KR102021587B1 - Coating composition - Google Patents

Abstract

The present invention relates to a coating composition capable of forming a coating film having excellent chemical resistance.

Description

Coating composition {COATING COMPOSITION}

The present invention relates to a coating composition.

A coating composition containing an epoxy resin is used for painting inside a tank installed in a transport vessel. The coating film inside the tank formed of the paint composition containing epoxy is blistered to the coating film inside the tank when a liquid compound such as acetone or vinyl acetate monomer, which may damage the coating film, is loaded inside the tank. Does not occur and can be used easily.

However, the rate at which the loaded liquid compound is absorbed by the coating film inside the tank is high, and a recovery time is needed until the coating film returns to normal after unloading the liquid compound stored in the tank, so that other shipments can be immediately loaded into the tank. In many cases, transportation efficiency is lowered because it is impossible.

In addition, the epoxy coating composition uses a bimodal type (bimodal type) containing two epoxy resins, the bimodal type epoxy paint is a resorcinol epoxy resin (Resorcinol Epoxy resin) to improve the chemical resistance of the paint It is applied in excess (60-80 wt% based on the total sum of the two epoxy). Resorcinol epoxy resin is a very sensitive material for the skin, which can cause skin irritation during the work when the worker coats the inside of the tank. In the case of using excessive resorcinol epoxy resin, the chemical resistance may be excellent, but the drying time of the entire coating film is very slow, the ductility of the formed coating film is low, and the recoating interval is shortened.

Therefore, there is a need in the art for the development of paint applied to the inside of the tank of the transport vessel used to transport the liquid compounds as described above by land or sea.

Korean Unexamined Patent Publication No. 2015-0140607 (published Dec. 16, 2015)

The present invention provides a coating composition.

Moreover, this invention provides the coating film formed using the said coating composition.

The present invention includes an epoxy resin mixture comprising a resorcinol epoxy resin and a novolak epoxy resin, an amine curing agent mixture comprising an aliphatic amine compound and an alicyclic amine compound, an accelerator including an imidazole compound, and an additive. On the basis of 100% by weight of the epoxy resin mixture, to provide a coating composition comprising 40 to 55% by weight of resorcinol epoxy resin and 45 to 60% by weight of a novolak epoxy resin.

Moreover, this invention provides the coating film formed using the said coating composition.

The coating composition according to the present invention can minimize the skin irritation of the operator when painting inside the tank. In addition, the coating film absorption rate of liquid compounds such as acetone and vinyl acetate monomer to the coating film formed inside the tank by this composition is very low, which can shorten the recovery time of the coating film after loading the liquid compound. There is an effect that can form a very good coating film.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The present invention provides a coating composition.

The coating composition of the present invention is an epoxy resin mixture comprising a resorcinol epoxy resin and a novolak epoxy resin, an amine curing agent mixture comprising an aliphatic amine compound and an alicyclic amine compound, an accelerator including an imidazole compound, and It may include an additive.

Hereinafter, the individual components will be described in more detail.

<Epoxy resin mixture>

The epoxy resin mixture included in the coating composition of the present invention includes a resorcinol epoxy resin and a novolac epoxy resin.

The resorcinol epoxy resin may specifically include a resorcinol diglycidyl ether epoxy resin, the epoxy equivalent may be 120 g / eq to 135 g / eq. By carrying out epoxy equivalent in the said range, the outstanding physical property can be ensured from a crosslinking density and a viscosity point.

The novolac epoxy resin may include one or more selected from the group consisting of cresol novolac epoxy resins, hydrocarbon novolac epoxy resins, bisphenol novolac epoxy resins, and phenol novolac epoxy resins, in one embodiment of the present invention. According to the present invention, a phenol novolac epoxy resin can be used in terms of securing physical properties of the coating film.

The novolac epoxy resin may have an epoxy equivalent of 172 g / eq to 181 g / eq. By carrying out epoxy equivalent in the said range, the outstanding physical property can be ensured from the flexible viewpoint of a coating film.

According to one embodiment of the invention, based on 100% by weight of the epoxy resin mixture, 40 to 55% by weight of resorcinol epoxy resin and 45 to 60% by weight of a novolak epoxy resin, in this case low The content of resorcinol epoxy resin prevents the occurrence of skin irritation of the worker, while ensuring the physical properties of the coating film.

In particular, when the content of the resorcinol epoxy resin is less than 40% by weight may reduce the chemical resistance of the coating film, when the content of more than 55% by weight may slow the drying of the coating film and the flexibility and recoating interval of the coating film may be inferior. In addition, when the content of the novolak epoxy resin is less than 45% by weight may increase the drying time of the coating film or cracks, when the content of more than 60% by weight may increase the coating film absorption rate for the liquid compound, or the drying time of the coating film may be faster. have.

The epoxy resin mixture in the coating composition of the present invention is a coating composition through two reaction pathways: reaction of an epoxy group of an epoxy resin with a functional group having active hydrogen in an amine curing agent and a reaction between the epoxy groups of an epoxy resin (post curing reaction). This may be cured.

<Amine Curing Agent Mixture>

The amine curing agent mixture included in the coating composition of the present invention may be an aliphatic amine compound and an alicyclic amine compound. By simultaneously including two or more different amine compounds different from each other as described above, the flexibility of the cured resin can be improved and the recoating interval for the coating film can be extended. In addition, due to the flexible structure, during the homopolymerization curing reaction, it is possible to promote the reaction to the unreacted epoxy sites to improve the crosslinking density, and the improvement of the crosslinking density minimizes the absorption rate of the liquid compound in the final formed coating film. .

The aliphatic amine compound is, for example, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexamethylenediamine (HMDA), N- (2-aminoethyl) -1,3-propanediamine (N ₃ -amine), N, N'-1,2-ethanediylbis-1,3-propanediamine (N ₄ -amine) and dipropylenetriamine It may be one or more selected from the group consisting of or an adduct compound of the aliphatic amine compound.

The alicyclic amine compound is, for example, 1,3-bisaminocyclohexylamine (1,3-BAC), isophorone diamine (IPDA), or 4,4'-methylenebiscyclohexanamine (PACM) and 4 It may include one or more selected from the group consisting of 4'-methylenebis- (2-methyl-cyclohexaneamine).

In addition, according to an embodiment of the present invention, when using the amine curing agent mixture, in order to obtain the effects described above, the aliphatic amine compound and the alicyclic amine compound may be included in a weight ratio of 1: 3 to 1: 5. If it is out of the above range, this effect may not be achieved.

<Accelerator>

The coating composition of the present invention may include an accelerator, and the accelerator may include an imidazole compound. In the epoxy resin mixture of the present invention using a relatively low content of resorcinol-based epoxy resin, the imidazole-based compound can induce an epoxy homopolymerization reaction smoothly, thereby maximizing crosslinking density and shortening drying time. By including such an accelerator, the coating film formed by the epoxy coating composition of one embodiment of the present invention can minimize the absorption rate of the liquid compound.

The imidazole compound is 1-methyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 1-phenyl-2-methyl imidazole, 2-heptadecyl imida Sol, 1-cyanoethyl-2-phenylimidazole-trimelitate, 2- (β- (2'-methylimidazoyl- (1 ')))-ethyl-4-6-diamino-s -Triazine, 2,4-dimethylimidazole 2-undecylimidazole, 2-heptadecenyl-4-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimida Sol, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, 2-vinylimidazole, 1-vinyl- 2-methylimidazole, 1-propyl-2-methylimidazole, 1- (3-aminopropyl) -imidazole, butylimidazole 1-cyanoethyl-2-methylimidazole, 1-sia Noethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-guanaminoethyl-2-methylimidazole, 1-cyanoethyl-2-iso Propylimidazole, 1-cyanoethyl-2-fe Imidazole, 1-aminoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- Phenyl-4-benzyl-5-hydroxymethylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1 -(Dodecyl benzyl) -2-methylimidazole, 2- (2-hydroxyl-4-t-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl)- 4,5-diphenylimidazole, 2- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl) -4,5-diphenylimidazole , 2- (2-hydroxyphenyl) -4,5-diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5 It may include one or more selected from the group consisting of -diphenylimidazole, 1-benzyl-2-methylimidazole, and 2-p-methoxystyrylimidazole.

<Additive>

The coating composition of the present invention may further comprise other optional ingredients, for example conventional additives known in the art. More specifically, catalysts for facilitating the reaction between the epoxy compound used and the curing agent, solvents for lowering the viscosity of the composition, other curing agents, fillers, pigments, toughening agents, flow modifiers, adhesion promoters, diluents, stabilizers, plasticizers , Catalytic deactivators, antifoams, wetting agents, rheology modifiers, other similar additive components used in epoxy coatings, and mixtures thereof.

Coating Composition

On the other hand, the coating composition of the present invention is an aliphatic at the time of coating application to the composition comprising the above-mentioned epoxy resin mixture comprising a resorcinol epoxy resin and a novolak epoxy resin, an accelerator including an imidazole compound, and an additive It may be a two-component composition prepared by blending a composition comprising an amine curing agent mixture comprising an amine compound and an alicyclic amine compound.

The final paint composition may comprise 30 to 40 parts by weight of an epoxy resin mixture, 2 to 5 parts by weight of an amine curing agent mixture, 0.5 to 1.5 parts by weight of accelerator, and 55 to 65 parts by weight of an additive.

Further, according to another embodiment of the present invention, it is possible to provide a coating film formed by coating the above-described coating composition on a substrate or the like in a marine tank.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example  And Comparative example

<Production of Coating Composition>

The paint compositions were prepared using the components and contents according to Tables 1 to 3 below.

<Manufacture of coating film>

The compositions of the above examples and comparative examples were applied to steel panels. Curing proceeded at room temperature until the composition solidified and dried. The panels were then post-cured (homopolymerized) by holding in a hot (80 ° C.) oven for 16 hours.

Experimental Example

Physical properties of the coating films obtained according to the above Examples and Comparative Examples were measured as follows, and the results are shown in Tables 1 to 3 below.

1) solidification drying

Solidification drying characteristics were measured according to ASTM D5895.

2) Absorption rate measurement

Absorption was measured after the deposition test on the specimen formed with the coating film for 16 hours at 80 ℃ 1 day at room temperature in acetone and vinyl acetate monomer (VAM) as a liquid compound.

Absorption rate (%) = (1-amount of remaining liquid compound / amount of the first liquid compound added) X100

3) repainting interval

After the first coating, the adhesiveness after immersing the specimen in seawater for 1 month after the second coating was confirmed.

4) Low temperature and room temperature cracking

The low temperature and room temperature crackability were observed in the panel after leaving the coating in the constant temperature and humidity chamber at 15 ° C. (low temperature) and 25 ° C. (room temperature), respectively, after the coating was completed.

Example 1 Example 2 Example 3 Example 4 Example 5 Resorcinol Epoxy
(DE-703 / Hajin Chemtech) 20 20 20 20 20 Phenol Novolac Epoxy
(YDPN638 / Kukdo Chemical) 17 17 17 - 17 Cresol Novolac Epoxy
(YDCN-500-80PCA60 / Kukdo Chemical) - - - 17 - Thickener 2 2 2 2 2 TiO ₂ 4 4 4 4 4 Barite 26 26 26 26 26 Feldspar 15 15 15 15 15 Solvent (Xylene) 9.8 9.8 9.8 9.8 9.8 Alicyclic Amine Curing Agent (PACM) 3.75 4 4.17 3.75 3.33 Polyethyleneamine 1.25 One 0.83 1.25 1.67 1-Methyl Imidazole - - - - - 2-Ethyl-4-Methyl Imidazole - - - - - Curing Accelerator (DMP-30, tris-2,4,6-dimethylaminomethyl phenol) 0.2 0.2 0.2 0.2 0.2 2-Methyl Imidazole One One One One One Acetone Absorption Rate (15 days) 0.17% 0.23% 0.28% 0.18% 0.17% VAM Absorption Rate (15 Days) 0.40% 0.43% 0.45% 0.39% 0.40% Solidification drying (15 ℃) 40 hours 40 hours 40 hours 43 hours 40 hours Room temperature cracking (25 ℃) Good Good Good Good Good Low Temperature Cracking (15 ℃) Good Good Good Good Good Repainting interval (25 ℃) 7 days 7 days 7 days 7 days 6 days

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Resorcinol Epoxy
(DE-703 / Hajin Chemtech) 27 - 21 21 21 Phenol Novolac Epoxy
(YDPN631 / Kukdo Chemical) 9 - 16 16 16 Phenol Novolac Epoxy
(YDPN638 / Kukdo Chemical) - 25 - - - Thickener 2 2 2 2 2 TiO ₂ 4 4 4 4 4 Barite 26 26 26 26 26 Feldspar 15 15 15 15 15 Solvent (Xylene) 10 16 10 10 10 Alicyclic Amine Curing Agent (PACM) 5 12 5 5 5 Polyethyleneamine - - - - - 1-Methyl Imidazole - - One - - 2-Ethyl-4-Methyl Imidazole One - - One - Curing Accelerator (DMP-30, tris-2,4,6-dimethylaminomethyl phenol) One - - - One 2-Methyl Imidazole - - - - - Acetone Absorption Rate (15 days) 0.17% 3.96% Not measurable 7.27% 6.19% VAM Absorption Rate (15 Days) 0.44% 4.98% Not measurable 17.26% 11.16% Solidification drying (15 ℃) 40 hours 12 hours Uncured 60 hours 50 hours Room temperature cracking (25 ℃) Good Good Good crack crack Low Temperature Cracking (15 ℃) crack Good Good crack crack Repainting interval (25 ℃) 4 days 21st Not measurable 6 days 6 days

Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Resorcinol Epoxy
(DE-703 / Hajin Chemtech) 21 21 21 21 20 Phenol Novolac Epoxy
(YDPN631 / Kukdo Chemical) 16 16 16 16 - Phenol Novolac Epoxy
(YDPN638 / Kukdo Chemical) - - - - 17 Thickener 2 2 2 2 2 TiO ₂ 4 4 4 4 4 Barite 26 26 26 26 26 Feldspar 15 15 15 15 15 Solvent (Xylene) 10 9.7 9.7 9.7 9.8 Alicyclic Amine Curing Agent (PACM) 5 5 4 4.17 5 Polyethyleneamine - - One 0.83 - 1-Methyl Imidazole - - - - - 2-Ethyl-4-Methyl Imidazole - - - - - Curing Accelerator (DMP-30, tris-2,4,6-dimethylaminomethyl phenol) - 0.3 0.3 0.3 0.2 2-Methyl Imidazole One One One One One Acetone Absorption Rate (15 days) 0.18% 0.18% 0.24% 0.30% 0.16% VAM Absorption Rate (15 Days) 0.45% 0.42% 0.45% 0.49% 0.39% Solidification drying (15 ℃) 43 hours 39 hours 40 hours 40 hours 39 hours Room temperature cracking (25 ℃) Good Good Good Good Good Low Temperature Cracking (15 ℃) crack crack Good Good crack Repainting interval (25 ℃) 4 days 5 days 6 days 6 days 5 days

Claims (8)

Epoxy resin mixtures, including resorcinol epoxy resins and novolac epoxy resins
An amine curing agent mixture comprising an aliphatic amine compound and an alicyclic amine compound in a weight ratio of 1: 3 to 1: 5,
An accelerator comprising an imidazole compound, and
Contains additives,
Paint composition comprising 40 to 55% by weight of resorcinol epoxy resin and 45 to 60% by weight of a novolak epoxy resin based on 100% by weight of the epoxy resin mixture. The method according to claim 1,
The novolak epoxy resin is a coating composition comprising one or more selected from the group consisting of cresol novolak epoxy resin, hydrocarbon novolak epoxy resin, bisphenol novolak epoxy resin and phenol novolak epoxy resin. The method according to claim 1,
The aliphatic amine compound is diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexamethylenediamine (HMDA), N- (2-amino Ethyl) -1,3-propanediamine (N ₃ -amine), N, N'-1,2-ethanediylbis-1,3-propanediamine (N ₄ -amine) and dipropylenetriamine A coating composition comprising at least one selected or an adduct compound of the aliphatic amine compound. The method according to claim 1,
The cycloaliphatic amine compound is 1,3-bisaminocyclohexylamine (1,3-BAC), isophorone diamine (IPDA), or 4,4'-methylenebiscyclohexanamine (PACM) and 4,4'- Coating composition containing one or more selected from the group consisting of methylenebis- (2-methyl-cyclohexanamine). delete The method according to claim 1,
The imidazole compound is 1-methyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 1-phenyl-2-methyl imidazole, 2-heptadecyl imida Sol, 1-cyanoethyl-2-phenylimidazole-trimelitate, 2- (β- (2'-methylimidazoyl- (1 ')))-ethyl-4-6-diamino-s -Triazine, 2,4-dimethylimidazole 2-undecylimidazole, 2-heptadecenyl-4-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimida Sol, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, 2-vinylimidazole, 1-vinyl- 2-methylimidazole, 1-propyl-2-methylimidazole, 1- (3-aminopropyl) -imidazole, butylimidazole 1-cyanoethyl-2-methylimidazole, 1-sia Noethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-guanaminoethyl-2-methylimidazole, 1-cyanoethyl-2-iso Propylimidazole, 1-cyanoethyl-2-fe Imidazole, 1-aminoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- Phenyl-4-benzyl-5-hydroxymethylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1 -(Dodecyl benzyl) -2-methylimidazole, 2- (2-hydroxyl-4-t-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl)- 4,5-diphenylimidazole, 2- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl) -4,5-diphenylimidazole , 2- (2-hydroxyphenyl) -4,5-diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5 A coating composition comprising at least one member selected from the group consisting of -diphenylimidazole, 1-benzyl-2-methylimidazole, and 2-p-methoxystyrylimidazole. The method according to claim 1,
30 to 40 parts by weight of an epoxy resin mixture,
2 to 5 parts by weight of the amine curing agent mixture,
0.5 to 1.5 parts by weight of accelerator, and
Paint composition comprising 55 to 65 parts by weight of the additive. The coating film formed using the coating composition of any one of Claims 1-4, 6, and 7.