KR101221321B1 - A polyurea resin paint composition for coating of steel pipes and its preparation process - Google Patents
A polyurea resin paint composition for coating of steel pipes and its preparation process Download PDFInfo
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
- B05D7/222—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of pipes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive 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
- C09D7/40—Additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- 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
- C09D7/80—Processes for incorporating ingredients
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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Abstract
Description
본 발명은 강관의 내,외부 코팅용 폴리우레아수지 도료조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 디이소시아네이트(Diisocyanate), 폴리옥시알킬렌 글리콜(Polyoxyalkylene glycol) 및 알킬렌 카보네이트(Alkylene carbonate)의 중합반응에 의해 생성되는 우레탄 프리폴리머(Urethane prepolymer)를 함유하는 주제부에 폴리에테르아민(Polyether amine), 습윤분산제, 안료, 사슬연장제, 부착력 증강제, 소포탈포제, 유동성 조절제를 함유하는 경화제부를 혼합하여 폴리우레아수지 도료조성물을 제조하는 경우, 상기 주제부에 중합반응 억제제(Polymerization inhibitor)를 첨가하여 미반응 이소시아네이트의 반응으로 인한 점도 상승이나 겔화 등을 미연에 방지하여 우레탄 프리폴리머의 중합반응을 종결시킴으로써, 장시간 저장 안정성은 물론, 물리적, 화학적 특성을 개선하여 이를 상,하수도, 일반용수 및 기타 유체 수송용 배관에 사용되는 강관 등 지하 매설 철구조물의 방수, 방식을 목적으로 다양하게 적용할 수 있는 환경 친화적인 강관 코팅용 폴리우레아수지 도료조성물 및 그 제조방법에 관한 것이다.The present invention relates to a polyurea resin coating composition for internal and external coating of steel pipes and a method of manufacturing the same, and more particularly to diisocyanate, polyoxyalkylene glycol, and alkylene carbonate. Part of the curing agent containing a polyetheramine, a wet dispersant, a pigment, a chain extender, an adhesion enhancer, an antifoaming agent, and a fluidity control agent to the main portion containing the urethane prepolymer produced by the polymerization reaction of In the case of preparing a polyurea resin coating composition by mixing, a polymerization inhibitor (Polymerization inhibitor) is added to the main portion to terminate the polymerization reaction of the urethane prepolymer by preventing the increase of viscosity or gelation due to the reaction of unreacted isocyanate. This improves long-term storage stability, as well as improving physical and chemical properties. Polyurea resin coating composition for environmentally-friendly steel pipe coating and its manufacturing method that can be applied to water, sewage, general water and other underground pipes such as steel pipes used for transporting fluids. It is about.
일반적으로 도시가스, 상,하수도나 각종 유체 수송용으로 사용되는 강관을 보면, 외면에는 폴리에틸렌 코팅층을 형성하고, 내면에는 무기물, 에폭시, 폴리우레탄, 폴리우레아 등을 주요 성분으로 하는 코팅층을 형성하여 녹이 발생되거나 외부의 충격으로 부터 제품에 손상이 가는 것을 방지하고 있다.In general, steel pipes used for city gas, water supply, sewage, and various fluid transportation include a polyethylene coating layer on the outer surface, and a coating layer containing inorganic, epoxy, polyurethane, and polyurea as the main components on the inner surface thereof. It prevents damage to the product from being generated or from external shocks.
강관의 내부나 외부에 코팅되는 도료는 높은 압력과 열, 화학반응 등이 작용하므로 내수성, 내식성, 내구성, 내굴곡성, 내충격성, 내마모성, 내약품성 등의 특성을 만족하여야 하며, 나아가 음용수 기준에도 부합되어야 하는데, 무기물과 에폭시수지를 이용하는 코팅공법의 경우에는 경화속도가 느리고 사람이 직접 작업을 해야 되는 단점이 있을 뿐만 아니라, 내구성, 내충격성 및 내한성이 떨어져 도막의 크랙 발생이 우려되며, 이러한 크랙 발생에 의해 배관 내부 막힘 현상이 발생할 가능성도 있다. 또한, 에폭시수지만을 사용하는 코팅공법의 경우는 경화가 느리기 때문에 열을 가하는 작업도 필요하며, 또한 내부 코팅용 도료 중에 포함된 비스페놀A 등이 잔존하여 인체에 치명적인 영향을 줄 수 있다. 그리고 내충격성, 내굴곡성이 취약하여 충격에 의한 손상이나 굴곡부위에서의 부분 박리가 일어날 가능성이 높다.The paint coated on the inside or outside of the steel pipe has high pressure, heat, chemical reaction, etc., so it must satisfy the characteristics such as water resistance, corrosion resistance, durability, bending resistance, impact resistance, abrasion resistance, and chemical resistance, and also meets drinking water standards. In the case of the coating method using inorganic and epoxy resins, there is a disadvantage in that the curing speed is slow and humans need to work directly, and there is a fear of cracking of the coating due to poor durability, impact resistance and cold resistance. This may cause clogging inside the pipe. In addition, in the case of the coating method using only epoxy resin, it is necessary to apply heat because curing is slow, and bisphenol A, which is contained in the coating material for internal coating, may remain harmful to the human body. In addition, the impact resistance and the bending resistance are weak, so there is a high possibility of damage due to impact or partial peeling at the bent portion.
한편, 폴리우레탄을 사용하는 코팅공법의 경우는 도료의 접착력이 양호한 편이나, 경화속도가 대체적으로 느리고 습도에 민감하여 도막이 발포될 가능성이 있으며, 반면에, 폴리우레아를 사용하는 코팅공법의 경우는 습도에는 안정적이나, 경화속도가 너무 빨라 소재와의 기밀성, 접착력이 떨어지고, 체질 안료(탄산칼슘, 황산바륨, 실리카 등)를 사용하지 않아 비중이 낮으며, 고온, 고압의 조건에서 분사되어 도포할 경우 분진이 많이 발생한다.On the other hand, in the case of the coating method using polyurethane, the adhesion of the paint is good, but there is a possibility that the coating film is foamed because the curing speed is generally slow and sensitive to humidity, whereas in the case of the coating method using polyurea, It is stable to humidity, but the curing speed is too fast, so the airtightness and adhesion with material are low, and the specific gravity is low because it does not use extender pigments (calcium carbonate, barium sulfate, silica, etc.), and it is sprayed under high temperature and high pressure. In this case, a lot of dust is generated.
이에 따라, 강관의 내부와 외부 코팅에 적합한 도료의 개발이 꾸준히 요구되고 있으나, 현재 우리나라의 배관 상태는 선진국에 비해 매우 낙후된 실정이며, 특히, 상수도관의 내부 코팅용 도료는 내구성, 내수성, 내식성, 내약품성, 접착력 및 내마모성의 특성이 좋지 않을 뿐만 아니라 균일한 도막을 형성하기 어려운 문제가 있다.Accordingly, the development of paints suitable for the internal and external coating of steel pipes is steadily required, but the current pipe condition of our country is very poor compared to the developed countries, in particular, the coating material for the internal coating of water pipes is durable, water resistance, corrosion resistance In addition to poor chemical resistance, adhesion and wear resistance, there is a problem that it is difficult to form a uniform coating film.
실제로, 강관에 대한 코팅제의 결합은 결합표면의 거친 정도나 코팅제의 가소성 변형 등에 대한 다양한 변수가 있기 때문에 단순히 물리적 부착이나 화학적 부착에 의해 코팅제의 부착성과 내구성을 다 설명하기는 어렵지만, 종래에는 국내의 상수도관이나 하수도관의 부식을 방지하고 오염을 방지하기 위하여 에폭시수지를 이용한 피막으로 많이 처리되어 왔다.Actually, since the binding of the coating agent to the steel pipe has various variables such as the roughness of the bonding surface or the plastic deformation of the coating agent, it is difficult to explain the adhesion and durability of the coating agent simply by physical or chemical adhesion. In order to prevent corrosion of water pipes and sewage pipes and to prevent contamination, they have been treated with a coating using epoxy resin.
이와 같이, 상수도관이나 하수도관의 부식을 방지하고 오염을 방지하기 위하여 국내에서는 주로 에폭시수지를 이용하여 피막 처리되어져 왔지만, 최근 해외에서는 에폭시수지가 많은 유해물을 함유하고 있고 상수관으로 사용할 때 많은 부작용이 있다고 알려짐으로써 폴리우레탄 또는 폴리우레아를 사용한 도료의 개발에 많은 노력을 기울이고 있다.As such, in order to prevent corrosion of water and sewage pipes and to prevent contamination, the film has been mainly treated with epoxy resins in Korea, but in recent years, epoxy resins contain many harmful substances and have many side effects when used as water pipes. It is known that there is a lot of effort in the development of paint using polyurethane or polyurea.
그러한 노력에도 불구하고, 상기 폴리우레탄 도료는 부착력이 떨어지고 반응성이 불균일하여 실용화하기에 어려움이 있었으나, 최근 실용화시키면서 부착강도가 1200psi 정도가 최대로 알려져 있을 정도이다. 아울러 코팅제의 물리적 부착강도를 높이기 위하여 강관의 표면을 숏(Shot), 그릿(Grit), 샌드(Sand) 등에 의한 블라스팅(Blasting)으로 처리하는 등의 방법을 동시에 강구하고 있는 실정이다. 그리고 일각에서는 폴리우레아수지를 강관의 표면에 직접 분사하여 도장하는 방법이 사용되고 있다.In spite of such efforts, the polyurethane paint is difficult to be practical due to the poor adhesion and uneven reactivity, but recently, the practical use of the adhesive strength is about 1200psi maximum. In addition, in order to increase the physical adhesive strength of the coating agent, the surface of the steel pipe is treated with blasting by shot, grit, sand, and the like. In some cases, a polyurea resin is sprayed directly onto the surface of a steel pipe to paint.
본 발명과 관련하여 종래기술을 살펴보면, 대한민국 등록특허 제10-0860009호(공고일자 : 2008. 09. 25)에는 기존의 폴리우레아에 비하여 초기 반응성은 다소 떨어지지만 중합반응시 합성 중합반응이 거의 동시에 진행되면서 미세한 부분의 미세기포가 형성되지 않도록 하기 위해, (A) 디이소시아네이트, 폴리옥시알킬렌 글리콜 및 알킬렌 카보네이트를 혼합하여 프리폴리머를 합성하는 단계, (B) 아민류 사슬확장자 및 소포제를 포함하는 경화제 조성물을 제공하는 단계, (C) 상기 프리폴리머와 상기 경화제 조성물을 반응시켜 폴리우레아 코팅제를 합성하는 단계를 포함하는 제조방법을 개시하고 있고, 상기 발명은 2단계로 진행되는 반응 단계를 가지며 반응하는 동안 용매를 사용하지 않는 폴리우레아 코팅제의 제조방법에 있어서, 특정 성분의 조합에 의해 합성된 프리폴리머와 경화제 조성물을 가열한 상태에서 혼합하여 합성하는 폴리우레아 코팅제의 제조방법 및 코팅방법에 관한 기술이 기재되어 있다.Looking at the prior art with respect to the present invention, the Republic of Korea Patent No. 10-0860009 (Date: 2008. 09. 25) is slightly lower initial reactivity compared to the conventional polyurea, but the synthetic polymerization during the polymerization reaction is almost the same In order to prevent the formation of microbubbles in the minute portion as it proceeds, (A) mixing a diisocyanate, polyoxyalkylene glycol and alkylene carbonate to synthesize a prepolymer, (B) a curing agent comprising an amine chain extender and an antifoaming agent Providing a composition, (C) reacting the prepolymer and the curing agent composition to synthesize a polyurea coating agent, the invention has a reaction step proceeds in two steps and during the reaction In the manufacturing method of the polyurea coating agent which does not use a solvent, by combination of a specific component The generated prepolymer and poly description of the manufacturing method and the coating method of the coating material for synthesizing urea by mixing in a heated state, the curing agent compositions are described.
또한, 대한민국 등록특허 제10-0993243호(공고일자 : 2010. 11. 10)에 개시하고 있는 상수도관 내부코팅용 폴리우레탄-폴리우레아 도료는 디이소시아네이트와 폴리올의 반응에 의해 얻어진 우레탄 프리폴리머, 제1 안료 및 제1 반응첨가제를 반응시켜 형성된 주제부 100 중량부 및 아민, 제2 안료, 필러 및 제2 반응첨가제를 반응시켜 형성된 경화제부 40 내지 70 중량부를 포함하며, 상기 주제부의 이소시아네이트기와 상기 경화제부의 아민기의 몰비는 1:0.8 내지 1:1이다. 상술한 도료로 형성된 상수도관 내부코팅막은 우레탄 프리폴리머에 의해 유연성이 우수하고, 우레아에 의해 내구성이 우수하며, 경화시간이 빨라 신속하게 공사를 수행할 수 있으며, 오랫동안 방수성능을 유지할 수 있다고 한다.In addition, the polyurethane-polyurea paint for internal water pipe coating disclosed in Korean Patent Registration No. 10-0993243 (Date: 2010. 11. 10) is a urethane prepolymer obtained by the reaction of diisocyanate and polyol, the first 100 parts by weight of the main portion formed by reacting the pigment and the first reaction additive, and 40 to 70 parts by weight of the curing agent portion formed by reacting the amine, the second pigment, the filler, and the second reaction additive, wherein the isocyanate group of the main portion and the curing agent portion The molar ratio of amine groups is 1: 0.8 to 1: 1. The water coating inner coating film formed of the above-described paint is excellent in flexibility by urethane prepolymer, excellent in durability by urea, and can be quickly carried out due to fast curing time, and can maintain waterproof performance for a long time.
한편, 본 발명은 우레탄 프리폴리머를 합성하는데 사용되는 이소시아네이트(-NCO) 및 이와 반응하는 화합물(-OH, -NH, -SH)을 고온에서 중합 반응시킨 후 미반응 이소시아네이트기가 잔존시 시간이 경과함에 따라 미반응 이소시아네이트의 반응으로 인한 점도 상승이나 겔화 등을 미연에 방지하기 위해 추가적으로 중합반응 억제제를 첨가하여 반응을 종결시킴으로써 장시간 저장 안정성을 확보할 수 있고, 그로부터 제조된 폴리우레아수지 도료조성물은 균일하고 우수한 코팅품질을 확보할 수 있다는 점에 착안하여 본 발명을 완성한 것이다.On the other hand, the present invention is the polymerization of the isocyanate (-NCO) and the compound (-OH, -NH, -SH) and the reacting compound (-OH, -NH, -SH) used in synthesizing the urethane prepolymer at a high temperature as the time remaining when the unreacted isocyanate groups remain In order to prevent increase in viscosity or gelation due to the reaction of unreacted isocyanate, additional polymerization inhibitor can be added to terminate the reaction to ensure long-term storage stability, and the polyurea resin coating composition prepared therefrom is uniform and excellent. The present invention has been completed by paying attention to the fact that the coating quality can be secured.
본 발명의 목적은, 디이소시아네이트(Diisocyanate), 폴리옥시알킬렌 글리콜(Polyoxyalkylene glycol) 및 알킬렌 카보네이트(Alkylene carbonate)의 중합반응에 의해 생성되는 우레탄 프리폴리머(Urethane prepolymer)를 함유하는 주제부에 폴리에테르아민(Polyether amine), 습윤분산제, 안료, 사슬연장제, 부착력 증강제, 소포탈포제, 유동성 조절제를 함유하는 경화제부를 혼합하여 폴리우레아수지 도료조성물을 제조하는 경우, 상기 주제부에 중합반응 억제제(Polymerization inhibitor)를 첨가하여 미반응 이소시아네이트의 반응으로 인한 점도 상승이나 겔화 등을 미연에 방지하여 우레탄 프리폴리머의 중합반응을 종결시킴으로써 도료의 저장 안정성은 물론, 강관의 표면에 도장된 도막은 소지면과의 부착성, 내굴곡성, 내충격성, 내마모성 등 물리적 특성 및 내염수성, 내수성, 내알칼리성, 내휘발유성 등 화학성 특성이 우수하며, 또한 음극박리(Cathodic disbondment) 시험에 대한 저항성이 매우 양호하여 국부 전류에 의한 도막의 손상 및 박리가 발생되지 않는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물 및 그 제조방법을 제공함에 있다.An object of the present invention is to provide a polyether to the main portion containing a urethane prepolymer produced by polymerization of diisocyanate, polyoxyalkylene glycol and alkylene carbonate. When a polyurea resin coating composition is prepared by mixing a curing agent portion containing an amine, a wet dispersant, a pigment, a chain extender, an adhesion enhancer, an antifoaming agent, and a fluidity control agent, a polymerization inhibitor (Polymerization) is prepared in the main part. by adding an inhibitor) to prevent the increase of viscosity or gelation due to the reaction of unreacted isocyanate and to terminate the polymerization reaction of urethane prepolymer, so that not only the storage stability of the paint but also the coating film coated on the surface of the steel pipe Physical properties such as bending resistance, impact resistance, abrasion resistance, and saline resistance, water resistance, egg resistance Polyurea resin for internal and external coating of steel pipes that has excellent chemical properties such as chemical resistance, gasoline resistance, and resistance to cathodic disbondment test, and does not cause damage or peeling of coating due to local current. The present invention provides a coating composition and a method of manufacturing the same.
본 발명의 다른 목적은, 무용제형 타입의 속경화형 도료로서 점도가 균일하게 유지되어 강관의 내면과 외면의 기밀성과 접착력을 향상시키고 도막의 두께를 자유롭게 조절할 수 있으며, 또한 고온(40℃ 이상), 고압(1500psi 이상)의 스프레이 분사압력으로 도포되더라도 기존 도료에 비해 후막도장이 가능하고 분진 발생이 저감되어 재료의 낭비가 적으며, 더불어 작업성이 양호하고 환경 친화적인 강관의 내,외부 코팅용 폴리우레아수지 도료조성물 및 그 제조방법을 제공함에 있다.Another object of the present invention is a solvent-free type of hardening type paint, the viscosity of which is maintained uniformly to improve the airtightness and adhesion of the inner and outer surfaces of the steel pipe, and to control the thickness of the coating film freely, and also high temperature (40 ℃ or more), Even when applied under high pressure spraying pressure (1500psi or higher), thick film coating is possible compared to the existing paint, and dust generation is reduced, thus reducing the waste of materials and good workability and environmentally friendly poly for internal and external coating of steel pipe. The present invention provides a urea resin paint composition and a method of manufacturing the same.
상기와 같은 과제를 해결하기 위한 본 발명의 강관의 내,외부 코팅용 폴리우레아수지 도료조성물은, 디이소시아네이트(Diisocyanate) 55 ~ 70중량부, 폴리옥시알킬렌 글리콜(Polyoxyalkylene glycol) 25 ~ 35중량부 및 알킬렌 카보네이트(Alkylene carbonate) 5 ~ 15중량부의 중합반응에 의해 생성되는 우레탄 프리폴리머(Urethane prepolymer) 100중량부를 기준으로 중합반응 억제제(polymerization inhibitor) 0.01 ~ 0.1중량부를 함유하는 주제부; 폴리에테르아민(Polyether amine) 100 중량부를 기준으로 습윤분산제 0.1 ~ 0.4중량부, 안료 4 ~ 7중량부, 사슬연장제 5 ~ 8중량부, 부착력 증강제 0.4 ~ 0.7중량부, 소포탈포제 0.4 ~ 0.7중량부, 유동성 조절제 0.1 ~ 2.0중량부를 함유하는 경화제부로 구성되며, 상기 주제부와 경화제부는 각각 40 ~ 60중량%의 비율로 포함하여 이루어짐을 특징으로 하고 있다.Polyurea resin coating composition for internal and external coating of the steel pipe of the present invention for solving the above problems, 55 to 70 parts by weight of diisocyanate, 25 to 35 parts by weight of polyoxyalkylene glycol (Polyoxyalkylene glycol) And a main part containing 0.01 to 0.1 parts by weight of a polymerization inhibitor based on 100 parts by weight of a urethane prepolymer produced by a polymerization reaction of 5 to 15 parts by weight of alkylene carbonate. 0.1 to 0.4 parts by weight of a wet dispersant, 4 to 7 parts by weight of pigment, 5 to 8 parts by weight of chain extender, 0.4 to 0.7 parts by weight of adhesion enhancer, and 0.4 to 0.7 antifoaming agent based on 100 parts by weight of polyether amine It is composed of a hardener portion containing 0.1 parts by weight to 2.0 parts by weight of the flow control agent, wherein the main portion and the hardener portion is characterized in that it comprises a ratio of 40 to 60% by weight, respectively.
또한, 본 발명의 강관의 내,외부 코팅용 폴리우레아수지 도료조성물의 제조방법은, 디이소시아네이트(Diisocyanate) 55 ~ 70중량부, 폴리옥시알킬렌글리콜(Polyoxyalkylene glycol) 25 ~ 35중량부, 알킬렌카보네이트(Alkylene carbonate) 5 ~ 15중량부를 반응용기에 투입한 후 교반하면서 서서히 승온하여 60 ~ 90℃에서 2 ~ 5시간 동안 등온유지하고, 이소시아네이트기(Isocyanate group, -N=C=O)의 함량이 15 ~ 25%일 때 열을 차단하고 서서히 냉각하여 우레탄 프리폴리머(Urethane prepolymer)를 합성하되, 50℃ 이하에서 상기 우레탄 프리폴리머 100중량부를 기준으로 중합반응 억제제(Polymerization inhibitor) 0.01 ~ 0.1중량부를 투입하여 0.5 ~ 1.5시간 동안 균일하게 교반하여 주제부를 형성하는 단계; 폴리에테르아민(Polyether amine) 25 ~ 30중량부, 습윤분산제 0.1 ~ 0.4중량부, 안료 4 ~ 7중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시킨 다음, 다시 폴리에테르아민(Polyether amine) 65 ~ 70중량부, 사슬연장제 5 ~ 8중량부, 부착력 증강제 0.4 ~ 0.7중량부, 소포탈포제 0.4 ~ 0.7 중량부, 유동성 조절제 0.1 ~ 2.0중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하여 경화제부를 형성하는 단계; 상기와 같이 형성된 주제부와 경화제부를 각각 40 ~ 60중량%의 비율로 혼합하는 단계로 이루어지는 것을 특징으로 한다.In addition, the production method of the polyurea resin coating composition for coating the inner and outer coating of the steel pipe of the present invention, diisocyanate 55 ~ 70 parts by weight, polyoxyalkylene glycol 25 ~ 35 parts by weight, alkylene 5-15 parts by weight of carbonate (Alkylene carbonate) was added to the reaction vessel and then gradually heated up with stirring to maintain isothermal temperature at 60-90 ° C. for 2-5 hours, and the content of isocyanate group (-N = C = O). When the 15 to 25% of the heat is cut and gradually cooled to synthesize a urethane prepolymer (Urethane prepolymer), at 50 ℃ or less based on 100 parts by weight of the polymerization reaction inhibitor (Polymerization inhibitor) by adding 0.01 ~ 0.1 parts by weight Uniformly stirring for 0.5 to 1.5 hours to form a main portion; 25 to 30 parts by weight of polyether amine, 0.1 to 0.4 parts by weight of a wet dispersant, and 4 to 7 parts by weight of a pigment are added to a separate container and dispersed to have a particle size of 20 μm or less, and then polyetheramine ( Polyether amine) 65 ~ 70 parts by weight, chain extender 5 ~ 8 parts by weight, adhesion enhancer 0.4 ~ 0.7 parts by weight, antifoaming agent 0.4 ~ 0.7 parts by weight, fluidity regulator 0.1 ~ 2.0 parts by adding 1 to 2 hours at 2000rpm Stirring to form a hardener portion; The main portion and the curing agent formed as described above is characterized in that it comprises a step of mixing at a ratio of 40 to 60% by weight, respectively.
그리고 본 발명의 강관의 표면에 폴리우레아수지 도료조성물을 코팅하는 방법은 위와 같이 형성된 주제부와 경화제부를 각각 준비하는 단계; 상기 주제부와 경화제부를 50 ~ 80℃의 온도로 가열한 상태에서 각각 40 ~ 60중량%의 비율로 혼합하여 제조된 폴리우레아수지 도료조성물을 강관의 내부 또는 외부에 1500 ~ 3000psi의 스프레이 분사압력으로 도포하는 단계를 포함하여 이루어지는 것을 특징으로 한다.And the method of coating the polyurea resin coating composition on the surface of the steel pipe of the present invention comprises the steps of preparing a main portion and a hardener portion formed as described above; The polyurea resin coating composition prepared by mixing the main portion and the hardener portion at a temperature of 50 to 80 ° C. at a ratio of 40 to 60% by weight, respectively, was sprayed at a pressure of 1500 to 3000 psi to the inside or the outside of the steel pipe. Characterized in that it comprises a step of applying.
이하, 본 발명의 구체적인 실시예에 있어서의 각 구성성분은 다음과 같다.Hereinafter, each component in the specific Example of this invention is as follows.
상기 중합반응 억제제는 2-에틸헥실산 포스페이트(2-Ethylhexyl acid Phosphate), 인산(H3PO4, Phosphoric acid) 중 어느 1종 이상을 사용한다.The polymerization inhibitor is used any one or more of 2-ethylhexyl acid phosphate (2-Ethylhexyl acid Phosphate), phosphoric acid (H 3 PO 4 , Phosphoric acid).
상기 습윤분산제는, 안료 친화그룹을 가진 고분자량의 블록 공중합체 용액, 산성 폴리머의 알킬암모늄염 용액, 안료 친화그룹을 가진 하이드록시 관능기 카르복실산 에스테르 용액, 저분자 불포화 폴리카르복실산 폴리머 용액, 폴리실록산 공중합체와 저분자 불포화 폴리카르복실산 폴리머 용액, 폴리카르복실산의 알킬암모늄염 용액, 산성그룹을 가진 공중합체 용액, 저분자 불포화 폴리카르복실산 폴리머 중 어느 1종 이상을 사용할 수 있다.The wet dispersant is a high molecular weight block copolymer solution having a pigment affinity group, an alkylammonium salt solution of an acidic polymer, a hydroxy functional group carboxylic ester solution having a pigment affinity group, a low molecular unsaturated polycarboxylic acid polymer solution, a polysiloxane air Any one or more of copolymer and low molecular weight unsaturated polycarboxylic acid polymer solution, alkylammonium salt solution of polycarboxylic acid, copolymer solution having acidic group, and low molecular weight unsaturated polycarboxylic acid polymer can be used.
상기 안료는 이산화티탄(Titanium dioxide), 카본블랙(Carbon black), 프탈로시아닌 블루(Phthalocyanine blue), 프탈로시아닌 그린(Phthalocyanine green), 산화아연, 황화아연 중 어느 1종 이상을 사용할 수 있다.The pigment may be any one or more of titanium dioxide, carbon black, phthalocyanine blue, phthalocyanine green, phthalocyanine green, zinc oxide, and zinc sulfide.
상기 사슬연장제는 디에틸-톨루엔디아민(Diethyl-toluenediamine, DETDA), 티메틸티오-톨루엔디아민(Dimethylthio-toluenediamine, DMTDA), N,N′--디(sec-부틸)-아미노-비페닐메탄(N,N′-di(sec.butyl)-amino-biphenyl methane, DBMDA), 4,4′-메틸렌비스-(3-클로로-2,6-디에틸)-아닐린(4,4′-methylenebis-(3-chloro, 2,6-diethyl)-aniline, MCDEA), 환상지방족 아민(Cycloaliphatic amine), 2차 지방족 아민(Secondary aliphatic amine), 2차 지방족 디아민(Secondary aliphatic diamine), 2차 방향족 디아민(Secondary aromatic diamine) 중 어느 1종 이상을 사용할 수 있다.The chain extender is diethyl-toluenediamine (DETDA), dimethylthio-toluenediamine (DMTDA), N, N'-di (sec-butyl) -amino-biphenylmethane (N, N′-di (sec.butyl) -amino-biphenyl methane, DBMDA), 4,4′-methylenebis- (3-chloro-2,6-diethyl) -aniline (4,4′-methylenebis -(3-chloro, 2,6-diethyl) -aniline, MCDEA), cycloaliphatic amine, Secondary aliphatic amine, Secondary aliphatic diamine, Secondary aromatic diamine Any one or more of (Secondary aromatic diamine) can be used.
상기 부착력 증강제는 2-(3,4 에폭시시클로헥실)-에틸트리메톡시실란(2-(3,4 epoxycyclohexyl)-ethyltrimethoxysilane), 3-글리시독시프로필메틸 디에톡시실란(3-glycidoxypropylmethyl diethoxysilane), 3-아미노프로필 트리에톡시시란(3-aminopropyl triethoxysilane), N-(2-아미노에틸)3-아미노프로필 메틸 디메톡시실란(N-(2-aminoethyl)3-aminopropylmethyl dimethoxysilane), N-(2-아미노에틸)3-아미노프로필 트리메톡시실란(N-(2-aminoethyl)3-aminopropyl trimethoxysilane), N-(2-아미노에틸)3-아미노프로필 트리에톡시실란(N-(2-aminoethyl)3-aminopropyl triethoxysilane), 3-아미노프로필 트리메톡시실란(3-aminopropyl trimethoxysilane), 3-메르캅토프로필 트리메톡시실란(3-mercaptopropyl trimethoxysilane), 3-글리시독시프로필 트리메톡시실란(3-Glycidoxypropyl trimethoxysilane), 감마-글리시독시프로필 트리메톡시실란(Gamma-glycidoxypropyl trimethoxysilane) 중에서 선택되는 어느 1종 이상의 실란 커플링제(Silane coupling agent)를 사용할 수 있다.The adhesion enhancing agent is 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane (2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane), 3-glycidoxypropylmethyl diethoxysilane, 3-aminopropyl triethoxysilane, N- (2-aminoethyl) 3-aminopropyl methyl dimethoxysilane (N- (2-aminoethyl) 3-aminopropylmethyl dimethoxysilane), N- (2 -Aminoethyl) 3-aminopropyl trimethoxysilane (N- (2-aminoethyl) 3-aminopropyl trimethoxysilane), N- (2-aminoethyl) 3-aminopropyl triethoxysilane (N- (2-aminoethyl) 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane (3- Glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane Select at least any one silane coupling that can be used for agent (Silane coupling agent).
상기 소포탈포제는 미네랄 오일계 소포제, 실리콘계 소포제, 비실리콘계 폴리머 소포제 중 어느 1종 이상을 사용할 수 있다.The antifoaming agent may be any one or more of mineral oil-based antifoaming agent, silicone antifoaming agent, non-silicone-based polymer antifoaming agent.
상기 유동성 조절제는 발연 실리카(Fumed silica), 우레아수지(Urea resin), 폴리아마이드왁스(Polyamide wax), 벤토나이트(Bentonite) 중 어느 1종 이상을 사용할 수 있다.The fluidity regulator may be any one or more of fumed silica, urea resin, polyamide wax, and bentonite.
본 발명의 강관의 내,외부 코팅용 폴리우레아수지 도료조성물은, 디이소시아네이트(Diisocyanate), 폴리옥시알킬렌 글리콜(Polyoxyalkylene glycol) 및 알킬렌 카보네이트(Alkylene carbonate)의 중합반응에 의해 생성되는 우레탄 프리폴리머(Urethane prepolymer)를 함유하는 주제부에 중합반응 억제제(Polymerization inhibitor)의 작용에 의해 미반응 이소시아네이트의 반응으로 인한 점도 상승이나 겔화 등을 미연에 방지하여 우레탄 프리폴리머의 중합반응을 종결시킴으로써 저장 안정성은 물론, 강관의 표면에 도포된 도막은 소지면과의 부착성, 내굴곡성, 내충격성, 내마모성 등 물리적 특성 및 내염수성, 내수성, 내알칼리성, 내휘발유성 등 화학성 특성이 우수하게 되며, 또한 음극박리(Cathodic disbondment) 시험에 대한 저항성이 매우 양호하여 국부 전류에 의한 도막의 손상 및 박리가 발생되지 않는 고강도, 고내구성의 코팅막을 형성하는 효과가 있다.Polyurea resin coating composition for coating the inner and outer coatings of the steel pipe of the present invention is a urethane prepolymer produced by the polymerization of diisocyanate, polyoxyalkylene glycol and alkylene carbonate ( In addition to storage stability, the urethane prepolymer can be terminated by preventing the increase of viscosity or gelation due to the reaction of unreacted isocyanate by the action of the polymerization inhibitor (Polymerization inhibitor) on the main part containing urethane prepolymer. The coated film coated on the surface of the steel pipe has excellent physical properties such as adhesion to the surface, bending resistance, impact resistance and abrasion resistance, and chemical properties such as salt water resistance, water resistance, alkali resistance, and gasoline resistance, and also cathodic disbondment. ) The resistance to the test is very good, so that the coating film is damaged and There is an effect of forming a high-strength, high durability coating film that does not occur.
또한, 본 발명의 제조방법으로 제조된 강관의 내,외부 코팅용 폴리우레아수지 도료조성물은, 점도가 균일하게 유지되어 강관의 내면과 외면의 기밀성과 접착력을 향상시키며, 강관의 표면에 고온(40℃ 이상), 고압(1500psi 이상)의 스프레이 분사압력으로 도포되어 시공되더라도 기존의 코팅제에 비해 분진 발생이 저감되어 재료의 낭비가 적고 작업성이 양호하며, 무용제형 타입의 속경화형 도료로서 1회에 후막(1㎜ 이상) 도장이 가능할 뿐만 아니라 유해물질이 유출되지 않는 관계로 환경에 친화적인 코팅막을 제공하는 효과가 있다.In addition, the polyurea resin coating composition for coating the inner and outer coating of the steel pipe manufactured by the manufacturing method of the present invention, the viscosity is uniformly maintained to improve the airtightness and adhesion of the inner and outer surfaces of the steel pipe, the high temperature (40 ℃)), even when applied under high pressure spraying pressure (1500psi or more), it generates less dust than conventional coatings, so it is less waste of materials and has good workability. It is a solvent-free type of fast curing paint Thick film (1 mm or more) is not only possible to paint, but also has an effect of providing an environmentally friendly coating film because the harmful substances do not leak.
본 발명의 강관의 내,외부 코팅용 폴리우레아수지 도료조성물의 제조방법은, 디이소시아네이트(Diisocyanate) 55 ~ 70중량부, 폴리옥시알킬렌글리콜(Polyoxyalkylene glycol) 25 ~ 35중량부, 알킬렌카보네이트(Alkylene carbonate) 5 ~ 15중량부를 반응용기에 투입한 후 교반하면서 서서히 승온하여 60 ~ 90℃에서 2 ~ 5시간 동안 등온유지하고, 이소시아네이트기(Isocyanate group, -N=C=O)의 함량이 15 ~ 25%일 때 열을 차단하고 서서히 냉각하여 우레탄 프리폴리머(Urethane prepolymer)를 합성하되, 50℃ 이하에서 상기 우레탄 프리폴리머 100중량부를 기준으로 중합반응 억제제(Polymerization inhibitor) 0.01 ~ 0.1중량부를 투입하여 0.5 ~ 1.5시간 동안 균일하게 교반하여 주제부를 형성하는 단계; 폴리에테르아민(Polyether amine) 25 ~ 30중량부, 습윤분산제 0.1 ~ 0.4 중량부, 안료 4 ~ 7중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시킨 다음, 다시 폴리에테르아민(Polyether amine) 65 ~ 70중량부, 사슬연장제 5 ~ 8중량부, 부착력 증강제 0.4 ~ 0.7중량부, 소포탈포제 0.4 ~ 0.7중량부, 유동성 조절제 0.1 ~ 2.0중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하여 경화제부를 형성하는 단계; 상기와 같이 형성된 주제부와 경화제부를 각각 40 ~ 60중량%의 비율로 혼합하는 단계를 차례로 포함하여 이루어진다.Method for producing a polyurea resin coating composition for coating the inner and outer coating of the steel pipe of the present invention, diisocyanate 55 to 70 parts by weight, polyoxyalkylene glycol 25 to 35 parts by weight, alkylene carbonate ( Alkylene carbonate) 5-15 parts by weight were added to a reaction vessel, and then gradually warmed up with stirring to maintain isothermal temperature at 60-90 ° C. for 2-5 hours, and the content of isocyanate group (-N = C = O) was 15 ~ 25% to cut off the heat and slowly cool to synthesize a urethane prepolymer (Urethane prepolymer), at 50 ℃ or less based on 100 parts by weight of the polymerization reaction (Polymerization inhibitor) 0.01 ~ 0.1 parts by weight of 0.5 ~ Stirring uniformly for 1.5 hours to form the main part; 25 to 30 parts by weight of polyether amine, 0.1 to 0.4 parts by weight of a wet dispersant, and 4 to 7 parts by weight of a pigment are added to a separate container and dispersed to have a particle size of 20 μm or less, and then polyetheramine ( Polyether amine) 65 ~ 70 parts by weight, chain extender 5 ~ 8 parts by weight, adhesion force enhancer 0.4 ~ 0.7 parts by weight, antifoaming agent 0.4 ~ 0.7 parts by weight, fluidity regulator 0.1 ~ 2.0 parts by adding 1 to 2 hours at 2000rpm Stirring to form a hardener portion; It comprises a step of mixing the main portion and the curing agent portion formed as described above in a ratio of 40 to 60% by weight, respectively.
이하에서는, 본 발명의 구성에 대한 작용을 상세하게 설명하되, 이는 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 예시하기 위한 것이므로, 본 발명의 기술적 범위에 포함되는 균등물 내지 대체물을 포함하는 것으로 이해되어야 하며, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, the operation of the configuration of the present invention will be described in detail, which is intended to illustrate to the extent that one of ordinary skill in the art to which the present invention pertains can easily carry out the invention, and thus the technical scope of the present invention. It should be understood to include equivalents or substitutes included therein, which does not mean that the technical spirit and scope of the present invention are limited.
먼저, 주제부를 형성하는 단계는, 디이소시아네이트(Diisocyanate) 55 ~ 70중량부, 폴리옥시알킬렌글리콜(Polyoxyalkylene glycol) 25 ~ 35중량부, 알킬렌카보네이트(Alkylene carbonate) 5 ~ 15중량부를 반응용기에 투입한 후 교반하면서 서서히 승온하여 60 ~ 90℃에서 2 ~ 5시간 동안 등온유지하고, 이소시아네이트기(Isocyanate group, -N=C=O)의 함량이 15 ~ 25%일 때 열을 차단하고 서서히 냉각하여 우레탄 프리폴리머(Prepolymer)를 합성하되, 50℃ 이하에서 상기 우레탄 프리폴리머 100중량부를 기준으로 중합반응 억제제(Polymerization inhibitor) 0.01 ~ 0.1중량부를 투입하여 0.5 ~ 1.5시간 동안 균일하게 교반하는 것이다.First, forming the main part, 55 to 70 parts by weight of diisocyanate, 25 to 35 parts by weight of polyoxyalkylene glycol, 5 to 15 parts by weight of alkylene carbonate in the reaction vessel After the addition, the mixture is gradually heated while stirring and isothermally maintained at 60 to 90 ° C. for 2 to 5 hours. When the content of the isocyanate group (-N = C = O) is 15 to 25%, the heat is blocked and gradually cooled. By synthesizing the urethane prepolymer (Prepolymer), by adding 0.01 ~ 0.1 parts by weight of a polymerization inhibitor (Polymerization inhibitor) based on 100 parts by weight of the urethane prepolymer at 50 ℃ or less to uniformly stirred for 0.5 to 1.5 hours.
상기 주제부의 우레탄 프리폴리머는 디이소시아네이트, 폴리옥시알킬렌글리콜, 알킬렌카보네이트가 반응하여 우레탄 결합을 형성하며, 강관의 내부 및 외부 코팅용 도료에 적합한 강도와 유연성을 갖는다. 일반적으로 상기 우레탄 프리폴리머의 말단에는 이소시아네이트기가 15% 미만으로 유지되도록 반응을 하게 되나, 본 발명에서는 상기 우레탄 프리폴리머 중의 이소시아네이트기 잔존율이 15 ~ 25%일 때 열을 차단하고 중합반응 억제제를 첨가하여 미반응 이소시아네이트의 반응으로 인한 점도 상승이나 겔화 등을 미연에 방지하여 우레탄 프리폴리머의 중합반응을 종결시킴으로써 저장 안정성을 양호하게 하고, 강관의 내면과 외면에 대한 부착성능을 향상시킨다. 이때, 상기 우레탄 프리폴리머의 분자량은 5,000 내지 100,000이 바람직한데, 이는 상기 우레탄 프리폴리머의 분자량이 5,000 미만이면 도막의 굴곡성과 내충격성이 취약해지고, 상기 분자량이 100,000을 초과하면 도료의 점도가 높아 스프레이 작업성이 나빠지기 때문이다.The urethane prepolymer of the main part reacts with diisocyanate, polyoxyalkylene glycol, alkylene carbonate to form a urethane bond, and has strength and flexibility suitable for paint for internal and external coating of steel pipe. In general, the end of the urethane prepolymer is reacted to maintain the isocyanate group to less than 15%, but in the present invention, when the isocyanate group residual ratio in the urethane prepolymer is 15 to 25%, the heat is blocked and a polymerization inhibitor is added to prevent the reaction. By preventing the increase in viscosity or gelation due to the reaction of the reaction isocyanate and terminating the polymerization reaction of the urethane prepolymer, the storage stability is improved and the adhesion to the inner and outer surfaces of the steel pipe is improved. At this time, the molecular weight of the urethane prepolymer is preferably 5,000 to 100,000, which is when the molecular weight of the urethane prepolymer is less than 5,000, the flexibility and impact resistance of the coating film is weak, if the molecular weight exceeds 100,000, the paint viscosity is high spray workability Because it gets worse.
상기 디이소시아네이트(Diisocyanate)는 우레탄 프리폴리머를 합성하는데 사용되는 화합물로서 도막 내에서 하드 블록(Hard Segment)을 형성하여 기계적 강도, 인장 강도, 탄성, 내마모성, 내노화성, 내유성, 내용제성, 내충격성 및 저온 안정성의 특성을 나타내며, 그 종류는 특별한 제한없이 지방족 이소시아네이트, 방향족 이소시아네이트를 모두 사용될 수 있지만, 일반적으로 방향족 이소시아네이트가 사용되면 지방족 이소시아네이트가 사용되어 합성된 폴레우레탄(또는 폴리우레아)보다 녹는점과 경도가 더 높은 물질이 합성된다.The diisocyanate is a compound used to synthesize a urethane prepolymer and forms a hard block in a coating film, thereby providing mechanical strength, tensile strength, elasticity, wear resistance, aging resistance, oil resistance, solvent resistance, impact resistance, and low temperature. It shows the characteristics of stability, and its type can be used both aliphatic isocyanate and aromatic isocyanate without particular limitation, but in general, when aromatic isocyanate is used, the melting point and hardness is higher than that of synthesized polyurethane (or polyurea) using aliphatic isocyanate. Higher materials are synthesized.
본 발명에서는 디이소시아네이트 화합물로서, 4,4′-디페닐메탄 디이소시아네이트(4,4′-Diphenylmethane diisocyanate, MDI), 사이클로헥실메탄 디이소시아네이트(Cyclohexylmethane diisocyanate, H12MDI), 1,6-헥사메틸렌 디이소시아네이트(1,6-Hexamethylene diisocyanate, HDI), 이소포론 디이소시아네이트(Isophorone diisocyanate, IPDI) 등을 단독으로 사용하거나 혼합하여 사용하였으며, 우레탄 프리폴리머 100중량부를 기준으로 55 ~ 70중량부로 사용하는 것이 도막의 강도와 유연성을 동시에 발휘하기에 적합함과 동시에 내구성이 양호한 것으로 연구되었다. 만일 이소시아네이트기가 과량 첨가되어 반응이 진행된다면 고분자 내에 있는 새롭게 형성된 다른 작용기와 반응할 수도 있기 때문이다.In the present invention, as the diisocyanate compound, 4,4'-diphenylmethane diisocyanate (MDI), cyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (1,6-Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or the like was used alone or mixed, and used as a 55 ~ 70 parts by weight based on 100 parts by weight of the urethane prepolymer It has been studied to be suitable for showing both flexibility and flexibility, and at the same time, good durability. If the reaction proceeds by adding an isocyanate group in excess, it may react with other newly formed functional groups in the polymer.
상기 폴리옥시알킬렌글리콜(Polyoxyalkylene glycol)은 알킬렌 산화물(Alkylene oxide)계 유도체로서 투명한 무색 액체이며 유동점이 낮다. 분자량 분포곡선이 매우 좁기 때문에 우레탄 프리폴리머 중합반응시 디올(Diol) 또는 트리올(Triol)의 히드록실 관능기(-OH, Hydroxyl group)를 갖는 폴리올 화합물이 많이 사용되며, 신장률, 내마모성, 고탄성, 인장강도, 경도 및 유연성 향상 등을 목적으로 사용된다.The polyoxyalkylene glycol is an alkylene oxide derivative and is a transparent colorless liquid and has a low pour point. Since the molecular weight distribution curve is very narrow, polyol compounds having a hydroxyl functional group (-OH, Hydroxyl group) of diol or triol are frequently used in the urethane prepolymer polymerization reaction, and elongation, wear resistance, high elasticity and tensile strength are used. It is used for the purpose of improving hardness and flexibility.
상기 알킬렌카보네이트(Alkylene carbonate)는 폴리우레탄 프리폴리머의 저장성 개선 및 점도 저하, 주제부와 경화제부의 균일한 혼합 및 도료의 스프레이 도장시의 도장면 레벨링(levelling)을 향상시킴을 목적으로 사용된다.The alkylene carbonate is used for the purpose of improving the storage properties and viscosity of the polyurethane prepolymer, lowering the uniformity of the main part and the curing agent, and improving the leveling of the coating surface during spray coating of the paint.
그리고 상기 중합반응 억제제는 우레탄 프리폴리머 합성시 2-에틸헥실산 포스페이트(2-Ethylhexyl acid phosphate) 또는 인산(H3PO4, Phosphoric acid) 중 어느 1종 이상을 우레탄 프리폴리머 100중량부를 기준으로 0.01 ~ 0.1중량부 투입함으로써, 우레탄 프리폴리머를 합성하는데 사용되는 이소시아네이트(-NCO) 및 이와 반응하는 화합물(-OH, -NH, -SH)을 고온에서 중합반응 시킨 후 미반응 이소시아네이트기가 잔존시 시간이 경과함에 따라 미반응 이소시아네이트의 반응으로 인한 점도 상승이나 겔화 발생을 미연에 방지하고 반응을 종결시키게 되며, 이로 인하여 폴리우레탄 프리폴리머의 장시간 저장 안정성이 증대되고 균일하게 부착력이 양호한 폴리우레아 수지조성물을 얻을 수 있는 것이다.And the polymerization inhibitor is 0.01 ~ 0.1 based on 100 parts by weight of any one or more of the 2-ethylhexyl acid phosphate (2-Ethylhexyl acid phosphate) or phosphoric acid (H 3 PO 4 , Phosphoric acid) when the urethane prepolymer is synthesized By weight part, the polymerization of the isocyanate (-NCO) and the compound (-OH, -NH, -SH) and the reacting compound (-OH, -NH, -SH) used to synthesize the urethane prepolymer at a high temperature, the time after the unreacted isocyanate group remaining This prevents the increase in viscosity or gelation caused by the reaction of unreacted isocyanate and terminates the reaction, thereby increasing the long-term storage stability of the polyurethane prepolymer and obtaining a polyurea resin composition having good adhesion.
다음으로, 경화제부를 형성하는 단계는, 폴리에테르아민 25 ~ 30중량부, 습윤분산제 0.1 ~ 0.4중량부, 안료 4 ~ 7중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시킨 다음, 다시 폴리에테르아민 65 ~ 70중량부, 사슬연장제 5 ~ 8중량부, 부착력 증강제 0.4 ~ 0.7중량부, 소포탈포제 0.4 ~ 0.7중량부, 유동성 조절제 0.1 ~ 2.0중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하는 것이다.Next, the step of forming the curing agent portion, 25 to 30 parts by weight of polyetheramine, 0.1 to 0.4 parts by weight of the wet dispersant, 4 to 7 parts by weight of the pigment is added to a separate container and dispersed so that the particle size is 20㎛ or less Again, 65 to 70 parts by weight of polyetheramine, 5 to 8 parts by weight of chain extender, 0.4 to 0.7 parts by weight of adhesion enhancer, 0.4 to 0.7 parts by weight of antifoaming agent, and 0.1 to 2.0 parts by weight of flow control agent were added at 1 to 2000 rpm. Stir for 2 hours.
상기 경화제부를 형성하는 단계 중 제1공정은, 폴리에테르아민 25 ~ 30중량부, 습윤분산제 0.1 ~ 0.4 중량부, 안료 4 ~ 7중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시키는 것으로, 상기 폴리에테르아민은 1차 아민 그룹(Primary amine group)을 가진 분자량이 200 ~ 5,000g/mol인 다양한 화합물로 이소시아네이트 관능기(-NCO)와의 반응이 매우 빠르기 때문에 유연성과 강인성 향상 및 저점도의 배합 설계를 가능하게 하며, 이에 습윤분산제와 안료를 적당량 첨가하여 분산시킴으로써 균질한 제품의 제조를 가능하게 한다.The first step of forming the curing agent portion, 25 to 30 parts by weight of polyetheramine, 0.1 to 0.4 parts by weight of the wet dispersant, 4 to 7 parts by weight of the pigment is added to a separate container and dispersed so that the particle size is 20㎛ or less In this case, the polyetheramine Various compounds with a molecular weight of 200 to 5,000 g / mol with primary amine groups are very fast to react with isocyanate functional groups (-NCO), allowing for improved flexibility, toughness and low viscosity formulations. This makes it possible to produce a homogeneous product by adding and dispersing an appropriate amount of the wet dispersant and the pigment.
상기 습윤분산제는, 안료 친화그룹을 가진 고분자량의 블록 공중합체 용액, 산성 폴리머의 알킬암모늄염 용액, 안료 친화그룹을 가진 하이드록시 관능기 카르복실산 에스테르 용액, 저분자 불포화 폴리카르복실산 폴리머 용액, 폴리실록산 공중합체와 저분자 불포화 폴리카르복실산 폴리머 용액, 폴리카르복실산의 알킬암모늄염 용액, 산성그룹을 가진 공중합체 용액, 저분자 불포화 폴리카르복실산 폴리머 중 어느 1종 이상을 0.1 ~ 0.4중량부로 사용하며, 액상의 수지(resin 또는 binder)에 고체의 안료(pigment)를 균일하게 분산하여 저장 중 응집 및 침전 방지와 도장 작업 후의 색분리, 색상 변화, 흐름성, 평활성 개선과 경화된 도막의 광택 저하를 방지하는 작용을 한다. 또한, 안료와 수지 용액 사이의 접촉각을 낮추어 액체가 안료 응집체 구조내로 보다 빠르게 침투될 수 있도록 하며, 분산제는 안료 표면에 흡착하여 정전기적 반발력이나 입체 장애 효과로 안료와 안료 사이의 간격을 일정하게 유지시켜 안료들이 재응집되는 것을 막아 준다.The wet dispersant is a high molecular weight block copolymer solution having a pigment affinity group, an alkylammonium salt solution of an acidic polymer, a hydroxy functional group carboxylic ester solution having a pigment affinity group, a low molecular unsaturated polycarboxylic acid polymer solution, a polysiloxane air 0.1 to 0.4 parts by weight of any one or more of a polymer and a low molecular unsaturated polycarboxylic acid polymer solution, an alkyl ammonium salt solution of polycarboxylic acid, a copolymer solution having an acidic group, a low molecular unsaturated polycarboxylic acid polymer Uniformly disperse solid pigments in resin (resin or binder) to prevent agglomeration and sedimentation during storage, to improve color separation, color change, flowability, smoothness after painting and to prevent gloss of cured coating film It works. In addition, the contact angle between the pigment and the resin solution is lowered to allow the liquid to penetrate into the pigment aggregate structure more quickly. The dispersant adsorbs onto the pigment surface to maintain a constant gap between the pigment due to electrostatic repulsion or steric hindrance. This prevents pigments from reaggregating.
상기 안료는 이산화티탄(Titanium dioxide), 카본블랙(Carbon black), 프탈로시아닌 블루(Phthalocyanine blue), 프탈로시아닌 그린(Phthalocyanine green), 산화아연, 황화아연 중 어느 1종 이상을 4 ~ 7중량부 사용하며, 액상 수지와 함께 미세 입자로 분산되어 도막의 색상을 부여하며 주로 백색, 흑색, 청색, 녹색 및 회색을 나타낸다. 그밖에도 주제부와 경화제부를 구분하여 혼합 안정성을 확인할 수 있도록 주제부 또는 경화제부의 총중량 대비 약 1 ~ 3중량% 이내로 첨가할 수 있다.The pigment is used 4 to 7 parts by weight of any one or more of titanium dioxide, carbon black (Carbon black), phthalocyanine blue (Phthalocyanine blue), phthalocyanine green (Phthalocyanine green), zinc oxide, zinc sulfide, Disperse into fine particles together with the liquid resin to give the color of the coating film, mainly white, black, blue, green and gray. In addition, it may be added within about 1 to 3% by weight based on the total weight of the main part or the curing agent to determine the mixing stability by distinguishing the main part and the curing agent.
상기 경화제부를 형성하는 단계 중 제2공정은, 상기 제1공정에서 분산과정을 거쳐 제조된 분산액에 더하여, 폴리에테르아민 65 ~ 70중량부, 사슬연장제 5 ~ 8중량부, 부착력 증강제 0.4 ~ 0.7중량부 및 소포탈포제 0.4 ~ 0.7중량부, 유동성 조절제 0.1 ~ 2.0중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하는 것으로, 각 구성성분의 적절한 조성과 작용에 의해 본 발명에서 요구되는 바람직한 특성을 발휘하게 된다.The second step of forming the curing agent portion, in addition to the dispersion prepared by the dispersion process in the first step, 65 to 70 parts by weight of polyetheramine, 5 to 8 parts by weight of chain extender, 0.4 ~ 0.7 adhesion strength enhancer By adding 0.4 to 0.7 parts by weight of the antifoaming agent and 0.1 to 2.0 parts by weight of the antifoaming agent and stirring at 2000 rpm for 1 to 2 hours, the desired properties required by the present invention are determined by appropriate composition and action of each component. Will be exercised.
상기 사슬연장제는 디에틸-톨루엔디아민(Diethyl-toluenediamine, DETDA), 티메틸티오-톨루엔디아민(Dimethylthio-toluenediamine, DMTDA), N,N′--디(sec-부틸)-아미노-비페닐메탄(N,N′-Di(sec.butyl)-amino-biphenyl methane, DBMDA), 4,4′-메틸렌비스-(3-클로로-2,6-디에틸)-아닐린(4,4′-Methylenebis-(3-chloro, 2,6-diethyl)-aniline, MCDEA), 환상지방족 아민(Cycloaliphatic amine), 2차 지방족 아민(Secondary aliphatic amine), 2차 지방족 디아민(Secondary aliphatic diamine), 2차 방향족 디아민(Secondary aromatic diamine) 중 어느 1종 이상을 5 ~ 8중량부 포함하는바, 이는 도막 형성시 하드 블록(Hard block)을 형성하는데 기여하고 경화된 도막의 내열성을 부여하며, 반응성을 지연(조절)시켜 도장 작업성과 도막의 평활성을 향상시킨다.The chain extender is diethyl-toluenediamine (DETDA), dimethylthio-toluenediamine (DMTDA), N, N'-di (sec-butyl) -amino-biphenylmethane (N, N′-Di (sec.butyl) -amino-biphenyl methane, DBMDA), 4,4′-methylenebis- (3-chloro-2,6-diethyl) -aniline (4,4′-Methylenebis -(3-chloro, 2,6-diethyl) -aniline, MCDEA), cycloaliphatic amine, Secondary aliphatic amine, Secondary aliphatic diamine, Secondary aromatic diamine 5 to 8 parts by weight of any one or more of (Secondary aromatic diamine), which contributes to the formation of a hard block (Hard block) when forming a coating film, imparts heat resistance of the cured coating film, delays (controls) reactivity This improves the coating workability and the smoothness of the coating film.
상기 부착력 증강제는 2-(3,4 에폭시시클로헥실)-에틸트리메톡시실란(2-(3,4 Epoxycyclohexyl)-ethyltrimethoxysilane), 3-글리시독시프로필메틸 디에톡시실란(3-Glycidoxypropylmethyl diethoxysilane), 3-아미노프로필 트리에톡시시란(3-Aminopropyl triethoxysilane), N-(2-아미노에틸)3-아미노프로필 메틸 디메톡시실란(N-(2-Aminoethyl)3-aminopropylmethyl dimethoxysilane), N-(2-아미노에틸)3-아미노프로필 트리메톡시실란(N-(2-Aminoethyl)3-aminopropyl trimethoxysilane), N-(2-아미노에틸)3-아미노프로필 트리에톡시실란(N-(2-Aminoethyl)3-aminopropyl triethoxysilane), 3-아미노프로필 트리메톡시실란(3-Aminopropyl trimethoxysilane), 3-메르캅토프로필 트리메톡시실란(3-Mercaptopropyl trimethoxysilane), 3-글리시독시프로필 트리메톡시실란(3-Glycidoxypropyl trimethoxysilane), 감마-글리시독시프로필 트리메톡시실란(Gamma-glycidoxypropyl trimethoxysilane) 중에서 선택되는 어느 1종 이상의 실란 커플링제(Silane coupling agent)를 0.4 ~ 0.7중량부 포함하는 것으로, 다양한 종류의 소지면과의 반응 및 결합력을 증강시켜 우수한 부착력을 부여하게 된다.The adhesion enhancing agent is 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane (2- (3,4 Epoxycyclohexyl) -ethyltrimethoxysilane), 3-glycidoxypropylmethyl diethoxysilane, 3-aminopropyl triethoxysilane, N- (2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N- (2 -Aminoethyl) 3-aminopropyl trimethoxysilane (N- (2-Aminoethyl) 3-aminopropyl trimethoxysilane), N- (2-aminoethyl) 3-aminopropyl triethoxysilane (N- (2-Aminoethyl) 3-aminopropyl triethoxysilane), 3-aminopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane (3- Glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane A silane coupling agent which is selected at least one kinds (Silane coupling agent) to include 0.4 to 0.7 parts by weight, to enhance the reaction and the bonding strength between the different types of sojimyeon thereby giving excellent adhesion.
상기 소포탈포제는 미네랄 오일계 소포제, 실리콘계 소포제, 비실리콘계 폴리머 소포제 중 어느 1종 이상을 0.4 ~ 0.7중량부 포함함으로써, 이는 낮은 표면장력을 가진 액체로 도료의 제조 공정 중이나 도장작업 중 도료 내에 혼입된 기포나 피도체의 형상에 의해 발생되는 기포를 빠른 시간 내에 제거하여 건조된 도막의 물리적 특성 유지와 외관을 개선하는 역할을 한다.The antifoaming agent includes 0.4 to 0.7 parts by weight of any one or more of a mineral oil-based antifoaming agent, a silicone-based antifoaming agent, and a non-silicone-based polymer antifoaming agent, which is a liquid having a low surface tension and incorporated into the paint during the manufacturing process of the coating or during the painting operation. By removing the bubbles generated by the bubbles or the shape of the object in a short time, it serves to maintain the physical properties and improve the appearance of the dried coating film.
상기 유동성 조절제는 발연 실리카(Fumed silica), 우레아수지(Urea resin), 폴리아마이드 왁스(Polyamide wax), 벤토나이트(Bentonite) 중 어느 1종 이상을 0.1 ~ 2.0중량부 포함하게 되는데, 이들의 작용을 예로 들면, 도막의 표면에 실라놀 그룹을 함유한 발연 실리카 입자들은 수소결합에 의해 3차원적인 구조를 형성하여 점도를 증가시키고 요변성을 부여하게 되며, 우레아수지는 대단히 미세한 수정 모양의 침상 구조를 갖는 3차원 망상구조를 형성하고 도료가 도장되는 동안에 낮은 점도가 요구되는 도료에서 형성된 망상구조는 낮은 전단력에 의해서도 충분히 파괴되고 도장된 후 도막에서 이 구조는 매우 빠르게 재생되기 때문에 도막의 점도는 매우 빠르게 증가하여 안료의 흐름방지 효과를 발휘하게 된다.The fluidity regulator includes 0.1 to 2.0 parts by weight of any one or more of fumed silica, urea resin, polyamide wax, bentonite, and the like. For example, fumed silica particles containing silanol groups on the surface of the coating film form a three-dimensional structure by hydrogen bonding to increase viscosity and give thixotropy, and urea resin has a very fine crystal shaped needle structure. When the three-dimensional network is formed and the network formed in the paint that requires a low viscosity while the paint is applied is sufficiently destroyed by the low shear force, the structure of the coating is very fast because the structure is regenerated very quickly after the paint is applied. To exhibit the effect of preventing the pigment flow.
마지막으로, 혼합하는 단계는 상기와 같이 형성된 주제부와 경화제부를 각각 40 ~ 60중량%의 비율로 혼합하는 것으로, 위와 같은 혼합비율에 의해 통상적으로 요구되는 특성, 예를 들면, 부착강도, 내굴곡성, 내충격성, 흡수율, 경도, 내마모성, 내약품성 등을 충분히 만족할 수 있는 것으로 연구되었으며, 가장 바람직하게는 주제부와 경화제부의 부피비(volume ratio)는 1.00, 중량비(weight ratio)는 1.10 ~ 1.30 정도로 설정하는 것이 좋다.Finally, the mixing step is to mix the main portion and the curing agent portion formed as described above in a ratio of 40 to 60% by weight, respectively, the characteristics typically required by the above mixing ratio, for example, adhesion strength, flex resistance , Impact resistance, water absorption, hardness, wear resistance, chemical resistance, etc. have been studied to satisfy sufficiently, most preferably, the volume ratio of the main part and the hardener part is set to 1.00 and the weight ratio is set to 1.10 to 1.30. Good to do.
또한, 본 발명에 의해 제조된 폴리우레아수지 도료조성물을 강관의 표면에 코팅하는 방법을 일례로 들어 설명하면, 상기와 같이 제조된 주제부와 경화제부를 50 ~ 80℃의 온도로 가열한 상태에서 각각 40 ~ 60중량%의 비율로 혼합하여 폴리우레아수지 도료조성물을 제조한 후, 강관의 내부 및/또는 외부에 1500 ~ 3000psi의 스프레이 분사압력으로 도포하는 단계를 거쳐 도장이 완료되며, 이때 지촉건조시간은 대략 50 ~ 150초(23℃ 기준)로서 비교적 속경화성을 나타낸다.In addition, the method of coating the polyurea resin coating composition prepared according to the present invention on the surface of the steel pipe as an example, will be described, respectively, in the state of heating the main portion and the hardener portion prepared as described above at a temperature of 50 ~ 80 ℃ After preparing a polyurea resin coating composition by mixing at a ratio of 40 to 60% by weight, the coating is completed by applying a spray injection pressure of 1500 ~ 3000psi to the inside and / or outside of the steel pipe. Is about 50 to 150 seconds (23 ° C. standard) and shows relatively fast curing properties.
이상에서 살펴본 바와 같이 본 발명은 수많은 실험을 거쳐 완성되었으나, 이하에서는 당업자가 용이하게 이해하고 실시할 수 있을 정도의 바람직한 실시예를 통하여 본 발명을 설명한다.As described above, the present invention has been completed through numerous experiments. Hereinafter, the present invention will be described through preferred embodiments to be easily understood and implemented by those skilled in the art.
<실시예 1>≪ Example 1 >
(주제부의 제조)(Production of the subject matter)
4,4′-디페닐메탄 디이소시아네이트(4,4′-Diphenylmethane diisocyanate, MDI) 55중량부, 폴리옥시알킬렌글리콜(Polyoxyalkylene glycol) 35중량부, 알킬렌카보네이트(Alkylene carbonate) 10중량부를 반응용기에 투입한 후 교반하면서 서서히 승온하여 70℃에서 3시간 동안 등온유지한 다음, 이소시아네이트기(Isocyanate group, -N=C=O)의 함량이 15 ~ 25%일 때 열을 차단하고 서서히 냉각하여 우레탄 프리폴리머(Urethane prepolymer)를 합성하되, 50℃ 이하에서 상기 우레탄 프리폴리머 100중량부를 기준으로 2-에틸헥실산 포스페이트(2-Ethylhexyl acid phosphate) 0.01중량부를 투입하여 1시간 동안 균일하게 교반하여 주제부를 제조하였다.55 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI), 35 parts by weight of polyoxyalkylene glycol, 10 parts by weight of alkylene carbonate The solution was gradually heated and stirred at 70 ° C. for 3 hours. Then, when the content of the isocyanate group (-N = C = O) was 15-25%, the heat was cut off and cooled slowly. Synthesis of a prepolymer (Urethane prepolymer) was carried out at 50 ° C or less, based on 100 parts by weight of the urethane prepolymer, 0.01 parts by weight of 2-ethylhexyl acid phosphate was added and stirred uniformly for 1 hour to prepare a main part. .
(경화제부의 제조)(Production of Hardener Part)
폴리에테르아민(Polyether amine) 25중량부, 습윤분산제 0.1중량부, 안료 5중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시킨 다음, 다시 폴리에테르아민(Polyether amine) 70중량부, 사슬연장제 6중량부, 부착력 증강제 0.5중량부, 소포탈포제 0.5중량부, 유동성 조절제 1.5중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하여 경화제부를 제조하였다.25 parts by weight of polyether amine, 0.1 parts by weight of a wet dispersant, and 5 parts by weight of pigment are added to a separate container, dispersed to have a particle size of 20 μm or less, and then 70 parts by weight of polyether amine. , 6 parts by weight of chain extender, 0.5 parts by weight of adhesion enhancer, 0.5 parts by weight of antifoaming agent, 1.5 parts by weight of fluidity regulator were added and stirred at 2000 rpm for 1 to 2 hours to prepare a curing agent part.
(코팅막의 형성)(Formation of Coating Film)
고압충돌 혼합식 전용 도장기(Two Line System, 2개의 별도 라인으로 주제부, 경화제부가 공급되어 스프레이건 내부의 혼합 모듈(mix module)에서 고압충돌 혼합되어 분사됨. GRACO사 ‘REACTOR E-XP2’ 사용)를 이용하여 상기 주제부와 경화제부가 각각 40 : 60의 중량비로 혼합된 폴리우레아수지 도료조성물을 약 70℃의 온도에서 1500 ~ 3000psi의 분사압력으로 상수도관 내부에 도포하여 코팅막을 형성하였다. 이때 도료의 지촉건조시간은 23℃를 기준으로 60초였다.High Pressure Collision Mixer (Two Line System) Two main lines are supplied with the main part and the hardener part, and are sprayed by high pressure impact mixing from the mix module inside the spray gun GRACO 'REACTOR E-XP2' Polyurea resin coating composition in which the main portion and the curing agent portion were mixed at a weight ratio of 40:60, respectively, was applied to the inside of the water supply pipe at an injection pressure of 1500 to 3000 psi at a temperature of about 70 ° C. to form a coating film. At this time, the dry contact time of the paint was 60 seconds based on 23 ℃.
<실시예 2><Example 2>
(주제부의 제조)(Production of the subject matter)
4,4′-디페닐메탄 디이소시아네이트(4,4′-Diphenylmethane diisocyanate, MDI) 60중량부, 폴리옥시알킬렌글리콜(Polyoxyalkylene glycol) 30중량부, 알킬렌카보네이트(Alkylene carbonate) 10중량부를 반응용기에 투입한 후 교반하면서 서서히 승온하여 80℃에서 3시간 동안 등온유지한 다음, 이소시아네이트기(Isocyanate group, -N=C=O)의 함량이 15 ~ 25%일 때 열을 차단하고 서서히 냉각하여 우레탄 프리폴리머(Urethane prepolymer)를 합성하되, 50℃ 이하에서 상기 우레탄 프리폴리머 100중량부를 기준으로 2-에틸헥실산 포스페이트(2-Ethylhexyl acid phosphate) 0.05중량부를 투입하여 1시간 동안 균일하게 교반하여 주제부를 제조하였다.60 parts by weight of 4,4'-Diphenylmethane diisocyanate (MDI), 30 parts by weight of polyoxyalkylene glycol, 10 parts by weight of alkylene carbonate The solution was gradually heated and stirred at 80 ° C. for 3 hours. Then, when the content of the isocyanate group (-N = C = O) was 15-25%, the heat was cut off and gradually cooled to urethane. Synthesis of a prepolymer (Urethane prepolymer), at 50 ℃ or less based on 100 parts by weight of the urethane prepolymer was added to 0.05 parts by weight of 2-ethylhexyl acid phosphate (2-Ethylhexyl acid phosphate) was uniformly stirred for 1 hour to prepare a main part. .
(경화제부의 제조)(Production of Hardener Part)
폴리에테르아민(Polyether amine) 25중량부, 습윤분산제 0.2중량부, 안료 5중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시킨 다음, 다시 폴리에테르아민(Polyether amine) 70중량부, 사슬연장제 7중량부, 부착력 증강제 0.6중량부, 소포탈포제 0.6중량부, 유동성 조절제 1중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하여 경화제부를 제조하였다.25 parts by weight of polyether amine, 0.2 parts by weight of a wet dispersant, and 5 parts by weight of pigment are added to a separate container, and dispersed to have a particle size of 20 μm or less, and then 70 parts by weight of polyether amine. , 7 parts by weight of chain extender, 0.6 parts by weight of adhesion enhancer, 0.6 parts by weight of antifoaming agent, and 1 part by weight of flow control agent were added, followed by stirring at 2000 rpm for 1 to 2 hours to prepare a curing agent part.
(코팅막의 형성)(Formation of Coating Film)
고압충돌 혼합식 전용 도장기(Two Line System, 2개의 별도 라인으로 주제부, 경화제부가 공급되어 스프레이건 내부의 혼합 모듈(mix module)에서 고압충돌 혼합되어 분사됨. GRACO사 ‘REACTOR E-XP2’ 사용)를 이용하여 상기 주제부와 경화제부가 각각 50 : 50의 중량비로 혼합된 폴리우레아수지 도료조성물을 약 60℃의 온도에서 1500 ~ 3000psi의 분사압력으로 상수도관 내부에 도포하여 코팅막을 형성하였다. 이때 도료의 지촉건조시간은 23℃를 기준으로 90초였다.High Pressure Collision Mixer (Two Line System) Two main lines are supplied with the main part and the hardener part, and are sprayed by high pressure impact mixing from the mix module inside the spray gun GRACO 'REACTOR E-XP2' Polyurea resin coating composition mixed with the main portion and the curing agent portion at a weight ratio of 50: 50 was applied to the inside of the water supply pipe at an injection pressure of 1500 to 3000 psi at a temperature of about 60 ° C. to form a coating film. At this time, the dry contact time of the paint was 90 seconds based on 23 ℃.
<실시예 3><Example 3>
(주제부의 제조)(Production of the subject matter)
4,4′-디페닐메탄 디이소시아네이트(4,4′-Diphenylmethane diisocyanate, MDI) 65중량부, 폴리옥시알킬렌글리콜(Polyoxyalkylene glycol) 25중량부, 알킬렌카보네이트(Alkylene carbonate) 10중량부를 반응용기에 투입한 후 교반하면서 서서히 승온하여 80℃에서 3시간 동안 등온유지한 다음, 이소시아네이트기(Isocyanate group, -N=C=O)의 함량이 15 ~ 25%일 때 열을 차단하고 서서히 냉각하여 우레탄 프리폴리머(Urethane prepolymer)를 합성하되, 50℃ 이하에서 상기 우레탄 프리폴리머 100중량부를 기준으로 2-에틸헥실산 포스페이트(2-Ethylhexyl acid phosphate) 0.1중량부를 투입하여 1시간 동안 균일하게 교반하여 주제부를 제조하였다.65 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI), 25 parts by weight of polyoxyalkylene glycol, 10 parts by weight of alkylene carbonate The solution was gradually heated and stirred at 80 ° C. for 3 hours. Then, when the content of the isocyanate group (-N = C = O) was 15-25%, the heat was cut off and gradually cooled to urethane. Synthesis of a prepolymer (Urethane prepolymer), but at 50 ℃ or less based on 100 parts by weight of the urethane prepolymer 0.1 parts by weight of 2-ethylhexyl acid phosphate (2-Ethylhexyl acid phosphate) was added to uniformly stirred for 1 hour to prepare a main part. .
(경화제부의 제조)(Production of Hardener Part)
폴리에테르아민(Polyether amine) 30중량부, 습윤분산제 0.2중량부, 안료 5중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시킨 다음, 다시 폴리에테르아민(Polyether amine) 65중량부, 사슬연장제 8중량부, 부착력 증강제 0.7중량부, 소포탈포제 0.7중량부, 유동성 조절제 0.5중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하여 경화제부를 제조하였다.30 parts by weight of polyether amine, 0.2 parts by weight of a wet dispersant, and 5 parts by weight of pigment are added to a separate container and dispersed to have a particle size of 20 μm or less, and then 65 parts by weight of polyether amine. , 8 parts by weight of chain extender, 0.7 parts by weight of adhesion enhancer, 0.7 parts by weight of antifoaming agent, 0.5 parts by weight of fluidity regulator was added and stirred at 2000 rpm for 1 to 2 hours to prepare a curing agent part.
(코팅막의 형성)(Formation of Coating Film)
고압충돌 혼합식 전용 도장기(Two Line System, 2개의 별도 라인으로 주제부, 레진부가 공급되어 스프레이건 내부의 혼합 모듈(mix module)에서 고압충돌 혼합되어 분사됨. GRACO사 ‘REACTOR E-XP2’ 사용)를 이용하여 상기 주제부와 경화제부가 각각 60 : 40의 중량비로 혼합된 폴리우레아수지 도료조성물을 약 60℃의 온도에서 1500 ~ 3000psi의 분사압력으로 상수도관 내부에 도포하여 코팅막을 형성하였다. 이때 도료의 지촉건조시간은 23℃를 기준으로 120초였다.High Pressure Collision Mixing Special Sprayer (Two Line System, two separate lines, main part and resin part are supplied and sprayed by high pressure impact mixing from the mixing module inside the spray gun.) GRACO 'REACTOR E-XP2' Polyurea resin coating composition mixed with the main portion and the curing agent portion at a weight ratio of 60: 40, respectively, was applied to the inside of the water supply pipe at an injection pressure of 1500 to 3000 psi at a temperature of about 60 ° C. to form a coating film. At this time, the touch drying time of the paint was 120 seconds based on 23 ° C.
<비교예 1> ~ <비교예 3><Comparative Example 1> to <Comparative Example 3>
비교예 1 내지 비교예 3에 따른 폴리우레아수지 도료조성물의 제조는, 주제부의 합성시 중합반응 억제제로서 2-에틸헥실산 포스페이트를 첨가하지 않은 것을 제외하고는, 각각 실시예 1 내지 실시예 3과 동일한 구성성분과 동일한 조건으로 제조하였으며, 아울러 동일한 방법에 의해 상수도관 내부에 도포하여 코팅막을 형성하였다. 이때, 도료의 지촉건조시간은 23℃를 기준으로 각각 40초, 65초, 100초로 나타내었다.Preparation of the polyurea resin coating composition according to Comparative Examples 1 to 3 was carried out in each of Examples 1 to 3, except that 2-ethylhexyl acid phosphate was not added as a polymerization inhibitor during synthesis of the main part. Prepared under the same conditions and the same components, and by the same method was applied inside the water pipe to form a coating film. At this time, the touch-drying time of the paint is represented as 40 seconds, 65 seconds, 100 seconds based on 23 ℃.
<실험예><Experimental Example>
실시예 1 내지 3, 비교예 1 내지 3에서 각각 형성된 코팅막을 미국수도협회(AWWA C 222- 99) 규격에 규정된 시험기준에 따라 5회 반복 측정하고, 그 평균값을 아래 표 1에 나타내었다.
The coating films formed in Examples 1 to 3 and Comparative Examples 1 to 3, respectively, were repeatedly measured five times according to the test criteria defined in the American Water Association (AWWA C 222-99). The average values are shown in Table 1 below.
없음More than
none
없음More than
none
없음More than
none
없음More than
none
없음More than
none
없음More than
none
발생Pinhole
Occur
발생Pinhole
Occur
발생Pinhole
Occur
없음More than
none
없음More than
none
없음More than
none
발생Pinhole
Occur
발생Pinhole
Occur
발생Pinhole
Occur
내약품성
(상온 30일간 침적)
Chemical resistance
(Immersion for 30 days at room temperature)
10% H2SO4
10% H 2 SO 4
변화율(%)weight
% Change
변화율(%)diameter
% Change
변화율(%)thickness
% Change
30% NaCl
30% NaCl
변화율(%)weight
% Change
변화율(%)diameter
% Change
변화율(%)thickness
% Change
30% NaOH
30% NaOH
변화율(%)weight
% Change
변화율(%)diameter
% Change
변화율(%)thickness
% Change
#2 디젤연료유
# 2 diesel fuel oil
변화율(%)weight
% Change
변화율(%)diameter
% Change
변화율(%)thickness
% Change
상기 [표 1]에서와 같이, 본 발명에 따라 상수도관 내부에 코팅막이 형성된 실시예 1 내지 실시예 3은 우레탄 프리폴리머 합성시 중합반응 억제제를 첨가함으로써 비교예들에 비해 부착강도, 내굴곡성, 내충격성, 흡수율, 경도, 핀홀시험, 음극박리, 내마모성, 내약품성 등의 물리적, 화학적 성질이 현저히 개선된 것으로 나타났으며, 또한 도료의 점도가 균일하게 유지되고 지촉건조시간이 약 20초 정도로 지연되어 강관의 내면과 외면에 대한 기밀성과 접착력이 향상되었음을 확인할 수 있었다.As shown in Table 1, Example 1 to Example 3, wherein the coating film is formed inside the water supply pipe according to the present invention, by adding a polymerization inhibitor when synthesizing the urethane prepolymer, the adhesive strength, bending resistance, and The physical and chemical properties such as impact, water absorption, hardness, pinhole test, negative electrode peeling, abrasion resistance, and chemical resistance were remarkably improved, and the viscosity of the paint was kept uniform and the drying time was delayed by about 20 seconds. It was confirmed that the airtightness and adhesion to the inner and outer surfaces of the steel pipe were improved.
그리고 본 발명의 폴리우레아수지 도료조성물은 고온(40℃ 이상) 및 고압(1500psi 이상)의 스프레이 분사압력으로 도포되더라도 기존의 도료에 비해 분진 발생이 저감되어 재료의 낭비가 적고 작업성이 양호하며, 무용제형 타입의 속경화형 도료로서 1회에 후막(1㎜ 이상) 도장이 가능할 뿐만 아니라 유해물질이 유출되지 않는다는 장점도 있다.And even if the polyurea resin coating composition of the present invention is applied at a spray injection pressure of high temperature (40 ℃ or more) and high pressure (1500 psi or more), the generation of dust is reduced compared to the conventional paint is less waste of material and good workability, It is a solvent-free type of quick-curing paint that can not only coat thick films (1 mm or more) at a time, but also has the advantage that no harmful substances are spilled.
따라서 본 발명의 고강관의 내,외부 코팅용 폴리우레아수지 도료조성물은 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지로 치환, 변형 및 변경이 가능한 것으로, 상,하수도, 일반용수 및 기타 유체 수송용 배관에 사용되는 강관 등 지하 매설 철구조물의 내외부 방수, 방식 목적으로 다양하게 적용할 수 있는 환경 친화적인 소재로서 다양한 용도와 형태로 사용되어 질 수 있다.Accordingly, the polyurea resin coating composition for coating the inner and outer coatings of the steel pipe of the present invention may be substituted, modified, and changed in various ways without departing from the technical spirit of the present invention, and water, sewage, general water, and other fluids. It is an environmentally friendly material that can be used for various purposes such as waterproofing and anticorrosive purposes of underground buried steel structures such as steel pipes used for transportation piping, and can be used in various uses and forms.
Claims (10)
폴리에테르아민(Polyether amine) 100중량부를 기준으로 습윤분산제 0.1 ~ 0.4중량부, 안료 4 ~ 7중량부, 사슬연장제 5 ~ 8중량부, 부착력 증강제 0.4 ~ 0.7중량부, 소포탈포제 0.4 ~ 0.7중량부, 유동성 조절제 0.1 ~ 2.0중량부를 함유하는 경화제부; 로 구성되며,
상기 주제부와 경화제부는 각각 40 ~ 60중량%의 비율로 포함하여 이루어짐을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물.Urethane prepolymer produced by polymerization of 55 to 70 parts by weight of diisocyanate, 25 to 35 parts by weight of polyoxyalkylene glycol and 5 to 15 parts by weight of alkylene carbonate A main part containing 0.01 to 0.1 parts by weight of a polymerization inhibitor based on 100 parts by weight;
0.1 to 0.4 parts by weight of wet dispersion agent, 4 to 7 parts by weight of pigment, 5 to 8 parts by weight of chain extender, 0.4 to 0.7 parts by weight of adhesion enhancer, and 0.4 to 0.7 antifoaming agent based on 100 parts by weight of polyether amine Part by weight, a curing agent part containing 0.1 to 2.0 parts by weight of a fluidity regulator; Lt; / RTI >
The main portion and the hardener portion of the polyurea resin coating composition for the inner and outer coating of the steel pipe, characterized in that comprises a ratio of 40 to 60% by weight, respectively.
상기 중합반응 억제제는 2-에틸헥실산 포스페이트(2-Ethylhexyl acid phosphate), 인산(H3PO4, Phosphoric acid) 중 어느 1종 이상인 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물.The method of claim 1,
The polymerization inhibitor is a polyurea resin coating composition for internal and external coating of steel pipes, characterized in that any one or more of 2-ethylhexyl acid phosphate, phosphoric acid (H 3 PO 4 , Phosphoric acid). .
상기 습윤분산제는, 안료 친화그룹을 가진 고분자량의 블록 공중합체 용액, 산성 폴리머의 알킬암모늄염 용액, 안료 친화그룹을 가진 하이드록시 관능기 카르복실산 에스테르 용액, 저분자 불포화 폴리카르복실산 폴리머 용액, 폴리실록산 공중합체와 저분자 불포화 폴리카르복실산 폴리머 용액, 폴리카르복실산의 알킬암모늄염 용액, 산성그룹을 가진 공중합체 용액, 저분자 불포화 폴리카르복실산 폴리머 중 어느 1종 이상인 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물.The method of claim 1,
The wet dispersant is a high molecular weight block copolymer solution having a pigment affinity group, an alkylammonium salt solution of an acidic polymer, a hydroxy functional group carboxylic ester solution having a pigment affinity group, a low molecular unsaturated polycarboxylic acid polymer solution, a polysiloxane air Inner and outer coating of steel pipes, characterized in that any one or more of a polymer and a low molecular unsaturated polycarboxylic acid polymer solution, an alkyl ammonium salt solution of polycarboxylic acid, a copolymer solution having an acidic group, a low molecular unsaturated polycarboxylic acid polymer Polyurea resin paint composition.
상기 안료는 이산화티탄(Titanium dioxide), 카본블랙(Carbon black), 프탈로시아닌 블루(Phthalocyanine blue), 프탈로시아닌 그린(Phthalocyanine green), 산화아연, 황화아연 중 어느 1종 이상인 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물.The method of claim 1,
The pigment may be any one or more of titanium dioxide, carbon black, carbon black, phthalocyanine blue, phthalocyanine green, phthalocyanine green, zinc oxide, and zinc sulfide. Polyurea resin paint composition for coating.
상기 사슬연장제는 디에틸-톨루엔디아민(Diethyl-toluenediamine, DETDA), 티메틸티오-톨루엔디아민(Dimethylthio-toluenediamine, DMTDA), N,N′--디(sec-부틸)-아미노-비페닐메탄(N,N′-Di(sec.butyl)-amino-biphenyl methane, DBMDA), 4,4′-메틸렌비스-(3-클로로-2,6-디에틸)-아닐린(4,4′-Methylenebis-(3-chloro, 2,6-diethyl)-aniline, MCDEA), 환상지방족 아민(Cycloaliphatic amine), 2차 지방족 아민(Secondary aliphatic amine), 2차 지방족 디아민(Secondary aliphatic diamine), 2차 방향족 디아민(Secondary aromatic diamine) 중 어느 1종 이상인 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물The method of claim 1,
The chain extender is diethyl-toluenediamine (DETDA), dimethylthio-toluenediamine (DMTDA), N, N'-di (sec-butyl) -amino-biphenylmethane (N, N′-Di (sec.butyl) -amino-biphenyl methane, DBMDA), 4,4′-methylenebis- (3-chloro-2,6-diethyl) -aniline (4,4′-Methylenebis -(3-chloro, 2,6-diethyl) -aniline, MCDEA), cycloaliphatic amine, Secondary aliphatic amine, Secondary aliphatic diamine, Secondary aromatic diamine Polyurea resin coating composition for internal and external coating of steel pipes, characterized in that at least one of (Secondary aromatic diamine)
상기 부착력 증강제는 2-(3,4 에폭시시클로헥실)-에틸트리메톡시실란(2-(3,4 Epoxycyclohexyl)-ethyltrimethoxysilane), 3-글리시독시프로필메틸 디에톡시실란(3-Glycidoxypropylmethyl diethoxysilane), 3-아미노프로필 트리에톡시시란(3-Aminopropyl triethoxysilane), N-(2-아미노에틸)3-아미노프로필 메틸 디메톡시실란(N-(2-Aminoethyl)3-aminopropylmethyl dimethoxysilane), N-(2-아미노에틸)3-아미노프로필 트리메톡시실란(N-(2-Aminoethyl)3-aminopropyl trimethoxysilane), N-(2-아미노에틸)3-아미노프로필 트리에톡시실란(N-(2-Aminoethyl)3-aminopropyl triethoxysilane), 3-아미노프로필 트리메톡시실란(3-Aminopropyl trimethoxysilane), 3-메르캅토프로필 트리메톡시실란(3-Mercaptopropyl trimethoxysilane), 3-글리시독시프로필 트리메톡시실란(3-Glycidoxypropyl trimethoxysilane, 감마-글리시독시프로필 트리메톡시실란(Gamma-glycidoxypropyl trimethoxysilane) 중에서 선택되는 어느 1종 이상의 실란 커플링제(Silane coupling agent)로 구성되는 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물.The method of claim 1,
The adhesion enhancing agent is 2- (3,4 epoxycyclohexyl) -ethyltrimethoxysilane (2- (3,4 Epoxycyclohexyl) -ethyltrimethoxysilane), 3-glycidoxypropylmethyl diethoxysilane, 3-aminopropyl triethoxysilane, N- (2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, N- (2 -Aminoethyl) 3-aminopropyl trimethoxysilane (N- (2-Aminoethyl) 3-aminopropyl trimethoxysilane), N- (2-aminoethyl) 3-aminopropyl triethoxysilane (N- (2-Aminoethyl) 3-aminopropyl triethoxysilane), 3-aminopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane (3- From Glycidoxypropyl trimethoxysilane, Gamma-glycidoxypropyl trimethoxysilane Polyurea resin coating composition for internal and external coating of steel pipe, characterized in that composed of any one or more selected silane coupling agent (Silane coupling agent).
상기 소포탈포제는 미네랄 오일계 소포제, 실리콘계 소포제, 비실리콘계 폴리머 소포제 중 어느 1종 이상인 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물.The method of claim 1,
The antifoaming agent is a polyurea resin coating composition for internal and external coating of steel pipes, characterized in that any one or more of mineral oil-based defoamer, silicone-based defoamer, non-silicone-based polymer defoamer.
상기 유동성 조절제는 발연 실리카(Fumed silica), 우레아수지(Urea resin), 폴리아마이드 왁스(Polyamide wax), 벤토나이트(Bentonite) 중 어느 1종 이상인 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물.The method of claim 1,
The fluidity modifier is a polyurea resin coating for internal and external coating of steel pipes, characterized in that any one or more of fumed silica, urea resin, polyamide wax, bentonite Composition.
폴리에테르아민(Polyether amine) 25 ~ 30중량부, 습윤분산제 0.1 ~ 0.4중량부, 안료 4 ~ 7중량부를 별도의 용기에 투입한 후 입도가 20㎛ 이하가 되도록 분산시킨 다음, 다시 폴리에테르아민(Polyether amine) 65 ~ 70중량부, 사슬연장제 5 ~ 8중량부, 부착력 증강제 0.4 ~ 0.7중량부, 소포탈포제 0.4 ~ 0.7중량부, 유동성 조절제 0.1 ~ 2.0중량부를 첨가하여 2000rpm으로 1 ~ 2시간 동안 교반하여 경화제부를 형성하는 단계;
상기와 같이 형성된 주제부와 경화제부를 각각 40 ~ 60중량%의 비율로 혼합하는 단계;
로 이루어지는 것을 특징으로 하는 강관의 내,외부 코팅용 폴리우레아수지 도료조성물의 제조방법.55 to 70 parts by weight of diisocyanate, 25 to 35 parts by weight of polyoxyalkylene glycol, and 5 to 15 parts by weight of alkylene carbonate were added to the reaction vessel, and the temperature was gradually increased while stirring. Urethane isothermal is maintained at ~ 90 ℃ for 2 to 5 hours, when the content of isocyanate group (-N = C = O) is 15 to 25%, heat is blocked and gradually cooled to synthesize urethane prepolymer However, at 50 ° C. or less, based on 100 parts by weight of the urethane prepolymer, 0.01 to 0.1 parts by weight of a polymerization inhibitor (Polymerization inhibitor) is added to uniformly stir for 0.5 to 1.5 hours to form a main part;
25 to 30 parts by weight of polyether amine, 0.1 to 0.4 parts by weight of a wet dispersant, and 4 to 7 parts by weight of a pigment are added to a separate container and dispersed to have a particle size of 20 μm or less, and then polyetheramine ( Polyether amine) 65 ~ 70 parts by weight, chain extender 5 ~ 8 parts by weight, adhesion force enhancer 0.4 ~ 0.7 parts by weight, antifoaming agent 0.4 ~ 0.7 parts by weight, fluidity regulator 0.1 ~ 2.0 parts by adding 1 to 2 hours at 2000rpm Stirring to form a hardener portion;
Mixing the main portion and the hardener portion formed as described above at a ratio of 40 to 60% by weight, respectively;
Method for producing a polyurea resin coating composition for internal and external coating of steel pipe, characterized in that consisting of.
상기 주제부와 경화제부를 50 ~ 80℃의 온도로 가열한 상태에서 각각 40 ~ 60중량%의 비율로 혼합하여 제조된 폴리우레아수지 도료조성물을 강관의 내부 또는 외부에 1500 ~ 3000psi의 스프레이 분사압력으로 도포하는 단계;
를 포함하여 이루어지는 것을 특징으로 하는 강관의 표면에 폴리우레아수지 도료조성물을 코팅하는 방법.Preparing a main part and a curing agent part according to any one of claims 1 to 8;
Polyurea resin coating composition prepared by mixing the main portion and the hardener portion at a temperature of 50 to 80 ° C. at a ratio of 40 to 60% by weight, respectively, with a spray injection pressure of 1500 to 3000 psi inside or outside the steel pipe. Applying;
Method for coating a polyurea resin coating composition on the surface of the steel pipe comprising a.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20000067192A (en) * | 1999-04-24 | 2000-11-15 | 전춘택 | Production Method of 2-Liquid Reactive Adhesive |
KR100860009B1 (en) | 2006-12-13 | 2008-09-25 | (주)아텍스 | A method of manufacturing high adhesive polyurea coating agents and a method of coating high adhesive polyurea |
-
2011
- 2011-07-27 KR KR1020110074427A patent/KR101221321B1/en active IP Right Grant
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20000067192A (en) * | 1999-04-24 | 2000-11-15 | 전춘택 | Production Method of 2-Liquid Reactive Adhesive |
KR100860009B1 (en) | 2006-12-13 | 2008-09-25 | (주)아텍스 | A method of manufacturing high adhesive polyurea coating agents and a method of coating high adhesive polyurea |
Cited By (14)
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---|---|---|---|---|
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