KR20020058709A - Nontoxic, antifouling paints composition - Google Patents

Nontoxic, antifouling paints composition Download PDF

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KR20020058709A
KR20020058709A KR1020000086839A KR20000086839A KR20020058709A KR 20020058709 A KR20020058709 A KR 20020058709A KR 1020000086839 A KR1020000086839 A KR 1020000086839A KR 20000086839 A KR20000086839 A KR 20000086839A KR 20020058709 A KR20020058709 A KR 20020058709A
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KR100751450B1 (en
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김덕현
김범성
남태구
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정종순
주식회사 금강고려화학
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Abstract

PURPOSE: Provided is a non-toxic antifouling paint composition containing a specific binder component, a curing accelerator component, and oil components, which has antifouling property for a long time. CONSTITUTION: The non-toxic antifouling paint composition contains 100pts.wt. of the binder(formula 1), 0.01-30pts.wt. of the curing accelerator, 0.5-50pts.wt. of the oil component(formula 2), and 0.1-50pts.wt. of the oil component(formula 3), wherein the curing accelerator is at least one compound selected from the group consisting of a titanium compound, a silicon compound, a tin compound, and a zirconium compound. In the formula 1, n is an integer, R is hydrogen, hydroxy, linear branched alkyl, alkoxy, acid, cyanine, amino, or epoxy, R1 and R2 are each hydrogen, hydroxy, linear branched alkyl, alkoxy, allyl, or fluorine contained organic residue. In the formula 2, n is an integer, R3 is alkyl or allyl, R4 and R5 are each alkyl, allyl, or phenyl. In the formula 3, m is an integer of 0-5, x and y are rational numbers, R3 and R4 are the same as in the formula 2, and R5 is an organic residue having at least one of ether, acetyl, amino, carbonyl, or polyglycol.

Description

무독성 방오도료 조성물{Nontoxic, antifouling paints composition}Nontoxic antifouling paints composition

본 발명은 무독성 방오도료 조성물에 관한 것으로, 보다 상세하게는 특정의 바인더 성분, 경화촉진제 성분, 오일 성분 등을 포함하는 것을 특징으로 하는 방오성이 우수하고 무독성인 방오도료 조성물에 관한 것이다.The present invention relates to a non-toxic antifouling coating composition, and more particularly, to an antifouling and nontoxic antifouling coating composition comprising a specific binder component, a curing accelerator component, an oil component and the like.

종래의 기술로는 틴을 함유한 가수분해 수지를 이용한 방오도료가 있으나, 이는 수지로부터 용출되는 틴 화합물의 해양생물에 대한 독성 및 체내 축적에 의한 생물 임포섹스(impo-sex) 현상을 유발하여 점차 규제의 대상이 되고 있다. 이에 보다 발전된 기술로는 틴을 함유하지 않은 수지에 아산화동 및 유기방오제를 혼합하여 제조되어지는 틴을 함유하지 않는 방오도료가 있으나, 이는 도막표면에서 용출되는 아산화동 및 유기방오제의 독성에 대한 문제점이 제기되고 있으며, 최장 5년마다 재도장하여야 하는 문제점을 안고 있다.Conventional techniques include antifouling paints using hydrolyzable resins containing tin, which gradually cause bio-impo-sex phenomena due to toxicity and marine accumulation of the tin compounds eluted from the resin. It is targeted for regulation. More advanced technologies include tin-free antifouling paints made by mixing copper oxide and organic antifouling agents with tin-free resins, but this is due to the toxicity of copper oxide and organic antifouling agents eluted from the coating surface. There is a problem that has to be raised, and has to repaint every five years.

이러한 용출형 제품에 비하여 진보한 기술로 도막의 표면에너지를 최소화하여 동·식생물의 부착을 방지하는 기술들이 미국특허 제5,959,116호 및 유럽특허 제273,457호에 개시되어 있다. 미국특허 제5,959,116호에서는, 반응성 실리콘 러버(rubber)나 레진(resin)에 실리콘 오일과 실리카를 적용한 방오도료 조성물을 제시하고 있으나, 도막표면의 강도(hardness)가 너무 약하여 선저(船底)에 적용하기 힘들며, 특히 도막표면의 표면에너지를 낮추기 위하여 실리콘 오일을 혼용하고 있으나, 이러한 오일로는 장기적인 방오성능을 발휘하기 어렵다. 유럽특허 제273,457호에서는 아크릴실리콘을 제시하고 있는데, 이는 도막의 강도는 보강할 수 있으나 해양생물의 부착을 방지하기 위한 최소한의 표면에너지를 얻기에는 부족한 면이 있다.Techniques for minimizing the surface energy of the coating film to prevent the adhesion of animals and plants with the advanced technology compared to such eluted products are disclosed in US Pat. No. 5,959,116 and EP 273,457. U.S. Patent No. 5,959,116 proposes an antifouling coating composition in which silicone oil and silica are applied to a reactive silicone rubber or resin, but the hardness of the coating film is too weak to be applied to the bottom. It is difficult, and especially in order to lower the surface energy of the coating film, silicone oil is mixed, but it is difficult to exhibit long-term antifouling performance with such oil. EP 273,457 suggests acrylic silicon, which can reinforce the strength of the coating but lacks the minimum surface energy to prevent marine organisms from adhering.

본 발명의 목적은 상기의 종래 기술들의 문제점을 해결하기 위하여 도막강도가 표면강도 측정기(shore A type)로 40∼95이며, 도막의 내부로부터 도막표면으로 서서히 실리콘 오일이 표출되어 계속적으로 표면의 에너지를 낮출 수 있어 장기간의 방오성능을 가질 수 있는 비용출형, 무독성 방오도료 조성물을 제공하는 것이다.An object of the present invention is to solve the problems of the prior art, the film strength is 40 ~ 95 as the surface strength measuring instrument (shore A type), the silicone oil is gradually exposed to the surface of the coating film from the inside of the coating film, the energy of the surface continuously It can be lowered to provide a non-release, non-toxic antifouling coating composition that can have a long-term antifouling performance.

본 발명의 방오도료 조성물은 바인더 성분 A, 경화촉진제 성분 B, 오일 성분 C 및 D를 포함하는 것을 특징으로 한다.The antifouling coating composition of the present invention is characterized by comprising a binder component A, a curing accelerator component B, oil components C and D.

본 발명에서 사용되는 바인더 성분 A는 평균 분자량 1,000∼150,000의 실리콘 또는 실리콘 변성 바인더로, 이는 하기의 일반식 1과 같은 구조를 갖고 있다.The binder component A used in the present invention is a silicone or a silicone-modified binder having an average molecular weight of 1,000 to 150,000, which has a structure as shown in the following general formula (1).

일반식 1 Formula 1

(여기서, n은 정수; R은 수소기, 수산기, 선상 가지상의 알킬기, 알콕시기, 산기, 시아닌기, 아미노기 또는 에폭시기; R1, R2는 각각 수소기, 수산기, 선상 가지상의 알킬기, 알콕시기, 알릴기 또는 불소함유 유기잔기이다.)(Where n is an integer; R is a hydrogen group, a hydroxyl group, a linear branched alkyl group, an alkoxy group, an acid group, a cyanine group, an amino group or an epoxy group; R 1 , R 2 are each a hydrogen group, a hydroxyl group, a linear branched alkyl group, or an alkoxy group) , Allyl or fluorine-containing organic residue.)

상기 구조를 갖는 바인더의 성분장점을 보면, 경화후 도막의 강도가 표면강도 측정기(shore A type)로 40∼95로서, 이는 해양구조물 및 선박에 적용시 표면의 긁힘 현상에서도 견딜수 있는 최소한의 경도를 의미한다. 만약 이러한 경도를 갖지 못하는 경우 표면의 긁힘 현상에 의하여 방오성이 급격히 저하하는 현상과 도막의 외관이 좋지 않은 단점이 발생하게 된다. 성분 A의 바인더는 분자량은 1,000∼150,000 사이가 좋다. A의 바인더의 분자량이 1000 미만이면 도막의 인장강도가 나쁘며, 150,000을 초과하면 작업성이 떨어져서 바람직하지 못하다.In view of the component advantages of the binder having the above structure, the strength of the coating film after curing is 40-95 with the surface strength measuring instrument (shore A type), which is the minimum hardness that can withstand the scratches of the surface when applied to marine structures and ships. it means. If it does not have such hardness, a phenomenon that the antifouling property is sharply lowered due to the surface scratching phenomenon and the appearance of the coating film is not good. The molecular weight of the binder of component A is preferably between 1,000 and 150,000. If the molecular weight of the binder of A is less than 1000, the tensile strength of the coating film is bad, and if it exceeds 150,000, workability is poor, which is not preferable.

본 발명의 조성물에서, 성분 B로 표시되는 경화촉진제는 성분 A가 도막을 형성할시 도막의 경화촉진과 더불어 도막의 경도도 향상시킬 수 있는 작용을 하게 된다. 성분 B는 금속화합물을 쓰는 것이 바람직하며, 티탄화합물, 실리콘 화합물, 틴화합물, 질코늄 화합물 등이 있으며, 이들을 단독 혹은 혼합하여 사용이 가능하다. 실리콘 화합물로는 옥시미노 실란, 케티미녹시 실란, 아실록시 실란, 트리메톡시 실란 등이 있으며, 이러한 예가 본 발명을 한정하는 것이 아니다. 티탄계 화합물로는 테트라이소프로필 티타네이트, 테트라-n-부틸 티타네이트, 티타니윰 에틸아세토아세테이트 등이 있으며, 이러한 예가 본 발명을 한정하는 것은 아니다. 틴화합물로는 디부틸틴나우릴레이트, 트리부틸 틴옥사이드 등이 있으며, 이러한 예가본 발명을 한정하는 것은 아니다. 사용상에 있어 상기 성분 B를 성분 A와 혼합저장하여 1액형으로 사용하여도 무방하나, 2액형처럼 사용시 성분 A와 혼합하여 사용하여도 무방하다. 이러한 경화촉진 및 경화보조제는 성분 A 100중량부에 대하여 0.01∼30중량부를 사용하는 것이 바람직하다. 사용함량에 있어 0.01중량부 미만에서는 그 효과를 얻기 어려우며, 30중량부를 초과할 경우는 성분 A의 효과를 반감할 수 있음으로 바람직하지 않다.In the composition of the present invention, the curing accelerator represented by component B has an effect of improving the hardness of the coating film as well as promoting curing of the coating film when component A forms the coating film. It is preferable to use a metal compound as the component B, and there are a titanium compound, a silicon compound, a tin compound, a zirconium compound, and the like, which can be used alone or in combination. Examples of the silicone compound include oxymino silane, ketiminoxy silane, acyloxy silane, trimethoxy silane, and the like. These examples do not limit the present invention. Examples of the titanium compound include tetraisopropyl titanate, tetra-n-butyl titanate, titanison ethylacetoacetate, and the like. However, these examples do not limit the present invention. Tin compounds include dibutyl tinnaurate, tributyl tin oxide, and the like, but these examples do not limit the present invention. In use, the component B may be mixed and stored with the component A to be used in one-component form, but may be used in combination with the component A when used as a two-component form. It is preferable to use 0.01-30 weight part of such hardening accelerators and hardening adjuvant with respect to 100 weight part of components A. If the content is less than 0.01 parts by weight, the effect is difficult to obtain, and if it exceeds 30 parts by weight, the effect of component A can be halved.

본 발명의 조성물에서, 성분 C와 D는 표면의 윤활작용을 극대화하여 장기 방오성능을 유지하기 위한 오일 성분들이다.In the composition of the present invention, components C and D are oil components for maximizing surface lubrication and maintaining long-term antifouling performance.

일반적으로 이용되는 오일은 단기적으로 표면의 윤활성을 극대화하여 표면에너지를 낮출 수 있지만, 점차 표면으로부터 오일이 이탈되어 급격한 방오효과를 떨어뜨리게 된다. 그러므로 장기적인 방오성능 효과를 발휘하기 위해서는 도막내부로부터 오일 성분이 지속적으로 용출이 되어 표면의 윤활성이 지속적으로 유지될 수 있도록 하여야 한다. 이러한 오일의 장기표면 윤활효과를 위해서, 본 발명에서는 2종의 오일 성분 C와 D를 혼합하여 사용한다.Generally used oil can lower the surface energy by maximizing the lubricity of the surface in the short term, but the oil is gradually removed from the surface to reduce the rapid antifouling effect. Therefore, in order to exhibit long-term antifouling performance effect, oil must be continuously eluted from the inside of the coating film to maintain the lubricity of the surface continuously. For the long-term surface lubrication effect of such oils, two oil components C and D are mixed and used in the present invention.

본 발명에서는 성분 C는 하기의 일반식 2로 표현되는 것을 사용하는 것이 바람직하며, 도막건조후 초기표면에 윤활작용을 하게 된다.In the present invention, it is preferable to use the component C represented by the following general formula (2), and lubricate the initial surface after drying the coating film.

일반식 2 Formula 2

(여기서, n은 정수; R3는 알킬기 또는 알릴기; R4, R5는 각각 알킬기, 알릴기 또는 페닐기이다.)(Wherein n is an integer; R 3 is an alkyl group or an allyl group; R 4 , R 5 are each an alkyl group, an allyl group, or a phenyl group.)

상기 기술한 일반식 2의 오일의 특징은 도막도포시 표면에 표출되어 도막의 초기 미끄러짐현상(슬립성)을 향상시키는 역할을 하게 된다. 이 오일을 사용함에 있어, 페닐기를 함유한 오일을 사용하는 경우 도막의 강도를 향상시킬 수 있는 효과도 얻을 수 있으나 많이 사용하는 경우 성분 A의 상용성 문제를 야기할 수 있어 적절한 양의 사용이 요구된다. 사용되어지는 양은 성분 A 100중량부에 대하여 0.5∼50중량부, 바람직하게는 1∼40중량부를 사용하는 것이 좋다. 또한 점도는 50∼5,000 센티스톡(CENTI STOCK)이 적절하며, 50 센티스톡 미만이면 건조속도가 너무 느린 단점이 있어 바람직하지 않으며, 5,000 센티스톡를 초과하면 도막표면으로 표출되기 어려운 단점이 있어 방오효과를 반감시키게 된다.The characteristics of the oil of the general formula 2 described above is expressed on the surface during the coating film serves to improve the initial slip phenomenon (slip) of the coating film. In using this oil, it is possible to obtain an effect of improving the strength of the coating film when using an oil containing a phenyl group, but when used a lot, it may cause compatibility problems of component A. do. The amount to be used is 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight based on 100 parts by weight of component A. In addition, the viscosity is 50 ~ 5,000 centistokes (CENTI STOCK) is suitable, less than 50 centistokes is not preferable because the drying speed is too slow, and if it exceeds 5,000 centistokes, there is a disadvantage that it is difficult to be expressed on the surface of the coating film has antifouling effect Halved.

본 발명의 조성물에서, 또 다른 표면윤활제로는 장기적으로 도막내부에서 표면으로 표출되어 장기 방오성을 향상시키는 역할을 하는 아래의 일반식 3으로 표현되는 성분 D이다. 이러한 오일은 분자내에 최소한 1개 이상의 에테르(ETHER)기, 아세테이트(ACETATE)기 및 아민기를 갖고 있어, 습기에 의하여 서서히 도막표면으로 분출되게 되는 특성을 갖고 있다. 성분 D를 사용함에 있어서는 적절한 사용량에 주의하여야 한다. 특히 알콕시 경화형의 경우 경화를 지연시키는 단점이 있어, 사용량을 다른 경화기구에 비하여 적게 사용하여야 한다. 적절한 사용함량은 성분 A 100중량부에 대하여 0.1∼50중량부가 바람직하나, 가장 적절하게는 0.5∼30중량부가 바람직하다. 그러나 성분 C와 D의 사용이 필히 혼용되어야 하며, 합계 사용함량이 성분 A 100중량부에 대하여 60중량부 이상 넘지는 않아야 한다. 이러한 이유로는 60중량부를 초과할 경우 본 발명에서 요구되는 도막의 강도를 얻을 수 없기 때문이다.In the composition of the present invention, another surface lubricant is component D represented by the following general formula (3), which serves to improve the long-term antifouling property by being expressed on the surface in the coating film in the long term. These oils have at least one ether (ETHER) group, an acetate (ACETATE) group and an amine group in the molecule, and have a characteristic of being ejected to the coating film surface gradually by moisture. In using component D, care should be taken in the proper usage. 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 amount of use is preferably 0.1 to 50 parts by weight, most preferably 0.5 to 30 parts by weight based on 100 parts by weight of component A. However, the use of components C and D must be used interchangeably and their total content should not exceed 60 parts by weight relative to 100 parts by weight of component A. This is because the strength of the coating film required in the present invention cannot be obtained when it exceeds 60 parts by weight.

일반식 3 Formula 3

(여기서, m은 0∼5의 정수; x, y는 유리수; R3, R4는 상기와 동일; R5는 에테르기, 아세틸기, 아미노기, 카르보닐기 또는 폴리글리콜기를 1개 이상 가진 유기 잔기이다.)Where m is an integer of 0 to 5; x and y are free numbers; R 3 and R 4 are the same as above; R 5 is an organic residue having at least one ether, acetyl, amino, carbonyl or polyglycol group. .)

또한 본 발명의 조성물은, 도막의 강도 보강 및 점탄성 조절제 성분으로서 미분 실리카(fumed silica)(성분 E)를 더 포함할 수 있다. 미분 실리카의 사용량은 성분 A 100중량부에 대하여 1∼20중량부로 하는 것이 바람직하다. 1중량부 미만에서는 그 성능을 발휘하기 어렵고, 20중량부 이상에서는 도막특성이 나빠지는 경향이 있어 바람직하지 않다.In addition, the composition of the present invention may further include fumed silica (component E) as a strength reinforcement and viscoelastic modifier component of the coating film. The amount of finely divided silica is preferably 1 to 20 parts by weight based on 100 parts by weight of component A. If it is less than 1 weight part, the performance will hardly be exhibited, and in 20 weight part or more, a coating film characteristic tends to worsen, and it is unpreferable.

본 발명에서는 성분 A, B, C 및 D를 필수성분으로 하고, 선택성분으로서 성분 E를 더 사용할 수 있으며, 또한 첨가제로서 무기 및 유기안료를 조성에 맞게 조합할 수 있다.In the present invention, components A, B, C and D are essential components, component E may be further used as an optional component, and inorganic and organic pigments may be combined as additives according to the composition.

이하 실시예를 통하여 본 발명을 상세히 설명하며, 실시예에서의 단위는 중량부로 제한되며, 이러한 실시예가 본 발명을 한정하는 것은 아니다.Hereinafter, the present invention will be described in detail by way of example, and the units in the examples are limited to parts by weight, and the examples do not limit the present invention.

실시예Example

방오도료 제조Antifouling paint manufacturing

성분 AComponent A

A-1:말단이 알콕시이며, 분자량이 5000인 디메틸 실란A-1: Dimethyl silane having alkoxy at the terminal and molecular weight of 5000

A-2:말단이 하이드록시이며, 분자량이 5000인 디메틸페닐 실란A-2: Dimethylphenyl silane having hydroxyl at the end and molecular weight of 5000

A-3:말단이 하이드록시이며, 분자량이 1000인 디메틸 실란A-3: Dimethyl silane with hydroxyl at the end and molecular weight of 1000

성분 BComponent B

B-1:오소 티타네이트B-1: Oso titanate

B-2:메틸트리메톡시 실란B-2: methyltrimethoxy silane

B-3:디부틸 틴 라우릴레이트B-3: dibutyl tin laurate

성분 CComponent C

C-1:DC-550(다우코닝 제품)C-1: DC-550 (Dow Corning Products)

C-2:KF-56(신에츠 제품)C-2: KF-56 (Shin-Etsu)

성분 DComponent D

D-1:ISI4700(도시바 실리콘 제품, R5는 아미노기임)D-1: ISI4700 (Toshiba Silicone, R 5 is an amino group)

D-2:XI-42-411((도시바 실리콘 제품, R5는 카르보닐기임)D-2: XI-42-411 (Toshiba Silicon, R 5 is a carbonyl group)

D-3:SH-3700(도레이사 실리콘 제품, R5는 폴리글리콜기임)D-3: SH-3700 (Toray Silicone, R 5 is a polyglycol group)

표 1Table 1

실시예 1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 실시예7Example 7 실시예8Example 8 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3 비교예4Comparative Example 4 성분 AA-1A-2A-3Component AA-1A-2A-3 7070 6060 7070 6060 6060 7070 6060 5050 9090 8080 3030 2020 성분 BB-1B-2B-3Component BB-1B-2B-3 50.550.5 50.550.5 50.550.5 50.550.5 50.550.5 50.550.5 50.550.5 50.550.5 100.5100.5 50.550.5 50.550.5 50.550.5 성분 CC-1C-2Component CC-1C-2 1515 1010 1515 1515 1515 1515 1515 2020 -- 1515 4040 4040 성분 DD-1D-2D-3Component DD-1D-2D-3 1010 1515 1010 1010 1515 1515 1515 1010 -- -- 3030 4040 실리카Silica 33 33 33 33 33 33 33 33 33 33 33 33 자이렌Zyren 100100 100100 100100 100100 100100 100100 100100 100100 100100 100100 100100 100100 도막강도Coating strength 7575 8080 8585 7575 9595 9090 8585 8585 9090 8585 4545 4040

실험예Experimental Example

10cm ×130cm ×2mm 철판에 하도로 에폭시 도료를 도장후 7일간 건조한 다음, 상기 실시예들에서 제조된 방오도료를 건조 도막이 200 마이크론이 될 수 있도록 도장하여 5일간 건조하여, 동해안 수심 1m에 침적하여 방오성 시험을 하였고, 그 결과를 하기 표 2에 나타내었다.After coating epoxy coating with 10cm × 130cm × 2mm iron plate with a degree of drying for 7 days, the antifouling paint prepared in the above examples was coated so that the dry coating film could be 200 microns and dried for 5 days, and then deposited at 1m deep on the east coast. An antifouling test was carried out, and the results are shown in Table 2 below.

표 2. 방오성 시험결과Table 2. Antifouling test results

실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 실시예7Example 7 실시예8Example 8 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3 비교예4Comparative Example 4 3개월3 months OO OO OO OO OO OO OO OO OO OO OO OO 6개월6 months OO OO OO OO OO OO OO OO XX XX OO OO 12개월12 months OO OO OO OO OO OO OO OO -- -- OO OO 24개월24 months OO OO OO OO OO OO OO OO -- -- OO OO 36개월36 months OO OO OO OO OO OO OO OO -- -- OO OO

상기 표 2에서 나타난 것과 같이, 본 발명의 오일 성분들이 없는 경우(비교예 1, 2) 방오성이 불량하며, 오일의 함량이 많은 경우(비교예 3, 4) 방오성은 좋으나 도막의 강도가 약하여 선박용 도료로 적용하기 어렵다. 반면에 본 발명에 따른 실시예들의 도료는 방오성 뿐만 아니라 선박용에도 충분히 적용할 수 있는 우수한 도막강도를 제공할 수 있다.As shown in Table 2, when there are no oil components of the present invention (Comparative Examples 1 and 2), poor antifouling property, when the oil content is large (Comparative Examples 3, 4) good antifouling, but the strength of the coating film for ships Difficult to apply as paint On the other hand, the paints of the embodiments according to the present invention can provide excellent coating strength that can be sufficiently applied to marine use as well as antifouling properties.

이상에서 알 수 있는 바와 같이, 본 발명에 따른 방오도료 조성물은 방오성이 매우 우수할 뿐만 아니라, 선박용에도 충분히 적용할 수 있는 도막강도를 제공할 수 있으며, 해양구조물 취수구, 원자력 취수관 및 선저에 생물이 오염되는 것을 방지할 수 있다.As can be seen from the above, the antifouling coating composition according to the present invention is not only excellent in antifouling properties, but also can provide a coating film strength that can be sufficiently applied to ships, marine structures intake, nuclear intake pipes and ships This can be prevented from contamination.

Claims (6)

일반식 1의 바인더 성분 A, 경화촉진제 성분 B, 일반식 2의 오일 성분 C 및 일반식 3의 오일 성분 D를 포함하는 것을 특징으로 하는 방오도료 조성물:An antifouling coating composition comprising a binder component A of Formula 1, a curing accelerator component B, an oil component C of Formula 2 and an oil component D of Formula 3: 일반식 1 Formula 1 (여기서, n은 정수; R은 수소기, 수산기, 선상 가지상의 알킬기, 알콕시기, 산기, 시아닌기, 아미노기 또는 에폭시기; R1, R2는 각각 수소기, 수산기, 선상 가지상의 알킬기, 알콕시기, 알릴기 또는 불소함유 유기잔기이다.)(Where n is an integer; R is a hydrogen group, a hydroxyl group, a linear branched alkyl group, an alkoxy group, an acid group, a cyanine group, an amino group or an epoxy group; R 1 , R 2 are each a hydrogen group, a hydroxyl group, a linear branched alkyl group, or an alkoxy group) , Allyl or fluorine-containing organic residue.) 일반식 2 Formula 2 (여기서, n은 정수; R3는 알킬기 또는 알릴기; R4, R5는 각각 알킬기, 알릴기 또는 페닐기이다.)(Wherein n is an integer; R 3 is an alkyl group or an allyl group; R 4 , R 5 are each an alkyl group, an allyl group, or a phenyl group.) 일반식 3 Formula 3 (여기서, m은 0∼5의 정수; x, y는 유리수; R3, R4는 상기와 동일; R5는 에테르기, 아세틸기, 아미노기, 카르보닐기 또는 폴리글리콜기를 1개 이상 가진 유기 잔기이다.)Where m is an integer of 0 to 5; x and y are free numbers; R 3 and R 4 are the same as above; R 5 is an organic residue having at least one ether, acetyl, amino, carbonyl or polyglycol group. .) 제1항에 있어서, 성분 B는 티탄화합물, 실리콘화합물, 틴화합물 및 질코늄 화합물로 구성된 군에서 선택된 하나 이상의 화합물인 것을 특징으로 하는 방오도료 조성물.The antifouling coating composition according to claim 1, wherein component B is at least one compound selected from the group consisting of titanium compound, silicon compound, tin compound and zirconium compound. 제1항에 있어서, 성분 A 100중량부에 대하여 성분 B는 0.01∼30중량부, 성분 C는 0.5∼50중량부 및 성분 D는 0.1∼50중량부인 것을 특징으로 하는 방오도료 조성물.The antifouling coating composition according to claim 1, wherein component B is 0.01 to 30 parts by weight, component C is 0.5 to 50 parts by weight and component D is 0.1 to 50 parts by weight based on 100 parts by weight of component A. 제1항에 있어서, 성분 C 및 성분 D의 합계량이 성분 A 100중량부에 대하여 60중량부를 넘지 않는 것을 특징으로 하는 방오도료 조성물.The antifouling coating composition according to claim 1, wherein the total amount of component C and component D does not exceed 60 parts by weight with respect to 100 parts by weight of component A. 제1항 내지 제4항중 어느 한항에 있어서, 성분 E로서 실리카를 더 포함하는 것을 특징으로 하는 방오도료 조성물.The antifouling coating composition according to any one of claims 1 to 4, further comprising silica as component E. 제5항에 있어서, 실리카의 함량은 성분 A 100중량부에 대하여 1∼20중량부인 것을 특징으로 하는 방오도료 조성물.The antifouling coating composition according to claim 5, wherein the content of silica is 1 to 20 parts by weight based on 100 parts by weight of component A.
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