years, however, there has been a growing awareness of environmental pollution, a demand for environmental regulations due to the reduction of volatile organic compounds, and consideration of work stability have increased the demand for replacing solvents with waterborne or water-soluble paints. And the content thereof is still lowering in the reduction of the organic solvent.

In the case of coatings used for ships of large structures, it is difficult to heat and dry. Therefore, it should be possible to dry at room temperature. It should maintain a beautiful appearance and gloss like solvent type.

However, water-based paints containing hydrophilic functional groups such as carboxyl groups and polyethylene oxide, compared with solvent type, generally have poor water resistance, dryness and adhesiveness due to the high surface tension and high latent heat of evaporation, and the corrosion resistance is also lower than that of the solvent type.

When the neutralized salt is left in the coating, the anionic type hydrophilic group is neutralized and becomes water-soluble. When the salt is left in the coating, the compatibility is poor and the gloss is lowered.

Various studies have been conducted to develop an aqueous resin composition exhibiting properties similar to those of a solvent type resin composition in terms of water resistance, corrosion resistance, drying property and adhesion property. However, in comparison with an oil-based resin composition, The development of water-soluble resin compositions and water-based paints is ongoing.

In addition, in the case of waterborne paints applied to the inside of ships with the reduction of volatile organic compounds, it is essential to provide a flame retardant performance for protecting lives from fire owing to the specificity of ships, and to prepare for fire at sea.

In general, the flame-retardant additive is generally used for imparting flame retardancy. However, in this case, the performance is limited. Recently, a method of imparting flame retardancy to a resin and a flame- It is actively underway.

On the other hand, Korean Patent No. 10-1281344 discloses a water-soluble epoxy ester-modified vinyl resin which is improved in adhesiveness by introducing a phosphoric acid ester compound and has excellent anticorrosion and water resistance and excellent drying and storage stability.

However, in the case of the prior art, the content of phosphorus in the phosphoric acid ester compound is low, so that the storage stability of the adherent and low viscosity state can be influenced, but the role of the flame retardant performance is insufficient.

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing a resin composition excellent in adhesion, anticorrosion and water resistance and excellent in drying and storage stability while imparting a flame retardant performance and a coating composition using the same do.

According to the present invention, there is provided a process for producing a flame-retardant epoxy ester compound, comprising the steps of: A) preparing 10 to 20 parts by weight of an epoxy resin and 10 to 20 parts by weight of a fatty acid having an unsaturated bond in a molecule to produce 20 to 35 parts by weight of a flame- 8 to 20 parts by weight of a vinyl-based monomer and 0.01 to 2 parts by weight of a phosphoric acid ester compound having an intramolecular double bond are added to the flame-retardant-containing epoxy ester compound produced in the step A to effect graft polymerization and neutralization with a basic neutralizing agent; And (C) dissolving the neutralized neutralized product in step (B) in water; (Or brominated) epoxy resin, or a mixture of a halogen (or bromine) epoxy resin and a bisphenol A epoxy resin, and the halogen content of the halogenated epoxy resin is in the range of 10 - 70%, the bromine content of the brominated epoxy resin is 10 to 60%, and the epoxy equivalent of the bisphenol A type epoxy resin is 180 to 2100, respectively. Can be achieved by a method for producing an epoxy ester-modified vinyl resin composition.

Here, the step A may include a step A 'of diluting the flame retardant-containing epoxy ester compound produced in the step A with a solvent; .

The fatty acid may be 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 can be provided as one.

In the step (B), the vinyl monomer may be at least one monomer selected from the group consisting of styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, Acrylate, and the like.

Further, in the step B, the phosphoric acid ester compound has the following chemical formula.

(Wherein R1 and R2 are H or CH3).

delete

On the other hand, an object of the present invention is to provide a waterborne epoxy ester-modified vinyl resin composition for ships having a flame retardant performance, comprising 20 to 35 parts by weight of an epoxy ester resin, 8 to 20 parts by weight of a vinyl-based monomer; 3 to 10 parts by weight of a volatile organic compound; 0.01 to 2 parts by weight of a phosphoric acid ester compound; Wherein the epoxy resin is prepared through an esterification reaction of 10 to 20 parts by weight of an epoxy resin and 10 to 20 parts by weight of a fatty acid having an unsaturated bond in a molecule and the epoxy resin is a halogen (or bromine) A halogenated (or brominated) epoxy resin and a bisphenol A-type epoxy resin, wherein the halogenated epoxy resin has a halogen content of 10 to 70%, and the bromine content of the brominated epoxy resin The epoxy equivalent of the bisphenol A type epoxy resin may be 180 to 2100, and the flame retardant property may be imparted to the water-soluble epoxy ester-modified vinyl resin composition.

The solid content of the water-soluble epoxy ester-modified vinyl resin composition for ships having the flame retardant property is 30 to 50 parts by weight.

The water-soluble epoxy ester-modified vinyl resin composition for a ship to which the flame retardant performance is imparted may further include at least one of a metal dryer, a leveling agent, an ultraviolet absorber, an antioxidant, a defoamer, a dispersant and a flame retardant.

As described above, according to the present invention, in the course of the polymerization of the flame-retardant epoxy ester compound and the vinyl monomer, the 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 for a coating material, the phosphate ester compound contained in the resin composition imparts an effect of adhesion enhancement as well as a low viscosity effect upon water-solubility, so that the content of the volatile organic compound is low, It is possible to manufacture a resin, and it is possible to impart flame retardancy to an epoxy resin having halogen (bromine) with an effect of improving adhesion to a steel surface and improving 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.

<Description of Method>

The water-soluble epoxy ester-modified vinyl resin composition (hereinafter referred to as &quot; resin composition &quot;) to which the flame retardant property of the present invention is imparted may be a halogenated (or brominated) epoxy resin alone or a bisphenol A type epoxy resin, a fatty acid, Solvents, amine-based neutralizers, and water.

The solid content of the water-soluble epoxy ester-modified vinyl resin composition for a ship to which the flame retardancy is imparted according to the present invention is 30 to 50 parts by weight, preferably 35 to 45 parts by weight. At this time, the solid content can be defined as a non-volatile component excluding water and an organic solvent contained in the resin composition.

The resin composition is obtained by first synthesizing a flame retardant-containing epoxy ester compound produced by esterifying a fatty acid having an unsaturated bond in a molecule by mixing with a halogen (or bromine) epoxy resin alone or a bisphenol A type epoxy resin, Containing monomer having an intramolecular double bond and then graft-polymerizing the carboxyl group-containing monomer, and then neutralizing the carboxyl group of the carboxyl-containing monomer used in the polymer with an amine-based neutralizing agent and dissolving it in water. This will be described in detail as follows.

Step A

In this step, a process for producing a flame retardant-containing epoxy ester compound proceeds by esterification reaction of a fatty acid having an unsaturated bond in a molecule by mixing with a brominated epoxy resin alone or with a bisphenol A type epoxy resin.

The halogenated brominated epoxy resin which can be used is not particularly limited, but is preferably a brominated epoxy resin having an epoxy bromine content of 10 to 60% by weight (for example, YDB-228, YDB-400, YDB -406 and KB-560), and a similar grade epoxy resin produced by another company may be applied.

The epoxy resin which can be used is not particularly limited, but is preferably a bisphenol A type epoxy resin having an epoxy equivalent of 180 to 2100 (for example, YD-128, YD-011, YD-014 and YD-017 ), And a similar grade epoxy resin produced by another company may be applied.

The brominated epoxy resin may be used alone or in combination with a bisphenol A type epoxy resin.

When a resin having a high halogen content is used in the halogenated epoxy resin used above, the epoxy ester compound produced by the esterification reaction may have improved flame retardancy but may have an increased viscosity, resulting in deterioration of water dispersibility. Conversely, the halogen content of the halogenated epoxy resin When a small resin is used, the viscosity is low and the water dispersibility is improved. However, since sufficient flame retardancy can not be exhibited, the halogen content of the halogenated epoxy resin to be used is preferably 10 to 70 (% by weight).

When a resin having a large epoxy equivalent is used in the bisphenol A type epoxy resin used above, the epoxy ester compound produced by the esterification reaction has improved hardness, dryness, corrosion resistance, and water resistance but has increased viscosity, On the other hand, when a resin having a small epoxy equivalent of an epoxy resin is used, the water-dispersibility is improved but the hardness, water resistance, corrosion resistance and drying property of the final coating film may be lowered. Therefore, the epoxy equivalent of the epoxy resin used is preferably 180 to 2100 desirable.

Such an epoxy resin is preferably contained in an amount of 10 to 20 parts by weight. If the epoxy resin is contained in an amount of less than 10 parts by weight, the adhesion to the substrate may be deteriorated and the corrosion resistance and water resistance of the coating film may be deteriorated. However, the viscosity of the resin composition to be produced is increased, the content of the solid content is decreased during the water-solubilization, and adhesion and corrosion resistance may be deteriorated due to high viscosity even after the preparation of the coating.

On the other hand, the fatty acid having a carboxyl group present at the terminal of the molecule reacts with an epoxy group existing at both ends of the epoxy resin and further reacts with a hydroxyl group which is formed by reacting with an epoxy group and a hydroxyl group of the epoxy resin, In order to produce an esterified compound of an epoxy resin and a fatty acid, the unsaturated bond in a molecule of a fatty acid is formed by graft polymerization with a vinyl-based monomer and a phosphoric ester compound having an intramolecular double bond in step B, Water.

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

By reacting the fatty acid with the epoxy resin in this manner, the crosslinking density of the resin composition is increased, and the water resistance, corrosion resistance, and drying property of the room temperature curing type can be improved.

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 . The fatty acids may be used singly or in combination of two or more kinds, if desired, and they are preferably contained in an amount of 10 to 20 parts by weight. If the amount of the fatty acid is less than 10 parts by weight, the crosslinking density of the resin composition may be insufficient due to insufficient unsaturation of the resin composition, resulting in deterioration of the water resistance and corrosion resistance during the formation of the coating film. If the amount of the fatty acid is more than 20 parts by weight, It is because.

In addition, the introduction of the unsaturated group in the flame-retardant-containing epoxy ester resin compound may include not only a fatty acid but also an organic acid including an unsaturated group such as maleic acid and fumaric acid. At this time, it is preferable that the amount is 0.01 to 5 parts by weight. If the amount of the organic acid is more than 5 parts by weight, the hardness and curability of the resin composition to be produced will be high. However, since the viscosity of the resin is high, the content of the organic solvent may be increased because of the strength of the water.

In the production of the flame retardant-containing epoxy ester compound, the esterified compound of the epoxy resin and the fatty acid preferably comprises 20 to 40 parts by weight, more preferably 20 to 35 parts by weight.

2. Step A '

In this step, a step of diluting the epoxy ester compound produced in Step A with a solvent is performed. That is, when the viscosity of the produced flame retardant-containing epoxy ester compound is high according to the epoxy resin used in the step A, an organic solvent may be used to dissolve the resin compound.

When the flame-retardant epoxy ester compound and the vinyl monomer are graft-polymerized, the organic solvent used in the embodiment of the present invention should be compatible with the solvent when water is graft-polymerized, Based acetates may be used.

The above-mentioned organic solvent may be partially removed before and after the water-soaked in order to control the volatile organic solvent content. Specifically, the organic solvent is preferably contained in an amount of 3 to 10 parts by weight in consideration of water solubility, viscosity of the resin composition, and storage stability.

3. Step B

In this step, a vinyl-based monomer and a phosphate ester compound having an intramolecular double bond are added to the flame retardant-containing epoxy ester compound produced in Step A, and the resultant is graft-polymerized and neutralized with a basic neutralizing agent.

The vinyl-based monomer that can be used is not particularly limited, and examples of the vinyl-based monomer include styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate and isobonyl (meth) acrylate.

Such a vinyl-based monomer can improve the dryness and hardness of the final coating film by performing a graft polymerization reaction with the unsaturated bond portion present in the flame-retardant-containing epoxy ester compound, by the double bond portion of the vinyl group present in the monomer.

In addition, the carboxyl group derived from (meth) acrylic acid contained in the vinyl monomer can act as a hydrophilic group when dispersing the polymer prepared in Step (B) in water in Step (C), so that the water-solubility of the polymer can be increased.

Such vinyl monomers are preferably contained in an amount of 8 to 20 parts by weight in consideration of water solubility, strength of the film, dryness and water resistance.

Here, a polymerization initiator can be used in graft polymerization of a flame-retardant epoxy ester compound and a vinyl monomer and a phosphoric acid ester compound. The polymerization initiator that can be used is not particularly limited. For example, 2,2-azobisisobutylonitrile Or an azo compound such as benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate May be used alone or in admixture of two or more.

Further, a phosphate ester compound having an intramolecular double bond is added to improve the adhesion of the resin composition to the substrate. That is, when the phosphoric acid ester compound is added during the graft polymerization of the epoxy ester compound and the vinyl monomer, the double bonds of the phosphoric acid ester compound are polymerized with the vinyl group of the vinyl monomer so that the compound of the phosphate ester contained in the resin composition is hydrophobic And the hydrophilic property. Thus, the resin composition of the present invention not only lowers the viscosity of the resin composition to be produced, but also improves the adhesion of the substrate due to the increase in adhesion property, which is a characteristic of the phosphoric acid ester compound, Can be prepared.

Here, the phosphoric acid ester compound is represented by the following formula.

[Chemical Formula]

(Wherein R1 and R2 are H or CH3).

On the other hand, the phosphate ester compound is preferably contained in an amount of 0.01 to 2 parts by weight. If the phosphoric acid ester compound is contained in an amount of less than 0.01 part by weight, it is difficult to expect the adhesion effect of the resin composition to the substrate. When the amount exceeds 2 parts by weight, the viscosity of the resin composition may increase during the synthesis, , The content of the volatile organic solvent can not be reduced because the content of the organic solvent increases during the reaction.

Also, in this step, a process of neutralizing the polymer produced by the graft polymerization with an amine-based neutralizing agent proceeds. That is, the amine-based neutralizing agent neutralizes the carboxyl groups present in the side chain of the polymerized product obtained by polymerizing the vinyl monomer and the phosphoric acid ester compound with the flame-retardant-containing epoxy ester compound. The carboxyl group neutralized at this time is concretely a carboxyl group derived from (meth) acrylic acid contained in the vinyl monomer.

 Examples of the amine neutralizing agent include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylethanolamine, diethylethanolamine and ammonia And may be used singly or in a mixture of two or more kinds, if necessary.

Step C

In this step, the step of dissolving the neutralized neutralized product in the step B is carried out. That is, in step B, water is added to the neutralized polymer neutralized with an amine-based neutralizing agent to render it water-soluble. At this time, the final acid value after the water-solubilization is about 10 to 40 (mgKOH / g) and has an average molecular weight of 3,000 to 15,000.

In addition, the water-soluble resin composition of the present invention may exhibit a viscosity in the range of 500 to 20,000 cps. 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 contained in the resin composition.

&Lt; Description of Coating Composition >

The present invention can provide a paint comprising the resin composition described above. At this time, in addition to the water-soluble resin composition to which the flame retardant performance is imparted, the water-based coating composition of the present invention may further contain additives suitable for various applications such as a metal dryer, a leveling agent, an ultraviolet absorber, an antioxidant, Flame retardants and the like may be included.

The method for producing the water-soluble paint composition is not particularly limited and includes, for example, a filler such as calcium carbonate, a pigment such as titanium oxide, an additive, various additives after being dispersed with the water-soluble resin composition, Adding a thickener for adjusting viscosity to the composition and water and mixing them.

Such a coating material of the present invention can be formed by coating with airless coating, using a brush or roller, or the like, by a conventional method, followed by natural drying.

The base material which can be coated with the water-soluble coating composition of the present invention is not particularly limited, but can be generally used for coating metal, base materials such as iron, zinc and aluminum, and large structures such as wood.

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

[Example 1]

12 parts by weight of tall oil retaining dispersion, 6 parts by weight of YDB-400 (Kido Chemical Co., brominated epoxy resin), YD-011 (manufactured by Kukdo Chemical Co., Ltd.) were added to a four-necked flask equipped with a stirrer, a thermometer, Bisphenol A type epoxy resin) were added in a fixed amount, and the mixture was heated to 230 캜 while being mixed and stirred. The xylene was refluxed at 230 ° C and the resulting water in the water separator was dehydrated while keeping it for 8 hours to effect the esterification reaction. When the acid value of the reaction reached 1.0 (mgKOH / g) or less, the pressure was gradually reduced, and the xylene used as the refluxing solvent was recovered until it was no longer recovered and cooled. 6 parts by weight of butyl cellosolve was added at 150 캜 or lower and diluted to obtain an epoxy ester compound.

Thereafter, the temperature was maintained at 150 占 폚, and a mixture of 12.8 parts by weight of styrene, 2.8 parts by weight of acrylic acid and 1.0 part by weight of benzoyl peroxide was added dropwise to the reaction part over 2 hours and further reacted for 5 hours to obtain a polymer.

Thereafter, the polymer was cooled to 80 DEG C, neutralized by adding 3.2 parts by weight of triethylamine (TEA) to the reaction part, and 50 parts by weight of ion-exchanged water was slowly added thereto to obtain 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 contents shown in Table 1 were used.

[Example 3]

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

[Example 4]

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

[Example 5]

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

[Example 6]

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

[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 phosphoric acid ester compound was used and the contents shown in Table 1 below were 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 YDB-400 (Kukdo Chemical Co., brominated epoxy resin) was excluded and the contents shown in the following Table 1 were applied

[Measurement method and evaluation result 1]

The 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 by the following methods. The results are shown in Table 1 below.

1. Determination of solid content (non-volatile matter)

Each resin composition prepared above was taken in a flat dish having an inner diameter of about 80 mm and the bottom was flatly kneaded so as to be well dried, then placed in a thermostat (105 ± 2 ° C), dried for 3 hours and then measured for solid content Respectively.

2. Molecular weight measurement

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

3. Viscosity measurement

The viscosity was measured in a Brookfield viscometer LVF using a non-Newtonian viscometer LVF of ASTM D 2196 after holding the resin composition in a constant temperature water bath at 25 ± 2 ° C for 30 minutes and measuring the spindle No. 4 and 30 RPM. The unit was cps mPa.s) unit was used.

4. Storage stability after storage

The resultant resin composition was then dissolved in a transparent glass bottle and stored in a constant temperature bath (25 ± 2 ° C.) for 10 days. The state of each resin composition was visually observed. As a reference.

- No layer separation of the resin composition, little or no change in viscosity: Good (O)

- No layer separation of the resin composition and a lot of viscosity change: 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 Tall oil preservation 12 14 16 14 14 14 14 14 YD-011 6 7 8 10 4 - - 14 YDB-400 6 7 8 4 10 14 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 8.8 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 - 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 (%) 40.0 40.4 40.1 40.3 40.2 40.3 40.0 40.1 Molecular weight (Mn) 7000 7200 7300 7100 7500 6800 6900 7000 Viscosity (cps) 4900 4500 4000 4100 4800 5100 13000 3800 Storage stability ○ ○ ○ ○ ○ ○ △ - ○ ○

As can be seen from Table 1, the resin compositions according to the present invention show that the higher the content of the halogen (or bromine) epoxy resin is, the higher the molecular weight and viscosity are, but the comparatively good viscosity and storage stability are good in Examples 1 to 6 Comparative Example 1 in which phosphoric acid ester compound was not used showed too high viscosity at the time of water-solubility and Comparative Example 2 in which no halogen (or bromine) epoxy resin was used showed low viscosity and good storage stability.

[Production Example 1]

Titanium oxide (TiO2), calcium carbonate (CaCO3), and additives were mixed and dispersed in the resin compositions prepared in Example 1 in the amounts shown in Table 2 below. A drying agent, a thickener and water were added to the dispersion thus prepared, followed by stirring and mixing to prepare a water-soluble paint.

[Production Example 2]

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

[Production Example 3]

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

[Production Example 4]

An aqueous coating material was prepared in the same manner as in Preparation Example 1, except that the resin composition prepared in Example 4 was used.

[Production Example 5]

An aqueous coating material was prepared in the same manner as in Preparation Example 1, except that the resin composition prepared in Example 5 was used.

[Production Example 6]

An aqueous coating material was prepared in the same manner as in Preparation Example 1, except that the resin composition prepared in Example 6 was used.

[Production Example 7]

An aqueous coating material was prepared in the same manner as in Preparation Example 1, except that the resin composition prepared in Comparative Example 1 was used.

[Production Example 8]

An aqueous coating material was prepared in the same manner as in Preparation Example 1, except that the resin composition prepared in Comparative Example 2 was used.

[Measurement method and evaluation result 2]

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

1. Drying (solidification drying)

Drying time is measured according to the drying time test method of KS M 5000-2511 (when the arm is vertical on the coated surface and the coating is stretched or wrinkled when it is twisted at 90 degrees while pressing with the thumb) Respectively.

 - 10 hours or less before solidification: ○

 - Time to solidification is 10 hours to 15 hours: △

- 15 hours or more before solidification: X

2. 60 ° gloss

The 60 ° gloss was measured by a 60 ° specular gloss test of the coating of KS M 5000-3312 (the reflectance was measured when the incident angle and the horizontal angle were 60 °, respectively, and the percentage of the specular surface gloss of the glass tube, And the average value measured five times) was measured and evaluated.

3. Water resistance

The test piece was coated with 100 탆 of a coating film and dried at room temperature for 24 hours. The resulting plate was immersed in water at room temperature for 240 hours, and the degree of peeling of the coating film from the blister was visually determined.

 - No abnormality in coating film: ○

 - There is a little blister without peeling of the film: △

- With film peeling and blister: X

4. Agility

The test piece was cross-cut so that the coating film was visible, and the degree of peeling of the coating film and the degree of corrosion after the 240 hours test were measured by a salt water spray tester (35 ± 2 ° C., 5% sodium chloride aqueous solution)

 - If there is no rubbing on the crosscut section: ○

 - If the cross cut section is less than 1: △

- If the number of strokes in the crosscut section is 1 or more: X

5. Flammability

And measured according to UL-94, a flame retardancy evaluation method.

To determine the flame retardancy grade, a test specimen of 5 inches in length and 0.5 inches in width is contacted with a flame for 10 seconds, and then the flame is removed. When the specimen is turned off, another 10 seconds is contacted and the flame is removed. In each item, the sum of the first and second burning time and the fire fighting time of each specimen, the sum of the first and second burning times of five specimens, and the burning of the cotton due to the flame fall were measured.

- V-0: In the sample where the long axis of the specimen is positioned parallel to the flame, the sum of the first and second burning time and the fire extinguishing time of each specimen should not exceed 10 seconds, , The total burning time shall not exceed 50 seconds. Also, none of the vertically positioned specimens should drop combustion particles that ignite the cotton sheet lying 30 cm below.

- V-1: In the sample where the long axis of the specimen is positioned parallel to the flame, the sum of the first and second burning time and the flame extinguishing time of each specimen should not exceed 30 seconds. , The total burning time shall not exceed 250 seconds. Also, none of the vertically positioned specimens should drop combustion particles that ignite the cotton sheet lying 30 cm below.

- V-2: In the sample where the long axis of the specimen is positioned parallel to the flame, the sum of the first and second burning time and the flame extinguishing time of each specimen should not exceed 10 seconds, , The total burning time shall not exceed 50 seconds. Also, none of the vertically positioned samples drop combustion particles that ignite the cotton wool lying 30 cm below.

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 50 50 50 50 50 50 50 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 Defoamer 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 Flame retardant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - water 7.2 7.2 7.2 7.2 7.2 7.2 12.2 7.7 system 100 100 100 100 100 100 105 100 Drying ○ △ △ △ ○ △ △ ○ Polishes (60) 69 67 68 68 67 67 58 68 Water resistance ○ ○ ○ ○ ○ ○ X ○ Improvisation ○ - △ ○ ○ ○ ○ ○ X ○ Flame retardant performance V-1 V-1 V-1 V-2 V-0 V-0 V-0 none

As can be seen from the above 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 to the paper was increased due to the influence of the phosphate ester compound, 7, and in the case of Production Example 7, the viscosity was so high that the solids content was lowered during the preparation of the coating, thereby lowering the gloss. Further, it was confirmed that as the content of halogen (or bromine) epoxy resin increases (Production Examples 1 to 6), the flame retardant performance was excellent. In Production Example 8, halogen (or bromine) The flame retardant performance could not be secured.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. It is to be understood that the scope of the present invention is to be construed as being limited only by the following claims and their equivalents.

Claims (9)

10 to 20 parts by weight of an epoxy resin and 10 to 20 parts by weight of a fatty acid having an unsaturated bond in a molecule to produce 20 to 35 parts by weight of a flame retardant-containing epoxy ester compound;
8 to 20 parts by weight of a vinyl-based monomer and 0.01 to 2 parts by weight of a phosphoric acid ester compound having an intramolecular double bond are added to the flame-retardant-containing epoxy ester compound produced in the step A to effect graft polymerization and neutralization with a basic neutralizing agent; And
A step C for dissolving the neutralized neutralized product in step B in water; / RTI &gt;
The epoxy resin may be a brominated epoxy resin alone or a mixture of a brominated epoxy resin and a bisphenol A type epoxy resin,
The bromine content of the brominated epoxy resin is set to 10 to 60% by weight,
Wherein the bisphenol A epoxy resin has an epoxy equivalent of 180 to 2100
A method for producing a water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance.
The method according to claim 1,
In the step A,
A 'step of diluting the flame retardant-containing epoxy ester compound produced in the step A with a solvent; &Lt; RTI ID = 0.0 &gt;
A method for producing a water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance. The method according to claim 1,
In the step A,
Wherein 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, tung oil fatty acid, rice bran oil fatty acid, sunflower fatty acid and cottonseed oil fatty acid
A method for producing a water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance. The method according to claim 1,
In the step B,
The vinyl monomer may be at least one selected from the group consisting of styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobonyl (meth) acrylate. And at least one of
A method for producing a water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance. The method according to claim 1,
In the step B,
The phosphate ester compound is characterized by having the following formula
A method for producing a water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance.

(Wherein R1 and R2 are H or CH3). delete Based on 100 parts by weight of a water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance,
20 to 35 parts by weight of an epoxy ester resin;
8 to 20 parts by weight of a vinyl-based monomer;
3 to 10 parts by weight of a volatile organic compound;
0.01 to 2 parts by weight of a phosphoric acid ester compound; And
Water as the balance,
The epoxy ester resin is prepared through an esterification reaction of 10 to 20 parts by weight of an epoxy resin and 10 to 20 parts by weight of a fatty acid having an unsaturated bond in a molecule,
The epoxy resin may be a brominated epoxy resin alone or a mixture of a brominated epoxy resin and a bisphenol A type epoxy resin,
The bromine content of the brominated epoxy resin is set to 10 to 60% by weight,
Wherein the bisphenol A epoxy resin has an epoxy equivalent of 180 to 2100
A water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance. 8. The method of claim 7,
The solid content of the water-soluble epoxy ester-modified vinyl resin composition for ships to which the flame retardant performance is imparted is in the range of 30 to 50 parts by weight
A water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance. 8. The method of claim 7,
The water-soluble epoxy ester-modified vinyl resin composition for ships having the flame retardant performance further comprises at least one additive selected from the group consisting of a metal dryer, a leveling agent, an ultraviolet absorber, an antioxidant, a defoaming agent, a dispersant, and a flame retardant
A water-soluble epoxy ester-modified vinyl resin composition for ships having a flame retardant performance.