KR19980048619A - Coating composition - Google Patents
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- KR19980048619A KR19980048619A KR1019960067230A KR19960067230A KR19980048619A KR 19980048619 A KR19980048619 A KR 19980048619A KR 1019960067230 A KR1019960067230 A KR 1019960067230A KR 19960067230 A KR19960067230 A KR 19960067230A KR 19980048619 A KR19980048619 A KR 19980048619A
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09D5/16—Antifouling paints; Underwater paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/69—Particle size larger than 1000 nm
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Abstract
본 발명은 코팅용 조성물에 관한 것으로, 더욱 상세하게는 금속이나 비금속 기재의 표면에 코팅하여 내부식성, 내후성, 내약품성 등이 양호하면서 도막에 유연성을 부여하여 내충격성 및 내균열성을 향상시킬 수 있는 코팅용 조성물에 관한 것이다.The present invention relates to a coating composition, and more particularly, by coating on the surface of a metal or non-metallic substrate to improve the corrosion resistance, weather resistance, chemical resistance, etc., while providing flexibility to the coating film, thereby improving impact resistance and crack resistance. The present invention relates to a coating composition.
Description
본 발명은 코팅용 조성물에 관한 것으로, 더욱 상세하게는 금속이나 비금속 기재의 표면에 코팅하여 내부식성, 내후성, 내약품성 등이 양호하면서 도막에 유연성을 부여하여 내충격성 및 내균열성을 향상시킬 수 있는 코팅용 조성물에 관한 것이다.The present invention relates to a coating composition, and more particularly, by coating on the surface of a metal or non-metallic substrate to improve the corrosion resistance, weather resistance, chemical resistance, etc., while providing flexibility to the coating film, thereby improving impact resistance and crack resistance. The present invention relates to a coating composition.
최근 내열성, 내식성, 내비등수성, 내약품성, 내수성, 내마모성, 내후성, 밀착성 등이 우수하고 또한 저온 경화시킬 수 있으며 내균열성이 우수한 코팅용 조성물이 요구되고 있다. 이와같은 요구의 일부를 만족시키는 실리카-유기금속알콕시 실란계 코팅조성물로서는 일본특허공고 제39691호(1977년), 일본특허공개 제87736호(1979년), 미합중국특허 제3,986,997호 등에 제안되어 있다.Recently, there is a need for a coating composition that is excellent in heat resistance, corrosion resistance, boiling resistance, chemical resistance, water resistance, abrasion resistance, weather resistance, adhesiveness, low temperature curing, and excellent crack resistance. As a silica-organic metal alkoxy silane-based coating composition that satisfies some of these demands, Japanese Patent Publication No. 39691 (1977), Japanese Patent Publication No. 87736 (1979), US Patent No. 3,986,997 and the like have been proposed.
그러나, 상기 종래의 코팅용 조성물은 다음과 같은 문제점이 지적되어 왔다.However, the following problems of the conventional coating composition has been pointed out.
첫째, 코팅두께를 10 ㎛ 이하로 조정해야 하는데 만일 이 도막두께 이상으로 두꺼울 경우 도막에서 열적수축으로 인하여 가속 내후성 시험 및 이와 유사한 시험에 의해 균열이 발생한다.First, the coating thickness should be adjusted to 10 μm or less. If it is thicker than this film thickness, cracking occurs by accelerated weather resistance test and similar test due to thermal shrinkage in the film.
둘째, 도막의 경도가 높고 유연성이 없기 때문에 내충격성이 약하고 기재와 도막의 열적수축팽창율의 차이로 인하여 장기적으로 도막의 균열이 발생될 수 있으며 이로 인해 기재의 부식을 초래할 수 있다.Second, since the hardness of the coating film is high and there is no flexibility, the impact resistance is weak and the crack of the coating film may be generated in the long term due to the difference in thermal contraction expansion rate between the substrate and the coating film, which may cause corrosion of the substrate.
이와같은 문제점으로 인하여 실리카-유기관능성알콕시 실란계 코팅조성물은 내후성, 내수성, 내비등수성, 내오염성 등이 우수함에도 불구하고 그 사용에 제한을 받고 있는 실정이다.Due to these problems, silica-organic functional alkoxy silane-based coating composition is limited in its use despite its excellent weather resistance, water resistance, boiling resistance, and fouling resistance.
본 발명은 무기수지와의 상용성이 양호한 저분자량의 유기수지인 불포화 에틸렌 모노머를 사용하여 무기수지의 빈약한 유연성을 유기수지에 의해 보완하여 도막의 내균열성이 우수하고 또한 얻어지는 도막이 내후성, 내수성, 내약품성, 내오염성 및 기재와의 밀착성이 우수한 코팅용 조성물을 제공하는 데 그 목적이 있다.The present invention uses an unsaturated ethylene monomer, which is a low molecular weight organic resin having good compatibility with inorganic resins, to compensate for the poor flexibility of inorganic resins with organic resins, thereby providing excellent crack resistance of the coating film, and the resulting coating film has excellent weather resistance, water resistance, It is an object of the present invention to provide a coating composition excellent in chemical resistance, stain resistance and adhesion to a substrate.
본 발명은 코팅용 조성물에 있어서, 가) 다음 화학식 1로 표시되는 유기관능성알콕시실란 30 ∼ 60 중량부와 수분산성 실리카 40 ∼ 70 중량부의 혼합물을 가수분해시켜 얻은 실리카-유기관능성알콕시실란 합성물 30 ∼ 60 중량%; 나) 친수성 유기용제 20 ∼ 50 중량%; 다) 불포화 에틸렌 수지 10 ∼ 20 중량%; 라) 표면활성제 0.1 ∼ 5.0 중량%; 그리고 마) 경화촉매 0.1 ∼ 2.0 중량%로 구성된 것을 그 특징으로 한다.In the coating composition, a) a silica-organic functional alkoxysilane compound obtained by hydrolyzing a mixture of 30 to 60 parts by weight of an organofunctional alkoxysilane represented by the following formula (1) and 40 to 70 parts by weight of a water dispersible silica: 30 to 60 wt%; B) 20 to 50% by weight of a hydrophilic organic solvent; C) 10 to 20% by weight of unsaturated ethylene resin; D) 0.1 to 5.0% by weight of surfactant; And e) 0.1 to 2.0% by weight of a curing catalyst.
[화학식 1][Formula 1]
R4-nSi(OR')n R 4-n Si (OR ') n
상기식에서,In the above formula,
R은 탄소원자수 1 ∼ 5의 알킬기, 탄소원자수 1 ∼ 5의 할로알킬기, 탄소원자수 1 ∼ 5의 알케닐기, 페닐기, 탄소원자수 1 ∼ 8의 에폭시알킬기이고;R is an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a phenyl group and an epoxy alkyl group having 1 to 8 carbon atoms;
R'는 탄소원자수 1 ∼ 5의 알킬기 또는 탄소원자수 1 ∼ 4의 아실기이고;R 'is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms;
n은 2 또는 3이다.n is 2 or 3.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명에서 사용된 실리카-유기관능성알콕시실란 합성물은 코팅용 조성물의 결합제로서 작용하는 바, 이는 유기관능성알콕시실란과 수분산성 실리카를 가수분해반응시켜 제조한다. 본 발명의 실리카-유기관능성알콕시실란 합성물의 제조방법은 1단계로 수분산성 실리카에 상기 화학식 1로 표시되는 유기관능성알콕시실란(n=3)을 투입하여 가수분해반응을 시켜 수분산성 실리카의 표면을 개질시키고, 2단계로 1단계에서 얻어진 합성반응물에 화학식 1로 표시되는 유기관능성알콕시실란(n=2) 즉, 가수분해성 유기관능기를 갖는 이방향성 실란화합물을 서서히 첨가하며 3 ∼ 5시간동안 교반을 통해 실리카-유기관능성알콕시실란 합성물을 제조한다.The silica-organofunctional alkoxysilane composite used in the present invention acts as a binder of the coating composition, which is prepared by hydrolyzing an organofunctional alkoxysilane and a water dispersible silica. In the method of preparing the silica-organofunctional alkoxysilane composite of the present invention, the organic functional alkoxysilane (n = 3) represented by the formula (1) is added to the water dispersible silica in one step to perform a hydrolysis reaction to obtain a water dispersible silica. 3 to 5 hours while modifying the surface, gradually adding an organofunctional alkoxysilane represented by the formula (1), that is, a bidirectional silane compound having a hydrolyzable organic functional group, to the synthesis reaction obtained in step 1 in 2 steps. Silica-organofunctionalalkoxysilane composites are prepared via stirring.
실리카-유기관능성알콕시실란 합성물 제조시 사용되는 상기 화학식 1로 표시되는 유기관능성알콕시실란에 있어서, R을 보다 구체화하면 메틸기, 에틸기, 프로필기 등의 알킬기, γ-클로로프로필기, 페닐기, 비닐기, 3,4-에톡시사이크로헥실에틸기, γ-글리시독시프로필기, γ-메타크릴옥시프로필기, γ-머캅토프로필기 등이 있다. 또한 R'를 보다 구체화하면, 메틸기, 에틸기, 프로필기, 부틸기, 아세틸기 등이 있다. 이들 유기관능성알콕시실란을 구체적으로 예시하면, 메틸트리메톡시실란, 메틸트리에톡시실란, 페닐트리메톡시실란, β-(3,4-에톡시사이클로헥실)-트리에폭시실란, γ-글리시톡시프로필트리메톡시실란, γ-머캅토프로필트리메톡시실란, γ-메타크릴옥시프로필트리메톡시실란, 디메틸디메톡시실란, 디메틸디에톡시실란, 디페닐디메톡시실란 등을 들 수 있다. 이들 유기관능성알콕시실란은 단독 사용하여도 좋으나, 보다 바람직하기로는 2종 이상을 병용하는 것이다.In the organofunctional alkoxysilane represented by the formula (1) used in the preparation of the silica-organofunctional alkoxysilane compound, R is more specifically, an alkyl group such as methyl group, ethyl group, or propyl group, γ-chloropropyl group, phenyl group, vinyl Groups, 3,4-ethoxycyclohexylethyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, and the like. When R 'is further specified, there are methyl group, ethyl group, propyl group, butyl group, acetyl group and the like. Specific examples of these organofunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, β- (3,4-ethoxycyclohexyl) -triepoxysilane and γ-gly Methoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and the like. Although these organofunctional alkoxysilanes may be used independently, More preferably, they use 2 or more types together.
실리카-유기관능성알콕시실란 합성물 제조시 사용되는 수분산성 실리카로는 pH가 3 ∼ 5이고, 고형분 함량이 10 ∼ 33 중량%이고, 입자크기가 5 ∼ 20 ㎛인 산성 형태의 수분산성 실리카를 사용하거나, 또는 pH가 8.5 ∼ 10.5이고, 고형분 함량이 20 ∼ 50 중량%이고, 입자크기가 5 ∼ 20 ㎛인 알카리성 형태의 수분산성 실리카를 사용할 수 있다. 알카리성 형태의수분산성 실리카를 사용할 경우 염산, 황산, 질산, 아세트산, 아크릴산류와 같은 산성의 pH변환제를 사용하여 알카리성 형태를 산성화시켜야 한다. 만일 알카리성 형태의 수분산성 실리카를 그대로 사용할 경우 가수분해 반응시 유기관능성알콕시실란과의 반응이 지연되어 겔화될 수 있다.As the water dispersible silica used for preparing the silica-organofunctional alkoxysilane compound, an acid dispersible silica having a pH of 3 to 5, a solid content of 10 to 33% by weight, and a particle size of 5 to 20 μm is used. Alternatively, water-dispersible silica in alkaline form having a pH of 8.5 to 10.5, a solid content of 20 to 50% by weight, and a particle size of 5 to 20 μm can be used. If alkaline dispersible silica is used, acidic pH conversion agents such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid and acrylic acid should be used to acidify the alkaline form. If the alkaline dispersible silica is used as it is, the reaction with the organofunctional alkoxysilane may be delayed and gelate during the hydrolysis reaction.
상기 실리카-유기관능성알콕시실란에서 사용되는 수분산성 실리카의 고형분 함량이 10 중량% 미만이면 도막 경도가 저하하고 후도막화가 어려우며, 50 중량%를 초과할 경우 도막의 균열이 발생될 수 있으며 내충격성이 저하된다. 또한 n=3인 유기관능성알콕시실란으로는 메틸트리메톡시실란, 메틸트리에톡시실란을 사용하고, n=2인 유기관능성알콕시실란으로는 디메틸디메톡시실란, 디메틸디에톡시실란을 사용하는 것이 경도와 수익성의 관점에서 바람직하다. 그리고, n=3인 유기관능성알콕시실란과 n=2인 유기관능성알콕시실란의 비율은 중량비로 1 : 0.5 ∼ 1 : 1 정도가 양호하다. 만일 그 중량비가 1 : 0.5 미만일 경우 합성물의 저장 안정성이 떨어지고 1 : 1을 초과할 경우 도막의 경도, 저장안정성 등이 저하된다.If the solid content of the water-dispersible silica used in the silica-organofunctional alkoxysilane is less than 10% by weight, the coating film hardness is lowered and the thickening of the film is difficult, and when the content exceeds 50% by weight, cracking of the coating film may occur and impact resistance is achieved. Is lowered. In addition, methyltrimethoxysilane and methyltriethoxysilane are used as n = 3 organic functional alkoxysilane, and dimethyldimethoxysilane and dimethyldiethoxysilane are used as n = 2 organic functional alkoxysilane. It is preferable from the viewpoint of hardness and profitability. And the ratio of the organic functional alkoxysilane of n = 3 and the organic functional alkoxysilane of n = 2 is about 1: 0.5-1: 1 by weight ratio. If the weight ratio is less than 1: 0.5, the storage stability of the composite is lowered. If the weight ratio is greater than 1: 1, the hardness, storage stability, etc. of the coating film are lowered.
상기와 같은 제조방법에 의해 제조된 실리카-유기관능성알콕시실란 합성물은 본 발명의 코팅용 조성물중에 30 ~ 60 중량% 함유되는 것이 바람직하다. 실리카-유기관능성알콕시실란 합성물의 함량이 30 중량% 미만이면 도막의 경도, 내오염성, 내후성 등이 저하되고, 60 중량%를 초과하면 내균열성, 내충격성, 저장안정성 등이 저하된다.The silica-organofunctional alkoxysilane composite prepared by the above production method is preferably contained in 30 to 60% by weight in the coating composition of the present invention. When the content of the silica-organofunctional alkoxysilane compound is less than 30% by weight, the hardness, fouling resistance, weather resistance, etc. of the coating film are lowered, and when it exceeds 60% by weight, crack resistance, impact resistance, storage stability, and the like are lowered.
또한, 본 발명에 따른 코팅용 조성물에 함유되는 친수성 유기용제는 실리카-유기관능성알콕시실란 합성물의 저장안정성과 불포화 에틸렌 수지와의 상용성을 부여하며, 조성물의 고형분을 조정하고 조성물의 분산 안정성과 도장 안정성을 향상시킨다. 이러한 친수성 유기용제로서는 메탄올, 에탄올, 노르말프로필알코올, 이소프로필알코올, 테트라부틸알코올, 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 에틸렌글리콜모노부틸에테르, 아세트산에틸렌글리콜모노에틸에테르 등을 들 수 있다. 이들 친수성 유기용제는 단독 사용하여도 좋으나, 2종 이상 병용하면 도장 작업성과 향상된 도막외관을 얻을 수 있다.In addition, the hydrophilic organic solvent contained in the coating composition according to the present invention imparts the storage stability of the silica-organic functional alkoxysilane compound and compatibility with an unsaturated ethylene resin, adjusts the solid content of the composition, Improve paint stability. Examples of such hydrophilic organic solvents include methanol, ethanol, normal propyl alcohol, isopropyl alcohol, tetrabutyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and the like. These hydrophilic organic solvents may be used alone, but when used in combination of two or more, it is possible to obtain coating workability and improved coating appearance.
친수성 유기용제는 본 발명의 코팅용 조성물중에 20 ~ 50 중량% 함유되는 것이 바람직하다. 친수성 유기용제의 함량이 20 중량% 미만이면 조성물의 보존 안정성이 저하되고 점도의 상승으로 인하여 도막의 불균일화를 초래할 수 있고, 50 중량%를 초과하면 도막의 내균열성, 광택이 저하되고 후도막화가 불가능하게 된다.The hydrophilic organic solvent is preferably contained 20 to 50% by weight in the coating composition of the present invention. When the content of the hydrophilic organic solvent is less than 20% by weight, the storage stability of the composition may be lowered, and the viscosity may be increased, resulting in unevenness of the coating film. When the content of the hydrophilic organic solvent is higher than 50% by weight, the crack resistance and gloss of the coating film may be reduced, and the thick film may be Anger becomes impossible.
또한, 본 발명에 따른 코팅용 조성물에 함유되는 불포화 에틸렌 수지로는 메타아크릴레이트, 에틸아크릴레이트, 2-에틸헥실아크릴레이트, 테트라부틸아크릴레이트, 2-하이드록시에틸아크릴레이트, 2-하이드록시프로필아크릴레이트, 메틸메타아크릴레이트, 에틸메타아크릴레이트, 노르말부틸아크릴레이트, 이소부틸아크릴레이트, 테트라부틸메타아크릴레이트, 글리시딜메타아크릴레이트, 2-하이드록시에틸아크릴레이트, 2-하이드록시프로필메타아크릴레이트, 디메틸아미노에틸메타아크릴레이트, 디에틸아미노에틸메타아크릴레이트, 2-에틸헥실메타아크릴레이트, 메톡시디에틸렌글리콜아크릴레이트, 메톡시디에틸렌글리콜아크릴레이트, 메톡시테트라에틸렌글리콜메타아크릴레이트 등의 불포화 에틸렌 모노머 중에서 선택된 1종 또는 2종 이상을 중합시켜 제조한 것이다. 이러한 불포화 에틸렌 수지의 폴리스티렌 환산 중량평균분자량은 1000 ∼ 10000 정도인 것을 사용한다. 분자량이 1000 미만이면 실리카-유기관능성알콕시실란과의 상용성은 양호하나 도막의 밀착성과 내균열성이 저하되고, 10000을 초과하면 조성물의 보존 안정성과 상용성 그리고 도막의 경도가 저하된다.In addition, the unsaturated ethylene resin contained in the coating composition according to the present invention is methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, tetrabutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, methyl methacrylate, ethyl methacrylate, normal butyl acrylate, isobutyl acrylate, tetrabutyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl meth Acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-ethylhexyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxy tetraethylene glycol methacrylate, etc. One or two or more selected from unsaturated ethylene monomers To be manufactured sum. The polystyrene reduced weight average molecular weight of such unsaturated ethylene resin uses about 1000-10000. If the molecular weight is less than 1000, compatibility with the silica-organofunctional alkoxysilane is good, but adhesion and crack resistance of the coating film are lowered, and if it exceeds 10000, storage stability and compatibility of the composition and hardness of the coating film are lowered.
불포화 에틸렌 수지는 본 발명의 코팅용 조성물중에 10 ~ 20 중량% 함유되는 것이 바람직하다. 만약, 불포화 에틸렌 수지의 함량이 10 중량% 미만이면 도막 경화시 발생되는 열적수축에 의한 균열을 방지할 수 없으며 도막의 내충격성을 개선할 수 없게 된다. 또한 불포화 에틸렌 수지의 함량이 20 중량부를 초과하면 도막의 경도, 상용성, 내오염성, 내후성 등이 저하된다.The unsaturated ethylene resin is preferably contained 10 to 20% by weight in the coating composition of the present invention. If the content of the unsaturated ethylene resin is less than 10% by weight, it is not possible to prevent cracks due to thermal contraction generated during coating film curing and to improve the impact resistance of the coating film. In addition, when the content of the unsaturated ethylene resin exceeds 20 parts by weight, the hardness, compatibility, fouling resistance, weather resistance, etc. of the coating film is lowered.
또한, 본 발명에 따른 코팅용 조성물에 함유되는 표면활성제로는 조성물의 가공성과 기재 도포시 균일한 도장성을 위해 사용되는 것으로서, 비온계, 양이온계, 음이온계가 사용될 수 있으며, 특히 조성물의 보존안정성을 위해서는 비이온계를 사용하는 것이 바람직하다. 비이온계 표면활성제로는 폴리에틸렌글리콜, 폴리하이드릭알콜, 폴리에틸렌아민, 아세틸렌알콜, 플루오르화 알킬기나 실리콘을 함유하는 화합물이 적당하다.In addition, as the surface active agent contained in the coating composition according to the present invention, which is used for uniformity in processability of the composition and coating the substrate, nonionic, cationic, and anionic systems may be used, and in particular, the storage stability of the composition For this purpose, it is preferable to use a nonionic system. As the nonionic surfactant, a compound containing polyethylene glycol, polyhydric alcohol, polyethyleneamine, acetylene alcohol, alkyl fluorinated group or silicone is suitable.
표면활성제는 본 발명의 코팅용 조성물중에 0.1 ~ 5.0 중량% 함유되는 것이 바람직하다. 만약, 표면 활성제의 함량이 0.1 중량% 미만이면 첨가효과를 기대할 수 없고, 5.0 중량%를 초과하면 기재와의 부착성이 저하되며, 내수성, 내오염성, 내후성 등의 물성이 불량하게 된다.The surface active agent is preferably contained 0.1 to 5.0% by weight in the coating composition of the present invention. If the content of the surface active agent is less than 0.1% by weight, the effect of addition cannot be expected. If the content of the surface active agent exceeds 5.0% by weight, the adhesion to the substrate is lowered, and the physical properties such as water resistance, fouling resistance and weather resistance are poor.
또한, 본 발명에 따른 코팅용 조성물에 함유되는 경화촉매는 조성물을 저온에서도 빠르게 경화시키기 위해서 사용하는 것으로서, 티탄네이트 화합물, 알칼리성 화합물, 산성 화합물, 아민 화합물 및 아민계 실란 화합물중에서 선택된 1종 또는 2종 이상을 병용한다. 예컨대, 티탄네이트 화합물으로는 테트라이소프로필티탄네이트, 테트라부틸티탄네이트, 테트라메틸티탄네이트, 테트라에틸헥실티탄네이트, 트리에탄올아민티탄네이트, 티타늄아세톤티탄네이트, 티타늄락테이트, 이소프로필티타늄이소스티레이트 등을 사용한다. 알칼리성 화합물로는 수산화칼륨, 수산화나트륨 등을 사용한다. 산성 화합물로는 알킬티탄산, 인산, 톨루엔술포산, 프탈산 등을 사용한다. 아민 화합물로는 에틸렌아민, 헥산디아민, 디에틸렌트리아민, 트리에틸렌트리아민, 트리에틸렌테트라아민, 테트라에틸렌펜타아민, 피페리딘, 피페라진, 메타페닐디아민, 에탄올아민, 트리에틸아민 등을 사용한다. 아민계 실란 화합물으로는 γ-아미노프로필트리에톡시실란, γ-(2-아미노에틸)-아미노프로필트리메톡시실란, γ-(2-아미노에틸)-아미노프로필메틸디메톡시실란, γ-아닐리노프로필트리메톡시실란 등이 사용된다.In addition, the curing catalyst contained in the coating composition according to the present invention is used to rapidly cure the composition even at low temperature, and at least one selected from a titanate compound, an alkaline compound, an acidic compound, an amine compound and an amine silane compound. Use more than one species together. For example, as the titanate compound, tetraisopropyl titanate, tetrabutyl titanate, tetramethyl titanate, tetraethylhexyl titanate, triethanolamine titanate, titanium acetone titanate, titanium lactate, isopropyl titanium isostyrene Etc. Potassium hydroxide, sodium hydroxide, etc. are used as an alkaline compound. Alkyl titanic acid, phosphoric acid, toluenesulfonic acid, phthalic acid, etc. are used as an acidic compound. Ethyleneamine, hexanediamine, diethylenetriamine, triethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, piperidine, piperazine, metaphenyldiamine, ethanolamine, triethylamine, etc. are used as the amine compound. do. Examples of the amine-based silane compounds include γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, and γ-anyl Linopropyltrimethoxysilane and the like are used.
경화촉매는 본 발명의 코팅용 조성물중에 0.1 ~ 2.0 중량% 함유되는 것이 바람직하다. 경화촉매의 함량이 0.1 중량% 미만이면 경화온도가 높아지고 경화속도가 느려지며, 2.0 중량%를 초과하면 조성물의 점도 상승과 경화속도가 빨라서 도장 작업성이 저하된다.The curing catalyst is preferably contained 0.1 to 2.0% by weight in the coating composition of the present invention. If the content of the curing catalyst is less than 0.1% by weight, the curing temperature is increased and the curing speed is slow. If the content of the curing catalyst is more than 2.0% by weight, the viscosity of the composition is increased and the curing speed is increased, thereby decreasing the painting workability.
상기에서 설명한 바와 같은 본 발명의 코팅용 조성물로 피복할 수 있는 기재로는 알루미늄, 알루미늄 합금, 스테인레스, 세라믹, 시멘트, 철, 철합금 등이 있다.Substrates which can be coated with the coating composition of the present invention as described above include aluminum, aluminum alloy, stainless, ceramic, cement, iron, iron alloy and the like.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
제조예 1 ~ 5: 실리카-유기관능성알콕시실란 합성물의 제조Preparation Examples 1 to 5: Preparation of Silica-organofunctional Alkoxysilane Compounds
다음 표1과 같은 조성으로 수분산성 실리카에 실란화합물을 서서히 첨가하는데 이때 교반속도는 100 ∼ 200 rpm 정도로 하고 실란화합물의 전체 첨가시간은 3 ∼ 4시간으로 조정하여야 하며 반응온도는 25 ∼ 30 ℃ 정도를 유지한다. 합성물의 안정성과 고형분 함량을 조절하기 위해 유기용제로서 이소프로필알콜을 첨가하였다.The silane compound is slowly added to the water-dispersible silica with the composition shown in Table 1, where the stirring speed is about 100 to 200 rpm, and the total time for adding the silane compound is adjusted to 3 to 4 hours, and the reaction temperature is about 25 to 30 ° C. Keep it. Isopropyl alcohol was added as an organic solvent to control the stability and solid content of the composite.
[표 1]TABLE 1
제조예 6 ~ 10: 불포화 에틸렌 수지의 제조Preparation Examples 6 to 10: Preparation of Unsaturated Ethylene Resin
환류냉각기와 교반기가 장치된 반응기에 메틸아크릴레이트, 테트라부틸메타아크릴레이트, 2-하이드록시에틸아크릴레이트, 메틸메타아크릴레이트가 1/1/1/1 중량비로 혼합되어 있는 모노머 혼합물을 이소프로필알코올과 아세트산에틸렌글리콜모노에틸에테르이 1/2 중량비로 혼합된 혼합용제에 희석하였다. 질소 개스하에서 중합 개시제로 아조비스이소부티로나트릴(AIBN)을 첨가하고 80℃의 온도에서 약 8시간동안 중합반응을 실행하였다. 이때 혼합용제와 중합개시제의 첨가량을 조절하여 4종의 중량평균분자량을 갖는 불포화 에틸렌 수지를 제조하고, 에틸렌글리모노부틸에테르를 첨가하여 이들의 고형분 함량이 30 중량%가 되도록 조절하였다.A monomer mixture containing methyl acrylate, tetrabutyl methacrylate, 2-hydroxyethyl acrylate, and methyl methacrylate in a 1/1/1/1 weight ratio in a reactor equipped with a reflux cooler and a stirrer isopropyl alcohol And ethylene glycol monoethyl ether were diluted in a mixed solvent mixed in a 1/2 weight ratio. Azobisisobutyronitrile (AIBN) was added as a polymerization initiator under nitrogen gas, and polymerization was carried out at a temperature of 80 ° C. for about 8 hours. At this time, the amount of the mixed solvent and the polymerization initiator was adjusted to prepare an unsaturated ethylene resin having four weight average molecular weights, and ethyleneglycol butyl ether was added to adjust the solids content to 30% by weight.
[표 2]TABLE 2
실시예 1 ~ 7 및 비교예 1 ~ 3: 코팅용 조성물의 제조Examples 1 to 7 and Comparative Examples 1 to 3: Preparation of the coating composition
다음 표3의 조건으로 코팅용 조성물을 제조하였다.To prepare a coating composition under the conditions of the following Table 3.
[표 3]TABLE 3
실험예Experimental Example
실시예 1 ~ 7과 비교예 1 ~ 3에서 제조된 코팅용 조성물의 각각을 탈지 전처리된 알루미늄 시편(7cm × 15cm × 3T)에 20 ㎛의 도막두께로 도포하고 150 ℃/30분동안 가열 경화시킨 후 다음과 같은 시험을 통해 도막의 물성을 시험하였다. 그 결과는 다음 표4에 나타내었다.Each of the coating compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 was applied to a degreasing pretreated aluminum specimen (7 cm × 15 cm × 3T) with a film thickness of 20 μm and heat cured for 150 ° C./30 minutes. Then, the physical properties of the coating film were tested through the following test. The results are shown in Table 4 below.
가) 부착성 시험: KS D6711-92 기준에 의한 2 mm/2 mm 크로스컷(Cross Cut)한 후 테이프 박리시험을 실시함A) Adhesion test: Tape peel test after 2 mm / 2 mm cross cut according to KS D6711-92 standard
나) 연필경도: KS D6711-92 기준에 의한 45。/1 kg 하중으로 1 cm를 5회 긋는 시험B) Pencil hardness: Test to draw 1 cm 5 times with 45。/1 kg load according to KS D6711-92 standard
다) 내후성: KS D6711-92 기준에 의한 썬샤인 웨더 미터(sunshine weater meter) 5000시간 조사시험을 행하여 도막의 상태를 관찰함C) Weatherability: 5000 hours of sunshine weater meter test according to KS D6711-92 standard is used to observe the condition of coating film.
라) 내오염성: KS D6711-92 기준에 의한 5% 염수를 1000시간 분무시험 후 도막의 외관을 관찰함D) Pollution resistance: Observe the appearance of coating after spraying 1000% of 5% saline solution according to KS D6711-92 standard.
마) 내산성: KS D6711-92 기준에 의한 5% 황산수용액을 도막상에 1 ㎖를 적가하여 1일 경과 후 도막외관 관찰함E) Acid resistance: 1 ml of 5% sulfuric acid solution according to KS D6711-92 standard was added dropwise onto the coating film, and the appearance of the coating film was observed after 1 day.
바) 내비등수성: 비등수 2시간 침적 후 도막상태 관찰함F) Boiling water resistance: Observe the coating state after 2 hours of boiling water deposition.
사) 내용제성: 도막을 이소프로필알콜, 메틸에틸케톤, 톨루엔으로 100회 문지름G) Solvent resistance: Rub the coating film 100 times with isopropyl alcohol, methyl ethyl ketone and toluene.
[표 4]TABLE 4
본 발명의 코팅용 조성물은 도막의 내균열성이 우수하고 또한 얻어지는 도막이 내후성, 내수성, 내약품성, 내오염성 및 기재와의 밀착성이 우수하므로 알루미늄, 알루미늄 합금, 스테인레스, 세라믹, 시멘트, 철, 철합금 등의 피복재료로 유용하다.The coating composition of the present invention is excellent in crack resistance of the coating film, and the resulting coating film is excellent in weather resistance, water resistance, chemical resistance, fouling resistance and adhesion to the base material, such as aluminum, aluminum alloy, stainless steel, ceramic, cement, iron, iron alloy. It is useful as a coating material, for example.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100315629B1 (en) * | 1999-09-16 | 2001-12-12 | 박호군 | Silica-based binder and its preparation method |
| KR101042252B1 (en) * | 2008-12-30 | 2011-06-17 | 한국생산기술연구원 | Coating composition and for the improvement of compactness and smoothness of silica coating and method of forming coating |
| KR20220162294A (en) * | 2021-06-01 | 2022-12-08 | 주식회사 포스코건설 | Eco-friendly biodegracable resin based dust reducing agent and manufacturing method thereof |
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| KR101032486B1 (en) | 2007-12-27 | 2011-05-04 | 동부제철 주식회사 | Nano inorganic coating composition and manufacturing method of a zinc coated steel using the same |
| KR101571834B1 (en) | 2013-08-12 | 2015-12-04 | 주식회사 태광뉴텍 | Coating composition and method for manufacturing of the same |
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| JP2559598B2 (en) * | 1987-09-09 | 1996-12-04 | 大阪有機化学工業株式会社 | Coating composition |
| JPH0598212A (en) * | 1991-10-08 | 1993-04-20 | Nissan Chem Ind Ltd | Coating composition |
| JPH069928A (en) * | 1992-06-26 | 1994-01-18 | Okitsumo Kk | Heat-resistant polysiloxane coating composition |
| JPH06248197A (en) * | 1993-02-26 | 1994-09-06 | Asahi Tec Corp | Inorganic high-molecular composite coating material and structure of aluminum or aluminum alloy member coated therewith |
| KR0177322B1 (en) * | 1996-02-07 | 1999-04-01 | 성재갑 | Abrasion resistant coating composition with excellent weather resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100315629B1 (en) * | 1999-09-16 | 2001-12-12 | 박호군 | Silica-based binder and its preparation method |
| KR101042252B1 (en) * | 2008-12-30 | 2011-06-17 | 한국생산기술연구원 | Coating composition and for the improvement of compactness and smoothness of silica coating and method of forming coating |
| KR20220162294A (en) * | 2021-06-01 | 2022-12-08 | 주식회사 포스코건설 | Eco-friendly biodegracable resin based dust reducing agent and manufacturing method thereof |
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