KR20040073711A - Tar-free anti-corrosive resin and coating composition having fast-curable property at low temperature - Google Patents

Abstract

The present invention relates to a non-tar low temperature fast curing anticorrosive coating resin and an anticorrosive coating composition comprising the same. More specifically, the present invention has two or more epoxy groups in a molecule and has a specific equivalent epoxy resin (A), a low molecular epoxy resin, An amine curing agent (C) comprising, as a main component, an epoxy acrylate resin (B) obtained by addition reaction of unsaturated carboxylic acid, and containing an epoxy adduct amine curing agent (C-1) and a polyamine curing agent (C-2) at a specific ratio. ) And petroleum-based resin (D) containing phenolic hydroxyl groups, which can be used under low temperature coating conditions, have a long pot life, excellent paintability, and fast curing, and excellent solvent resistance and corrosion resistance. It is especially useful for painting in ballast tanks of ships as a part that comes into contact with seawater, and does not contain tar and does not cause safety and environmental problems. Non-tartar low temperature hardening type anticorrosive coating resin, which contains less whitening phenomenon after coating, excellent adhesion between layers during repainting, and excellent hardening properties such as anticorrosion, (water) and chemical resistance. It relates to an anticorrosive coating composition.

Description

Tar-free anti-corrosive resin and coating composition having fast-curable property at low temperature}

The present invention relates to a non-tar low temperature fast curing anticorrosive coating resin and an anticorrosive coating composition comprising the same. More specifically, the present invention has two or more epoxy groups in a molecule and has a specific equivalent epoxy resin (A), a low molecular epoxy resin, An amine curing agent (C) comprising, as a main component, an epoxy acrylate resin (B) obtained by addition reaction of unsaturated carboxylic acid, and containing an epoxy adduct amine curing agent (C-1) and a polyamine curing agent (C-2) at a specific ratio. ) And petroleum-based resin (D) containing phenolic hydroxyl groups, which can be used under low temperature coating conditions, have a long pot life, excellent paintability, and fast curing, and excellent solvent resistance and corrosion resistance. It is especially useful for painting in ballast tanks of ships as a part that comes into contact with seawater, and does not contain tar and does not cause safety and environmental problems. Non-tartar low temperature hardening type anticorrosive coating resin, which contains less whitening phenomenon after coating, excellent adhesion between layers during repainting, and excellent hardening properties such as anticorrosion, seawater and chemical resistance. It relates to an anticorrosive coating composition.

Conventionally, tar-based epoxy paints are used as anticorrosive paints for ships, steel structures, and the like. Although this paint has excellent corrosion resistance, water resistance, chemical resistance, etc., it contains tar, which not only causes safety and hygiene problems, but also is difficult to maintain due to its black color, and it becomes dark in a closed place, thus causing a risk of work. There was a problem such as being.

Recently, non-tar epoxy coatings using petroleum resins in place of tar have also been developed. For example, Japanese Patent Laid-Open No. 59-52656, Japanese Patent Laid-Open No. 9-263713, Japanese Patent Laid-Open No. 11-343454 and the like have been proposed.

However, the epoxy coating of the patent is composed of an epoxy resin, an amine curing agent, a petroleum resin, etc., but the curing time is poor due to poor curing at low temperature (below 5 ° C.) in winter, which leads to a long painting time, and to drying after painting. It was not sufficient to be applied to the ballast tank of a ship, that is, a problem of delayed coating process, high corrosion resistance in coating properties, water resistance, etc. requiring direct contact with seawater.

In addition, the epoxy-based anticorrosive paints conventionally used have been widely used various polyamine compounds, especially aliphatic polyamine compounds as an epoxy resin curing agent for room temperature curing. However, the curing agent absorbs carbon dioxide or water vapor in the air, and thus, carbamate is easily generated, thereby causing the whitening of the cured coating film. If water droplets are dropped on the coating film during curing, the whitening of the part becomes severe and the appearance deteriorates. And when coating the coating film there was also a problem that the adhesion between the layers of the coating film is reduced.

In order to improve the above problems, various polyamine compounds are used as various modified substances. Representative modification methods include modification by Mannich reaction with a phenol compound and a carbonyl compound and modification with a epoxy compound, and a carboxyl group. Denaturation by reaction with a compound having;

However, in general, the modified curing agent can obtain satisfactory physical properties when applied in a temperature range such as room temperature, that is, 20 to 40 ℃, but the curing property of the coating film is insufficient in the winter season of 10 ℃ or less, especially low temperature below 5 ℃, The modified product by the Mannich reaction, which has conventionally been used as a resin for low temperature curing, also has a problem of insufficient curability of the coating film.

In addition, the polyamide resin reacted with the compound having a carboxyl group in the above-mentioned modified curing agent has a disadvantage that the low temperature curing properties are very poor. In addition, the epoxy adduct resin reacted with the epoxy compound also has a problem in that the discoloration and weather resistance of the coating film due to the outdoor exposure when the single use is insufficient, and the adhesion between the layers is lowered during repainting.

In addition, tertiary amine compounds, typically dimethylaminomethylphenols, are used as curing accelerators used as ring-opening catalysts for epoxy groups. However, they have a strong odor and insufficient curing at low temperatures, and benzyl alcohol is typically used. Although there is some effect of promoting hardenability, it remains in the coating film after coating, which causes deterioration of physical properties such as corrosion resistance, water resistance, and chemical resistance.

In order to solve this problem, U.S. Patent No. 5,783,644 and Japanese Patent Application Laid-open No. Hei 9-40759 include modified epoxy curing agents prepared by known Mannich reactions using amine compounds containing primary and tertiary amine groups in the molecule. Is disclosed. However, when the coating film was formed by curing with an epoxy resin at an appropriate molar ratio known in the above patent, it was effective in improving low temperature curability and whitening of the coating film. However, the main physical properties required for heavy anticorrosive paints were corrosion resistance, water resistance, and resistance. Insufficient results in chemical properties were obtained.

Accordingly, the present invention uses an epoxy acrylate resin (B) in which a bisphenol-A epoxy resin and an unsaturated carboxylic acid are reacted with an epoxy resin (A) and an epoxy resin to solve the above problems, or the epoxy resin. In the case of using amine-based curing agent (C) and petroleum-based resin (D) containing phenolic hydroxyl group in addition to (A) and epoxy acrylate resin (B), curing of the amine-based curing agent (C) and epoxy resin Reaction and Michael addition reaction of amine-based curing agent (C) and epoxy acrylate resin (B) occur simultaneously to allow rapid curing at low temperature, allowing winter and four seasons painting work, and hydroxyl-containing petroleum resin (D) It was found that the above problems can be solved by including the present invention to complete the present invention.

Therefore, the present invention does not contain tar and does not cause safety and environmental problems, less whitening of the coating film after coating, excellent interlayer adhesion during repainting, and excellent curing such as anticorrosion, seawater resistance, and chemical resistance. An object of the present invention is to provide an anticorrosive coating resin having physical properties and an anticorrosive coating composition comprising the same.

The present invention has an epoxy equivalent of 150 to 600 g / eq, and adds 80 to 98% by weight of an epoxy resin (A) having at least two or more epoxy groups in the molecule, and a low molecular weight epoxy resin and an unsaturated carboxylic acid in a 1: 0.5 to 1 molar ratio. It is characterized by the resin for anticorrosive coating containing 2 to 20 weight% of the epoxy acrylate resin (B) which was made to react.

Moreover, this invention is 150-600 g / eq of epoxy equivalents, and 80-98 weight% of epoxy resins (A) which have at least 2 or more epoxy groups in a molecule | numerator, and a low molecular weight epoxy resin and unsaturated carboxylic acid in a 1: 0.5-1 molar ratio. Another feature of the anticorrosive coating composition comprising 2 to 20% by weight of the added epoxy acrylate resin (B) and 10 to 100 parts by weight of the amine curing agent (C) based on 100 parts by weight of the total amount of the epoxy resin. It is done.

The present invention will be described in detail as follows.

The present invention has an epoxy acrylate resin (B) having two or more epoxy groups in a molecule and additionally reacting a specific equivalent epoxy resin (A) with a low molecular weight epoxy resin and an unsaturated carboxylic acid. It contains C) and petroleum-based resin (D) containing phenolic hydroxyl group, and can be used under low temperature painting conditions by using pigments, fillers and other additives commonly used, and have long pot life and excellent painting workability. In addition, as it hardens, it forms a coating film having excellent solvent resistance and anticorrosion property, and is particularly useful for painting in ballast tanks of ships as a part in contact with seawater. In addition, it does not contain tar and does not cause safety and environmental problems.It has little whitening phenomenon after coating, excellent adhesion between layers when repainting, and excellent hardening properties such as corrosion resistance, water resistance, and chemical resistance. Eggplant relates to a non-tar low temperature rapid curing anticorrosive coating resin and an anticorrosive coating composition comprising the same.

The present invention has an epoxy equivalent of 150 to 600 g / eq, and adds 80 to 98% by weight of an epoxy resin (A) having at least two or more epoxy groups in the molecule, and a low molecular weight epoxy resin and an unsaturated carboxylic acid in a 1: 0.5 to 1 molar ratio. It contains 2 to 20 weight% of the reacted epoxy acrylate resin (B) as a main component.

The epoxy resin (A) used by this invention has at least 2 or more epoxy groups in 1 molecule, It is preferable that it is epoxy equivalent 150-600 g / eq, Preferably it is 180-500 g / eq. As the above epoxy resin (A), bisphenol type epoxy resin, aliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, phenol noblock type epoxy resin, cresol type epoxy resin and dimer acid modified epoxy resin 1 type, or 2 or more types of mixtures chosen from these etc. can be used.

The epoxy acrylate resin (B) used for this invention uses what was produced by addition-reacting low molecular weight epoxy resin and unsaturated carboxylic acid in molar ratio 1: 0.5-1. The low molecular weight epoxy resin uses an epoxy equivalent of 180 to 500 g / eq. The said carboxylic acid uses what contains (meth) acrylic acid (Hereinafter, "acrylic acid" shows acrylic acid or (meth) acrylic acid) 30% or more by carboxyl equivalent. In this case, when the content of acrylic acid is less than 30%, there is a problem of lowering the polymerizability of the epoxy acrylate. Unsaturated carboxylic acids used to prepare the epoxy acrylate resin include acrylic acid, methacrylic acid, fumaric acid and itaconic acid.

Epoxy acrylate resin (B) is generally produced by a method of reacting epoxy resin and acrylic acid in the presence of a reaction catalyst and a radical polymerization inhibitor in the temperature range of 70 to 150 ° C. The most important part in the preparation of the epoxy acrylate resin (B) is to prevent gelation during production.

Examples of radical polymerization inhibitors used in the production of the epoxy acrylate resin (B) include hydroquinones, polyhydric phenols and their alkyl ethers, copper salts such as copper chloride, nitro compounds, and the like commonly used in the relevant fields of the present invention. There is this. The use amount of the radical polymerization inhibitor is generally used in a ratio in the range of 0.0001 to 0.5 parts by weight based on 100 parts by weight of the total amount of the low molecular weight epoxy resin and the carboxylic acid component used in the production of the epoxy acrylate resin (B). In addition, the catalyst used to promote the addition reaction of the low molecular weight epoxy resin and the carboxylic acid component used in the production of the epoxy acrylate resin (B) can be used that is commonly used in the field of the present invention, Examples of the catalyst include metal hydroxides such as potassium hydroxide and lithium hydroxide, lithium chloride, potassium bromide, tin chloride, potassium chloride, lithium bromide, zinc halides, zinc chloride and zirconium chloride, metal halides, amines, inorganic acid salts, organic acid salts, and quaternary ammonium salts. , Amido, organic acid alkali metal, phosphoric acid, sulfonic acid, and sulfonium, etc., and the amount of catalyst used is the total amount of the low molecular weight epoxy resin and carboxylic acid component used in the production of epoxy acrylate resin (B). It is generally used in the ratio of the range of 0.001-5 weight part with respect to 100 weight part. Thereby, the epoxy acrylate resin (B) which is a viscosity of 2.000-10,000 mPas (60 degreeC) is manufactured.

The resin prepared by mixing the epoxy resin (A) and the epoxy acrylate resin (B) as described above shows excellent effects as a resin for anticorrosive coatings, and when used in a composition for anticorrosive coatings, it shows an excellent effect.

In the mixing ratio of the epoxy resin (A) used as the main component of the anticorrosive coating composition of the present invention and the epoxy acrylate resin (B) prepared by the above method, 2% by weight of the epoxy acrylate resin (B) If it is used below, there is a problem in winter workability due to delay in curing at low temperature, and when used in excess of 20% by weight, a large number of ester bonds in the coating film containing epoxy acrylate resin (B) exist, resulting in water resistance and alkali resistance of the coating film. A problem arises in which physical properties such as corrosion resistance and chemical resistance are lowered.

Epoxy acrylate resin (B) prepared as described above is Michael addition reaction with the amine group contained in the amine-based curing agent (C) which is a characteristic of the present invention to be described later (Scheme 1).

The secondary amine acrylate adduct produced by the above reaction reacts with another acrylic ester or epoxy resin to ultimately form a high crosslinking film to form a medium coating film which can exhibit excellent physical properties (Scheme 2) ).

here, ,

or to be.

That is, the epoxy adduct produced by reacting the epoxy resin (A) used as the main ingredient and the epoxy acrylate resin (B) obtained by reacting the epoxy resin with an acrylic acid monomer and reacting the Mannich curing agent with the epoxy compound as a curing agent. An amine curing agent (C) is prepared by mixing an amine curing agent (C-1) with a polyamine curing agent (C-2) obtained by a Mannich reaction alone or with an amine compound in which the primary and tertiary amines in the molecule coexist. do. The epoxy resin (A) and the epoxy acrylate resin (B) are cured by Michael addition reaction, and thus can be quickly cured at low temperature, thereby allowing four seasons to be painted. In addition, it contains hydroxyl group-containing petroleum-based resin (D), and does not contain tar, which does not cause safety and environmental problems, has less whitening phenomenon after coating, and has excellent interlayer adhesion during repainting, and is excellent in corrosion resistance, water resistance, An anticorrosive coating composition containing an amine-based curing agent and epoxy resin having excellent curing properties such as chemical resistance can be prepared.

The anticorrosive coating composition of the present invention contains 10 to 100 parts by weight of the amine curing agent (C) based on 100 parts by weight of the main component consisting of the epoxy resin (A) and the epoxy acrylate resin (B).

The amine curing agent (C) used in the present invention is an epoxy adduct amine prepared by reacting a Mannich curing agent obtained by condensation reaction of a polyamine compound, a phenolic compound and a carbonyl compound with an epoxy resin containing at least one epoxy group in a molecule. The curing agent (C-1) and the amine compound in which primary and tertiary amines coexist in the molecule alone or the polyamine curing agent (C-2) in which the amine compound is reacted with each other may be used alone or in combination, and may be used in combination. It is possible to obtain a more preferable effect to use.

As the polyamine compound, a polyamine compound having at least one primary amine group in a molecule is used as a curing agent for an epoxy resin, for example, ethylenediamine, trimethylenediamine, hexamethylenediamine, octamethylenediamine, diethylenetriamine, Aliphatic polyamines such as triethylenetetraamine and pentaethylenehexaamine, aromatic polyamines such as orthoxylenediamine, methaxylenediamine and paraxylenediamine, and isophoronediamine, norbornenediamine and 1.3-bisaminomethylcyclohexane It can use 1 type (s) or 2 or more types chosen from denture-substituted polyamines. The phenolic compound may be selected from the group consisting of a reaction product of phenol, an alkylphenol substituted with an alkyl group such as cresol, nonylphenol and butyl phenol, bisphenol A or bisphenol F, toluene or xylene, and formaldehyde or It can mix and use 2 or more types. As the carbonyl compound, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, perpraldehyde and the like may be used as the compound having at least one CHO group or> C═O group in the molecule, more preferably at 37%. It is preferable to use aqueous solution of formaldehyde.

On the other hand, the epoxy resin used in the preparation of the epoxy adduct amine curing agent (C-1) is reacted with an excess of epichlorohydrin, a polyhydric phenol and a chlorine compound, in the presence of caustic soda, and the additionally produced chlorine ions are treated by a purification process. As a result, it is preferable to use a low molecular epoxy resin having an epoxy equivalent of 180 to 500 g / eq and to use a bisphenol-type epoxy resin represented by the following formula (1) and a noblock epoxy resin represented by the formula (2) alone or in combination.

Here, n is an integer between 0 and 3, X <_1> is a hydrogen atom or a C1-C4 alkyl group, i is an integer of 4 or less, and A is as follows.

In Formula 2, n is 0.1 to 4, m is an integer of 0 to 2, X ₁ is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, X ₂ is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms and are the same as each other Or i, i is an integer of 4 or less, and R is

In addition, the reaction ratio of the Mannich curing agent used in the preparation of the above-mentioned epoxy adduct amine curing agent (C-1) and the epoxy resin containing at least one epoxy group in the molecule can be controlled by those skilled in the art depending on the components used. In general, it is preferable to use the equivalent ratio of the active hydrogen of the Mannich curing agent and the epoxy group of the epoxy resin in the range of 1 / 0.05 to 1 / 0.15. At this time, if the equivalent ratio of the epoxy group is less than 0.05, there is a problem of whitening of the coating film and a decrease in chemical resistance. If the equivalent ratio is more than 0.15, there is a concern of gelation during the manufacture of the resin. There is a problem.

In the present invention, the polyamine curing agent (C-2) used in admixture with the epoxy adduct amine curing agent (C-1) includes an amine compound represented by the following formula (3), and the amine compound alone or by a known Mannich reaction. It is a product, Specifically, For example, 1 type (s) or 2 or more types chosen from dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, etc. can be mixed and used.

Here, X, R ₁ and R ₂ are the same or different and each is an alkyl group having 1 to 4 carbon atoms.

The polyamine curing agent (C-2) as described above is preferably used by mixing 5 to 15% by weight with the epoxy adduct amine curing agent (C-1). When generated and used in excess of 15% by weight, the tertiary amine group may cause a sharp decrease in water resistance, corrosion resistance, and chemical resistance.

The new amine-based curing agent (C) prepared by the above method reacts with the epoxy resin (A) as a main component of the anticorrosive coating composition of the present invention to form a cured product. The amount of the amine-based curing agent (C) is amine It depends on the epoxy group equivalent of the active hydrogen and the epoxy resin (A) contained in the system curing agent (C), and the epoxy of the active hydrogen and the epoxy resin (A) is used in a ratio of 1/8 to 1 / 1.2 equivalents.

As described above, the mixing ratio of the epoxy resin (A), the epoxy acrylate resin (B), and the amine curing agent (C) varies depending on the type of each component, and in the present invention, the epoxy resin (A) and the epoxy acrylic The amine curing agent (C) of the present invention is used in the range of 10 to 100 parts by weight based on 100 parts by weight of the main component comprising the late resin (B). When using the said amine hardening | curing agent (C), it is more preferable to select so that it may become the range of 0.5-1.0 of the active hydrogen equivalent / epoxy equivalent in an epoxy in a hardening | curing agent normally.

In addition, the non-tar anticorrosive coating composition of the present invention may include a phenolic hydroxyl group-containing petroleum resin (D).

The petroleum resin (D) uses a resin having a hydroxyl equivalent weight of 400 to 2,000 g / eq as the liquid aromatic hydrocarbon petroleum resin. At this time, if the hydroxyl equivalent is less than 400 g / eq, the water resistance and sea water resistance of the anti-corrosive coating film is low, the resin component leaks on the surface of the coating film may cause a problem that the stickiness remains, the hydroxyl equivalent exceeds 2,000 g / eq It is not preferable because the viscosity of the paint becomes high because workability decreases or coating film properties decrease. In addition, the viscosity of the petroleum-based resin (D) is in the range of 50 to 2500 mPas (25 ℃), if the viscosity is less than 50 mPas (25 ℃), the water resistance and sea water resistance of the anti-corrosive coating film is low, the resin component on the surface of the coating film Leakage may cause a problem of sticking, and if it exceeds 2,500 mPas (25 ° C), the viscosity of the paint is increased, the workability is lowered, or the coating film properties are not preferable. The hydroxyl group-containing petroleum resin (D) that can be used in the anticorrosive coating composition of the present invention is 1,1,3-trimethyl-3-phenyl-indene, 2,4-diphenyl-4-methyl- as a liquid aromatic hydrocarbon resin. 1-pentene, 2,4-diphenyl-4-methyl-2-pentene, para-cumylphenol, ortho-, para-dicumylphenol, 2,4,6-triphenyl-4,6-dimethylhepta-1 One or a mixture of two or more selected from -ene and 2,4,6-triphenyl-4,6-dimethylhepta-2-ene and the like can be used. In particular, the hydroxyl group-containing aromatic petroleum-based resin can obtain more excellent water resistance or seawater resistance.

2 to 100 parts by weight of a petroleum resin (D) containing a phenolic hydroxyl group with respect to 100 parts by weight of the solid content of the mixture consisting of the epoxy resin (A), the epoxy acrylate resin (B) and the amine curing agent (C) component. Include. At this time, when the amount of the hydroxyl group-containing petroleum resin (D) is less than 2 parts by weight, a coating film having sufficient water resistance and seawater resistance cannot be obtained, and when it exceeds 100 parts by weight, the coating film is easily broken and good physical properties cannot be obtained.

The anticorrosive coating composition of the present invention comprising the above-described composition components, pigments such as extender pigments, rust preventive pigments and coloring pigments, reactive diluents, organic solvents, sedimentation inhibitors, flow inhibitors, wetting agents, reaction promoters, adhesion, if necessary Ordinary paint additives selected from emollients and dehydrating agents can be used.

The composition of the present invention is a two-component coating composed of a main component containing an epoxy resin (A) and an epoxy acrylate resin (B) and a curing agent, preferably an amine curing agent (C). It is coated on the primary rustproof coating. That is, first, shot blasting is performed on the steel sheet to remove the mill scale, and an inorganic zinc primer such as ethyl silicate is applied, and then the coating composition of the present invention is coated.

The primer is not limited to zinc silicate and the like, and various primers can be used. In addition, even if the steel plate is not treated with a primer can be applied, a sufficient anticorrosive effect may be exhibited.

The paint is a coating method, and generally known methods such as air spray, airless spray, roller, brush, etc. may be employed, and the coating composition may be coated with a dry film thickness of 150 to 500 μm with a dry film thickness. It is possible.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Preparation Example 1 Preparation of Amine Curing Agent

Four-necked flask equipped with nitrogen gas pipe, air condenser, stirrer, thermometer, and heater was added 209 g (1 mol) of nonylphenol, 258 g (2 mol) of methaxylenediamine and 51 g of toluene, and then stirred slowly under nitrogen gas injection. Heated up to 90 ° C. When the temperature reached 90 ° C, 170 g (2.2 mol) of formaldehyde 37% aqueous solution was slowly added dropwise over 1 hour, and after the dropping was completed, the temperature was maintained at 90 to 100 ° C and aged for 2 hours. When the aging was completed, the temperature was raised to 120 ° C. to proceed to atmospheric dehydration. When the atmospheric dehydration was completed, the vacuum degree was maintained at 600 to 700 cmHg, and dehydration was performed to recover 144 g of effluent. At this time, the amine value of the Mannich curing agent dehydrated is 373 mgKOH / g and the active hydrogen equivalent is 90 g / eq.

108 g (0.1 eq) of bisphenol A epoxy resin OREPOXY R8828 (epoxy equivalent 189 g / eq, manufactured by KCC), which was liquid at room temperature, was slowly added to the Mannich curing agent at 80 ° C. for 2 hours. At this time, if the dropping speed is high, the risk of gelation will be accompanied. When the dropping of the epoxy resin was completed, the temperature was raised to 100 to 110 ° C., and aged for 1 hour, and then 400 g of xylene was added to obtain an epoxy adducted amine curing agent (a) having a solid content of 60%. The epoxy adduct amine curing agent (a) thus obtained was a resin having an amine value of 172 mgKOH / g and an active hydrogen equivalent weight of 203 g / eq.

Polyamine curing agent used in admixture with the epoxy adsorbed amine curing agent (a) (b) Nonylphenol 485 g (1 mol) and dimethylaminopropyl under the same environment as the preparation of the epoxy adsorbed amine curing agent (a) After adding 450 g (2 mol) of amine and 110 g of toluene, the temperature was raised to 90 ° C., and 447 g (2.5 mol) of formaldehyde 37% aqueous solution was slowly added dropwise thereto over 1 hour, and the temperature was lowered to 90∼ After aging for 2 hours while maintaining the temperature at 100 ℃, the temperature is raised to 120 ℃ to proceed to atmospheric dehydration, and after the completion of atmospheric pressure dehydration to maintain a vacuum degree of 600 ~ 700 cmHg and dehydration under reduced pressure to 380 g of effluent water Recovered. At this time, the dehydrated polyamine curing agent (b) was a resin having an amine value of 306 mgKOH / g and an active hydrogen equivalent of 304 g / eq.

Preparation Example 2 Preparation Example of Amine Curing Agent

Under the same conditions as in Example 1, 218 g (1 mol) of nonylphenol, 204 g (2 mol) of diethylenetriamine, and 48 g of toluene were added, and 177 g (2.2 mol) of 37% aqueous formaldehyde solution was added under the same reaction conditions. After dropping, aged, and dehydration, 150 g of effluent was recovered. At this time, the amine value of the obtained resin was 616 mgKOH / g and the active hydrogen equivalent was 59 g / eq.

As described above, 150 g (0.1 eq) of the liquid bisphenol A epoxy resin OREPOXY R8828 (epoxy equivalent 189 g / eq, manufactured by KCC) was added dropwise to the resin in the same manner as in Example 1, followed by reaction, and the solid content was added by adding 400 g of xylene. An epoxy adducted amine curing agent (c) having a content of 60% was obtained.

The epoxy adduct amine curing agent (c) obtained at this time was a resin whose amine value is 218 mgKOH / g and active hydrogen equivalent weight 145 g / eq. The epoxy adduct amine curing agent (c) and the polyamine curing agent (b) prepared in Example 1 were mixed and used.

Comparative Production Example. Amine curing agent

Under the same conditions as in Example 1, 535 g (1 mol) of nonylphenol, 331 g (1 mol) of metha xylenediamine, and 88 g of toluene were added, and then 237 g (1.2 mol) of 37% aqueous formaldehyde solution was added under the same reaction conditions. 201 g of effluent was recovered by dropping, aging and dehydration. When 100 g of xylene was added thereto, a curing agent (d) having a solid content of 90% was obtained. The Mannich curing agent obtained at this time had an amine number of 268 mgKOH / g and an active hydrogen equivalent weight of 148 g / eq.

Preparation Example 3 Preparation of Epoxy Acrylate Resin

500 g of bisphenol-A epoxy resin R8828 (epoxy equivalent 184-194 g / eq, KCC Co., Ltd.) and 190 g of acrylic acid were added at room temperature, and the temperature was gradually raised to 90-110 ° C., 0.35 g of hydroquinone as a reaction retardant. As a reactive catalyst, 0.9 g of triphenylphosphine (Fluka chemika) was dissolved in methanol as a 10% solution and added. The acid value of the resin thus produced was 0.2 mgKOH / g, and an epoxy acrylate resin (e) having a viscosity of 3,600 mPa · s (60 ° C.) was obtained.

Preparation Example 4 Preparation of Epoxy Acrylate Resin

The acid value of the resin prepared by addition reaction by adding 500 g of liquid epoxy resin R8828 (epoxy equivalent 184-194 g / eq, manufactured by KCC Co., Ltd.) and 228 g of methacrylic acid in the same manner as in Preparation Example 3 was 0.3 mg. Epoxyacrylate resin (f) which is KOH / g and viscosity 5200 mPa.s (60 degreeC) was obtained.

Examples 1-4 and Comparative Examples 1-3: Preparation of Anticorrosive Coating Composition

Using the resin prepared above, the composition shown in Table 1 was included, and an anticorrosive paint was prepared by a conventional method.

The first step is a premixing step, which is inserted into the premixing tank and premixed with the ingredients and compositions shown in the following Table 1. The second step is a dispersing step, wherein the paint premixed in the first step is extruder and kneader. (PLK-46, PCM-30, ZSK-25) using an extruder was melt-dispersed at 80 ~ 120 ℃ to produce a chip to a thickness such that no problem in grinding. The third step is a pulverization step, by grinding the chip prepared in the second step with a high speed mixer to prepare a powder coating having a 320 mesh average particle size of 40 ~ 60 ㎛, particle distribution of 10 ~ 100 ㎛.

Test Example 1. Coating Film Properties

The coating conditions of the anticorrosive coating compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were first completely removed from rust, dust, moisture, oil, and other contaminants on the surface of the substrate using fresh water or an appropriate solvent. Blaster polishing is carried out to 탆.

Then, use the airless spray to prepare the prepared specimens with a nozzle diameter of 0.019 to 0.025 ", spray pressure of 1,700 to 2,200 psi / 120 to 150 atm, and spray angle of 65 °, then apply a dry film thickness of 100 to 200 µm. The temperature condition of 5 to 32 ℃ but the coating composition is a coating that can be cured at a low temperature can be painted at a low temperature of-18 ℃ The physical properties of the coating film is simply described in the following Table 2.

As described above, the anticorrosive coating composition prepared using the novel amine-based curing agent (C), epoxy resin (A), epoxy acrylate resin (B) and petroleum resin (D) according to the present invention is a conventional anticorrosive paint Physical properties such as low temperature curing and lack of composition during the winter coating and re-coating of the coating layer during the re-coating have been improved, and the physical properties such as chemical resistance and anticorrosive properties required for the anticorrosive coating also have excellent effects. That is, it can be hardened at low temperature, so it is possible to paint four seasons, and it contains hydroxy resin-containing petroleum resin and does not contain tar, which does not cause safety and environmental problems. It is possible to prepare an anticorrosive coating composition containing an amine-based curing agent and an epoxy resin having excellent adhesion properties and excellent curing properties such as corrosion resistance, water resistance, and chemical resistance. It is more effective when applied to ballast tanks.

Claims (6)

Epoxy resin 150-600 g / eq, 80-98 weight% of epoxy resins (A) which have at least 2 or more epoxy groups in a molecule | numerator, A resin for anticorrosive coating comprising 2 to 20% by weight of an epoxy acrylate resin (B) obtained by addition reaction of a low molecular weight epoxy resin and an unsaturated carboxylic acid in a 1: 0.5 to 1 molar ratio. The anticorrosive coating resin according to claim 1, wherein the carboxylic acid contains 30% or more of acrylic acid as the carboxyl equivalent. 80 to 98% by weight of epoxy resin (A) having an epoxy equivalent weight of 150 to 600 g / eq and at least two or more epoxy groups in the molecule; 2 to 20% by weight of an epoxy acrylate resin (B) obtained by addition reaction of a low molecular weight epoxy resin and an unsaturated carboxylic acid in a 1: 0.5 to 1 molar ratio, and An anticorrosive coating composition comprising 10 to 100 parts by weight of an amine curing agent (C) based on 100 parts by weight of the total amount of the epoxy resin. 4. The amine curing agent (C) is a mixture consisting of 85 to 95 wt% of an epoxy adduct amine curing agent (C-1) and 5 to 15 wt% of a polyamine curing agent (C-2). Anticorrosive coating composition. The epoxy resin of claim 3, wherein the epoxy adduct amine curing agent (C-1) has an equivalent ratio of the active hydrogen of the Mannich curing agent and the epoxy group of the epoxy resin. Anticorrosive coating composition characterized in that the reaction was in the range of 1 / 0.05 to 1 / 0.15. The anticorrosive coating composition according to claim 3, wherein the polyamine curing agent (C-2) is prepared by reacting alone or Mannich the amine compound in which the primary and tertiary amine groups coexist in the molecule.