KR102121812B1 - Solvent free paint composition - Google Patents

Abstract

The present invention relates to a solvent-free coating composition comprising a novolac epoxy resin, a curing agent resin comprising an amine compound, a toughening agent, an inorganic filler and an additive.

Description

Solvent-free paint composition {SOLVENT FREE PAINT COMPOSITION}

The present invention relates to a solvent-free coating composition.

Epoxy resins are generally used by adding curing agents and various compounding subsidiary materials to thermosetting materials, and can exhibit various physical properties depending on the composition, so adhesives can be used in various fields such as electricity, electronics, civil engineering, architecture, automobiles, plants, and ships. , Inorganic fillers, abrasives, coatings, waterproofing agents, insulation, etc.

The coating film formed of a solvent-free coating composition containing an epoxy resin is excellent in water resistance and abrasion resistance and has a durability for a long period of time, so it can be used in a harsh environment such as a splash zone by maintaining a hard and tough coating film. On the other hand, the conventional solvent-free epoxy coatings basically have excellent mechanical and chemical properties of the coating film, but showed poor physical properties in terms of fresh water deposition at 60°C or higher and high pressure conditions or chemical component deposition conditions such as amine aqueous solutions. In the case of a general solvent-free epoxy coating, the crosslinking density is not dense, and in particular, in a fresh water deposition condition of only 60° C. or more, a coating film defect such as blister occurs due to an osmosis pressure phenomenon. For this reason, general solvent-free epoxy paints are applied to petrochemical plants operated at high temperature of 150℃ or higher and high pressure of 1,000 psi or higher, and deposits of gas oil separation plant tanks in offshore fields. The high temperature water resistance, chemical resistance, and heat resistance were poor, resulting in a large number of coating film defects such as blisters and cracks.

Korean Registered Patent Publication No. 709,071

The present invention provides a solvent-free coating composition.

The present invention includes a novolac epoxy resin, a curing agent resin containing an amine compound, a toughening agent, an inorganic filler and an additive, and a weight ratio of the novolac epoxy resin and the inorganic filler is contained in an amount of 1:2 to 1:7. It provides a solvent-free paint composition.

The solvent-free coating composition according to the present invention has improved physical properties such as heat resistance and chemical resistance under high temperature conditions of 150° C. or higher and high pressure conditions of 1,000 psi or higher, and excellent workability of the coating material even at high temperature and high pressure, compared to the conventional coating composition. .

Hereinafter, the present invention will be described in detail.

The present invention provides a solvent-free coating composition.

The solvent-free coating composition of the present invention includes a novolac epoxy resin, a curing agent resin, a toughening agent, an inorganic filler and an additive.

1. Novolac epoxy resin

The novolac epoxy resin used in the present invention serves to improve the chemical and heat resistance properties of the coating film.

The novolac epoxy resin may be cresol novolac epoxy resin, hydrocarbon novolac epoxy resin, bisphenol novolac epoxy resin, phenol novolac epoxy resin, and the like.

The novolac epoxy resin may be represented by the following formula (1).

[Formula 1]

In Chemical Formula 1, p is a real number of 0.1 to 100 as the number of repeating units in parentheses, a and b are integers of 1 to 20, u, v and w are integers of 1 to 20, r1 and r3, respectively. Is an integer from 1 to 4, and r2 is an integer from 1 to 3.

A1 to A3 are C ₂ to C ₂₀ hydrocarbon groups each containing an epoxy group.

The hydrocarbon group of C ₂ to C ₂₀ containing the epoxy group may include one or two or more epoxy groups in the substituent, and the hydrocarbon group may be an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or the like.

Each of A1 to A3 may be an epoxy group.

R1 to R3 are hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, or a C ₃ to C ₂₀ cycloalkyl group.

Formula 1 may be the following Formula 1-1.

[Formula 1-1]

The novolac epoxy resin may be a phenol novolac epoxy resin in terms of securing physical properties of the coating film. In particular, in the case of using a phenol novolac epoxy resin among the novolac epoxy resins, when mixed with other liquid epoxy resins, the viscosity is low and the physical properties are also excellent.

The novolac epoxy resin may be included in an amount of 10% by weight to 30% by weight based on the total weight of the solvent-free coating composition, for example, 15% by weight to 25% by weight. When the content of the novolac epoxy resin is less than 10% by weight, unreacted amine is generated due to an excessive amount of the curing agent at high temperature and high pressure as the content of the curing agent is relatively high, and the unreacted amine reacts with moisture to cause surface blister (Blister). ) There is a possibility that film defects such as occurrence or discoloration may occur. When the content of the novolac epoxy resin is more than 30% by weight, the content of the curing agent is relatively reduced as the content of the epoxy resin is relatively high, so that the crosslink density in the coating film is reduced, so that water and chemical resistance at high temperatures and pressures, mechanical Physical properties decrease.

The epoxy equivalent of the novolac epoxy resin may be 140 g/eq to 250 g/eq, for example, 140 g/eq to 200 g/eq. When the epoxy equivalent of the novolac epoxy resin is less than 140 g/eq, the strength of the coating film decreases, and when the epoxy equivalent exceeds 250 g/eq, the flexibility of the coating film decreases.

The novolak epoxy resin may have a weight average molecular weight of 100 g/mol to 3,000 g/mol. When the weight average molecular weight of the novolac epoxy resin is less than 100 g/mol, problems may arise in heat resistance and chemical resistance at high temperatures and pressures, and when it exceeds 3,000 g/mol, problems may arise in workability at high temperatures.

2. Hardener resin

The curing agent resin used in the present invention may include an amine compound.

The amine compound includes an amine group which is a functional functional group, and when applied to the novolac epoxy resin used in the present invention, increases the crosslinking density of the coating film, thereby improving physical properties such as chemical resistance and water resistance at high temperatures, It serves to improve the workability of the paint.

The curing agent resin may include a cycloaliphatic amine in which an amine compound is condensed by reaction of an alicyclic amine compound for curing at normal temperature of the novolac epoxy resin. The amine compound may further include an aliphatic amine group or an aromatic amine group to react with the novolac epoxy resin to improve crosslinking density. In this case, the molar ratio of the number of moles of the aliphatic amine group or aromatic amine group to the number of moles of the alicyclic amine group may be 1:1 to 1:5.

The amine compound is 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), dipropylenetriamine, 2,2- Bis(3-amino-4-hydroxycyclohexyl)hexafluoropropane (3,3'-dimethyl-4,4'-diaminodi Cyclohexylmethane (MACM), 4,4'-methylenebicyclohexylamine (PACM), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclo Hexane (1,4-BAC), cis-1,2-cyclohexanedimethanamine, trans-1,2-cyclohexanedimethanamine, bis(4-aminocyclohexyl) ether (H-ODA), N- (4-aminocyclohexyl)-1,4-cyclohexanediamine, isophorone diamine (IPDA), or a compound having a chemical structure represented by Formula 2 below.

[Formula 2]

In Formula 2, q and r are each an integer of 0 to 2 as the number of repeating units in parentheses, x1, y1 and z1 are integers of 1 or 2, and x2 and y2 are each 1 to 4 as the number of substituents in parentheses. Is an integer, z2 is the number of substituents in parentheses, an integer from 1 to 3, x, y and z are integers from 1 to 3, n and m are integers from 0 to 10, and r4 to r6 are each 0. It is an integer of 4-4.

When n, m, and q are 0, it means a direct bond.

When r is 0, it means that hydrogen is substituted at the bonded site.

L1 to L3 are each a direct bond or a divalent linking group, wherein the linking group is a C ₁ to C ₂₀ alkylene group, a C ₆ to C ₂₀ arylene group, or a C ₃ to C ₂₀ cycloalkylene group, for example, the linking group Is a C ₁ to C ₁₀ alkylene group, a C ₆ to C ₁₀ arylene group, or a C ₃ to C ₁₀ cycloalkylene group.

R4 to R6 are each a hydrogen, an amine group, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, or a C ₃ to C ₂₀ cycloalkyl group, for example, R4 to R6 are each a hydrogen or amine group , C ₁ to C ₁₀ alkyl group, C ₆ to C ₁₀ aryl group, or C ₃ to C ₁₀ cycloalkyl group.

x+y+z≧3.

Among the amine compounds, the alicyclic amine compound is 2,2-bis(3-amino-4-hydroxy cyclohexyl) hexafluoropropane (2,2-bis(3-amino-4-hydroxycyclohexyl)hexafluoropropane), 3, 3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM), 4,4'-methylenebiscyclohexylamine (4,4-Methylenebis-Cyclohexylamine), 1,3-bis(aminomethyl)cyclo Hexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), cis-1,2-cyclohexanedimethanamine, trans-1,2-cyclohexanedimethanane Amine, bis(4-aminocyclohexyl) ether (H-ODA), N-(4-aminocyclohexyl)-1,4-cyclohexanediamine, isophorone diamine (IPDA), or a compound represented by Formula 2 above Etc.

Formula 2 may be the following Formula 2-1.

[Formula 2-1]

The amine compound may be included in an amount of 5% to 20% by weight based on the total weight of the solvent-free coating composition. When the content of the amine compound is less than 5% by weight, the crosslinking density of the novolac epoxy resin is low, resulting in low water and chemical resistance and mechanical properties at high temperature and high pressure, and when it is more than 20% by weight, crosslinking density at high temperature and high pressure is high. There is a possibility of cracking due to the property that the coating film is hard, and there is a possibility that a film defect such as blistering or discoloration due to unreacted amine may occur.

3. Toughening agent

Toughening agents used in the present invention are included to improve the properties of the novolac epoxy resin.

It is necessary to use a toughening agent that maintains toughness even at low temperatures in order to improve the properties that are vulnerable to the impact or low temperature of the epoxy resin generated when the epoxy is used alone, and is not limited to use for other reasons. The toughening agent is mainly used by blending with an epoxy resin, and affects mechanical properties through a dispersed phase with the epoxy resin.

The toughening agent may use a reactive toughening agent (reactive toughening agent) and a non-reactive toughening agent (non-reactive toughening agent), and self-assembly with macro-phase separation characteristics. One property is the adjuvant that improves the toughness and flexibility of the novolac epoxy system.

The reactive toughening agent may be a reactive rubber system such as carboxyl terminated butadiene acrylonitrile (CTBN) and amine terminated butadiene acrylonitrile (ATTBN), and polyethersulfone , Polyetherimide, polycarbonate, polyimide, and the like. The non-reactive toughening agent may be polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like, but is not limited if it is a toughening agent that can be used in the epoxy resin coating.

The toughening agent may be included in an amount of 1% to 10% by weight based on the total weight of the solvent-free coating composition, for example, it may be included in an amount of 1% to 5% by weight. If the content of the toughening agent is less than 1% by weight, the thermal stability and flexibility of the coating film may be deteriorated, and if it is more than 10% by weight, the adhesion of the coating film decreases, and the crosslink density and epoxy resin properties of the coating film decrease, resulting in water resistance and chemical resistance. Lowering of the back may occur.

The viscosity of the toughening agent may be 3,200 mPas to 4,000 mPas, and specific gravity may be 1 to 1.5.

4. Inorganic filler

The inorganic filler used in the present invention is mainly intended to improve the mechanical properties of the novolac epoxy resin, reduce the thermal expansion rate and curing shrinkage, and can control heat generation during curing. In addition, it serves to control the viscosity of the coating composition, and also functions to provide a coating having excellent workability that enables airless spray through low viscosity of the solvent-free coating composition of the present invention.

The inorganic filler is talc, barite, feltspar, zinc oxide, glass bubble, glass flake, wollastonite, silica , Alumina hydroxide, magnesium carbonate, and the like, to facilitate heat resistance, chemical resistance, and workability at high temperatures and high temperatures of the solvent-free coating composition of the present invention, barite, zinc oxide. , May be at least one selected from Wollastonite.

The inorganic filler may be included in an amount of 50% to 70% by weight based on the total weight of the solvent-free coating composition. When the content of the inorganic filler is less than 50% by weight, the barrier effect of the coating composition decreases, resulting in defects in the coating film such as blisters due to poor water resistance, and when the content exceeds 70% by weight, the viscosity of the coating increases. Sex is impaired.

5. Additive

The solvent-free coating composition of the present invention may further include an additive.

The additive may include at least one selected from the group consisting of pigments, curing accelerators, thickeners, surface conditioners, light stabilizers, weathering additives, drying agents, appearance control agents, antifoaming agents, and ultraviolet absorbers.

The additive may be included in an amount of 0.1% to 10% by weight based on the total weight of the solvent-free coating composition.

The pigment may be a colored pigment to improve the appearance through the color of the coating film. The colored pigments include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, lead oxide, iron oxide, blue powder, lead chromate, zinc chromate, cadmium sulfide, iron sulfate, chromium oxide, chromium hydroxide, royal blue, ultramarine, manganese, carbon black, etc. Can be.

The pigment may be included in an amount of 0.1% to 10% by weight based on the total weight of the solvent-free coating composition, for example, 0.1% to 5% by weight. When the content of the pigment is less than 0.1% by weight, it is difficult to ensure proper color realization and hiding power, and when it is more than 10% by weight, workability of the paint may be deteriorated.

The curing accelerator maximizes crosslinking density even at high temperature and shortens the drying time at the same time, so that the curing of the novolac epoxy resin occurs efficiently.

The curing accelerator may be a compound containing a tertiary amine group, for example, benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri(dimethylaminomethyl)phenol, 2-2-(dimethylamino Methyl)phenol, 2,4,6-tris(diaminomethyl)phenol, tri-2-ethylhexyl acid salt, or imidazole-based compound.

Examples of the imidazole-based compound include 1-methyl imidazole, 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 1-phenyl-2-methyl imidazole, 2-heptadecyl Imidazole, 1-cyanoethyl-2-phenylimidazole-trimellitate, 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-methyl Imidazole, 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-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-guanaminoethyl-2-methylimidazole, 1-cyanoethyl- 2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 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-diphenylimidazole, 1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole, etc. .

The curing accelerator may be included in an amount of 0.1% to 10% by weight based on the total weight of the solvent-free coating composition, for example, 0.1% to 1% by weight. When the content of the curing accelerator is less than 0.1% by weight, the reaction rate at a low temperature is delayed to show a limitation that the curing degree cannot be increased within a short time, and if it exceeds 10% by weight, it affects the crosslink density of the coating film, and As a result of the addition reaction, blister generation and discoloration may occur.

The thickener is an additive that serves to control the viscosity of the coating composition, a polysaccharide-based thickener such as xanthan, a cellulose-based thickener such as carboxymethylcellulose, an acrylate thickener, a polyether-modified polyurethane thickener, a benton-based agent such as bentonite, etc. It may be a thickening agent, a metal-organic thickener such as titanate or zirconate, an organic clay-based, silica, wax, or the like.

Other surface modifiers, light stabilizers, weathering additives, drying agents, appearance control agents, antifoaming agents, and ultraviolet absorbers may be used without limitation as long as they are commonly used in paints.

6. Solvent-free paint composition

The solvent-free coating composition of the present invention includes a novolac epoxy resin, a curing agent resin containing an amine compound, a toughening agent, an inorganic filler, and an additive, and thus a hydrocarbon solution operated at a high temperature of 150°C or higher and a high pressure of 1,000 psi or higher. Applied to the immersion part of gas oil separation plant tank handling (Hydrocarbon solution), diglycolamine columns (DGA), desulfurizer, shower gas treatment device such as sulfur compounds, etc. can do.

In addition, it is designed to allow airless spray coating to improve paint workability, without blister and cracking, lamination, softening, and swelling. ) Can have excellent coating film properties.

In particular, the solvent-free coating composition of the present invention may contain a weight ratio of the novolac epoxy resin and the inorganic filler in an amount of 1:2 to 1:7, for example, an amount of 1:2.5 to 1:5. Can be. When the weight ratio of the novolac epoxy resin and the inorganic filler is less than 1:2, the content of the inorganic filler becomes small, so that the barrier effect of the coating film is not improved, and water resistance is poor, resulting in coating defects such as blisters. have. When the weight ratio of the novolac epoxy resin and the inorganic filler is greater than 1:7, the ratio of the novolac epoxy resin becomes small, resulting in a decrease in heat resistance and chemical resistance at high temperatures and high pressures after curing, resulting in high viscosity of the paint.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only for understanding the present invention, and the scope of the present invention is not limited to these examples in any sense.

<Examples 1 to 13>

It was formulated with the composition shown in Table 1 below to prepare a solvent-free coating composition.

<Comparative Examples 1 and 4>

It was formulated in the composition shown in Table 2 to prepare a solvent-free coating composition.

The structures used in Examples and Comparative Examples of Table 1 and Table 2 are as follows.

1. Bisphenol A type epoxy resin: Epoxy equivalent 470 g/eq, Viscosity: Z4 (25°C, Gardner viscosity), molecular weight 350 g/mol

2. Phenolic noblock epoxy resin 1: Epoxy equivalent 170 g/eq, viscosity 7,500 mPa·s (25°C), molecular weight 390 g/mol

3. Phenolic noblock epoxy resin 2: Epoxy equivalent 150 g/eq, viscosity 6,300 mPa·s (25℃), molecular weight 340 g/mol

4. Phenolic noblock epoxy resin 3: Epoxy equivalent 200 g/eq, viscosity 9,000 mPa·s (25°C), molecular weight 460 g/mol

5. Toughening agent: Poly(1,2-butylene glycol) + Polyethylene glycol, viscosity 3600 mPa·s (25℃), specific gravity 1.03 (g/ml)

6. Thickener: Organo-clay

7. Amine curing agent Ⅰ: Benzene-1,3-Dimethanamine

8. Amine curing agent Ⅱ: Isophorone diamine

9. Amine curing agent Ⅲ: Formaldehyde, polymer with benzene amine hydrogenated

10. Amine curing agent IV: 4,4-Methylenebis-Cyclohexylamine

11. Curing accelerator: 2-ethyl-4-methyl imidazole

12. Tertiary amine system: Tris-2,4,6-dimethylaminomethyl phenol

division Example One 2 3 4 5 6 7 8 9 10 11 12 13 Bisphenol A type epoxy resin - - - - - - - - - - - - - Phenolic noblock epoxy resin 1 500 500 500 500 500 - - 500 368.6 771.7 500 400 310 Phenolic noblock epoxy resin 2 - - - - - 500 - - - - - - - Phenolic noblock epoxy resin 3 - - - - - - 500 - - - - - - Toughening agent 50 50 50 50 50 50 50 50 36.99 70 50 50 50 Thickener 30 30 30 30 30 30 30 30 41.31 31.4 30 30 30 Titanium dioxide 100 100 100 100 100 100 100 100 108.5 81.2 100 100 100 Talc - - - - - - - - - - - - - Barite 1000 1000 1000 - 500 1000 700 1000 1084 953.1 588.2 941.2 - Feldspar - - - - - - - - - - - - - Zinc oxide 700 700 700 700 520 - - - 758.7 667.2 411.8 - 1112 Glass Bubble - - - - - - - - - - - - - Glass Flake - - - - - - - - - - - - - Wollastonite - - - 600 300 700 600 700 - - - 658.8 768 Amine curing agent Ⅰ - - - - - - - - - - - - - Amine curing agent Ⅱ - - - - - - - - - - - - - Amine curing agent Ⅲ 200 200 200 200 200 200 200 200 201.3 121.8 200 200 200 Amine curing agent Ⅳ 100 100 100 100 100 100 100 100 100.6 103.6 100 100 100 Curing accelerator - - 20 20 20 20 20 20 20 20 20 20 20 Tertiary amine - 20 - - - - - - - - - - - total 2680 2700 2700 2300 2320 2700 2300 2700 2720 2820 2000 2500 2690

(Unit: parts by weight)

division Comparative example One 2 3 4 Bisphenol A type epoxy resin 500 500 - - Phenolic noblock epoxy 1 - - 840 250 Phenolic noblock epoxy 2 - - - - Phenolic noblock epoxy 3 - - - - Toughening agent - - 84 46.25 Thickener 50 50 33.3 27.75 Titanium dioxide 200 150 111 92.5 Talc 300 - - - Barite - 100 889.41 1059 Feldspar - 400 - - Zinc oxide - - 622.59 741.25 Glass Bubble 80 - - - Glass Flake 80 - - - Wellastonite - - - - Amine curing agent Ⅰ 300 150 - - Amine curing agent Ⅱ - 150 - - Amine curing agent Ⅲ - - 252.3 185.25 Amine curing agent Ⅳ - - 141 92.5 Curing accelerator - - 26.4 18.5 Tertiary amine 20 - - - total 1530 1500 3000 2513

(Unit: parts by weight)

<Experimental Example>

Examples 1 to 13 prepared by mixing with the composition of Table 1, and the solvent-free coating composition of Comparative Examples 1 to 4 prepared by mixing with the composition of Table 2 were performed under the following conditions to measure the coating material properties. It is shown in Tables 3 to 5 below.

<Painting condition>

Airless spray method

Nozzle diameter: 533㎛ ~ 635㎛, Air pressure: 4 ~ 6 kgf/㎠ maintain constant

Maintain a constant distance between the nozzle inlet and the specimen in the range of 20 cm to 30 cm, move horizontally at a speed of 40 to 50 cm/sec, and paint at constant speed.

After painting, dry at room temperature

<Evaluation conditions>

1) High-temperature and high-pressure coating film property test (Autoclave Test): The test is carried out by half-depositing the specimens in four aqueous solutions under a pressurized condition of 150°C and 1,000 psi for 7 days. (4 types of aqueous solution: saturated water solution (FWB: Formation Water Brine), ionic water (DIW), diglycolamine (DGA) aqueous solution and methyl diethanolamin (MDEA) aqueous solution). After 7 days, the appearance, EIS (Electrochemical Impedance Scanning), and adhesion of the specimen are evaluated.

① Appearance evaluation: Evaluate the occurrence of blister, crack, delamination, coating film softening, swelling, color change, and lifting of the coating film.

② EIS evaluation: Evaluate using Electrochemical Impedance Scanning equipment.

Evaluation criteria: 1Ⅹ10 ⁸ ohm or more

③ Evaluation of Adhesion: It is evaluated using Pull off test and X-cut.

Evaluation standard: Min.18MPa (Pull off test) / Rate 10(0.6~0.8mm) (X-cut test)

2) Immersion Test: The test is carried out under a solution of 1:1 mixture of ionic water and [5% sodium chloride (NaCl) and mineral spirits) under 150℃ condition. Evaluate the appearance. Appearance evaluation is conducted to evaluate whether blister, crack, or corrosion occurs. Hardness evaluation is performed using (pencil hardness) equipment.

-Hardness evaluation: The pencil hardness value is evaluated by scratching with a pencil at an angle of 45 degrees.

Evaluation criteria: (Soft) 6B-5B-4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H (Hard)

-Adhesive evaluation: Pull off test and X-cut are used for evaluation.

Evaluation standard: Min.18MPa (Pull off test) / Rate 10(0.6~0.8mm) (X-cut test)

3) Cathodic Disbondment: Cathodic disbondment test is performed for 30 days at 90°C and 1.55V under the cathodic peel test, and measures the peeled distance after the test.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Autoclave Test
(150℃/
1,000psi) FWB Exterior Blister No.2D Blister No.2D Blister No.6D Blister No.8D EIS Thirteen Thirteen Thirteen Thirteen Adhesion Thirteen Thirteen Thirteen Thirteen DIW Exterior Blister No.2D Blister No.2D Blister No.6D Blister No.8D EIS Thirteen Thirteen Thirteen Thirteen Adhesion Thirteen Thirteen Thirteen Thirteen DGA Exterior Peel off Peel off Blister No.6F Blister No.8F EIS Thirteen Thirteen Thirteen Thirteen Adhesion Thirteen Thirteen Thirteen Thirteen MDEA Exterior Peel off Peel off Blister No.6F Blister No.8F EIS Thirteen Thirteen Thirteen Thirteen Adhesion Thirteen Thirteen Thirteen Thirteen Immersion Test (150℃) Exterior Blister No.2D Blister No.2D Blister No.6D Blister No.8D Hardness Thirteen Thirteen Thirteen Thirteen Adhesion Thirteen Thirteen Thirteen Thirteen Cathodic Disbondment Test (90℃) Thirteen Thirteen Thirteen Thirteen

division Example One 2 3 4 5 Autoclave Test
(150℃/
1,000psi) FWB Exterior No blister&
Crack No blister&
Crack No blister&
Crack No blister&
Crack No blister&
Crack EIS Great Great Great Great Great Adhesion Great Great Great Great Great DIW Exterior No blister&
Crack No blister&
Crack No blister&
Crack No blister&
Crack No blister&
Crack EIS Great Great Great Great Great Adhesion Great Great Great Great Great DGA Exterior Blister No.2D Blister No.2D No blister&
Crack No blister&
Crack No blister&
Crack EIS Thirteen Thirteen Great Great Great Adhesion Thirteen Thirteen Great Great Great MDEA Exterior Blister No.2D Blister No.2D No blister&
Crack No blister&
Crack No blister&
Crack EIS Thirteen Thirteen Great Great Great Adhesion Thirteen Thirteen Great Great Great Immersion Test (150℃) Exterior No blister&
Crack No blister&
Crack No blister&
Crack No blister&
Crack No blister&
Crack Hardness Great Great Great Great Great Adhesion Great Great Great Great Great Cathodic Disbondment Test (90℃) Great Great Great Great Great

division Example 6 7 8 9 10 11 12 13 Autoclave Test
(150℃/
1,000psi) FWB Exterior No blister No blister No blister No blister No blister No blister No blister No blister EIS Great Great Great Good Great Great Great Great Adhesion Great Great Great Good Great Great Great Great DIW Exterior No blister No blister No blister No blister No blister No blister No blister No blister EIS Great Great Great Good Great Great Great Great Adhesion Great Great Great Good Great Great Great Great DGA Exterior No blister No blister No blister No blister No blister No blister No blister No blister EIS Great Great Great Good Great Great Great Great Adhesion Great Great Great Good Great Great Great Great MDEA Exterior No blister No blister No blister No blister No blister No blister No blister No blister EIS Great Great Great Good Great Great Great Great Adhesion Great Great Great Good Great Great Great Great Immersion Test (150℃) Exterior No blister No blister No blister No blister No blister No blister No blister No blister Hardness Great Great Great Good Great Great Great Great Adhesion Great Great Great Good Great Great Great Great Cathodic Disbondment Test (90℃) Good Good Good Great Great Great Good Great

As a result of checking in Tables 3 to 5, in the case of a coating film using a solvent-free coating composition prepared according to Examples 1 to 13, blister occurrence is minimized or blister occurs even under high temperature and high pressure conditions. In view of not doing, it was confirmed that the physical properties of heat resistance and chemical resistance are very excellent.

In addition, it is designed to allow airless spray coating even in high temperature and high pressure environments, improving paint workability, without blisters and cracks, and lamination and softening. ), may have excellent coating film properties in terms of swelling.

In the above, the present invention has been described in detail only with respect to the described embodiments, but it is apparent to those skilled in the art that various modifications and variations are possible within the scope of the technical idea of the present invention, and it is natural that such modifications and modifications belong to the appended claims.

Claims (7)

Novolac epoxy resin,
Curing agent resin comprising an amine compound,
Toughening Agent,
Inorganic fillers and
Contains additives,
The weight ratio of the novolac epoxy resin and the inorganic filler is contained in an amount of 1:2 to 1:7,
The novolac epoxy resin is represented by the following formula (1),
The amine compound is a solvent-free coating composition comprising a compound having the chemical structure of Formula 2,
Based on the total weight of the solvent-free coating composition,
The novolac epoxy resin is 10% to 30% by weight,
The amine compound is 5% to 20% by weight,
The toughening agent is 1% to 10% by weight,
The inorganic filler is 50% to 70% by weight,
The additive is a solvent-free coating composition that is included in an amount of 0.1% to 10% by weight:
[Formula 1]

In Chemical Formula 1, p is a real number of 0.1 to 100 as the number of repeat units in parentheses, a and b are integers of 1 to 20, u, v and w are integers of 1 to 20, r1 and r3, respectively. Is an integer from 1 to 4, r2 is an integer from 1 to 3,
A1 to A3 are C ₂ to C ₂₀ hydrocarbon groups each containing an epoxy group,
R1 to R3 are hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, or a C ₃ to C ₂₀ cycloalkyl group.
[Formula 2]

In Chemical Formula 2, q and r are each an integer of 0 to 2 as the number of repeating units in parentheses, x1, y1 and z1 are integers of 1 or 2, and x2 and y2 are each 1 to 4 as the number of substituents in parentheses. Is an integer, z2 is the number of substituents in parentheses, an integer from 1 to 3, x, y and z are integers from 1 to 3, n and m are integers from 0 to 10, and r4 to r6 are each 0 Is an integer from 4 to 4,
L1 to L3 are each a direct bond or a divalent linking group, the linking group is a C ₁ to C ₂₀ alkylene group, a C ₆ to C ₂₀ arylene group, or a C ₃ to C ₂₀ cycloalkylene group,
R4 to R6 are each a hydrogen, an amine group, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, or a C ₃ to C ₂₀ cycloalkyl group. The method according to claim 1,
The novolac epoxy resin is a solvent-free coating composition comprising at least one selected from the group consisting of cresol novolac epoxy resin, hydrocarbon novolac epoxy resin, bisphenol novolac epoxy resin and phenol novolac epoxy resin. delete The method according to claim 1,
The inorganic filler is talc, barite, feltspar, zinc oxide, glass bubble, glass flake, wollastonite, silica , Solvent-free coating composition comprising at least one selected from the group consisting of alumina hydroxide and magnesium carbonate. delete delete The method according to claim 1,
The additive is a solvent-free coating composition comprising at least one selected from the group consisting of pigments, curing accelerators, thickeners, surface conditioners, light stabilizers, weathering additives, drying agents, appearance control agents, antifoaming agents and ultraviolet absorbers.