KR102036787B1 - Curing agent composition and paint composition comprising the same - Google Patents

Abstract

The present invention relates to a coating composition capable of forming a coating film having a high curing rate and excellent physical properties even at a relatively low temperature, including the curing agent composition and the curing agent composition.

Description

Curing agent composition and coating composition containing the same {CURING AGENT COMPOSITION AND PAINT COMPOSITION COMPRISING THE SAME}

The present invention relates to a coating composition comprising the curing agent composition and the curing agent composition.

In general, paints used for painting require physical properties such as chemical resistance, corrosion resistance, water resistance, etc., because the coating material must be protected from environmental impact.

Examples of the paint used in the coating may include a paint composition comprising an amine curing agent and an epoxy resin, wherein the incompatibility of the amine curing agent and the epoxy resin causes phase separation and thus the amine moves to the coating film surface. When painting with a coating composition, there is a problem that a cloudiness of the coating occurs.

That is, the amine is moved to the surface of the coating film, the amine is reacted with carbon dioxide (CO ₂ ) in the air carbamateization proceeds to cause a cloudy film of the coating film. Whitening of the coating film may damage the appearance of the coating film and cause adhesion defects. This problem may be exacerbated when the coating composition is applied or cured at a lower temperature than usual.

Accordingly, there is a demand for a coating composition capable of forming a coating film having excellent appearance, chemical resistance, corrosion resistance, and water resistance even when applied at a relatively low temperature.

Republic of Korea Patent Publication No. 2008-0041666

The present invention is to provide a curing agent composition to form a coating film excellent in physical properties while increasing the curing reactivity of the coating composition.

Moreover, this invention provides the coating composition containing the said hardening | curing agent composition.

The present invention provides a double bond with an acrylic acid having an alkyl group having 5 to 25 carbon atoms and a first acrylic resin polymerized including a monomer having a carboxylic acid group and an organic acid containing a hydroxyl group and having a chain length of 3 or more carbon atoms. It provides a curing agent composition comprising an epoxy-modified amine resin obtained by reacting a polymerized second acrylic resin and an epoxy resin and a piperazine derivative including a monomer having an acid group.

The acrylic monomers are ethylhexyl methacrylate, octyl acrylate, hexyl acrylate, ethylhexyl acrylate, stearyl methacrylate, noryl acrylate, noryl methacrylate, isobornyl acrylate, isobornyl methacrylate, la It may be at least one selected from the group consisting of uryl acrylate, cyclohexyl acrylate, phenyl acrylate and butyl cyclohexyl methacrylate.

The organic acid is hydroxystearic acid, 1-hydroxy-1-cyclopropanecarboxylic acid, hydroxyl methylbenzoic acid, hydroxymethylpyridinecarboxylic acid ( hydroxy methylpyridine carboxylic acid, hydroxyl-pyridine-2-carboxylic acid methyl ester, (hydroxy methoxyphenyl) propionic acid, hydroxy tetrahydro Isoquinolinecarboxylic acid (hydroxyl tetrahydro isoquinoline carboxylic acid), hydroxyl naphthoic acid, hydroxyl propylbenzoic acid methyl ester, hydroxyl methoxymandelic acid, hydroxy Hydroxyl methyl coumarinylacetic acid, hydroxyl-4- (2-hydroxyethoxy) -benzoic acid (hydroxyl-4- (2-hyd) roxyethoxy) benzoic acid), hydroxyl biphenylcarboxylic acid, and hydroxyl methyl benzofuran carboxylic acid.

The piperazine derivatives include amino ethyl piperazine, piperazine-1-sulfonamide, and 1- (3-aminopropyl) piperazine. , 4- (5-aminopyridin-2-yl) piperazine-1-carboxylic acid ter-butyl ester, 4- (5-aminopyridin-2-yl) piperazine-1-carboxylic acid tert-butyl ester, 1 -(4-aminophenyl) piperazine (1- (4-aminophenyl) piperazine), 1-amino-4- (2-hydroxyethyl) piperazine (1-amino-4- (2-hydroxyethyl) piperazine), Piperazine-2-carboxamide, 1- (4-methoxybenzyl) piperazine (1- (4-methoxybenzyl) piperazine), 1,4-bis (3-aminopropyl) pipe Razine (1,4-bis (3-aminopropyl) piperazine), 1-methyl-4- (6-aminopyridin-3-yl) piperazine (1-methyl-4- (6-aminopyridin-3-yl) piperazine ), 1- (3-aminopropyl) -4- (2-methoxyphenyl) piperazine (1- (3-aminopropyl) -4- (2-methoxyphenyl) piperazine), 4- (2-amino-phenyl) Piperazine-1-carboxylic acid tert-butyl Ester (4- (2-amino-phenyl) -piperazine-1-carboxylic acid tert-butyl ester), 4- (2-aminoethyl) -1-bok-piperazine (4- (2-aminoethyl) -1- boc-piperazine), 4-butyl-4- (2-amino-1-phenylethyl) piperazinecarboxylate (4-butyl-4- (2-amino-1-phenylethyl) piperazine carboxylate), ter-butyl 4- Tert-butyl 4- [2- (aminoethyl) phenyl] piperazine-1-carboxylate and tert-butyl 4- (aminobenzyl) piperazine-1 It may be one or more selected from the group consisting of -carboxylate (tert-butyl 4- (aminobenzyl) piperazine-1-carboxylate).

The curing agent composition may include 5 to 50 parts by weight of the first acrylic resin, 10 to 60 parts by weight of the second acrylic resin and 1 to 30 parts by weight of the epoxy-modified amine resin based on 100 parts by weight of the curing agent composition.

The curing agent composition may further include a modified acrylic resin.

The curing agent composition may further include an amide resin.

On the other hand, this invention provides the coating composition containing the main part containing a base resin, and the hardening | curing agent part containing the said hardening | curing agent composition.

As the coating composition of the present invention includes a base resin (epoxy resin) contained in the main part and a curing agent composition having excellent curing reactivity, it may exhibit a fast curing rate (drying rate) even when applied at low temperatures, and may include chemical resistance, corrosion resistance, The coating film excellent in water resistance etc. can be formed.

Hereinafter, the present invention will be described.

1. Curing agent composition

The hardener composition of this invention contains a 1st acrylic resin, a 2nd acrylic resin, and an epoxy modified amine resin.

The first acrylic resin included in the curing agent composition of the present invention may be polymerized including an acrylic monomer and a monomer having a carboxylic acid group.

The acrylic monomer has a bulky group having a large molecular weight, and may be an acrylic monomer having an alkyl group having 5 to 25 carbon atoms. These acrylic monomers Ethyl hexyl methacrylate, octyl acrylate, hexyl acrylate, ethyl hexyl acrylate, stearyl methacrylate, noryl acrylate, noryl methacrylate, isobornyl acrylate, isobonyl methacrylate, lauryl It may be at least one selected from the group consisting of acrylate, cyclohexyl acrylate, phenyl acrylate and butyl cyclohexyl methacrylate.

Monomers having the carboxylic acid group are, for example, methacrylic acid (acrylic acid), acrylic acid (acrylic acid), fumaric acid (fumaric acid), maleic acid (maleic acid), crotonic acid (crotonic acid), vinylbenzoic acid (vinylbenzoic acid) And it may be one or more selected from the group consisting of acrylic acid dimer (acrylic acid dimer).

The first acrylic resin obtained by polymerization of the acrylic monomer having an alkyl group having 5 to 25 carbon atoms and the monomer having the carboxylic acid group may be, for example, an acrylic resin having a repeating unit obtained by the following Scheme 1. .

Scheme 1

In Reaction Scheme 1, R ₁ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group having 3 to 25 carbon atoms, and n is an integer of 2 to 50.

The polymerization reaction for obtaining the first acrylic resin may further include a conventional acrylic monomer. The conventional acrylic monomers are, for example, ethyl acrylate, methyl acrylate, butyl acrylate, octyl acrylate, ethyl hexyl acrylate, lauryl acrylate, cyclohexyl acrylate, butyl methacrylate, phenyl acrylate, benzyl It may be at least one selected from the group consisting of acrylate and vinyl acrylate.

In addition, the polymerization reaction for obtaining the first acrylic resin may further include a monomer having an amine group. The monomer having an amine group is diethylamioethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, t-butylamioethyl methacrylate, dimethylaminoethyl acrylate. (dimethylaminoethyl acrylate), methacryl amide, acryl amide, n-methylol acryl amide, diacetone acryl amide, acrylonitrile It may be at least one selected from the group consisting of, methacrylonitrile (methacrylonitrile) and N, N-butoxy methyl acrylamide (N, N-butoxy methyl acryl amide).

In addition, the polymerization reaction for obtaining the first acrylic resin may further include a monomer having a benzene group. The monomer having the benzene group may be, for example, styrene, methylstyrene, butadiene, vinyltoluene, or mixtures thereof.

In addition, the polymerization reaction for obtaining the first acrylic resin may further include a polymerization initiator and a solvent. The polymerization initiator may be, for example, benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, octanoyl peroxide, cumene hydroperoxide, diisopropylbenzenehydroperoxide, or a mixture thereof. The solvent is an alcohol solvent such as butyl alcohol, propyl alcohol, isopropyl alcohol; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate; Aromatic solvents such as xylene and toluene; Or mixtures thereof.

The first acrylic resin may have a solid content of 60 to 80% by weight and a viscosity of X to Z7. In addition, the first acrylic resin may have an acid value of 10 to 80 mgKOH / g, a hydroxyl value of 0 to 30 mgKOH / g, an amine value of 10 to 80 mgKOH / g, and a glass transition temperature of 0 to 30 ° C.

Since the first acrylic resin is obtained by applying an acrylic monomer (hydrophobic acrylic monomer) having an alkyl group having 5 to 25 carbon atoms, when the curing agent composition containing the same is used for coating film formation, the water resistance of the coating film can be improved.

The content of the first acrylic resin may be 5 to 50 parts by weight based on 100 parts by weight of the curing agent composition. When the content of the first acrylic resin is less than 5 parts by weight, the water resistance of the coating film may be lowered, and when it exceeds 50 parts by weight, the drying property of the coating film may be slowed.

The second acrylic resin included in the curing agent composition of the present invention may be polymerized by including an organic acid having a chain length of 3 or more carbon atoms (for example, 3 to 20 carbon atoms) and a monomer including a double bond and having an acid group. .

The organic acid having a chain length of 3 or more carbon atoms may be a long chain organic acid including a hydroxy group and a carboxylic acid group at a chain end. The organic acid is, for example, hydroxystearic acid, 1-hydroxy-1-cyclopropanecarboxylic acid, hydroxyl methylbenzoic acid, hydroxymethyl Hydroxy methylpyridine carboxylic acid, hydroxyl-pyridine-2-carboxylic acid methyl ester, (hydroxy methoxyphenyl) propionic acid, hydroxy Hydroxy tetrahydro isoquinolinecarboxylic acid, hydroxyl naphthoic acid, hydroxyl propylbenzoic acid methyl ester, hydroxyl methoxymandelic acid , Hydroxyl methyl coumarinylacetic acid, hydroxyl-4- (2-hydroxyethoxy) -benzoic acid hydr at least one selected from the group consisting of oxyl-4- (2-hydroxyethoxy) benzoic acid), hydroxyl biphenylcarboxylic acid and hydroxylmethyl benzofuran carboxylic acid. have.

Monomers containing the double bond and having an acid group are, for example, methacrylic acid (acrylic acid), acrylic acid (acrylic acid), fumaric acid (maleic acid), crotonic acid (crotonic acid), vinyl benzoic acid ( vinylbenzoic acid) and acrylic acid dimers may be one or more selected from the group consisting of.

The second acrylic resin obtained by the polymerization reaction of the organic acid having a chain length of 3 or more carbon atoms and the monomer having an acid group may be, for example, an acrylic resin having a repeating unit obtained by the following Scheme 2.

Scheme 2

In Scheme 2, R ₁ and R ₂ are the same as or different from each other, and each independently an aliphatic hydrocarbon group having 1 to 25 carbon atoms (eg, an alkyl group), and n is an integer of 2 to 50.

The polymerization reaction for obtaining the second acrylic resin may further include a monomer having an amine group. The monomer having an amine group is diethylamioethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, t-butylamioethyl methacrylate, dimethylaminoethyl acrylate. (dimethylaminoethyl acrylate), methacryl amide, acryl amide, n-methylol acryl amide, diacetone acryl amide, acrylonitrile It may be at least one selected from the group consisting of, methacrylonitrile (methacrylonitrile) and N, N-butoxy methyl acrylamide (N, N-butoxy methyl acryl amide).

In addition, a polymerization reaction for obtaining the second acrylic resin may further include a conventional acrylic monomer. The conventional acrylic monomers are, for example, ethyl acrylate, methyl acrylate, butyl acrylate, ethylhexyl methacrylate, octyl acrylate, ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, butyl methacrylate. It may be at least one selected from the group consisting of, phenyl acrylate, benzyl acrylate and vinyl acrylate.

In addition, the polymerization reaction for obtaining the second acrylic resin may further include a monomer having a benzene group. The monomer having the benzene group may be, for example, styrene, methylstyrene, butadiene, vinyltoluene, or mixtures thereof.

In addition, the polymerization reaction for obtaining the second acrylic resin may further include a polymerization initiator and a solvent. The polymerization initiator may be, for example, benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, octanoyl peroxide, cumene hydroperoxide, diisopropylbenzenehydroperoxide, or a mixture thereof. The solvent is an alcohol solvent such as butyl alcohol, propyl alcohol, isopropyl alcohol; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate; Aromatic solvents such as xylene and toluene; Or mixtures thereof.

The second acrylic resin reacts the organic acid with the monomer having the acid group to obtain a long chain organic acid reactant, which is mixed and polymerized with the monomer having the amine group, the conventional acrylic monomer and the monomer having the benzene group. You can get it through the process.

The second acrylic resin may have a solid content of 60 to 80% by weight and a viscosity of Z3 to Z6. In addition, the second acrylic resin may have an acid value of 20 to 50 mgKOH / g, a hydroxyl value of 0 to 30 mgKOH / g, an amine value of 20 to 50 mgKOH / g, and a glass transition temperature of 0 to 30 ° C.

Since the second acrylic resin is obtained by applying an organic acid having a chain length of 3 or more carbon atoms, when the curing agent composition containing the same is used to form the coating film, the curing speed (curing reactivity with the subject resin) of the coating film can be increased.

The content of the second acrylic resin may be 10 to 60 parts by weight based on 100 parts by weight of the curing agent composition. When the content of the second acrylic resin is less than 10 parts by weight, the curing rate of the coating film may be lowered, and when it exceeds 60 parts by weight, the water resistance of the coating film may be lowered.

The epoxy modified amine resin included in the curing agent composition of the present invention may be obtained by reacting an epoxy resin with a piperazine derivative.

The epoxy resin may be a commonly known epoxy resin.

The piperazine derivative has an amine group, amino ethyl piperazine, piperazine-1-sulfonamide, 1- (3-aminopropyl) piperazine (1- ( 3-aminopropyl) piperazine), 4- (5-aminopyridin-2-yl) piperazine-1-carboxylic acid ter-butyl ester (4- (5-aminopyridin-2-yl) piperazine-1-carboxylic acid tert -butyl ester), 1- (4-aminophenyl) piperazine (1- (4-aminophenyl) piperazine), 1-amino-4- (2-hydroxyethyl) piperazine (1-amino-4- (2 -hydroxyethyl) piperazine), piperazine-2-carboxamide, 1- (4-methoxybenzyl) piperazine (1- (4-methoxybenzyl) piperazine), 1,4-bis ( 3-aminopropyl) piperazine (1,4-bis (3-aminopropyl) piperazine), 1-methyl-4- (6-aminopyridin-3-yl) piperazine (1-methyl-4- (6-aminopyridin -3-yl) piperazine), 1- (3-aminopropyl) -4- (2-methoxyphenyl) piperazine (1- (3-aminopropyl) -4- (2-methoxyphenyl) piperazine), 4- ( 2-amino-phenyl) -pipe Razine-1-carboxylic acid ter-butyl ester (4- (2-amino-phenyl) -piperazine-1-carboxylic acid tert-butyl ester), 4- (2-aminoethyl) -1-bok-piperazine ( 4- (2-aminoethyl) -1-boc-piperazine), 4-butyl-4- (2-amino-1-phenylethyl) piperazinecarboxylate (4-butyl-4- (2-amino-1-phenylethyl ) piperazine carboxylate), tert-butyl 4- [2- (aminoethyl) phenyl] piperazine-1-carboxylate and tert-butyl It may be at least one selected from the group consisting of 4- (aminobenzyl) piperazine-1-carboxylate (tert-butyl 4- (aminobenzyl) piperazine-1-carboxylate).

Such epoxy modified amine resin may have a viscosity of 3000 to 7000 cPs, and an amine number of 350 to 700 mgKOH / g.

Since the epoxy-modified amine resin is obtained by applying a piperazine derivative having a high amine value, when a curing agent composition containing the same is used to form a coating film, it acts as a curing catalyst to increase the curing rate of the coating film (cure reactivity with the subject resin). Can be.

The content of the epoxy-modified amine resin may be 1 to 30 parts by weight based on 100 parts by weight of the curing agent composition. When the content of the epoxy-modified amine resin is less than 1 part by weight, the curing rate of the coating film may be lowered, and when it exceeds 30 parts by weight, the water resistance of the coating film may be reduced.

Meanwhile, the curing agent composition of the present invention may further include a modified acrylic resin. The modified acrylic resin may be a resin obtained by reacting an acrylic monomer (or an acrylic polymer) with an epoxy compound or a silane compound.

The modified acrylic resin has a solid content of 60 to 80% by weight, a viscosity of Z3 to Z6, an acid value of 25 to 40 mgKOH / g, an amine value of 20 to 45 mgKOH / g, and a glass transition temperature of -5 to 25 May be ° C.

Since such modified acrylic resin is obtained by applying an epoxy compound or a silane compound, the viscosity of the curing agent composition including the same can be improved. When the viscosity of the curing agent composition is improved, workability at low temperatures (for example, in winter) can be improved.

The content of the modified acrylic resin may be 5 to 30 parts by weight based on 100 parts by weight of the curing agent composition. When the content of the modified acrylic resin is less than 5 parts by weight, the viscosity of the curing agent composition may increase, and when it exceeds 30 parts by weight, uncuring of the coating may be caused.

In addition, the curing agent composition of the present invention may further include an amide resin. The amide resin is a known amide resin, the solid content is 68.5 to 71.5% by weight, the viscosity is 4500 to 8500 cPs, the acid value is 3 mgKOH / g or less, the amine value can be 150 to 160 mgKOH / g have.

The content of the amide resin may be 5 to 30 parts by weight based on 100 parts by weight of the curing agent composition. When the content of the amide resin is less than 5 parts by weight, the curing rate of the coating film may be lowered, and when it exceeds 30 parts by weight, the water resistance of the coating film may be lowered.

Such a curing agent composition of the present invention may further include a conventionally known organic solvent to control the viscosity and dispersibility.

2. Paint Composition

The coating composition of this invention contains a main part and a hardening | curing agent part.

The subject portion comprises a base resin. The base resin may be a commonly known epoxy resin. Such subject matter may further comprise conventionally known pigments, auxiliary resins, dispersants, solvents, additives and the like.

The hardener portion includes the hardener composition described above.

Since the coating composition of the present invention includes the curing agent composition described above in the curing agent portion, even when applied at a low temperature, it can exhibit a fast curing rate (drying rate), and can form a coating film having excellent chemical resistance, corrosion resistance, and water resistance. . In particular, the coating composition of the present invention can be usefully used in the top coating process of winter ships.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.

[ Synthesis Example  One]

19 g of butyl alcohol was added to a four-necked synthetic flask equipped with a thermometer and a stirring device, and then heated to a reflux temperature of 125 ° C. under a nitrogen atmosphere. Next, 27.7 g of styrene, 18 g of butyl acrylate, 3.6 g of methacrylic acid, 6.7 g of dimethylaminoethyl methacrylate, and 14 g of ethylhexyl methacrylate were added and mixed, followed by mixing 1 g of benzoyl peroxide and 10 g of butyl alcohol over 4 hours. Evenly added dropwise. After completion of the dropwise addition, the mixture was polymerized at reflux for 2 hours to obtain a solid content of 70% by weight, a viscosity of Z3-Z6, an acid value of 34 mgKOH / g, an amine value of 34 mgKOH / g, and a glass transition temperature of 15 ° C. The first acrylic resin was obtained.

[ Synthesis Example  2]

1) Intermediate reactant synthesis

21 g of maleic acid, 49 g of hydroxystearic acid, and 30 g of butyl acetate were added to a four-necked synthetic flask equipped with a thermometer and a stirring device, and reacted at 80 ° C. for 6 hours. Thereafter, the reaction was performed until the acid value reached 271 mgKOH / g, followed by cooling to obtain an intermediate reactant (resin) having a solid content of 70% by weight, a viscosity of V-Z, and an acid value of 271.2 mgKOH / g.

2) Second Acrylic Resin Synthesis

16 g of butyl alcohol was added to a four-necked synthetic flask equipped with a thermometer and a stirring device, and then heated to a reflux temperature of 125 ° C. under a nitrogen atmosphere. Next, 26 g of styrene, 14 g of butyl acrylate, 12.5 g of long chain acid, 14 g of ethylhexyl methacrylate, and 7 g of dimethylaminoethyl methacrylate were added and mixed with 1 g of benzoyl peroxide and 10 g of butyl alcohol for 4 hours. Separation was carried out uniformly over. After completion of the dropwise addition, polymerization was performed at reflux for 2 hours to obtain a second acrylic resin having a solid content of 70% by weight, a viscosity of Z3, an acid value of 34 mgKOH / g, and an amine number of 34 mgKOH / g.

[ Synthesis Example  3]

1) Intermediate reactant synthesis

21 g of maleic acid, 25 g of hydroxylmethylbenzoic acid, and 19.7 g of butyl acetate were added to a four-necked synthetic flask equipped with a thermometer and a stirring device, followed by reaction at 80 ° C. for 6 hours. Thereafter, the reaction was performed until the acid value reached 271 mgKOH / g, followed by cooling to obtain an intermediate reactant (resin) having a solid content of 70% by weight, a viscosity of V-Z, and an acid value of 271.2 mgKOH / g.

2) Second Acrylic Resin Synthesis

16 g of butyl alcohol was added to a synthetic four-necked flask equipped with a thermometer and a stirring device, and then heated to a reflux temperature of 125 ° C. under a nitrogen atmosphere. Next, 26 g of styrene, 14 g of butyl acrylate, 12.5 g of long chain acid, 14 g of ethylhexyl methacrylate, and 7 g of dimethylaminoethyl methacrylate were added and mixed with 1 g of benzoyl peroxide and 10 g of butyl alcohol for 4 hours. Separation was carried out uniformly over. After completion of the dropwise addition, polymerization was performed at reflux for 2 hours to obtain a second acrylic resin having a solid content of 70% by weight, a viscosity of Z4, an acid value of 34 mgKOH / g, and an amine number of 34 mgKOH / g.

[ Synthesis Example  4]

53 g of amino ethyl piperazine and 46.4 g of epoxy resin (R8010) were added to a four-necked flask equipped with a thermometer and a stirring device, mixed, and reacted at 100 ° C. for 4 hours to obtain a viscosity of 5500 cPs. And the epoxy modified amine resin whose amine number is 560 mgKOH / g were obtained.

[ Synthesis Example  5]

58 g of amino propyl piperazine and 46.4 g of epoxy resin (R8010) were added to a four-necked flask equipped with a thermometer and a stirring device, and then reacted at 100 ° C. for 4 hours to obtain a viscosity of 4500 cPs. And the epoxy modified amine resin whose amine number is 560 mgKOH / g were obtained.

[ Synthesis Example  6]

19 g of butyl alcohol was added to a four-necked synthetic flask equipped with a thermometer and a stirring device, and then heated to a reflux temperature of 125 ° C. under a nitrogen atmosphere. Next, 26.1 g of styrene, 16 g of butyl acrylate, 4.4 g of methacrylic acid, 6.7 g of dimethylaminoethyl methacrylate, 14 g of ethylhexyl methacrylate, and 2.5 g of epoxy resin (CarduraE10p) were added and mixed, with 1 g of benzoyl peroxide. 10 g of butyl alcohol were added dropwise and uniformly over 4 hours. After completion of the dropwise addition, polymerization was performed at reflux for 2 hours to obtain a solid content of 70% by weight, a viscosity of Z3-Z6, an acid value of 33 mgKOH / g, an amine value of 34 mgKOH / g, and a glass transition temperature of 15 ° C. A modified acrylic resin was obtained.

[ Example  1 to 3]

To the curing agent composition having a composition of Table 1 was prepared in a conventional manner.

ingredient Example 1 Example 2 Example 3 1st acrylic resin (synthesis example 1) 6.5 26.8 26.8 2nd acrylic resin (synthesis example 2) 17.9 26.8 - 2nd acrylic resin (synthesis example 3) - - 26.8 Epoxy-Modified Amine Resin (Synthesis Example 4) 1.5 20.5 - Epoxy-Modified Amine Resin (Synthesis Example 5) - - 20.5  Modified Acrylic Resin (Synthesis Example 6) 6.5 - - Amide Resin (Kukdo Chemical, GX450) 3.6 3.6 3.6 Solvent (MOP) 64 22.3 22.3 Sum 100 100 100

[ Comparative example  1 to 7]

To the curing agent composition having a composition of Table 2 was prepared in a conventional manner.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 1st acrylic resin (synthesis example 1) - - - - 53.6 26.8 26.8 2nd acrylic resin (synthesis example 2) 53.6 - - - - 26.8 - Epoxy-Modified Amine Resin (Synthesis Example 4) - 41 - - - - 20.5 Modified Acrylic Resin (Synthesis Example 6) - - - 53.6 - - - Amide Resin (Kukdo Chemical, GX450) 3.6 3.6 12.9 3.6 3.6 3.6 3.6 Solvent (MOP) 42.8 55.4 87.1 42.8 42.8 42.8 49.1 Sum 100 100 100 100 100 100 100

[ Production Example  1 to 3 and Comparative Production Example  1 to 7]

A top coat composition was prepared by mixing the main composition (topic) (KCC, ET-5745) and the hardener composition (curing agent) prepared in Preparation Examples and Comparative Preparation Examples, respectively, in a weight ratio of 1.17: 1.

[ Experimental Example ]

Physical properties of the curing agent composition and the top coat composition were evaluated in the following manner, and the results are shown in Table 3 below.

1. Viscosity: 350 g of the curing agent composition was adjusted to 25 ° C. and measured with a KU viscometer.

2. Curing time: The top coat composition was applied to a glass plate of 2cm * 30cm size 10㎛ thickness, put into a low-temperature refrigerator (5 ℃) and the time spent until curing using a time recording machine was measured.

3. Water resistance: The top coat composition was applied to a glass plate having a size of 15 cm * 30 cm in a thickness of 10 μm and then cured at low temperature (5 ° C.) for 12 hours. Next, the water level was increased after immersion for 12 hours, the water level was increased after immersion for 12 hours, and then immersed for another 12 hours. Then, the glass plate was taken out to check the degree of discoloration of the coating film (good: when the coating film is not discolored / poor: when the coating film is severely discolored).

division Viscosity KU Curing time Water resistance Preparation Example 1 100 18 hours Good Preparation Example 2 118 18 hours Good Preparation Example 3 115 18 hours Good Comparative Production Example 1 108 20 hours Good Comparative Production Example 2 119 19 hours Bad Comparative Production Example 3 125 48 hours Bad Comparative Production Example 4 90 30 hours Good Comparative Production Example 5 120 23 hours Good Comparative Production Example 6 104 23 hours Good Comparative Production Example 7 116 24 hours Bad

Referring to Table 3 above, it can be seen that the coating film is formed of a top coat composition including the curing agent composition of the present invention to form a coating film having high curing reactivity at low temperature and excellent physical properties.

Claims (8)

A first acrylic resin polymerized including an acrylic monomer having an alkyl group having 5 to 25 carbon atoms and a monomer having a carboxylic acid group,
A second acrylic resin polymerized including an hydroxy group and an organic acid having a chain length of 3 or more carbon atoms and a monomer including a double bond and an acid group, and
A curing agent composition comprising an epoxy-modified amine resin obtained by reacting an epoxy resin and a piperazine derivative. The method according to claim 1,
The acryl monomer is ethylhexyl methacrylate, octyl acrylate, hexyl acrylate, ethylhexyl acrylate, stearyl methacrylate, noryl acrylate, noryl methacrylate, isobornyl acrylate, isobornyl methacrylate, la At least one hardener composition selected from the group consisting of uryl acrylate, cyclohexyl acrylate, phenyl acrylate and butyl cyclohexyl methacrylate. The method according to claim 1,
The organic acid is hydroxystearic acid, 1-hydroxy-1-cyclopropanecarboxylic acid, hydroxyl methylbenzoic acid, hydroxymethylpyridinecarboxylic acid ( hydroxy methylpyridine carboxylic acid, hydroxyl-pyridine-2-carboxylic acid methyl ester, (hydroxy methoxyphenyl) propionic acid, hydroxy tetrahydro Isoquinolinecarboxylic acid (hydroxyl tetrahydro isoquinolinecarboxylic acid), hydroxyl naphthoic acid, hydroxyl propylbenzoic acid methyl ester, hydroxyl methoxymandelic acid, hydroxyl Methylmethyl coumarinylacetic acid, hydroxyl-4- (2-hydroxyethoxy) -benzoic acid hydroxyl-4- (2-hydro xyethoxy) benzoic acid), hydroxyl biphenylcarboxylic acid (hydroxyl biphenylcarboxylic acid) and hydroxylmethyl benzofuran carboxylic acid (hydroxyl methyl benzofuran carboxylic acid) is at least one member selected from the group consisting of. The method according to claim 1,
The piperazine derivatives include amino ethyl piperazine, piperazine-1-sulfonamide, and 1- (3-aminopropyl) piperazine. , 4- (5-aminopyridin-2-yl) piperazine-1-carboxylic acid ter-butyl ester, 4- (5-aminopyridin-2-yl) piperazine-1-carboxylic acid tert-butyl ester, 1 -(4-aminophenyl) piperazine (1- (4-aminophenyl) piperazine), 1-amino-4- (2-hydroxyethyl) piperazine (1-amino-4- (2-hydroxyethyl) piperazine), Piperazine-2-carboxamide, 1- (4-methoxybenzyl) piperazine (1- (4-methoxybenzyl) piperazine), 1,4-bis (3-aminopropyl) pipe Razine (1,4-bis (3-aminopropyl) piperazine), 1-methyl-4- (6-aminopyridin-3-yl) piperazine (1-methyl-4- (6-aminopyridin-3-yl) piperazine ), 1- (3-aminopropyl) -4- (2-methoxyphenyl) piperazine (1- (3-aminopropyl) -4- (2-methoxyphenyl) piperazine), 4- (2-amino-phenyl) Piperazine-1-carboxylic acid ter-butyl to (4- (2-amino-phenyl) -piperazine-1-carboxylic acid tert-butyl ester), 4- (2-aminoethyl) -1-bok-piperazine (4- (2-aminoethyl) -1- boc-piperazine), 4-butyl-4- (2-amino-1-phenylethyl) piperazinecarboxylate (4-butyl-4- (2-amino-1-phenylethyl) piperazine carboxylate), ter-butyl 4- Tert-butyl 4- [2- (aminoethyl) phenyl] piperazine-1-carboxylate and tert-butyl 4- (aminobenzyl) piperazine-1 At least one hardener composition selected from the group consisting of carboxylates (tert-butyl 4- (aminobenzyl) piperazine-1-carboxylate). The method according to claim 1,
Based on 100 parts by weight of the curing agent composition,
5 to 50 parts by weight of the first acrylic resin,
10 to 60 parts by weight of the second acrylic resin and
Curing agent composition comprising 1 to 30 parts by weight of the epoxy-modified amine resin. The method according to claim 1,
Curing agent composition further comprising a modified acrylic resin. The method according to claim 1,
Curing agent composition further comprising an amide resin. A main body comprising a base resin and
The coating composition containing the hardening | curing agent part containing the hardening | curing agent composition of any one of Claims 1-7.