KR101314011B1 - Rust resisting paint composition for vessel - Google Patents
Rust resisting paint composition for vessel Download PDFInfo
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- KR101314011B1 KR101314011B1 KR1020060137887A KR20060137887A KR101314011B1 KR 101314011 B1 KR101314011 B1 KR 101314011B1 KR 1020060137887 A KR1020060137887 A KR 1020060137887A KR 20060137887 A KR20060137887 A KR 20060137887A KR 101314011 B1 KR101314011 B1 KR 101314011B1
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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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- C08K2003/0812—Aluminium
Abstract
본 발명은 에폭시 당량이 100~750g/eq인 에폭시 수지 15~50중량%, 지방산 유도체 조성물 1~30중량%, 알루미늄 플레이크(Flake) 안료 4~50중량% 및 아민계 경화제와 폴리아미드계 경화제 중 1종 이상의 경화제 2~20중량%를 포함하는 선박용 방식 도료 조성물에 관한 것이다. 본 발명에 의한 선박용 방식 도료 조성물은, 선박의 외판, 카고 홀드부 및 밸러스트 탱크부와 같은 주요부위에 사용되는 경우, 내수성, 내해수성, 방청성, 내크랙성 및 흐름성이 모두 우수한 효과를 나타낸다.The present invention is 15 to 50% by weight epoxy resin 100 ~ 750g / eq epoxy resin, 1 to 30% by weight fatty acid derivative composition, 4 to 50% by weight of aluminum flake (Flake) and amine-based curing agent and polyamide-based curing agent It relates to a marine anticorrosive coating composition comprising 2 to 20% by weight of one or more curing agents. The anticorrosive coating composition for ships according to the present invention exhibits excellent effects in all of water resistance, seawater resistance, rust resistance, crack resistance and flowability when used in major parts such as outer shells, cargo hold sections and ballast tank sections of ships.
방식 도료 조성물, 지방산 유도체, 알루미늄 플레이크 안료Anticorrosive coating composition, fatty acid derivative, aluminum flake pigment
Description
도 1은 시편의 내크랙성(crack resistance)을 관찰하기 위하여 적용된 시간대별 온도 조건을 그래프로 나타낸 것이다.1 is a graph showing the time-phase temperature conditions applied to observe the crack resistance (crack resistance) of the specimen.
본 발명은 에폭시 수지, 경화제, 알루미늄 플레이크(flake) 안료 및 지방산 유도체 조성물을 포함하는 것을 특징으로 하는 선박용 방식 도료 조성물에 관한 것이다.The present invention relates to a marine anticorrosive coating composition comprising an epoxy resin, a curing agent, an aluminum flake pigment and a fatty acid derivative composition.
현재 사용되는 선박용 에폭시 도료는 1회 도장시 건조 도막 두께가 100~150㎛ 정도로 도장 가능한 도료들이 주종을 이루고 있으나, 고도의 방청성능을 요구하는 워터 밸러스트 탱크(water ballast tank) 내부에 도장되는 도료의 경우에는, 건조 도막 두께가 300~400㎛ 정도를 요구하고 있다. Currently used epoxy paints for ships are mainly made of paints with a dry film thickness of 100 ~ 150㎛ in one coating. However, paints applied inside water ballast tanks requiring high rust prevention performance. In the case, dry coating film thickness is about 300-400 micrometers.
그러나, 일반적으로 고 고형분(high solid) 타입의 도료의 경우, 오랜 저장기간 중 도료의 점도가 저하되는 현상이 발생할 수 있으며, 이에 따라 실제 수직면 부위에 도장 작업시 요구하는 도막 두께 내에서 흐름현상(sagging)이 발생하게 된다. 이렇게 발생된 흐름현상은 작업자들에 의해 제거되며, 재도장(respray)된다. 이러한 과정은 작업시간을 늘릴 뿐만 아니라, 추가적인 인건비와 적용 도료 비용이 발생되는 문제점이 있었다.However, in general, in the case of a high solid type coating, the viscosity of the coating material may decrease during the long storage period. Accordingly, the flow phenomenon sagging will occur. The flow phenomenon thus generated is removed by workers and resprayed. This process not only increases work time but also incurs additional labor costs and applied paint costs.
일반적으로, 도료 배합 내에 흐름성을 향상시키기 위한 첨가제로서, 고상 파우더 형태의 수산화 알루미늄, 실리카, 탄산칼슘, 황산바륨, 산화티타늄, 인산칼슘, 탈크(talc), 점토(clay) 또는 유리분말 등과 액상 형태의 변성 우레아계, 우레아 변성 폴리우레탄 용액 또는 폴리하이드록시 카르복실산 아마이드 용액 등이 사용되고 있다.Generally, additives for improving flowability in paint formulations include liquids such as aluminum hydroxide, silica, calcium carbonate, barium sulfate, titanium oxide, calcium phosphate, talc, clay or glass powder in the form of a solid powder. Modified urea-based, urea-modified polyurethane solutions, polyhydroxy carboxylic acid amide solutions and the like are used.
그러나, 이와 같은 점증제 또는 유동성 첨가제들을 도료 배합 내에 적용하는 경우에는, 기본 도료 물성, 특히 방청성 및 내해수성 등이 나빠지며, 또한 가사 시간이나, 작업성에 나쁜 영향을 끼치는 경우가 많다. 그러므로 방식 도료의 기본 물성에 영향을 끼치지 않으면서 도료의 흐름성을 향상시키는 요구가 증대되고 있다.However, when such thickeners or flowable additives are applied in paint formulations, the basic paint properties, in particular rust resistance and seawater resistance, deteriorate, and also often adversely affect the pot life or workability. Therefore, there is an increasing demand for improving the flowability of the paint without affecting the basic physical properties of the anticorrosive paint.
한편, 복잡한 선박의 주요부위, 특히 카고 홀드(cargo hold) 및 밸러스트 구조체 내부의 일정 부위에 도료가 중첩 도포 됨으로써 경화 및 노화가 진행된 도막 표면에는 열적, 화학적 또는 외부의 기계적 충격에 의하여 크랙이 발생된다. 이렇게 만들어진 크랙은 철 소지면의 부식을 촉진시키며, 선박의 수명을 앞당기는 원인이 된다. 이것은 현재 선박을 건조하는 제조사에서 가장 중요시하는 부분 중의 하나로서, 여러 선박 도료업체에서 개선해야 할 물성으로 주목하고 있다.On the other hand, cracks are generated on the surface of hardened and aging coating layers by applying paints to major parts of complex ships, especially cargo hold and certain parts inside the ballast structure. . Cracks made in this way promote corrosion of the iron surface and cause the life of the vessel to be accelerated. This is one of the most important parts of manufacturers who are currently building ships, and many ship paint companies are paying attention to the physical properties to be improved.
이러한 관점에서 선박 및 중방식 분야에서는 방청성과 내크랙성이 우수하며, 수직면에 도장시 흐름현상이 발생하지 않는 뛰어난 도료의 개발이 요구되고 있다.From this point of view, the development of excellent paint which is excellent in rust prevention and crack resistance in the ship and heavy corrosion protection field, and does not cause flow phenomenon when painting on the vertical surface.
본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로서, 본 발명의 목적은 선박용, 특히 워터 발라스트 탱크와 같은 열악한 부식환경에서 방청성 및 내 크랙성이 매우 우수하며, 도장 작업시 흐름성이 매우 양호한 선박용 방식 도료 조성물을 제공하고자 하는 것이다.The present invention has been made to solve the above problems, the object of the present invention is very excellent in rust resistance and crack resistance in harsh corrosive environment, such as water ballast tanks for ships, and very good flowability during painting work It is to provide a marine anticorrosive coating composition.
상기의 목적을 달성하기 위하여, 본 발명의 선박용 방식 도료 조성물은, 에폭시 당량이 100~750g/eq인 에폭시 수지 15~50중량%, 지방산 유도체 조성물 1~30중량%, 알루미늄 플레이크(Flake) 안료 4~50중량% 및 아민계 경화제와 폴리아미드계 경화제 중 1종 이상의 경화제 2~20중량%를 포함하는 것을 특징으로 한다.In order to achieve the above object, the marine anticorrosive coating composition of the present invention, 15 to 50% by weight of epoxy resin having an epoxy equivalent of 100 to 750 g / eq, 1 to 30% by weight of fatty acid derivative composition, aluminum flake (Flake) pigment 4 It is characterized by including 2 to 20% by weight of at least 50% by weight and at least one of an amine curing agent and a polyamide curing agent.
본 발명의 선박용 방식 도료 조성물에 포함되는 상기 에폭시 수지는, 그 종류에 특별히 제한이 없으며, 예를 들면 비스페놀형 에폭시 수지, 지방족 에폭시 수지, 글리시딜에스테르계 에폭시 수지, 글리시딜 아민계 에폭시 수지, 페놀노볼락형 에폭시 수지 및 크레졸형 에폭시 수지로부터 선택되는 1종 이상을 혼합하여 사용할 수 있다.There is no restriction | limiting in particular in the kind in the said epoxy resin contained in the marine anticorrosive coating composition of this invention, For example, a bisphenol-type epoxy resin, an aliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin , A phenol novolak type epoxy resin and one or more types selected from cresol type epoxy resins can be mixed and used.
상기 에폭시 수지는 1분자 내에 적어도 2개 이상의 에폭시기를 갖는 것이며, 에폭시 당량은 100~750g/eq인 것이 바람직하며, 보다 바람직하게는 150~700g/eq이다. 방청성 및 내해수성과 내크랙성이 동시에 만족되기 위해서는 도료의 주 바인더의 가교도가 결정되어야 하는데, 상기 에폭시 당량이 100g/eq 미만인 경우에는 내크랙성이 열세하며, 750g/eq를 초과하는 경우에는 방청성과 내해수성 등의 물성이 나빠지는 문제점이 있다.The epoxy resin has at least two or more epoxy groups in one molecule, and the epoxy equivalent is preferably 100 to 750 g / eq, more preferably 150 to 700 g / eq. In order to satisfy rust resistance and seawater resistance and crack resistance at the same time, the degree of crosslinking of the main binder of the paint must be determined. If the epoxy equivalent is less than 100 g / eq, the crack resistance is inferior, and if it exceeds 750 g / eq, the rust resistance is There is a problem in that the physical properties such as seawater resistance.
상기 에폭시 수지의 함량은 15~50중량%로 사용하는 것이 바람직하다. 상기 함량은 조성물의 전체 고형성분 대비 안료(Pigment) 함량을 결정하는 것으로서, 도료 조성물 내의 안료 함량은 도막의 내구성에 매우 밀접한 영향을 미치는데, 상기 함량이 15중량% 미만인 경우에는 방청성 또는 내해수성이 나빠지며, 50중량%를 초과하는 경우에는 광택 및 내크랙성이 나빠진다.The content of the epoxy resin is preferably used in 15 to 50% by weight. The content is to determine the pigment (Pigment) content relative to the total solid component of the composition, the pigment content in the coating composition has a very close effect on the durability of the coating film, when the content is less than 15% by weight rust resistance or seawater resistance It worsens, and when it exceeds 50 weight%, gloss and crack resistance worsen.
본 발명의 선박용 방식 도료 조성물에 포함되는 지방산 유도체 조성물은, 지방산 유도체 0.1~10중량%, 케톤류 1~30중량%, 알코올류 1~30중량%, 하이드로카본류 10~30중량% 및 벤젠류 10~50중량%를 포함하여 이루어질 수 있으며, 바람직하게는 지방산 유도체 3~7중량%, 케톤류 10~20중량%, 알코올류 15~30중량%, 하이드로카본류 20~30중량% 및 벤젠류 20~40중량%를 포함한다.The fatty acid derivative composition contained in the marine anticorrosive coating composition of the present invention is 0.1 to 10% by weight of fatty acid derivatives, 1 to 30% by weight of ketones, 1 to 30% by weight of alcohols, 10 to 30% by weight of hydrocarbons and benzene 10 It may comprise ~ 50% by weight, preferably 3 to 7% by weight of fatty acid derivatives, 10 to 20% by weight ketones, 15 to 30% by weight alcohol, 20 to 30% by weight hydrocarbons and 20 to benzene 40 weight percent.
상기 지방산 유도체는, 다음의 일반식 (Ⅰ)의 구조를 가진다:The fatty acid derivative has the structure of the following general formula (I):
CH3(CH2)nCH=CH(CH2)mCH2CO-R1 (Ⅰ)CH 3 (CH 2 ) n CH = CH (CH 2 ) m CH 2 CO-R 1 (I)
여기에서, n은 5~14의 정수, m은 6~20의 정수를 나타내며, R1은 -OCH3, -NH2, -NHC2H5 또는 -CN이다.Here, n is an integer of 5-14, m represents an integer of 6-20, R 1 is -OCH 3 , -NH 2 , -NHC 2 H 5 or -CN.
상기 첨가제에 포함되는 케톤류는, 예를 들어 아세톤, 메틸에틸케톤, 메틸이소아밀케톤, 디이소부틸케톤, 디아세톤 알코올 및 시클로헥사논 등을 들 수 있다.Examples of the ketones contained in the additives include acetone, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone, and the like.
상기 첨가제에 포함되는 알코올류는, 예를 들어 메탄올, 에탄올, 이소프로필 알코올, n-부틸 알코올, 이소부틸 알코올, sec-부탄올, 2-에틸 헥사놀, 벤질 알코 올 및 메톡시 프로판올 등을 들 수 있다.Examples of the alcohols included in the additives include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butanol, 2-ethyl hexanol, benzyl alcohol, and methoxy propanol. have.
상기 첨가제에 포함되는 하이드로카본류는, 예를 들어 1,2,4-트리메틸벤젠, 크실렌 및 에틸벤젠 화합물; 나프탈렌 화합물; n-헵탄; 및 에틸벤젠, 스티렌, 트리메틸벤젠 및 테트라메틸벤젠 화합물 등을 들 수 있다.Hydrocarbons contained in the additive include, for example, 1,2,4-trimethylbenzene, xylene, and ethylbenzene compounds; Naphthalene compounds; n-heptane; And ethylbenzene, styrene, trimethylbenzene, tetramethylbenzene compound, and the like.
상기 첨가제에 포함되는 벤젠류는, 예를 들어 톨루엔 및 크실렌 등을 들 수 있다. Benzene contained in the said additive includes toluene, xylene, etc., for example.
본 발명의 선박용 방식 도료 조성물에 포함되는 지방산 유도체 조성물의 장점을 극대화시키기 위해서는, 조성물 내의 함량 선택이 매우 중요하다. 함량이 너무 적을 경우에는 도료의 주요 물성인 내크랙성 및 흐름성에 전혀 영향을 주지 않으며, 너무 많은 양을 사용하는 경우에는 지방산 유도체 내의 불포화 이중결합의 영향으로 도료가 도포되어, 도막 형성시 변색을 일으키며, 기존 도료의 기본 물성을 저해하는 요인이 된다. 따라서, 기존 도료의 기본 물성을 저해시키지 않으며, 내흐름특성과 내크랙성을 향상시키기 위해 상기 도료 조성물 총 중량을 기준으로 1~30중량%를 사용하는 것이 바람직하며, 보다 바람직하게는 2~10중량%이다.In order to maximize the advantages of the fatty acid derivative composition included in the marine anticorrosive coating composition of the present invention, the content selection in the composition is very important. If the content is too small, it does not affect the crack resistance and flowability, which are the main physical properties of the paint, and if the amount is used too much, the paint is applied under the influence of unsaturated double bonds in the fatty acid derivatives, thereby discoloring the film. It is a factor that hinders the basic physical properties of existing paints. Therefore, it is preferable to use 1 to 30% by weight based on the total weight of the coating composition in order to improve the flow resistance and crack resistance without impairing the basic physical properties of the existing paint, more preferably 2 to 10 Weight percent.
본 발명의 선박용 방식 도료 조성물에 포함되는 알루미늄 플레이크 안료는, 리핑형(Leafing type) 및 논리핑형(Non-leafing type) 안료로 나눌 수 있다.The aluminum flake pigment included in the marine anticorrosive coating composition of the present invention may be divided into a leafing type and a non-leafing type pigment.
상기 리핑형 알루미늄 플레이크는, 강구와 같이 강으로 된 구형의 연삭 매체를 갖는 볼밀과 같은 연삭기를 사용하고, 스테아린산과 같은 포화지방산 등의 연삭 윤활제를 사용하여, 미네랄 스피리트 또는 나프타 용매 등의 유기용매 내에서 알루미늄 분말을 습식 연삭하여 얻을 수 있다. 리핑형 알루미늄 플레이크는, 작은 표면 장력으로 인해 도료에 함유된 용매 또는 바인더에 대하여 약한 친화도를 갖는다. 따라서, 리핑형 알루미늄 플레이크 안료는 건조공정 동안에 도막의 표면에 이동되어 연속적으로 균일하게 배향되며, 이에 의한 우수한 금속감(metallic effect)과 베이스 마스킹 특성(base masking property)을 나타낸다. The ripping aluminum flakes are prepared in an organic solvent such as a mineral spirit or a naphtha solvent by using a grinding machine such as a ball mill having a spherical grinding medium made of steel such as steel balls, and a grinding lubricant such as saturated fatty acid such as stearic acid. The aluminum powder can be obtained by wet grinding. Ripping aluminum flakes have a weak affinity for the solvent or binder contained in the paint due to the small surface tension. Thus, the rip-type aluminum flake pigment is moved to the surface of the coating film during the drying process and is oriented continuously uniformly, thereby exhibiting excellent metallic effect and base masking property.
상기 논리핑형 알루미늄 플레이크는, 포화지방산 대신에 올레산과 같은 불포화지방산을 연삭 윤활제로 사용하여, 위에서 언급한 바와 유사한 연삭을 수행함으로써 얻을 수 있다. 논리핑형 알루미늄 플레이크 안료는, 표면장력이 그리 작지 않기 때문에 상기 도료에 함유된 용매 또는 바인더에 대하여 강한 친화력을 갖는다. 따라서, 논리핑형 알루미늄 플레이크는 도막 내에 균일하게 배향된 상태로 분산되며, 이에 의하여 도막에 금속감을 부여하고 동시에 판상인 입자형태에 의해 외부로부터 수분 등이 소지로 침투되는 것을 차단시키는 효과(barrier effect) 등의 도막의 방청성능 및 여러 가지 물성을 향상시킬 수 있다.The logicless aluminum flakes can be obtained by carrying out similar grinding as mentioned above, using unsaturated fatty acids such as oleic acid as grinding lubricant instead of saturated fatty acids. The logic-type aluminum flake pigment has a strong affinity for the solvent or binder contained in the paint because the surface tension is not so small. Therefore, the logic-type aluminum flake is dispersed in a uniformly oriented state in the coating film, thereby imparting a metallic feeling to the coating film and at the same time blocking the penetration of moisture or the like from the outside by the plate-shaped particle shape (barrier effect). The antirust performance and various physical properties of coating films, such as these, can be improved.
상기와 같은 특성을 고려하여, 본 발명의 선박용 방식 도료 조성물에 포함되는 알루미늄 프레이크 안료로는 논리핑형 알루미늄 플레이크 안료를 단독으로 사용하는 것이 바람직하지만, 도막의 방청성능을 저해하지 않으면서, 우수한 외관 특성을 발휘하도록 리핑형 알루미늄 플레이크 안료를 일부 혼용하여 사용할 수 있다. 바람직하게는 리핑형 알루미늄 플레이크 안료는 알루미늄 플레이크 안료 총 중량의 40중량%까지 사용할 수 있다. 만일, 리핑형 알루미늄 플레이크 안료가 알루미늄 플레이크 안료 총 중량의 40중량%를 초과하여 사용된다면 외부로부터 수분 등이 소지로의 침투되는 것을 차단시키는 효과가 감소되어, 도막의 방청성을 떨어뜨리게 된 다. In view of the above characteristics, as the aluminum flake pigment included in the marine anticorrosive coating composition of the present invention, it is preferable to use a logic-type aluminum flake pigment alone, but excellent appearance characteristics without impairing the rust preventing performance of the coating film. Some of the ripping type aluminum flake pigments can be used in combination. Preferably the ripping aluminum flake pigment can be used up to 40% by weight of the total weight of the aluminum flake pigment. If the ripping aluminum flake pigment is used in excess of 40% by weight of the total weight of the aluminum flake pigment, the effect of blocking the penetration of moisture or the like from the outside into the substrate is reduced, which lowers the rust resistance of the coating film.
또한, 알루미늄 플레이크 안료는 평균입자두께가 0.1~30㎛의 범위에 있으며, 평균입자직경이 5~80㎛의 범위에 있는 것을 사용한다. 바람직하게는 평균입자두께가 0.3~15㎛의 범위에 있으며, 평균입자직경이 10~30㎛의 범위에 있는 것이 적당하다. 도막의 금속감은 휘도, 명도, 광채 등의 조합으로 시각적으로 인식되지만, 일반적으로 높은 휘도를 갖는 도막을 원하는 경향이 있다. 일반적으로, 도막의 휘도와 알루미늄 플레이크 안료의 평균입자두께와 평균입자직경은 서로 연관되어 있어서, 평균입자두께와 평균입자직경이 증가할수록 휘도가 증가하게 된다. 하지만, 알루미늄 플레이크 안료의 평균입자두께와 평균입자직경이 너무 커지면, 알루미늄 플레이크 안료의 배향은 도막의 형성시 흐트러지는 경향이 있어 도막의 외관이 불균일한 광채를 보이게 되며, 또한 금속 입자에 스스로가 유도 전하를 띠고 있어서 금속 입자들 사이에 인력이 작용하여 도장 완료 후 메탈릭 도료의 금속분이 부분적으로 밀집하여 나타나게 됨으로써 도막에 얼룩짐 현상이 나타나는 원인이 되므로, 평균입자두께 및 평균입자직경을 상기 범위로 특정하는 것이 바람직하다.In addition, the aluminum flake pigment has an average particle thickness in the range of 0.1-30 micrometers, and uses an average particle diameter in the range of 5-80 micrometers. Preferably, the average particle thickness is in the range of 0.3 to 15 mu m, and the average particle diameter is in the range of 10 to 30 mu m. Although the metallic feeling of the coating film is visually recognized by a combination of brightness, brightness, brilliance, etc., there is a general tendency to want a coating film having a high brightness. In general, the brightness of the coating film, the average particle thickness and the average particle diameter of the aluminum flake pigment are related to each other, so that the brightness increases as the average particle thickness and the average particle diameter increase. However, if the average particle thickness and the average particle diameter of the aluminum flake pigment are too large, the orientation of the aluminum flake pigment tends to be disturbed during the formation of the coating film, resulting in uneven appearance of the coating film, and also inducing itself to the metal particles. Since an attractive force is applied between the metal particles due to the charge, the metal powder of the metallic paint is partially concentrated after the completion of the coating, which causes staining in the coating film. Therefore, the average particle thickness and the average particle diameter are specified within the above range. It is preferable.
상기 알루미늄 플레이크 안료는 총 조성물의 함량의 4~50중량%로 사용될 수 있다. 상기 함량이 4중량% 미만인 경우에는 알루미늄 플레이크 안료의 특성을 제대로 발현을 할 수 없으며, 50중량%를 초과하면 금속분의 함량 과다로 금속 입자의 표면에 피복된 수지만으로는 금속 입자들의 집중을 억제하기가 어려워져 도장 완료 후에 얼룩짐 현상이 발생하는 경향이 증가하게 된다.The aluminum flake pigment may be used in 4 to 50% by weight of the content of the total composition. If the content is less than 4% by weight, the characteristics of the aluminum flake pigment may not be properly expressed. If the content exceeds 50% by weight, it is difficult to suppress the concentration of metal particles only by coating the surface of the metal particles with an excessive amount of metal. It becomes more difficult to increase the tendency for spotting to occur after the completion of painting.
본 발명의 선박용 방식 도료 조성물에 포함되는 경화제는, 아민계 경화제 및 폴리아미드계 경화제 중 1종 이상을 선택하여 사용할 수 있다. The hardening | curing agent contained in the marine anticorrosive coating composition of this invention can select and use 1 or more types of an amine-type hardener and a polyamide-type hardener.
아민계 경화제는 특별히 한정되지 않으며, 상업적으로 생산되는 제품을 사용할 수 있다. 구체적인 예로서, 카돌라이트(Cardolite)사의 Lite2001LV, Lite2002, Lite2562, NC-541LV, NC-558, NC-562, NX-4903, NX-4913; 에어프로덕트(Air-product)사의 Ancamine1618, Ancamine1784, Ancamine2280, Ancamine2603; 국도화학 KH-600, KH-530S, KH-602, KH-531, KH-816/817/818/819, TH-435, TH-437 등을 들 수 있다.The amine curing agent is not particularly limited, and commercially produced products may be used. Specific examples include Lite2001LV, Lite2002, Lite2562, NC-541LV, NC-558, NC-562, NX-4903, NX-4913, manufactured by Cardolite; Ancamine1618, Ancamine1784, Ancamine2280, Ancamine2603 from Air-product; Kukdo Chemical KH-600, KH-530S, KH-602, KH-531, KH-816 / 817/818/819, TH-435, TH-437, etc. are mentioned.
아미드 경화제는 특별히 한정되지 않으며, 상업적으로 생산되는 제품을 사용 할 수 있다. 구체적인 예로서, 에어프로덕트(Air-product)사의 Sunmide153-60S, Sunmide305-70X, Sunmide307D-60, Sunmide353N, Sunmide350, Sunmide175-60, SunmideX-2700, Ancamide2353, Ancamide2050, Ancamide2396, Ancamide2386; 국도화학의 GX-533, GX-450, GX-433, GX-422, GX-328K, GX-322 등을 들 수 있다.Amide curing agents are not particularly limited, and commercially produced products may be used. Specific examples include Sunmide153-60S, Sunmide305-70X, Sunmide307D-60, Sunmide353N, Sunmide350, Sunmide175-60, SunmideX-2700, Ancamide2353, Ancamide2050, Ancamide2396, Ancamide2386 from Air-product; KX-533, GX-450, GX-433, GX-422, GX-328K, GX-322 etc. of Kukdo Chemical.
상기 경화제의 함량은 2~20중량%가 바람직하다. 아민계 및 아미드계 경화제의 함량은 결국 도료 내의 에폭시 수지와의 몰비(당량비)를 결정하는데, 이것은 가교밀도(cross-linking density)를 조정하여 도막의 내구성능을 결정 짖는 중요한 인자가 된다. 상기 함량이 2중량% 미만인 경우에는 층간부착성 및 유연성에는 유리하지만, 내약품성, 내수성 및 방청성능이 악화되며, 20중량%를 초과하는 경우에는 층간 부착성 및 내크랙성이 불리해진다.The content of the curing agent is preferably 2 to 20% by weight. The content of amine-based and amide-based curing agents ultimately determines the molar ratio (equivalent ratio) with the epoxy resin in the paint, which is an important factor in determining the durability of the coating by adjusting the cross-linking density. When the content is less than 2% by weight, it is advantageous for interlayer adhesion and flexibility, but the chemical resistance, water resistance and rust resistance are deteriorated, and when it exceeds 20% by weight, the interlayer adhesion and crack resistance are disadvantageous.
그 밖에, 본 발명의 선박용 방식 도료 조성물에는, 방청안료, 무기질 충진제, 침강 방지제, 유기용제 및 기타 첨가제를 추가적으로 더 첨가하여 사용할 수 있다.In addition, the marine anticorrosive coating composition of the present invention may be used by further adding an rust preventive pigment, an inorganic filler, an antisettling agent, an organic solvent, and other additives.
본 발명의 방식 도료 조성물의 도장 방법으로는, 에어 스프레이, 에어리스 스프레이, 롤러, 붓 등 종래 공지의 방법을 채용할 수 있다.As a coating method of the anticorrosive coating composition of this invention, conventionally well-known methods, such as an air spray, an airless spray, a roller, and a brush, can be employ | adopted.
이하, 실시예를 통하여 본 발명을 좀 더 구체적으로 설명한다. 아래의 실시예는 본 발명의 내용을 보다 구체적으로 설명하기 위한 것으로 본 발명의 범위가 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are provided to more specifically describe the contents of the present invention, but the scope of the present invention is not limited thereto.
[[ 실시예Example ] ]
1. 방식 도료 조성물의 제조1. Preparation of anticorrosive coating composition
표 1에 나타낸 성분 및 함량으로 다음의 방법에 따라 방식 도료 조성물을 제조하였다.The anticorrosive coating composition was prepared according to the following methods with the ingredients and contents shown in Table 1.
제1단계로서, 용기에 표 1의 주제 중 알루미늄 플레이크 안료를 제외한 성분들을 투입하고, 교반기로 혼합하였다. 제2단계는 분산단계로서, 교반기로 혼합한 혼합물을 분산기를 이용하여 분산시켜 평균 입도 60㎛이내인 도료 조성물을 제조하였다. 제3단계로 분산된 도료 조성물 내에 알루미늄 플레이크 안료를 투입하고, 혼합한 후, 교반기로 혼합하여 주제 도료 조성물을 얻었다. 이것에 경화제로서 지방산 유도체 조성물, 아민 경화제 또는 아민계와 폴리아미드계 혼용 경화제를 첨가하고 혼합교반하여 방식 도료 조성물을 얻었다. As a first step, the ingredients except for the aluminum flake pigment of the subject matter of Table 1 were added to the container and mixed with a stirrer. The second step is a dispersion step, in which a mixture mixed with a stirrer was dispersed using a disperser to prepare a coating composition having an average particle size of 60 μm or less. An aluminum flake pigment was added to the coating composition dispersed in the third step, mixed, and then mixed with a stirrer to obtain a main coating composition. As the curing agent, a fatty acid derivative composition, an amine curing agent, or an amine-based and polyamide-based curing agent was added and mixed and stirred to obtain an anticorrosive coating composition.
분phrase
minute
(g)Paint composition
(g)
주
제
week
My
플레이크
안료2 aluminum
flake
Pigment 2
경화제
Hardener
오일 유도체
첨가제5 fatty acid
Oil derivatives
Additive 5
1. 비스페놀 A형 에폭시 수지, 에폭시 당량=189g/eq1. Bisphenol A epoxy resin, epoxy equivalent = 189 g / eq
2. 논리핑형 알루미늄 플레이크 안료, 평균입자직경=15㎛2. Non-doped aluminum flake pigment, average particle diameter = 15㎛
3. 파우더상 점증제: Bentone #27(Bentonite계), Elementis(社)3. Powder thickener: Bentone # 27 (Bentonite), Elementis
4. 액상 점증제: 변성 우레아계, BYK Chemie4. Liquid thickener: modified urea, BYK Chemie
5. 지방산 유도체 조성물 : 에스테르 치환 지방산 유도체 6중량%, 메틸이소부틸케톤 13중량%, 메톡시프로판올 24중량%, kocosol#100 27중량% 및 크실렌 30중량%5. Fatty acid derivative composition: 6% by weight of ester-substituted fatty acid derivative, 13% by weight of methyl isobutyl ketone, 24% by weight of methoxypropanol, 27% by weight of kocosol # 100 and 30% by weight of xylene
2. 도장 방법2. How to paint
실시예 및 비교예 1~8의 방식 도료 조성물을 다음과 같은 조건으로 도장하였다.The anticorrosive coating compositions of Examples and Comparative Examples 1 to 8 were coated under the following conditions.
우선 소지표면의 녹, 먼지, 습기, 유분 및 기타 오염물을 청수나 적절한 용제를 사용하여 완전히 제거한 후, 표면조도 25~75㎛로 블라스팅 연마하였다. 다음으로, 준비된 시편에 에어리스 스프레이를 사용하여 노즐 구경 0.019~0.031", 분사 압력 120~150atm, 분사각도 65°로 설정한 후, 건조 도막 125~150㎛로 도장하였다.First, rust, dust, moisture, oil and other contaminants on the surface were completely removed using fresh water or a suitable solvent, and then blasted and polished to a surface roughness of 25 to 75 µm. Next, the prepared specimens were set to a nozzle diameter of 0.019 to 0.031 ", an injection pressure of 120 to 150 atm, and an injection angle of 65 ° using an airless spray, and then coated with a dry coating film of 125 to 150 µm.
3. 물성 측정3. Property Measurement
얻어진 도막에 대하여, 내수성, 내해수성, 방청성, 내크랙성 및 흐름성을 다음과 같은 기준으로 평가하고, 그 결과를 표 2 및 표 3에 나타내었다.About the obtained coating film, water resistance, seawater resistance, rust prevention property, crack resistance, and flowability were evaluated on the following references | standards, and the result is shown to Table 2 and Table 3.
(1)내수성(1) water resistance
도장된 시편을 소지면이 보일 때까지 가운데 10cm정도의 길이로 선을 긋고 청수침적 3개월 후 도막 평가.The coated specimen was drawn in a line about 10cm long until the surface of the paper was visible, and the film was evaluated after 3 months of water deposition.
(2)내해수성(2) seawater resistance
도장된 시편을 소지면이 보일 때까지 가운데 10cm정도의 길이로 선을 긋고 해수침적 3개월 후 도막 평가.The painted specimens were lined about 10cm in length until the surface of the paper was visible, and the film was evaluated 3 months after seawater deposition.
(3)방청성(3) Antirust
ASTM B117에 따른 도막 물성 평가.Coating Properties Evaluation According to ASTM B117.
(4)내크랙성(4) Crack resistance
T-모양 시편을 에어리스 도장기로 2000㎛으로 도장 후, -20~60℃에서, 6시간 간격으로 반복되는 열적 충격을 가함으로써 도포된 도막상태를 관찰(도 1 참고).After coating the T-shaped specimens with an airless coating machine at 2000 μm, the applied coating state was observed by applying thermal shock repeated at intervals of 6 hours at −20 to 60 ° C. (see FIG. 1).
(5)흐름성 (5) flowability
에어리스 도장기를 사용하여 1000mm×1000mm×10mm 크기의 브라스팅 처리된 철 시편의 수직면에 도료를 도막 두께 별(300, 400, 500, 600㎛)로 도장한 후, 도장된 도료가 수직면으로 흐르는 모습을 관찰하고, 도막이 건조된 후 건조도막 두께를 WFT(Wet Film Thickness) 게이지를 사용하여 측정.After painting the paint on the vertical surface of the 1000mm × 1000mm × 10mm sized blasted iron specimen using the airless sprayer (300, 400, 500, 600㎛), the coated paint flows in the vertical plane. Observe and measure the dry film thickness using a WFT (Wet Film Thickness) gauge after the coating has dried.
(3개월)Water resistance
(3 months)
(3개월)Seawater resistance
(3 months)
(Salt-Fog 1200시간)Antirust
(Salt-Fog 1200 hours)
* 기포 빈도: F = Few , M = Medium , D = Dense* Bubble size: No.2>No.4>No.6>No.8> No.10 (no bubble)
* Bubble Frequency: F = Few, M = Medium, D = Dense
(3개월)Water resistance
(3 months)
(3개월)Seawater resistance
(3 months)
(Salt-Fog 1200시간)Antirust
(Salt-Fog 1200 hours)
상기 결과에서 알 수 있는 바와 같이, 알루미늄 플레이크 안료 및 지방산 유도체 조성물을 모두 사용한 실시예의 경우에 내수성, 내해수성, 방청성, 내크랙성 및 흐름성이 모두 우수함을 알 수 있다.As can be seen from the above results, in the case of the embodiment using both the aluminum flake pigment and the fatty acid derivative composition, it can be seen that water resistance, seawater resistance, rust resistance, crack resistance and flowability are all excellent.
상기에서 상세히 설명한 바와 같이, 본 발명에 의한 선박용 방식 도료 조성물은, 선박의 외판, 카고 홀드부 및 밸러스트 탱크부와 같은 주요부위에 사용되는 경우, 내수성, 내해수성, 방청성, 내크랙성 및 흐름성이 모두 우수한 효과를 나타낸다.As described in detail above, the marine anticorrosive coating composition according to the present invention, when used in the main parts such as the outer shell, cargo hold portion and ballast tank portion of the vessel, water resistance, seawater resistance, rust resistance, crack resistance and flow resistance All of these show excellent effects.
Claims (4)
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| CN104327674A (en) * | 2014-11-18 | 2015-02-04 | 江苏科技大学 | Epoxy resin paint composition directly coating rust layer |
| CN106237798A (en) * | 2016-08-31 | 2016-12-21 | 芜湖恒耀汽车零部件有限公司 | The inner wall anti-corrosive coating of boiler waste gas purification device water tank |
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| RU2413745C2 (en) * | 2009-04-10 | 2011-03-10 | Александр Михайлович Барский | Anticorrosive pigment |
| CN102226045B (en) * | 2011-04-15 | 2014-05-07 | 贵阳神迪化工有限公司 | Aluminum-tripolyphosphate-doped polyaniline antirust pigment and preparation method thereof |
| JP7114914B2 (en) * | 2018-01-29 | 2022-08-09 | 株式会社東郷製作所 | Anti-rust treated metal parts and coating paint |
| CN113402954A (en) * | 2021-07-30 | 2021-09-17 | 深圳市宏宇辉科技有限公司 | Anti-flash aluminum sheet and preparation method and application thereof |
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| CN106237798A (en) * | 2016-08-31 | 2016-12-21 | 芜湖恒耀汽车零部件有限公司 | The inner wall anti-corrosive coating of boiler waste gas purification device water tank |
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