KR20150070600A - A manufacturing method of a fatty acid and a silane coupling agent modified epoxy resin, and coating composition for ship containing the modified epoxy resin - Google Patents

Abstract

The present invention relates to an epoxy resin with good re-coating and a manufacturing method of painting compositions using the same, comprising the steps of turning epoxy resin into fatty acid, so that a novel painting component is easily permeated into an existing painting and flexibility and low viscosity function are assigned by decreasing the level of cross-linking on the epoxy painting when re-coating; and turning a silane coupling agent into pendant in the epoxy resin, so that the novel painting component is easily permeated by improving attachment of the epoxy resin turned to fatty acid for objects and increasing free volume of the painting wherein the painting composition of the present invention has three-long-month re-coating intervals and is accordingly used in ship, tank and marine and iron structures.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent, and a method for manufacturing a coating composition for a marine using the same,

The present invention relates to an epoxy resin having excellent re-coatability and a method for producing a coating composition for marine use using the epoxy resin.

More particularly, the present invention relates to an epoxy resin which can be suitably applied to ships, offshore plants and steel structures by securing an excellent long-term re-applicability by incorporating an epoxy resin having a specific structure into the composition, and a method for producing a coating composition using the epoxy resin . The present invention relates to a method for producing a material excellent in adhesion and corrosion resistance at a re-coating interval due to long-term exposure (exposure) of an epoxy coating film.

According to the present invention, it is possible to obtain a coating composition excellent in re-coating interval due to long-term exposure of an epoxy coating film in ships, offshore plants, steel structures and the like.

Marine paints are excellent in corrosion resistance, adhesiveness, chemical resistance, and mechanical properties, but have a disadvantage of poor weatherability when exposed to the outside and have a limited re-coating interval due to the occurrence of yellowing and chalking . Furthermore, due to the demand for modernization, enlargement, high speed and economic operation of vessels, linkage studies of better quality rust preventive paints are becoming the most important part.

Marine paints are exposed to harsh environments such as seawater salinity and water immersion, so epoxy resin paints with excellent corrosion resistance, adhesion and chemical resistance properties are applied to protect the hull and maintain stability. Epoxy paint system is mostly used to protect steel hull from seawater. It is applied almost entirely from marine paint to hull plate, bottom structure, tank inner surface and so on.

The painting process of the ship is divided into the preliminary work (pre-installation block painting) and the post-work (post-block hull painting work), and the preceding work is about 85 ~ 98% Respectively. Especially, most of the anti-corrosive paint (A / C) coatings that are responsible for the ship method are applied in the preceding paint works.

Among the properties required for the coating system of the ship type, the compatibility with the top coat and the adhesion property have a great influence on the re-coating interval of the under coat. As a result, there is a necessity for repairing or repairing the coating film during finish painting or subsequent painting of the ship, and unexpected operations are additionally generated due to the limited re-coating interval.

The re-coating interval of most epoxy coatings is within 15 days to 1 month. Epoxy coatings undergo curing reaction over time, resulting in higher hardening density, making it difficult to penetrate new coatings into existing coatings. The adhesion force is decreased. Due to the limited reproducibility of these epoxy coatings, pre-coating of the coating film for the subsequent coating operation is additionally performed, and this is a main cause of the increase in the amount of the subsequent coating operation.

Therefore, if the re-coating interval of the epoxy coating is increased to about 3 months, it is possible to significantly reduce the pretreatment of the coating film before the subsequent coating operation, and to anticipate the correction operation and the additional operation, (M / H), simplification of painting process, reduction of applied coating film defect, and shortening of ship drying air can be contributed.

The inventors of the present invention have attempted to solve the problem caused by the short re-coating interval of conventional marine paint.

For this purpose, epoxy resin was modified with fatty acid to reduce the crosslinking degree of epoxy coating and to allow new coating components to penetrate easily in existing coatings and to give flexibility and low viscosity. In addition, the silane coupling agent was pendant to the resin to improve adhesion to the epoxy resin modified with the fatty acid and to increase the free volume of the coating film to facilitate penetration of the new film component.

The coating material according to the present invention can be applied to tanks, marine structures and steel structures in addition to vessels as a long-term re-coating interval of 3 months or more.

The 'method for producing a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent'

(1) The esterification reaction with a bisphenol A type epoxy resin is carried out by mixing the unsaturated fatty acids dimer acid, linoleic acid, palmitic acid, stearic acid, flax fatty acid, lauric acid, soybean oil fatty acid, castor fatty acid and derivatives thereof, To produce a fatty acid-modified epoxy resin; And

(2) To the double bond of the fatty acid of the fatty acid-modified epoxy resin prepared in (1) above, an epoxy silane coupling agent, an amine silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, an isocyanate A silane coupling agent, a styryl silane coupling agent, and derivatives thereof, singly or in the form of a mixture of two or more thereof in a pendant form.

The 'method for preparing a coating composition for marine use using a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent'

(1) 3 to 10 parts by weight of dimethylbenzene was added to the dispersion vessel, and while stirring at 300 to 600 rpm, the fatty acid synthesized above and the fatty acid synthesized with the silane coupling agent 10 to 25 parts by weight of a modified epoxy resin and 3 to 10 parts by weight of a bisphenol A type epoxy resin are added and stirred for 10 to 30 minutes, 0.1 to 0.5 parts by weight of a wet dispersant, more than 0 to 5 parts by weight of a reactive resin, 0.1 To 1.0 part by weight of silane coupling agent, and mixing and stirring at 600 to 900 rpm for 10 to 30 minutes;

(2) 1 to 5 parts by weight of a polyamide wax anti-settling agent is added to the agitated product of (1) above and dispersed and dissolved at 900 to 1200 rpm for 10 to 30 minutes. Then, at least one of talc, silica, 1 to 10 parts by weight of a white pigment, and 0.1 to 0.5 parts by weight of a black pigment as a rust-inhibitive pigment, at least one of aluminum strontium zinc phosphosilicate and 1 to 10 parts by weight of zinc phosphate, Stirring and wetting the mixture at 600 to 900 rpm for 10 to 30 minutes and dispersing the mixture at a temperature of 1400 to 1700 rpm for 30 to 50 minutes to a standard softening degree of 80 microns or less;

(3) adding 1 to 5 parts by weight of dimethylbenzene to the agitated product of (2) and agitating the mixture at 600 to 900 rpm for 5 to 10 minutes while stirring;

(4) At least one of calcium magnesium aluminum phyllosilicate minerals and 1 to 10 parts by weight of silicate mineral is added as a mica to the agitated product stirred in the step (3), and the mixture is heated at 1400-1700 rpm to 20 Dispersing the mixture in a degree of softening of 100 microns or less while stirring and dispersing the mixture for ~ 40 minutes, adding propylene glycol monoethyl ether in an amount of more than 0 to 5 parts by weight and stirring the mixture at 600 to 900 rpm;

(5) adding 0.1 to 2 parts by weight of a castor derivative flow inhibitor to the agitated product of (4) above, raising the temperature of the paint to 55 to 65 ° C at 1600 to 1900 rpm, and then cooling the paint to 40 ° C or less;

(6) 1 to 5 parts by weight of a polyamide wax, which is a flow inhibitor, is added to the above stirred product of (5) Dissolving at 1,400 to 1,700 rpm for 5 to 10 minutes; And

(7) The process according to (6), wherein at least one of 10 to 20 parts by weight of an aliphatic modified polyamide and 1 to 10 parts by weight of an aliphatic modified polyamine curing resin, 1 to 5 parts by weight of a curing accelerator, And aging for 10 to 40 minutes while stirring propylcarbinol. Herein, the curing accelerator is not a matter of the present invention, as it is possible to add a known material appropriately selected.

At this time, the fatty acid added to (1) and the fatty acid synthesized with the silane coupling agent The equivalent of the modified epoxy resin and the bisphenol A type epoxy resin is 180 to 500.

The wet dispersant of (1) is characterized in that it is a pigment-friendly group copolymer solution system (adsorbed on the pigment surface with strong affinity anchor groups on the pigment surface to deaggregate the pigment through steric stabilization of the pigment). Examples thereof include BYK 115, BYK 142, BYK 182 and the like.

The reactive resin in the first step is a polyfunctional diluent. Examples of the polyfunctional diluent include polyepoxy compounds, triphenyl phosphite, and the like.

The modified epoxy resin of the present invention and the composition containing the epoxy resin of the present invention have excellent adhesion with the adherend material and excellent adhesion with the new coating film upon repainting and have excellent mechanical properties such as water resistance, It is suitable for application as a paint.

It is also excellent in the re-coating interval due to the long-term exposure of the epoxy coating.

The use of mica pigment and weather-resistant low-viscosity curing resin having weather resistance for 3 months or longer to improve the adhesiveness improves the limitation of the re-coating interval of the epoxy and the problem of adhesion, and the re-coating interval It is possible to reduce the incidence of myolytic diseases caused by the subsequent painting of the last paint. In addition, by increasing the solids volume ratio, the organic solvent (VOC's) is reduced and the environment of the operator is improved by minimizing harmful factors affecting the human body.

As described above, the 'method for producing a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent'

(1) Esterification reaction with a bisphenol A type epoxy resin is carried out by mixing the unsaturated fatty acids dimer acid, linoleic acid, flax fatty acid, lauric acid, soybean oil fatty acid, castor fatty acid and derivatives thereof, Producing; And

(2) To the double bond of the fatty acid of the fatty acid-modified epoxy resin prepared in (1) above, an epoxy silane coupling agent, an amine silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, an isocyanate A silyl coupling agent, a styryl silane coupling agent, and a derivative thereof, singly or in the form of a mixture of two or more thereof in the form of a pendant; .

After the fatty acid-modified epoxy resin as shown in the following formula (1) was prepared through the reaction process of the above step (1)

Then, a silane coupling agent is mixed and pendanted through a reaction process of step (2) to produce a modified epoxy resin as shown in formula (2).

As the fatty acid of the formula (1), dimer acid, linoleic acid, palmitic acid, stearic acid, lauric acid, soybean oil fatty acid, castor fatty acid and derivatives thereof may be used singly or in combination of two or more, but not always limited thereto . Preferably, dimer acid, linoleic acid, palmitic acid, stearic acid and soybean oil fatty acids are used alone or in combination of two or more. The unsaturated fatty acid introduced into the epoxy resin uses a fatty acid having an iodine value of 110 to 180, preferably 110 to 150. When the iodine value of the fatty acid is 150 or more, yellowing due to oxidation may occur in the coating film.

The bisphenol A type epoxy resin is used alone or in combination with an epoxy equivalent of 150 to 2000 g / eq, preferably 170 to 1000 g / eq. When the epoxy equivalent used is more than 1000 g / eq, the viscosity of the prepared epoxy resin is so high that it is difficult to apply it as a coating material. When the epoxy equivalent is less than 170 g / eq, the coating strength of the coating film is high and the re- The physical properties of impact resistance and crack resistance are not good.

The method for producing the fatty acid-modified epoxy resin of formula (1) is as follows. In an amount of fatty acid is 3 to 30% by weight based on the raw material the total weight of the bisphenol A type epoxy resin specified above, more preferably 5 to 25 ^{wt.% 100 o C ~ 220 o C} , preferably 140 ^o C ~ At a temperature of 190 ^° C. When the fatty acid content is less than 3% by weight, the mechanical strength is increased but the flexibility and low viscosity properties are lowered, so that cracks and deformation may occur due to repetitive vibrations, and there is no effect of lowering the degree of crosslinking, When the content exceeds 25% by weight, the flexibility is increased but the strength and water resistance may be lowered.

The fatty acid-modified epoxy resin prepared by this reaction has an epoxy equivalent of 200 to 1100 g / eq and a viscosity of 5,000 to 50,000 cps (25 ^° C).

A silane coupling agent is introduced into the double bonds of fatty acids of the fatty acid-modified epoxy resin prepared above by pendantization by radical polymerization. In the above formula (2), R represents hydrogen or alkyl having 1 to 34 carbon atoms (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and most preferably 2 to 10 carbon atoms).

Examples of the silane coupling agent of Formula 2 include an epoxy silane coupling agent, an amine silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, an isocyanate silane coupling agent, a styryl silane coupling agent, But they are not limited thereto. Preferably, an epoxy silane coupling agent, a vinyl silane coupling agent, and an amine silane coupling agent are used singly or in combination of two or more. The silane coupling agent improves the adhesion with the adherend and improves the adhesion to the urethane top coat. The silane coupling agent is pendant to the epoxy resin to increase the free volume of the coating, thereby facilitating the penetration of the new coating component during the re-coating.

A method for introducing a silane coupling agent into a fatty acid-modified epoxy resin is as follows. A content of the silane coupling agent is 0.5 to 10% by weight based on the raw material the total weight of the fatty acid-modified epoxy resin specified above, more preferably 0.5 to 5 ^{wt% 100 o C ~ 150 o C} , preferably 110 ^o C ^Lt; RTI ID = 0.0 > 140 C. < / RTI > An organic peroxide catalyst is used to carry out the progress of the silane coupling agent introduction reaction smoothly. Examples of the organic peroxide catalyst include 2,2-bis (t-butylperoxy) butane, cumene hydroperoxide, diisopropyl benzene hydroperoxide, t-butyl cumyl peroxide, di-t-butyl peroxide and isobutyryl peroxide, Can be mixed and used. The amount of the organic peroxide catalyst to be used is 5 to 20% by weight, more preferably 5 to 10% by weight based on the total weight of the silane coupling agent.

The silane coupling agent-modified fatty acid-modified epoxy resin prepared by this reaction has an epoxy equivalent of 200 to 1100 g / eq and a viscosity of 5,000 to 50,000 cps (25 ^° C). An organic solvent can be used to lower the viscosity. Examples of the organic solvent include aromatic solvents such as dimethylbenzene and toluene, ketones such as acetone and methyl isobutyl ketone, cellosolves such as butyl cellosolve, ethers such as propylene glycol monomethyl ether, Can be mixed and used.

Hereinafter, the present invention will be described in detail with reference to examples. However, the scope of the present invention is not limited by the embodiments.

[Resin Part Example 1]

400 g of bisphenol A type epoxy resin (epoxy equivalent weight: 250 g / eq) and 50 g of soybean oil fatty acid were placed in a four-necked round flask (1 L) equipped with a thermometer, a condenser and a stirrer and slowly heated to 150 ^° C. Stirring was carried out the synthesis reaction while maintaining a temperature of 150 ^o C to 200rpm, the acid value of the reactants was prepared in a fatty acid-modified epoxy resin to complete the reaction when it is below 2mgKOH / g. The modified epoxy resin had an acid value of 0.41 mgKOH / g and an epoxy equivalent of 331 g / eq.

After the temperature of the flask containing the fatty acid-modified epoxy resin was cooled to 120 ^° C, a mixture of 45 g of the vinylsilane coupling agent and 4 g of the organic peroxide catalyst was dropped and reacted to prepare a fatty acid-modified epoxy resin modified with a silane coupling agent. The epoxy equivalent of the prepared silane-introduced modified epoxy resin was 345 g / eq and the viscosity was 15,300 cps. Dimethylbenzene was added to the resin so as to have a nonvolatile content of 90 wt.%. The viscosity of the resin prepared was 9,600 cps.

[Resin Part Comparative Example 1]

344 g of a liquid bisphenol A type epoxy resin KER 828 (epoxy equivalent 187 g / eq, manufactured by Kumho Pheny Kagaku K.K.) and KER 3001-X-75 (epoxy equivalent weight 475 g / eq, Dimethylbenzene 25%, manufactured by Kumho P & Chemical Co., Ltd.) was charged, and after the temperature was raised to 100 ° C, the two compounds were thoroughly mixed. The bisphenol A epoxy resin prepared had an epoxy equivalent of 307 g / eq and a viscosity of 12,100 cps.

[Comparison of physical properties of resin / curing agent system of Examples a, b, c and Comparative Examples a and b]

Using the resins prepared in the above-mentioned 'Resin Partial Example 1' and 'Resin Partial Comparative Example 1' (Examples a to c of the following Table 1 using the resin prepared in the 'Resin Partial Example 1' (KCA 3500XB70), an aliphatic modified polyamine (manufactured by Kumho P & Bib Chemicals, KCA 4112 (trade name, manufactured by Kumho P & -1), the film properties of the resin and the curing agent were measured (Table 1). The aliphatic modified polyamines of Examples b and c each had a curing agent resin having an amine value of 200 to 350 mgKOH / g and a hydroxyl value of 250 to 500 mgKOH / g.

The mixing ratio of the epoxy resin and the curing agent was mixed according to the equivalence ratio of the resin and the curing agent, and a coating film (dry film thickness 160 탆 x 1, 160 탆 x 2) was formed by using a film applicator manufactured by BYK. The coated film specimens were stored at room temperature for 15 days, 1 month, 2 months, and 3 months at a dry film thickness of 160 μm × 1 coat, and physical properties were measured. After 15 days, 1 month and 3 months after the initial film formation, The coating was repainted with a thickness of 160 탆 x 2 coat for the purpose of measuring the physical properties of the coating.

<Legend> Dolly Adhesion 1coat and 2coat Coating Interval Conditions: Outdoor exposure

  1) Bendability: BYK-Gardner Mandrel (ASTM D 522).

  2) Cross cut adhesion: 100/100 cross-cut in a checkerboard and then peeled off with Permacel 99 tape (ASTM D3359).

3) Dolly Adhesion: Pull-off Strength of Coatings Using Portable Adhesion Testers (ASTM D 4541) Each coat was coated with a dry coat of 160 microns in thickness of 1 micron, then exposed for 15 days, Adhesion test after coating with 2-coat.

As shown in the above Table 1, the epoxy resin modified with a silane coupling agent-introduced fatty acid (Examples a to c) had good drying time and excellent mechanical properties, and the adhesive strength between the resin and the adherend, It can be seen that the adhesive force is superior to that of the bisphenol A type epoxy coating films of Comparative Examples a to b.

The inventors conducted the composition and application experiments of the present invention as follows.

  1) Epoxy Resin - 지방: fatty acid-modified epoxy resin synthesized with fatty acid and silane Epoxy equivalent 180 ~ 500g / eq, viscosity 5,000 ~ 9,600 cps (manufactured by Kumho P &

  2) Epoxy resin -?: Bisphenol A type epoxy resin equivalent 180 to 340 g / eq, viscosity 9,000 to 12,100 cps (manufactured by Kumho P &amp;

  3) Wetting dispersant: pigment-friendly group copolymer solution system (BYK 142)

  4) Reactive resin: Difunctional polyglycidyl epoxide

  5) Silane coupling: Glycidoxypropyltrimethoxysilane series

6) Color Pigment: Titanium oxide (TiO ₂ R 900, DuPont), black pigment (Colombian)

  7) Extention Pigment: talc, silica, coal

  8) Rustproof pigments - ㉮: Aluminum strontium zinc phosphosilicate

     Rust-preventive pigment-㉯: zinc phosphate

  9) Mica-㉮: Silicate Minerals

     Mica-㉯: Calcium Magnesium Aluminum Phylosilicate Minerals

  10) Flow inhibitor-㉮: castor oil derivative anti-sag agent

  11) Anti-flow agent - ㉯: Polyamide wax powder anti-sag agent

  12) Aliphatic denatured polyamide hardener resin (manufactured product of Kumho Pheny Chemical Lab, manufactured by adding fatty acids and heating at 100 ~ 250 ℃ for 3 ~ 10 hours at 170 ℃)

  13) Aliphatic modified polyamine hardener resin (KCA 4112-1)

14) Curing accelerator: 2,4,6-tridimethylaminomethylphenol (Air Protect)

As shown in Table 2, one of the compositions 1 to 24 is added to a dispersion vessel, and the mixture is stirred at 300 to 600 rpm while the mixture is stirred at 600 to 900 rpm for 10 to 30 minutes. Thereafter, 7 is added and dissolved by stirring at 900 to 1200 rpm for 10 to 30 minutes. While stirring in the order of the process, the mixture is agitated at 600 to 900 rpm for 10 to 30 minutes and then dispersed at 1400 to 1700 rpm for 30 to 50 minutes within the standard softening degree. Thereafter, 15 was added and stirred and wetted at 600 to 900 rpm. 16 to 17 are added while stirring in the order of the process, the dispersion is dispersed at 1400 to 1700 rpm for 20 to 40 minutes within a standard softening degree of 100 microns, then 18 is added and stirred and wet at 600 to 900 rpm. Thereafter, 19 parts of the mixture is added while stirring in the order of the process, and the mixture is heated at 1600 to 1900 rpm at 55 to 65 ° C, and then cooled to 40 ° C with a stirrer. Thereafter, the mixture is stirred and melted at 1400 to 1700 rpm for 5 to 10 minutes.

The epoxy-based paint prepared in this manner contains air bubbles and is allowed to stand for a certain period of time. After stabilizing the paint, the hardeners of the items 21 to 24 are prepared, mixed and aged for 20 minutes and then painted on the substrate.

As the coating conditions, oil, grease, etc. are treated with surface treatment SSPC-SP 2, or mill scale and inorganic metal rust are treated with surface pretreatment SSPC SP-10 by sandblasting, sandblasting, 1 coat of paint Apply airless spray to dry film 160 ~ 200 microns. After 15 days, 1 month, 3 months, expose to outdoor 2 times Dry film 160 ~ 200 microns Thereby forming a coating film.

The epoxy-based coating composition prepared as described above had a nonvolatile content of 87 to 90% as measured by a Krebs-Unit viscometer and had a specific gravity in the range of 1.50 to 1.60 , And curing drying (20 ℃) for 10 hours or more. In addition, the test specimens were found to have unsatisfactory properties in terms of adhesion strength by seawater resistance and outdoor exposure, and were lower than the coating performance of 10 ⁹ Ωcm after 25 cycles of coating corrosion resistance. The crack resistance Which was lower than 30 cycles. In addition, sedimentation after storage at room temperature for 12 months resulted in poor sedimentation of the paint, and unstable properties due to many changes in the viscosity of the paint.

The above epoxy-based coating composition test method is a method of using an airless spraying device to mix the paint base and the curing agent in a weight ratio, and agitate with a motor for 10 to 20 minutes after aging. Table 3 shows the test results of the coating properties of the epoxy-based coatings tested for adhesion and corrosion resistance, adhesion after water-repellency, adhesion after outdoor exposure, coating film resistance, and ballast tank test.

&Lt; Paints and coating film properties test 1 >

  <Legend> ⊚: very good, ∘: good, ◐: fair, △: insufficient, X: bad

  1) Condition in the container: uniformly dispersed without dust, foreign matter, and sediment lumps

  2) Curing Drying: 20 占 폚 占 10 hours or less (dry coating 160 占 퐉 占 1coat)

  3) Stability of paint storage stability: Viscosity change within 20% when viscosity is measured at 40 ℃ × 1 month and 12 months at room temperature

  4) Airless Spray: The coating should be smoothly applied by coating with dry coat thickness of 160 ~ 200㎛ and 1coat.

  5) Hardness: Determining the Hardness of Organic Coatings with a Sward-Type Hardness rocker (ASTM D2134), within 10 ~ 15

  6) Pencil hardness: Use a drafting pencil and keep at 45 ° against the coating. Move the tip forward to the coating surface and measure until the coating shows marks (ASTM D3363)

  7) Abrasion resistance: Abrasion Resistance of Organic Coatings by the Taber Abraser (ASTM D4060), Wheels: CS-17, load: 1000g, Revolution: 1000 cycles,

8) Flexibility: metal plate 150 × 50 × 0.3t, caliber of the rods Mendrel 10 mm x 180 x 1 second bend (ASTM D 790)

  9) Adhesion: Pull-off Strength of Coatings Using Protective Adhesion Testers (ASTM D4541), 4 MPa or more 1coat: Epoxy coating (160 micron) 2coat after 1 day: Epoxy coating (160 micron) exam

  10) Impact resistance: ½ "× 500g × 30㎝ with DuPont impact tester

  11) Salt water No silence: 5% -NaCI, sprayed at 35 ℃, no abnormality in coating film and good adhesion

      1coat: epoxy-based paint (160 microns)

      2coat: Epoxy coating (160 microns) / Total 320 microns

      (ASTM B1117), 1000 hours or more

  12) Inland water condition: 1coat painting 20 ℃ × 7 days later, 2coat for 15 days, 1 month, 3 months period by immersion in seawater and after 20 ℃ × 7 days after 9 days. 4MPa or more

  13) Water temperature resistance: 60 ± 2 ℃ 15 days, 1 month, 3 months on hot water Change test such as swelling of paint film, rust, severe discoloration

  14) Moisture resistance: The specimens were raised vertically at a temperature of 49 ± 1 ° C and a humidity of 95% for 15 days, 1 month and 3 months.

  15) On-and-cold cycle: 40 ° C × 14 hours, -5 ° C × 10 hours = 1 cycle, 30 cycles Test for cracking and peeling of coating film

  16) Outdoor exposures: 1coat painting 20oC 7 days after exposure 15o, 1month, 3months 2coat painting by period, after 20oC 7 days 9) Adhesion measurement test method. 4MPa or more

  17) Accelerated weathering resistance: 1coat painted, 7 days after 1 day, test the degree of discoloration and aging of the coating

  18) Promotion Corrosion Resistance: After drying at 20 ℃ for 7 days, pH 3.0 ± 0.2, sodium chloride, estimated, hydrogen peroxide, distilled water accelerated solution was kept at 60 ± 2 ℃, immersed for 7 days, washed, washed for 2 hours, 25 Cross cut test

19) Coating corrosion resistance (EIS): NORSOK M501 and EIS measurements for 72 hours → 72 hours → UV exposure for 24 hours → low temperature (-20 ± 2 ° C) exposure and EIS measurements. 1 cycle (168 hours) ⇒ Total 25 cycles (4200 hours) (ISO 20340), more than 10 ⁹ Ω㎠

20) Ballast tank test: The water ballast tank simulation system was evaluated on the basis of the PSPC of the ship as defined by the International Maritime Organization (IMO) for two weeks (35 ° C artificial seawater + 1 The state of the empty cavity was checked in the condensation chamber test at 40 ± 2 ° C and 100% humidity for a total of 180 days (room temperature 23 ± 2 ° C) to confirm the swelling, rust,

As shown in Table 3, the mixed viscosity of the epoxy-based paint due to mixing of the epoxy resin and the epoxy equivalent is high, so that it is difficult to perform the work because the coating workability is not smooth during the winter, and the hardening dryness, -coating interval) 3 months Adhesiveness, water temperature resistance, accelerated weathering resistance, accelerated corrosion resistance test.

In order to improve the adhesion, it is necessary to mix the mica alone or two kinds of mica in order to increase the adhesion for a long period of time while maintaining an appropriate viscosity for the workability for winter according to the proper mixing ratio of the epoxy resin, It is necessary to suitably select the coating film properties such as performance, water temperature resistance, accelerated corrosion resistance, coating film corrosion resistance (EIS), etc., and the workability of painting in each season.

Therefore, in order to realize an epoxy-type paint having excellent adhesion and corrosion resistance at a re-coating interval based on the above-mentioned measurement results, it is required to have a low viscosity having excellent mixing ratio content of epoxy resin, A composition of a conventional paint according to a curing agent was developed, and examples related thereto are shown in Table 4 below. (In the following examples, the mixing ratio of epoxy resin and epoxy resin was adjusted to ensure long-term re-coatability properties.)

  1) Epoxy Resin - 지방: fatty acid-modified epoxy resin synthesized with fatty acid and silane Epoxy equivalent 180 ~ 500g / eq, viscosity 5,000 ~ 9,600 cps (manufactured by Kumho P &

  2) Epoxy resin -?: Bisphenol A type epoxy resin equivalent 180 to 340 g / eq, viscosity 9,000 to 12,100 cps (manufactured by Kumho P &amp;

  3) Wetting and dispersing agent: Pigment-friendly group copolymer solution system

  4) Reactive resin: Difunctional polyglycidyl epoxide

  5) Silane coupling: Glycidoxypropyltrimethoxysilane series

6) Color Pigment: Titanium oxide (TiO ₂ R 900, DuPont), black pigment (Colombian)

  7) Extention Pigment: talc, silica, coal

  8) Rustproof pigments - ㉮: Aluminum strontium zinc phosphosilicate

     Rust-preventive pigment-㉯: zinc phosphate

  9) mica-㉮: masilicate mineral

     Mica-㉯: Calcium Magnesium Aluminum Phylosilicate Minerals

  10) Flow inhibitor-㉮: castor oil derivative anti-sag agent

  11) Anti-flow agent - ㉯: Polyamide wax powder anti-sag agent

  12) Aliphatic denatured polyamide hardener resin (manufactured product of Kumho Pheny Chemical Lab, manufactured by adding fatty acids and heating at 100 ~ 250 ℃ for 3 ~ 10 hours at 170 ℃)

  13) Aliphatic modified polyamine hardener resin (KCA 4112-1)

14) Curing accelerator: 2,4,6-trimethylaminomethylphenol (Air Protect)

As shown in Table 4, one of the compositions 1 to 24 is added to a dispersion vessel, and the mixture is stirred at 300 to 600 rpm while the mixture is stirred at 600 to 900 rpm for 10 to 30 minutes. Thereafter, 7 is added and dissolved by stirring at 900 to 1200 rpm for 10 to 30 minutes. While stirring in the order of the process, the mixture is agitated at 600 to 900 rpm for 10 to 30 minutes and then dispersed at 1400 to 1700 rpm for 30 to 50 minutes within the standard softening degree. Thereafter, 15 was added and stirred and wetted at 600 to 900 rpm. 16 to 17 are added while stirring in the order of the process, and the mixture is dispersed at 1400 to 1700 rpm for 20 to 40 minutes within the standard softening degree, then 18 is added and stirred and wet at 600 to 900 rpm. Thereafter, 19 parts of the mixture is added while stirring in the order of the process, and the mixture is heated at 1600 to 1900 rpm at 55 to 65 ° C, and then cooled to 40 ° C with a stirrer. Thereafter, the mixture is stirred and melted at 1400 to 1700 rpm for 5 to 10 minutes.

The epoxy-based paint prepared in this manner contains air bubbles and is allowed to stand for a certain period of time. After stabilizing the paint, the hardeners of the items 21 to 24 are prepared, mixed and aged for 20 minutes and then painted on the substrate.

As painting conditions, oil, grease, etc. are treated with surface treated SSPC-SP 2, or mill scale and inorganic metal rust are treated with surface pretreatment SSPC SP-10 by sandblasting, sandblasting, One coat of epoxy paint with good adhesion and corrosion resistance at re-coating interval is coated with airless spray to make 160 ~ 200 micron dry film. After 15 days, 1 month, Coating layer having excellent adhesion and corrosion resistance at a re-coating interval of 160-200 microns.

The epoxy anticorrosive coating composition thus prepared had a nonvolatile content of 88 to 90% as shown in Table 5, a viscosity of 120 to 130 KU in a Krebs-Unit viscometer, and a specific gravity in the range of 1.50 to 1.60 , And curing drying (20 ℃) within 10 hours. In addition, it has excellent physical properties in seawater and outdoor exposures with periodic adhesion. It maintained 10 ⁹ Ωcm coating performance after 25 cycles in coating corrosion resistance, and maintained good physical properties after 30 cycles of crack resistance of specimens coated on weld seams , And after 12 months storage at room temperature, sedimentation was examined. As a result, the sedimentation of the coating material was good, and the viscosity of the coating material hardly changed. Thus, the coating material exhibited good physical properties in terms of stability, It has been confirmed that the paint has the function of an epoxy type paint having adhesion and corrosion resistance.

The coating workability test method of the epoxy anticorrosive coating composition having excellent adhesion and corrosion resistance in the re-coating interval of the present invention is a method in which the main body of the paint and the curing agent are mixed in a weight ratio using an airless spraying apparatus, The aging time is used after 10 to 20 minutes. Table 5 shows the results of the tests of the adhesion properties, the water resistance of the flame-retardant water, the water-repellency after water-repellency, the adhesion after outdoor exposure, the film corrosion resistance and the ballast tank test.

&Lt; Paints and coating film properties test 2 >

<Legend> ⊚: very good, ∘: good, ◐: fair, △: insufficient, X: bad

  1) Condition in the container: uniformly dispersed without dust, foreign matter, and sediment lumps

  2) Curing Drying: 20 占 폚 占 10 hours or less (dry coating 160 占 퐉 占 1coat)

  3) Stability of paint storage stability: Viscosity change within 20% when viscosity is measured at 40 ℃ × 1 month and 12 months at room temperature

  4) Airless Spray: The coating should be smoothly applied by coating with dry coat thickness of 160 ~ 200㎛ and 1coat.

  5) Hardness: Determining the Hardness of Organic Coatings with a Sward-Type Hardness rocker (ASTM D2134), within 10 ~ 15

  6) Pencil hardness: Use a drafting pencil and keep at 45 ° against the coating. Move the tip forward to the coating surface and measure until the coating shows marks (ASTM D3363)

  7) Abrasion resistance: Abrasion Resistance of Organic Coatings by the Taber Abraser (ASTM D4060), Wheels: CS-17, load: 1000g, Revolution: 1000 cycles,

10㎜ × 180° × 1초 굴곡시킴(ASTM D 790)8) Flexibility: metal plate 150 × 50 × 0.3t, caliber of the rods Mendrel

10 mm x 180 x 1 second bend (ASTM D 790)

  9) Adhesion: Pull-off Strength of Coatings Using Protective Adhesion Testers (ASTM D4541), 4 MPa or more 1coat: Epoxy coating (160 micron) 2coat after 1 day: Epoxy coating (160 micron) exam

  10) Impact resistance: ½ "× 500g × 30㎝ with DuPont impact tester

  11) Salt water No silence: 5% -NaCI, sprayed at 35 ℃, no abnormality in coating film and good adhesion

      1coat: epoxy-based paint (160 microns)

      2coat: Epoxy coating (160 microns) / Total 320 microns

      (ASTM B1117), 1000 hours or more

  12) Inland water condition: 1coat painting 20 ℃ × 7 days later, 2coat for 15 days, 1 month, 3 months period by immersion in seawater and after 20 ℃ × 7 days after 9 days. 4MPa or more

  13) Water temperature resistance: 60 ± 2 ℃ 15 days, 1 month, 3 months on hot water Change test such as swelling of paint film, rust, severe discoloration

  14) Moisture resistance: The specimens were raised vertically at a temperature of 49 ± 1 ° C and a humidity of 95% for 15 days, 1 month and 3 months.

  15) On-and-cold cycle: 40 ° C × 14 hours, -5 ° C × 10 hours = 1 cycle, 30 cycles Test for cracking and peeling of coating film

  16) Outdoor exposures: 1coat painting 20oC 7 days after exposure 15o, 1month, 3months 2coat painting by period, after 20oC 7 days 9) Adhesion measurement test method. 4MPa or more

  17) Accelerated weathering resistance: 1coat painted, 7 days after 1 day, test the degree of discoloration and aging of the coating

  18) Promotion Corrosion Resistance: After drying at 20 ℃ for 7 days, pH 3.0 ± 0.2, sodium chloride, estimated, hydrogen peroxide, distilled water accelerated solution was kept at 60 ± 2 ℃, immersed for 7 days, washed, washed for 2 hours, 25 Cross cut test

19) Coating corrosion resistance (EIS): NORSOK M501 and EIS measurements for 72 hours → 72 hours → UV exposure for 24 hours → low temperature (-20 ± 2 ° C) exposure and EIS measurements. 1 cycle (168 hours) ⇒ Total 25 cycles (4200 hours) (ISO 20340), more than 10 ⁹ Ω㎠

20) Ballast tank test: The water ballast tank simulation system was evaluated on the basis of the PSPC of the ship as defined by the International Maritime Organization (IMO) for two weeks (35 ° C artificial seawater + 1 The state of the empty cavity was checked in the condensation chamber test at 40 ± 2 ° C and 100% humidity for a total of 180 days (room temperature 23 ± 2 ° C) to confirm the swelling, rust,

As shown in Table 5, in Examples 4 to 6 according to the present invention, the mixture viscosity of the coating material properties and the coating viscosity was appropriate in the mixing of epoxy resin and epoxy equivalent, so that the coating workability was smooth in the winter season, re-coating interval) and 3 months adhesion, hot water resistance, accelerated weathering, 7 days accelerated corrosion resistance test.

Claims (5)

(1) The esterification reaction with a bisphenol A type epoxy resin is carried out by mixing the unsaturated fatty acids dimer acid, linoleic acid, palmitic acid, stearic acid, flax fatty acid, lauric acid, soybean oil fatty acid, castor fatty acid and derivatives thereof, To produce a fatty acid-modified epoxy resin; And
(2) To the double bond of the fatty acid of the fatty acid-modified epoxy resin prepared in (1) above, an epoxy silane coupling agent, an amine silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, an isocyanate A silyl coupling agent, a styryl silane coupling agent and a derivative thereof in the form of a pendant or a mixture of two or more thereof.
Modified fatty epoxy resin synthesized with a fatty acid and a silane coupling agent. (1) 10 to 25 parts by weight of a fatty acid-modified epoxy resin synthesized with the fatty acid and silane coupling agent prepared in (1) above and 3 to 10 parts by weight of dimethylbenzene are added to the dispersion vessel and stirred at 300 to 600 rpm, 10 parts by weight of a bisphenol A type epoxy resin is added and stirred for 10 to 30 minutes, 0.1 to 0.5 parts by weight of a wet dispersant, 0 to 5 parts by weight of a reactive resin and 0.1 to 1.0 part by weight of a silane coupling agent are sequentially added Mixing and stirring at 600 to 900 rpm for 10 to 30 minutes;
(2) 1 to 5 parts by weight of a polyamide wax anti-settling agent is added to the agitated product of (1) above and dispersed and dissolved at 900 to 1200 rpm for 10 to 30 minutes. Then, at least one of talc, silica, 1 to 10 parts by weight of a white pigment, and 0.1 to 0.5 parts by weight of a black pigment as a rust-inhibitive pigment, at least one of aluminum strontium zinc phosphosilicate and 1 to 10 parts by weight of zinc phosphate, Stirring and wetting the mixture at 600 to 900 rpm for 10 to 30 minutes and dispersing the mixture at a temperature of 1400 to 1700 rpm for 30 to 50 minutes to a standard softening degree of 80 microns or less;
(3) adding 1 to 5 parts by weight of dimethylbenzene to the agitated product of (2) and agitating the mixture at 600 to 900 rpm for 5 to 10 minutes while stirring;
(4) At least one of calcium magnesium aluminum phyllosilicate minerals and 1 to 10 parts by weight of silicate mineral is added as a mica to the agitated product stirred in the step (3), and the mixture is heated at 1400-1700 rpm to 20 And dispersed in a degree of softening of not more than 100 microns while stirring and dispersing for ~ 40 minutes, By weight of propylene glycol monoethyl ether with stirring at 600 to 900 rpm;
(5) adding 0.1 to 2 parts by weight of a castor derivative flow inhibitor to the agitated product of (4) above, raising the temperature of the paint to 55 to 65 ° C at 1600 to 1900 rpm, and then cooling the paint to 40 ° C or less;
(6) adding 1 to 5 parts by weight of a polyamide wax, which is a flow inhibitor, to the stirred product of (5), and dissolving the mixture at 1,400 to 1,700 rpm for 5 to 10 minutes; And
(7) The process according to (6), wherein at least one of 10 to 20 parts by weight of an aliphatic modified polyamide and 1 to 10 parts by weight of an aliphatic modified polyamine curing resin, 1 to 5 parts by weight of a curing accelerator, Propylcarbinol and aging for 10 to 40 minutes while stirring.
A method for producing a marine coating composition using a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent. 3. The method of claim 2,
The fatty acid added to (1) and the fatty acid synthesized with the silane coupling agent Wherein the equivalent of the modified epoxy resin and the bisphenol A type epoxy resin is from 180 to 500,
A method for producing a marine coating composition using a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent. The method according to claim 2,
Wherein the wet dispersant of (1) is a pigment-affinity group copolymer solution system.
A method for producing a marine coating composition using a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent. 3. The method of claim 2,
Characterized in that the reactive resin in the first step is a polyfunctional diluent.
A method for producing a marine coating composition using a fatty acid-modified epoxy resin synthesized with a fatty acid and a silane coupling agent.