KR101269390B1 - Anti-Fouling Composition - Google Patents

Abstract

The present invention relates to an antifouling coating composition, the antifouling coating composition according to the present invention comprises: a binder; a curing aid to assist in curing the binder; a silicone oil comprising a first silicone oil and a second silicone oil; Coating reinforcement material containing an acrylic polymer; And a slip agent containing a fluororesin.

Description

Anti-Fouling Composition

The present invention relates to an antifouling coating composition for preventing contamination of marine structures exposed to seawater.

The present invention relates to an antifouling paint for preventing pollution of marine structures, water intake pipes, nuclear power plants, bottoms and the like by marine life. As a conventional technique for this, antifouling paints using a hydrolyzable resin containing tin (TIN) are used, but this is a biological impo-sex due to toxicity and marine accumulation of tin compounds eluted from the resin to marine organisms. It is a phenomenon that is gradually becoming a target of regulation.

Therefore, as a anti-fouling paint containing no tin, a technique has been developed by mixing copper oxide and organic antifouling agent with a tin-free resin, but there is a problem about the toxicity of copper oxide and organic antifouling agent eluted from the surface of the coating film. This problem has been raised and has to be repainted every five years.

The more advanced technology to minimize the surface energy of the coating film to prevent the adhesion of marine life, US Patent No. 5,959,116 and European Patent No. 273,457 proposes a non-release antifouling paint.

In US Patent No. 5,959, 116, an antifouling coating composition in which silicone oil and silica are applied to a reactive silicone rubber or resin is applied, but the hardness of the coating film is too weak to be applied to the bottom. In particular, silicone oil is mixed in order to lower the surface energy of the surface of the coating film, but there is a problem that it is difficult to exhibit long-term antifouling performance with such oil.

In addition, EP 273,457 discloses acrylic silicon, which can reinforce the strength of the coating film, but it is insufficient to obtain the minimum surface energy to prevent the adhesion of marine organisms.

The present invention has been made to solve the above problems, the non-release antifouling paint according to the present invention is non-toxic antifouling that can implement a long-term antifouling performance at the same time by giving strength by increasing the elastic modulus inside the coating film and at the same time lowering the surface energy of the coating film It provides a coating composition.

The antifouling coating composition according to the present invention,

A binder represented by Formula 1;

A curing aid to assist in curing the binder;

A silicon oil comprising a first silicone oil represented by Formula 2 and a second silicone oil represented by Formula 3 below;

Coating reinforcement material containing an acrylic polymer; And

And a slip agent containing a fluororesin.

[Formula 1]

(n is an integer, R is a hydrogen group, hydroxyl group, linear branched alkyl group, alkoxy group, acid group, cyanine group, amino group, or epoxy group, R ₁ , R ₂ is hydrogen group, hydroxyl group, linear branched alkyl group, alkoxy group, allyl) Groups, or fluorine-containing organic residues)

[Formula 2]

(n is an integer, R ₃ is an alkyl group or allyl group, R ₄ , ₅ is an alkyl group, allyl group, or phenyl group)

(3)

(m is an integer of 0-5, y is a free number, R ₃ is an alkyl or allyl group, R ₄ is an alkyl group, allyl or phenyl group, R ₅ has at least one ether, acetyl or amino group) Organic residues)

At this time, based on 100 parts by weight of the binder,

The curing aid is included in 0.01 to 30 parts by weight,

The first silicon oil is 1 to 40 parts by weight, the second silicon oil is contained in 0.5 to 30 parts by weight,

The coating reinforcing material is included in 1 to 20 parts by weight,

The slip agent may be included in 1 to 10 parts by weight.

At this time, it is preferable that the sum total of the said 1st silicone oil and the said 2nd silicone oil is 60 weight part or less with respect to 100 weight part of said binders.

In addition, the curing aid is preferably a compound consisting of one or more selected from the group consisting of titanium compounds, tin compounds, zirconium compounds and silicon compounds.

In addition, the coating reinforcing material may be coated with calcium carbonate.

In addition, the slip agent preferably contains a fluororesin.

In addition, the slip agent may be used by coating a fluorine resin on a fluorine compound (Hydrogen Fluoride, Carbonyl Fluoride).

In addition, the slip agent is preferably in the form of a powder having a particle size of 4 to 8㎛.

When the antifouling coating composition of the present invention forms a coating film exposed to seawater, the mechanical and thermal modulus of the inside of the coating film is increased to improve the strength, thereby improving mechanical properties, and at the same time lowering the surface energy of the coating film to maintain long-term antifouling performance. It has an effect.

In addition, the antifouling coating composition of the present invention does not contain a tin compound that elutes from the resin and affects marine life, and thus does not disturb the ecosystem.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout the description and claims, unless the context requires otherwise, the word "comprise" is intended to include the stated article, step or group of articles, and steps; It is not meant to exclude an object, step or group of objects or a group of steps.

On the other hand, various embodiments of the present invention can be combined with any other embodiment unless clearly indicated to the contrary. In particular, any feature that is indicated to be advantageous or advantageous may be combined with any other feature or feature that is indicated to be advantageous or advantageous.

The antifouling coating composition according to one aspect of the present invention comprises a binder, a curing aid, a silicone oil, a coating film reinforcing material and an additive.

The binder has a number average molecular weight or a weight average molecular weight of 1000 to 150000 silicone and silicon modified binder, which has a structure as shown in the following formula (1).

[Formula 1]

(n is an integer, R is a hydrogen group, hydroxyl group, linear branched alkyl group, alkoxy group, acid group, cyanine group, amino group, or epoxy group, R ₁ , R ₂ is hydrogen group, hydroxyl group, linear branched alkyl group, alkoxy group, allyl) Groups, or fluorine-containing organic residues)

Component of the binder having the structure means a minimum hardness that can withstand the scratches of the surface when applied to marine structures and ships with a strength of the coating film 40 to 95 with a hardness measuring instrument (shore A type) after curing. If it does not have such hardness, there is a disadvantage that the antifouling property is sharply lowered due to the surface scratching phenomenon and the appearance of the coating film is not good.

In this case, the binder preferably has a number average molecular weight or a weight average molecular weight of 1,000 to 150,000. If it is less than 1,000, the tensile strength of the coating film is bad, and if the workability is less than 150,000.

A curing aid is included to improve the hardness of the coating as well as to promote curing of the coating when the binder forms the coating. The hardening aid is preferably a metal compound or a silicon compound, and there are titanium compounds, silicon mixtures, tin compounds, zirconium compounds, and the like, and these may be used alone or in combination.

The curing aid is used in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the binder. Less than 0.01 part by weight in the use content is difficult to obtain the effect, and if it exceeds 30 parts by weight, the effect of the binder is not preferable because it is half.

Examples of the silicone compound include, but are not limited to, oxymino silane, ketiminoxy silane, acyloxy silane, trimethoxy silane and the like. Examples of the titanium compound include, but are not limited to, tetraisopropyl titanate, tetra-n-butyl titanate, titanison ethylacetoacetate, and the like. Examples of tin compounds include, but are not limited to, dibutyltinnaurate, tributyl tinoxide, and the like.

The curing aid may be mixed and stored with the binder to be used as a one-part type, or as a two-part type to be mixed with an actual use binder.

Silicone oil is a component to maximize the lubrication of the surface to maintain long-term antifouling performance. Generally used oil can reduce the surface energy by maximizing the lubricity of the surface in the short term, but as the oil is released from the surface over time, the rapid antifouling effect is reduced. Therefore, in order to exhibit long-term antifouling performance effect, silicon oil must be eluted from the inside of coating film so that lubricity of surface can be maintained continuously.

Silicone oil may be used in any one or a mixture of the following formula (2) or formula (3), for the long-term surface lubricating effect of the silicone oil it is preferable to use two mixtures.

[Formula 2]

(n is an integer, R ₃ is an alkyl group or allyl group, R ₄ , ₅ is an alkyl group, allyl group, or phenyl group)

(3)

(m is an integer of 0-5, y is a free number, R ₃ is an alkyl or allyl group, R ₄ is an alkyl group, allyl or phenyl group, R ₅ has at least one ether, acetyl or amino group) Organic residues)

The first silicone oil represented by the formula (2) is advantageous for the lubricating action on the initial surface after drying the coating film, it is expressed on the surface when the coating film is applied to serve to improve the initial slip phenomenon (SLIP property) of the coating film.

In addition, the first silicone oil has a characteristic that can control the strength of the coating film, which can improve the strength of the coating film when using the oil containing phenyl group, but when used a lot of compatibility problems with component A It can be caused and an appropriate amount of use is required.

The amount used as the first silicone oil is preferably 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the binder. At this time, the viscosity of the first silicone oil is suitably 50 to 5000 centistokes (CENTI STOCK). In this case, the drying rate is less than 50 centistokes, so it is not preferable because the drying rate is too slow, and if it exceeds 5000 centistokes, it is difficult to be expressed on the surface of the coating film because the antifouling effect is halved.

The second silicone oil represented by the formula (3) is expressed on the surface of the coating film in the long term to improve the long-term antifouling properties, and has at least one ether (ETHER) group, acetate (ACETATE) group and amine group in the molecule It has a characteristic of being ejected to the coating film surface gradually by moisture.

The second silicone oil should be particularly careful of its proper content. In particular, the alkoxy curing type has the disadvantage of delaying the curing, so the amount of use should be used less than other curing mechanisms.

A suitable use amount of the second silicone oil is preferably 0.1 to 50 parts by weight to 100 parts by weight of the binder, but most preferably 0.5 to 30 parts by weight may be used.

On the other hand, the combined content of the first silicon oil and the second silicon oil should not exceed 60 parts by weight or more to 100 parts by weight of the binder. It is because the strength of the coating film required by this invention cannot be obtained when it exceeds 60 weight part.

The coating reinforcing material is a capsule coating the surface of the acrylic polymer as an elastic modifier to increase the mechanical or thermal expansion rate of the coating film.

That is, the coating film is contracted or expanded by thermal or mechanical shock from the outside, and the spherical capsule using the acrylic polymer as the elastic modifier is excellent in strength and gives elasticity of the coating film, thus shrinking / The expansion rate can be increased. At this time, calcium carbonate may be coated on the surface in order to improve the dispersibility of the paint.

It is preferable that the usage-amount of a coating film reinforcement shall be 1-20 weight part with respect to 100 weight part of binders. It is because it is hard to exhibit the performance below 1 weight part, and when 20 weight part is exceeded, the viscosity of a paint rises rapidly and it is impossible to obtain the coating composition disperse ideally.

The slip agent lowers the surface energy of the coating film without affecting the elastic modulus inside the coating film, thereby providing slip property of the surface to prevent adhesion of marine organisms and effectively detaching attached marine organisms. To give. Slip agent is a powder type containing a fluorine resin, the particle size is preferably used 4 to 8㎛, fluorine resin (Hydrogen Fluoride, Carbonyl Fluoride) is preferably used is coated with a fluorine resin.

In this case, the slip agent is preferably 1 to 10 parts by weight based on 100 parts by weight of the binder. It is because excellent long-term antifouling performance cannot be obtained at 1 part by weight or less, and at 10 parts by weight or more, the compatibility with the binder is significantly lowered, so that it is difficult to obtain an effective composition.

The antifouling paint composition according to the present invention may further include a coloring pigment, a extender pigment, and a solvent.

Various pigments of organic and inorganic pigments known in the art may be used as the coloring pigment. As the organic pigment, for example, carbon black, phthalocyanine blue, etc. may be used, and as the inorganic pigment, for example, titanium bag, bengal (iron) neutral pigments such as oxide red, iron oxide powder, chalk, and basic and reactive with acidic substances in paints such as zinc (ZnO, zinc oxide), white lead, red lead, etc. May be, but is not limited thereto. In the antifouling coating composition of the present invention, the colored pigment may preferably include 1 to 20 parts by weight based on 100 parts by weight of the total weight of the coating composition.

Sieve fuels include, for example, talc, silica, mica, clay, calcium carbonate, kaolin, magnesium carbonate, barium carbonate, barium sulfate, bentonite used as a sedimentation inhibitor, and may be used alone or in combination of two or more thereof. However, it is not limited thereto. In the antifouling paint composition of the present invention, the extender pigment may preferably include 1 to 40 parts by weight based on 100 parts by weight of the total coating composition.

Solvents are aliphatic and aromatic, for example, solvents such as xylene, toluene, sorbetho, and various solvents commonly used in antifouling paint compositions such as ketones, esters, ethers, and alcohol solvents, based on the paint properties, 1 to 50 parts by weight may be included.

The antifouling coating composition described above was prepared in a composition as shown in Table 1 below.

Example

Example Comparative example X1 X2 X3 X4 X5 X6 X7 X8 Y1 Y2 Y3 Y4 Y5 Y6 1.Binder 70 70 70 60 70 70 70 60 80 70 70 75 80 60 2. Curing
Supplements 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 3-1.
First surface
Lubricant A 15 15 15 15 15 15 15 3-2.
First surface
Lubricant B 15 15 15 15 15 15 15 4. Second Surface Lubricant 10 10 5 20 10 10 5 20 20 10 20 30 5. Coating film
reinforcement 9 12 12 9 9 12 12 9 9 12 12 6. Slipper 6 3 6 3 6 3 6 3 6 6 6 7. Silica 3 3 5 6 3 3 5 6 3 2 6 3 6 2 8. Bangalore 3 3 3 3 3 3 3 3 3 3 3 3 3 3 9. Xylene 80 80 80 80 80 80 80 80 80 80 80 80 80 80

1.Binder: Dimethyl silane having alkoxy terminal and molecular weight of 5000

2. Curing aid: Dibutyl tin laurate

3-1. 1st silicone oil A: C-1: DC-550 (Dow Corning)

3-2. 1st silicone oil B: C-2: KF-56 (Shin-Etsu Co., Ltd.)

4. Second silicone oil: ISI4700 (Toshiba Silicon Products)

5. Coating reinforcement: MFL-SEVEN (Matsumoto Yoshi-Seiyaku)

6. Slipper: Zonyl MP 1100 (dupont product)

Other ingredients

7. Silica: Aerosil R972 (made by Degussa)

8. Bengala: Iron Oxide Red

9. Xylene: Xylene

Experimental Example

The coating film strain and antifouling performance evaluation of the above-described embodiments were conducted in the following manner.

Evaluation of paint film strength (Anti-coagulation test)

The sandblasted 100 × 300 × 3 (mm) steel sheet was coated with an epoxy anti-corrosive coat to 150 μm, and dried at room temperature (20 ° C.) for 1 day to form a coating film. An epoxy-silicon binder coat (Sealer coat) is additionally coated on the surface of the coating film to 100 µm, and dried at room temperature (20 ° C) for 1 day to form a coating film.

Thereafter, the antifouling coating composition prepared by the formulation shown in Table 1 was continuously coated at 150 μm (dry coating film thickness) at daily intervals, and cured and dried at room temperature for one week to prepare test specimens.

After drying the test specimen at room temperature, a 20 × 20 × 20 (mm) wooden block was placed on the upper part of the test coating film, and 200 kgf / cm 3 pressure was applied for 40 minutes in a vertical direction from above the wooden coating film thickness. The strain of was measured. The film thickness strain was measured by decreasing the film thickness by measuring the film thickness after applying pressure to the neck piece from the initial film thickness of the dry film.

The evaluation of the anti-seizure test is expressed as a 7-day strain result on the basis of the following criteria.

5: less than 1% strain

4: 1 to 3% strain

3: 3-7% strain

2: 7-10% strain

1: 10% or more strain

In addition, by visually observing the state of the coating film was evaluated based on the following criteria.

○ ○: No dents and no damage to the coating when visually observed

l △: Pressing when visual observation, but no damage to coating

l X: Pressing marks are visible to the naked eye, and the coating film is damaged.

The coating film strength evaluation (banner settle pressurization test) results are summarized in Table 2.

Identity Antifouling performance test in state

Antifouling coating composition prepared by sandblasting 550 × 150 × 2 (mm) steel sheet with 200μm epoxy-based anticorrosive coat, 100μm epoxy-silicone binder coat and the formulation shown in Table 1. 300 μm (based on the dry coating thickness) was continuously coated at a daily interval, and cured and dried at room temperature for one week.

Thus prepared specimens were immersed at a position below 1 (m) sea level using a raft-type test device (Raft) installed in the Ulsan defense port (East coast) and Geoje offshore (South coast). Every three months after the deposition, the degree of contamination of the coating due to the attachment of marine organisms was periodically observed for 12 months, and the antifouling performance was evaluated as shown in Table 3 according to the criteria described below.

Evaluation criteria are as follows;

5: no attachment of marine life (non-pollution),

4: the thin slime layer is observed,

3: thick slime layer observed or vegetable contaminated area less than 20% of the effective area of the specimen,

2: the plant contamination area is 20-50% of the effective area of the specimen,

1: The plant contamination area is 50 to 100% of the effective area of the specimen (X: animal contamination).

Example Comparative example X1 X2 X3 X4 X5 X6 X7 X8 Y1 Y2 Y3 Y4 Y5 Y6 Strain 5 5 5 5 5 5 5 5 4 3 5 3 4 One Visual result ○ ○ ○ ○ ○ ○ ○ ○ △ X ○ X △ X

As shown in Table 2, in the case of Y2, Y4, and Y6, which do not include the coating reinforcement used as the elastic modifier, a test result of returning to the original state after a certain period of time after applying a forced deformation to the coating film was obtained.

Example Comparative example X1 X2 X3 X4 X5 X6 X7 X8 Y1 Y2 Y3 Y4 Y5 Y6 3 months 5 5 5 5 5 5 5 5 5 5 5 5 4 5 6 months 5 5 5 5 5 5 5 5 5 5 4 4 4 5 9 months 5 5 5 5 5 5 5 5 5 5 4 4 3 5 12 months 5 5 5 5 5 5 5 5 4 5 3 4 2 5

As shown in Table 3, when the silicone oil or the slip agent is not included, it can be confirmed that the antifouling performance is significantly reduced.

Therefore, the antifouling coating composition according to the present invention can provide an antifouling coating film having excellent mechanical properties as well as antifouling properties.

The features, structures, effects and the like described in the foregoing embodiments are included in at least one embodiment of the present invention and are not necessarily limited to one embodiment. In addition, the features, structures, effects, and the like illustrated in the embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

Claims (8)

A binder represented by the following formula (1) and composed of silicon or modified silicon having a number average molecular weight of 1000 to 150,000;
A curing aid to assist in curing the binder;
A silicone oil comprising a first silicone oil composed of a linear silicone oil represented by Formula 2 and a second silicone oil composed of a modified silicone oil represented by Formula 3 below;
Coating reinforcement material containing an acrylic polymer; And
An antifouling coating composition comprising a slip agent containing a fluororesin.
[Formula 1]

(n is an integer, R is a hydrogen group, hydroxyl group, linear branched alkyl group, alkoxy group, acid group, cyanine group, amino group, or epoxy group, R ₁ , R ₂ is hydrogen group, hydroxyl group, linear branched alkyl group, alkoxy group, allyl) Groups, or fluorine-containing organic residues)
(2)

(n is an integer, R ₃ is an alkyl group, or an allyl group, R ₄ , ₅ is an alkyl group, an allyl group, or a phenyl group)
(3)

(m is an integer of 0-5, y is a free number, R ₃ is an alkyl or allyl group, R ₄ is an alkyl group, an allyl group or a phenyl group, R ₅ has at least one ether, acetyl or amino group) Organic residues) The method of claim 1,
Per 100 parts by weight of the binder,
The curing aid is included in 0.01 to 30 parts by weight,
The first silicon oil is 1 to 40 parts by weight, the second silicon oil is contained in 0.5 to 30 parts by weight,
The coating reinforcing material is included in 1 to 20 parts by weight,
The slip agent comprises an antifouling paint composition 1 to 10 parts by weight. The method of claim 1,
The antifouling coating composition wherein the sum of the first silicon oil and the second silicon oil is 60 parts by weight or less based on 100 parts by weight of the binder. The method of claim 1,
The curing aid is an antifouling coating composition which is a compound consisting of one or more selected from the group consisting of titanium compounds, tin compounds, zirconium compounds and silicon compounds. The method of claim 1,
The coating reinforcing material is an antifouling coating composition coated with calcium carbonate. The method of claim 1,
The slip agent is an antifouling paint composition containing a fluororesin. The method according to claim 6,
The slip agent is an antifouling paint composition used by coating a fluorine resin on a fluorine compound (Hydrogen Fluoride, Carbonyl Fluoride). The method according to claim 6,
The slip agent is an antifouling paint composition having a particle size of 4 to 8㎛ in powder form.