KR20000059589A - Anticorrosive coating composition having high hardness - Google Patents

Anticorrosive coating composition having high hardness Download PDF

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KR20000059589A
KR20000059589A KR1019990007301A KR19990007301A KR20000059589A KR 20000059589 A KR20000059589 A KR 20000059589A KR 1019990007301 A KR1019990007301 A KR 1019990007301A KR 19990007301 A KR19990007301 A KR 19990007301A KR 20000059589 A KR20000059589 A KR 20000059589A
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weight
parts
coating composition
high hardness
corrosion coating
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KR100372830B1 (en
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위승용
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유재선
우신건축환경크리닉 주식회사
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/10Anti-corrosive paints containing metal dust
    • C09D5/106Anti-corrosive paints containing metal dust containing Zn
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic

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Abstract

PURPOSE: A coating composition for preventing corrosion is provided, which has high hardness, wear resistance and ductility, is easily handled at room or low temperature, and does not pollutes the environment when it is handled in wet condition. CONSTITUTION: The coating composition for preventing corrosion comprises 75-85 parts by weight of main component which consists of 29.42-77.88 wt% of urethane modified epoxy resin whose epoxy equivalent is 180-270 g/eq and 22.12-70.58 wt% of additives such as a silane-based binding agent, a filling agent, an improving agent, a stabilizer, a flowing preventer and an antibacterial agent; and 15-25 parts by weight of polyamide-based curing resin whose amine number is 280-380 KOH/g. Preferably the silane-based binding agent is 3-glycidoxy propyl trimethoxysilane, and the filling agent is zinc dust.

Description

고경도 부식 방지 코팅 조성물{ANTICORROSIVE COATING COMPOSITION HAVING HIGH HARDNESS}High hardness anti-corrosion coating composition {ANTICORROSIVE COATING COMPOSITION HAVING HIGH HARDNESS}

본 발명은 고경도 부식 방지 코팅 조성물에 관한 것으로, 더욱 상세하게는 콘크리트 및 철골구조물등의 코팅산업분야에 사용되는 것으로 실온 또는 저온에서도 취급이 용이하고, 습윤이나 수중상태에서 작업시 환경오염을 방지할 뿐만 아니라, 내마모성 및 연성 등을 갖는 고경도 부식 방지 코팅 조성물에 관한 것이다.The present invention relates to a high hardness anti-corrosion coating composition, and more particularly used in the coating industry, such as concrete and steel structures, easy to handle even at room temperature or low temperature, to prevent environmental pollution when working in wet or underwater conditions In addition, the present invention relates to a high hardness anti-corrosion coating composition having wear resistance, ductility, and the like.

종래에는 일반 에폭시수지를 이용한 코팅재가 주로 사용되어 왔으나 상기의 일반 에폭시수지는 습윤 및 수중에서 작업시 코팅막과 콘크리트 및 철골 구조물과의 접착력 저하, 열팽창 계수의 차이로 인한 박리현상, 내후성 불량 등의 여러 문제점이 발생되고 있는 실정이다.Conventionally, coating materials using general epoxy resins have been mainly used, but the above general epoxy resins have various effects such as deterioration of adhesion between coating film and concrete and steel structures, peeling phenomenon due to difference in thermal expansion coefficient, poor weather resistance, etc. Problems are occurring.

또한, 그뿐만 아니라, 콘크리트 및 철골구조물의 코팅산업분야에서는 실온 또는 저온에서도 취급하기가 쉽고 습윤이나 수중상태에서도 경화가 되는 일정한 조성물의 필요성이 인식되고 있는 것으로, 수중에서 작업시 환경의 오염문제가 심각하게 대두되고 있어 환경에 영향을 주지 않는 무용제형과 항균효과를 주면서 물에 불용성인 제품개발이 시급한 실정이다.In addition, in the coating industry of concrete and steel structures, the necessity of a certain composition that is easy to handle at room temperature or low temperature and that is cured even in wet or underwater conditions is recognized. As it is seriously emerging, it is urgent to develop a product that is insoluble in water while providing a solvent-free and antibacterial effect that does not affect the environment.

따라서, 본 발명은 상기와 같은 종래의 문제점을 감안하여 창출된 것으로, 그 목적은 수분의 존재하에서도 경화가 빠르고 접착력이 우수한 화합물로 수중 구조물-교각, 수문, 댐 등의 보수, 보강 및 신구콘크리트의 접착, 습윤상태에서도 코팅이 가능한 고경도 부식 방지 코팅 조성물을 제공함에 있다.Accordingly, the present invention has been made in view of the above-mentioned conventional problems, and its object is to repair, reinforce and reinforce concrete structures such as underwater structures-piers, sluices, dams, etc. with compounds that cure and exhibit excellent adhesion even in the presence of moisture. It is to provide a high hardness anti-corrosion coating composition that can be coated even in the adhesion, wet state.

상기와 같은 본 발명의 목적을 달성하기 위하여, 고경도 부식 방지 코팅 조성물은, 에폭시 당량이 180∼270g/eq 인 우레탄 변성에폭시 수지 77.88 ∼ 29.42 중량부 및 기타 첨가제 70.58 ∼ 22.12 중량부로 이루어진 주제혼합물 75∼85중량부와, 아민가 280∼380 KOH/g 인 폴리아미드계 경화성수지 15∼25중량부가 혼합되도록 구성된다.In order to achieve the object of the present invention as described above, the high hardness anti-corrosion coating composition is a main mixture 75 composed of 77.88 to 29.42 parts by weight of a urethane-modified epoxy resin having an epoxy equivalent of 180 to 270 g / eq and 70.58 to 22.12 parts by weight of other additives. It is comprised so that -85 weight part and 15-25 weight part of polyamide-type curable resins whose amines are 280-380 KOH / g.

상기 주제혼합물 75∼85중량부의 범위내에서는 경도, 접착력, 압축강도, 인장강도, 흡수율이 우수하다.It is excellent in hardness, adhesive force, compressive strength, tensile strength, and water absorption within the range of 75 to 85 parts by weight of the main mixture.

그 반면에 주제혼합물이 85중량부 이상 첨가될 경우에는 인장강도 및 접착력등이 감소되며, 75중량부이하로 첨가될 경우에는 물성등이 떨어지게 되어 접착성이 좋지 않다.On the other hand, when 85 parts by weight or more of the main mixture is added, tensile strength and adhesive strength are reduced, and when it is added below 75 parts by weight, physical properties and the like are poor, and thus the adhesiveness is not good.

상기 주제 혼합물의 기타 첨가제가 첨가범위보다 많거나 적게 첨가되었을 경우에는 접착성 및 경도등이 떨어지게 되므로 범위내에서 첨가되는 것이 바람직하다.When other additives of the above-mentioned main mixture are added to more or less than the range of addition, it is preferable to add them within the range since adhesiveness and hardness are reduced.

상기 구성된 본 발명의 고경도 부식 방지 코팅 조성물을 아래와 같이 상세하게 설명한다.The high hardness anti-corrosion coating composition of the present invention configured above will be described in detail as follows.

본 발명의 우레탄 변성에폭시수지는 비스페놀 A형 에폭시수지 (Bisphenol A Type Epoxy), 페놀 노볼락형 에폭시수지 (Phenol Novolac Type Epoxy), 브롬화 에폭시수지(Brominated Type Epoxy) 등과 같은 수지가 사용되는 것으로 본 발명에서는 주로 비스페놀 A형 에폭시수지를 사용하였으며, 비스페놀 A형 에폭시수지에 우레탄기를 도입한 우레탄형 MDI수지(Prepolymer,NCO:2중량부,SUJIN Com사) 를 사용하였다.The urethane-modified epoxy resin of the present invention is a resin such as bisphenol A type epoxy resin (Bisphenol A Type Epoxy), phenol novolac type epoxy resin (Bhenol Novolac Type Epoxy), brominated epoxy resin (Brominated Type Epoxy) is used. The bisphenol A epoxy resin was mainly used, and the urethane type MDI resin (Prepolymer, NCO: 2 parts by weight, SUJIN Com) which used a urethane group in the bisphenol A epoxy resin was used.

상기의 우레탄 변성에폭시수지는 비스 페놀 A형 에폭시 (당량: 220∼250 g/eq) 28.78중량부정도에 우레탄 MDI(NCO:2중량부)를 1.1 중량부정도를 일정한 비율로 혼합한후 TETA 0.01중량부 정도를 첨가하여 질소 존재하에서 100∼120℃에서 5시간정도 반응시켜 우레탄 변성에폭시수지인 WS-815 (Urethane Modified Epoxy(Wooshin Chem. KOREA, EPOXY 당량 :180∼200g/eq)29.89중량부를 상기와 같은 방법에서 합성시켜 제조한다.The urethane-modified epoxy resin is mixed with about 28.78 parts by weight of bisphenol A epoxy (equivalent: 220-250 g / eq) and about 1.1 parts by weight of urethane MDI (NCO: 2 parts by weight) in a fixed ratio, and then TETA 0.01 Add about 5 parts by weight and react for about 5 hours at 100-120 ° C. in the presence of nitrogen to modify the urethane-modified epoxy resin, WS-815 It is prepared by synthesis in the same manner.

상기와 같이 제조된 우레탄 변성에폭시수지 77.88∼29.42 중량부에 아래와 같은 기타 첨가제에 혼합하였다.77.88 to 29.42 parts by weight of the urethane-modified epoxy resin prepared as described above was mixed with the following other additives.

상기의 우레탄 변성에폭시수지는 77.88∼29.42 중량부의 범위내에서는 경도, 접착력, 압축강도, 인장강도, 흡수율이 우수한 특징이 있다.The urethane-modified epoxy resin is characterized by excellent hardness, adhesive force, compressive strength, tensile strength, and water absorption within the range of 77.88 to 29.42 parts by weight.

상기 우레탄수지에 혼합되는 첨가제는 실란계 결합제, 충진제, 개선제, 안정제, 흐름방지제, 항균제 등으로 혼합된다.The additive mixed in the urethane resin is mixed with a silane-based binder, filler, improver, stabilizer, anti-flow agent, antibacterial agent and the like.

상기 첨가제중 실란계 결합제는, 아미노계 실란 (Amino계 Silane), 에폭시계 실란 (Epoxy계 Silane), 클로로계 실란 (Chloro 계 Silane), 머캅토계 실란 (Mercapto계 실란) 등이 있으며, 본 발명에서는 주로 에폭시계 실란인 3 - 글리시독시 프로필 트리메톡시 실란 (3 - Glycidoxy propyl trimethoxysilane) 을 사용하였으며, 상기의 실란계 결합제는 주제혼합물의 수지성분의 0.05∼0.1 중량부를 차지하는 것으로 상기의 결합제가 일정범위이상 첨가되면 혼합물이 쉽게 뭉치게 되어 혼합력을 떨어트리는 문제점이 있으며, 일정범위이하로 첨가되게 되면, 기타 첨가제의 혼합력이 떨어지는 문제점이 있다.Among the additives, silane-based binders include amino silane (Amino Silane), epoxy silane (Epoxy Silane), chloro silane (Chloro Silane), mercapto silane (Mercapto silane) and the like. 3-Glycidoxy propyl trimethoxysilane, which is mainly an epoxy silane, was used, and the silane-based binder occupies 0.05 to 0.1 parts by weight of the resin component of the main mixture. If more than the range is added, the mixture is easily agglomerated and there is a problem of dropping the mixing power, if added below a certain range, there is a problem that the mixing power of the other additives fall.

상기 항균제는 ANBIGENT 20 (Cosmo Com.)을 첨가하였으며, 상기 항균제는 파이프 관속에 흐르는 물등을 오염시키지 않는 특징이 있으며, 그 사용량은 주제혼합물의 수지성분의 0.01∼0.1 중량부를 차지한다.The antimicrobial agent was added to ANBIGENT 20 (Cosmo Com.), The antimicrobial agent is characterized in that it does not contaminate the water flowing in the pipe tube, the amount of use is 0.01 to 0.1 parts by weight of the resin component of the main mixture.

상기 흐름방지제는, Aerosil 200, Benton #38, 클레이 볼락 수퍼 (Clay Vallac Super) 또는 텍사 ST (THIXOTROPIC ADDITIVE (TOTAL CO, USA) 등이 사용되면, 본 발명에서는 주로 텍사 ST 가 사용되며, 상기의 사용량은 0.5∼1.5중량부이다.When the flow inhibitor is used, such as Aerosil 200, Benton # 38, Clay Vallac Super or Texa ST (THIXOTROPIC ADDITIVE (TOTAL CO, USA), etc., the Texa ST is mainly used in the present invention, Is 0.5 to 1.5 parts by weight.

상기의 흐름방지제는 0.5∼1.5중량부의 범위 이하로 첨가되면, 보수작업시 부착면에서 쉽게 흘러내려 작업의 효율성을 떨어트리며, 상기의 범위 이상으로 첨가되었을 경우에는 보수면에 쉽게 접착되지 않는 문제점이 발생된다.When the flow preventing agent is added in the range of 0.5 to 1.5 parts by weight or less, it easily flows down from the attachment surface during maintenance work, thereby reducing the efficiency of the work, and when it is added in the above range, it is not easily adhered to the maintenance surface. Is generated.

상기 안정제는 BHT (Butylated Hydroxy Toluene), TPP(Tri Phenyl Phosphite),UV-1 등이며 단독 또는 혼합으로 사용되며, 그 사용량은 0.01∼0.1중량부이다.The stabilizer is BHT (Butylated Hydroxy Toluene), TPP (Tri Phenyl Phosphite), UV-1 and the like, used alone or in combination, the amount is 0.01 to 0.1 parts by weight.

상기 충진제는 지르코늄(Filler(Dong Yang Chem Korea)) 또는 Zinc-Dust(Filler(Han Chang Chem Korea)) 를 사용하며, 그 사용량은 주제혼합물의 20∼70중량부이고, 내부물성의 개선제로 소포제, 셀프레벨링제(Self-levelling제), 습윤제 (Wetting Agent)의 기능을 갖는 Foamex-N(DEFOAMING AGENT(TEGO, GERMANY), Tego 910 (WETTING AGENT(TEGO GERMANY), TEGO 1484 (Self Levelling Agent(TEGO,GRMANY) 등이 있으며, 이를 단독 또는 혼합하여 주제혼합물의 수지성분의 0.1∼0.3중량부이다.The filler is used zirconium (Filler (Dong Yang Chem Korea)) or Zinc-Dust (Filler (Han Chang Chem Korea)), the amount of the use is 20 to 70 parts by weight of the main mixture, the antifoaming agent, Foamex-N (DEFOAMING AGENT (TEGO, GERMANY), Tego 910 (WETTING AGENT (TEGO GERMANY), TEGO 1484 (Self Leveling Agent (TEGO,)) GRMANY) and the like, or 0.1 to 0.3 parts by weight of the resin component of the main mixture.

상기와 같이 혼합된 첨가제 70.58∼22.12중량부와 우레탄 변성 에폭시수지 77.88∼29.42중량부를 혼합하여 100중량부의 주제혼합물을 제조한다.70.58 to 22.12 parts by weight of the additives mixed as described above and 77.88 to 29.42 parts by weight of the urethane-modified epoxy resin are mixed to prepare 100 parts by weight of the main mixture.

상기 경화성수지는 폴리아미드계 경화성수지, 변성 방향족 아민수지, 산무수물, 제파민(Jeffamine) 등이 있으며, 주로 폴리아미드수지가 사용된다.The curable resins include polyamide-based curable resins, modified aromatic amine resins, acid anhydrides, and Jeffamines, and polyamide resins are mainly used.

상기의 경화성수지인 폴리아미드수지는 페놀30.92중량부 정도에 MXDA(Meta Xylene Diamine) 37.96중량부를 교반하면서 140℃로 승온시키고, 여기에 37%포름알데하이드(Formaldehyde)17.11중량부를 서서히 분할투입한다.The polyamide resin, which is a curable resin, is heated to 140 DEG C while stirring 37.96 parts by weight of MXDA (Meta Xylene Diamine) to about 30.92 parts by weight of phenol, and 17.11 parts by weight of 37% formaldehyde (Formaldehyde) are gradually added thereto.

상기와 같이 37%포름알데하이드를 완전하게 투입시킨후 180℃로 승온시켜 2∼3시간 반응시킨다.37% formaldehyde was completely added as described above, and then heated to 180 ° C. for 2 to 3 hours.

상기 수지의 점도가 실온 기준으로 20000∼40000cps/20℃가 되면 온도를 80℃로 낮춘후에 벤질 알콜 (Benzyl Alcohol) 10.40중량부를 투입하고, 다시 온도를 60∼70℃로 유지하면서 페놀 3.1중량부와 경화촉진제인 아민촉매 K-54를 0.51중량부 정도를 투입하여 1 시간정도 교반시킨후 반응을 종료시키면 폴리아미드수지인 WS-051(폴리아미드계 경화제(Wooshin Chem,korea, 에폭시 당량:220∼270g/eq) 100중량부가 생성된다.When the viscosity of the resin reaches 20000 to 40000 cps / 20 ° C. based on room temperature, after the temperature is lowered to 80 ° C., 10.40 parts by weight of benzyl alcohol is added thereto, and 3.1 parts by weight of phenol is maintained while maintaining the temperature at 60 to 70 ° C. After adding 0.51 parts by weight of the amine catalyst K-54, a curing accelerator, and stirring the mixture for about 1 hour, the reaction was terminated. WS-051 (polyamide-based curing agent (Wooshin Chem, Korea, Epoxy equivalent: 220-270g) / eq) 100 parts by weight is produced.

상기와 같이 혼합된 첨가제 70.58∼22.12중량부와 우레탄 변성 에폭시수지 77.88∼29.42중량부를 혼합하여 이루어진 주제혼합물 75∼85중량부와, 100중량부의 경화성 폴리아미드수지중 15∼25중량부만을 혼합시킨다.75 to 85 parts by weight of the main mixture obtained by mixing 70.58 to 22.12 parts by weight of the additive mixed as described above and 77.88 to 29.42 parts by weight of the urethane-modified epoxy resin, and 15 to 25 parts by weight of 100 parts by weight of the curable polyamide resin are mixed.

상기 본 발명의 제조과정은 우레탄 변성에폭시수지 WS-815 등을 77.88∼29.42중량부를 회전수가 20∼50rpm인 교반기를 이용하여 액온도를 50±5℃로 8∼12분정도 교반시킨다.In the manufacturing process of the present invention, the urethane-modified epoxy resin WS-815 and the like is stirred 77.88 to 29.42 parts by weight using a stirrer having a rotation speed of 20 to 50rpm at a liquid temperature of 50 ± 5 ℃ for about 8 to 12 minutes.

상기와 같이 교반된 우레탄 변성 에폭시수지에 기타 첨가제로서, 내부물성 개선제를 0.1∼0.3중량부를 첨가한다.As the other additives, 0.1 to 0.3 parts by weight of an internal physical property improving agent is added to the stirred urethane-modified epoxy resin as described above.

안정제로는 0.01∼0.1중량부를 첨가하고, 흐름방지제를 0.5∼1.5중량부를 첨가하여 액온도를 50±5℃로 17∼22분정도 교반시킨 후, 충진제를 20∼70중량부로 첨가시킨다.As a stabilizer, 0.01-0.1 weight part is added, 0.5-1.5 weight part of flow inhibitors are added, the liquid temperature is stirred at 50 +/- 5 degreeC for about 17 to 22 minutes, and a filler is added at 20-70 weight part.

상기의 충진제로 사용되는 지르코늄과 Zinc-Dust는 비중이 높으므로 한번에 다량을 투입하면 분산 분량입자가 탱크의 바닥 등에 침전될 수 있기 때문에 천천히 분할하여 투입하는 공정 및 배합비율에 의해 본 발명의 주제혼합물이 제조된다.Zirconium and Zinc-Dust used as the above fillers have a high specific gravity, so if a large amount is added at a time, the dispersed particles may be precipitated at the bottom of the tank. Is manufactured.

상기 주제혼합물에 혼합되는 경화성수지인 폴리아미드수지는, 페놀을 30.92 중량부 정도에 MXDA(Meta Xylene Diamine) 37.96 중량부를 교반하면서 140℃로 승온시키고, 여기에 37%포름알데하이드(Formaldehyde) 17.11 중량부를 서서히 분할투입한다.The polyamide resin, which is a curable resin mixed with the main mixture, is heated to 140 ° C while stirring 37.96 parts by weight of MXDA (Meta Xylene Diamine) to about 30.92 parts by weight of phenol, and 17.11 parts by weight of 37% formaldehyde (Formaldehyde). Slowly divide into portions.

상기와 같이 37%포름알데하이드를 완전하게 투입시킨후 180℃로 승온시켜 2∼3시간 반응시킨다.37% formaldehyde was completely added as described above, and then heated to 180 ° C. for 2 to 3 hours.

상기 수지의 점도가 실온 기준으로 20000∼40000 cps/20℃가 되면 온도를 80℃로 낮춘후에 벤질 알콜 (Benzyl Alcohol)을 10.40중량부를 투입하고, 다시 온도를 60∼70℃로 유지하면서 페놀 3.1중량부와 경화촉진제인 아민촉매 K54를 0.51중량부정도를 투입하여 1 시간정도 교반시킨후 반응을 종료시키면 폴리아미드수지인 WS-051(폴리아미드계 경화제(Wooshin Chem,korea. 에폭시 당량:220∼270g/eq))이 100중량부가 생성된다.When the viscosity of the resin is 20000 to 40000 cps / 20 ℃ based on the room temperature, after the temperature is lowered to 80 ℃ 10.40 parts by weight of benzyl alcohol, and the temperature is maintained at 60 to 70 ℃ again 3.1 weight of phenol After the reaction was terminated by adding about 0.51 parts by weight of the amine catalyst K54, which is a curing accelerator, and the reaction was completed, WS-051 (polyamide-based curing agent (Wooshin Chem, Korea. Epoxy equivalent: 220-270g) was used. / eq)) to 100 parts by weight.

상기와 같이 제조된 우레탄 변성 에폭시수지와 기타 첨가제를 혼합한 주제혼합물 75∼85 중량부와, 폴리아미드계 경화성수지 15∼25중량부를 혼합하면 고경도 부식 방지 코팅 조성물이 제조된다.The high hardness anti-corrosion coating composition is prepared by mixing 75 to 85 parts by weight of the main mixture of urethane-modified epoxy resin prepared as described above and 15 to 25 parts by weight of polyamide curable resin.

상기와 같이 제조된 본 발명의 고경도 부식 방지 코팅 조성물은 경도, 접착력, 압축강도, 인장강도, 흡수율등이 뛰어난 것이 특징이다.The high hardness anti-corrosion coating composition of the present invention prepared as described above is characterized by excellent hardness, adhesive strength, compressive strength, tensile strength, water absorption and the like.

또한, 속건조시간은 2시간으로 나타났으며, 완전경화시간은 24시간으로 나타난 것으로 종래의 보수제보다 빠른 경화시간을 보여주었으며, 습윤상태에서도 부착력이 좋으며, 경화되었을때의 외관상태도 양호한 것으로 나타난 것으로, 경화되어 사용가능한 시간이 20∼30분 (25℃)이며, 완전경화되는 시간은 24시간 (25℃)으로 매우 빠른 경화시간을 나타내고 있다.In addition, the quick drying time was 2 hours, the complete curing time was 24 hours, showing a faster curing time than the conventional repair agent, the adhesion was good even in the wet state, and the appearance was good when cured. The curing time is 20 to 30 minutes (25 ° C), and the curing time is 24 hours (25 ° C), indicating a very fast curing time.

상기와 같이 제조되는 본 발명의 고경도 부식 방지 코팅 조성물을 아래와 같이 실시예 및 비교예를 통해 더욱 상세하게 설명한다.The high hardness anti-corrosion coating composition of the present invention prepared as described above will be described in more detail through the following Examples and Comparative Examples.

실시예1Example 1

우레탄 변성에폭시수지 WS-815를 29.89중량부로 회전수가 40rpm인 교반기를 이용하여 액온도를 50±5℃로 10분정도 교반시킨다.The urethane modified epoxy resin WS-815 is 29.89 parts by weight, and the liquid temperature is stirred at 50 ± 5 ° C. for 10 minutes using an agitator having a rotation speed of 40 rpm.

상기와 같이 교반된 우레탄 변성 에폭시수지에 기타 첨가제로서, 내부물성 개선제로 FOAMEX-N을 0.05중량부와 Tego-910을 0.05중량부와, Tego-1484를 0.05중량부로 총 0.15중량부를 첨가하고, 항균제로는 ANBIGENT 20을 0.10중량부를 첨가한다.As other additives to the stirred urethane-modified epoxy resin, 0.05 parts by weight of FOAMEX-N, 0.05 parts by weight of Tego-910, and 0.05 parts by weight of Tego-1484 were added as an internal physical property improving agent. The furnace adds 0.10 parts by weight of ANBIGENT 20.

안정제로는 TPP를 0.10중량부로 첨가하고, 실란계 결합제인 3-글리시독시 프로필 트리메톡시 실란 (S-510(Chisso Corporation,USA)) 을 0.12중량부로 첨가하고, 흐름방지제인 텍사ST를 1.10중량부를 첨가하여 액온도를 50±5℃로 20분정도 교반시킨다.As a stabilizer, 0.15 part by weight of TPP was added, 0.12 part by weight of 3-glycidoxy propyl trimethoxy silane (S-510 (Chisso Corporation, USA)), a silane-based binder, and 1.10 part by weight of TEXA ST, a flow inhibitor, was added. Add a weight part and stir the liquid temperature at 50 ± 5 ° C. for about 20 minutes.

그 후에, 충진제로 지르코늄을 51.84중량부와 Zinc-Dust를 16.70중량부로 첨가시킨다.Thereafter, 51.84 parts by weight of zirconium and 16.70 parts by weight of Zinc-Dust are added as a filler.

상기의 충진제 지르코늄과 Zinc-Dust는 비중이 높으므로 한번에 다량을 투입하면 분산 분량입자가 탱크의 바닥 등에 침전될 수 있기 때문에 천천히 분할하여 투입하는 공정 및 배합비율에 의해 본 발명의 주제혼합물이 제조된다.Since the filler zirconium and Zinc-Dust have a high specific gravity, the main mixture of the present invention is prepared by the process of slowly dividing and adding the mixture, since the dispersed particles may be precipitated at the bottom of the tank when a large amount is added at a time. .

경화성수지인 폴리아미드수지는, 페놀을 30.92 중량부 정도에 MXDA(Meta Xylene Diamine) 37.96 중량부를 교반하면서 140℃로 승온시키고, 여기에 37%포름알데하이드(Formaldehyde) 17.11 중량부를 서서히 분할투입한다.The polyamide resin, which is a curable resin, was heated to 140 DEG C while stirring 37.96 parts by weight of MXDA (Meta Xylene Diamine) to about 30.92 parts by weight of phenol, and 17.11 parts by weight of 37% formaldehyde (Formaldehyde) were gradually added thereto.

상기와 같이 37% 포름알데하이드를 완전하게 투입시킨후 180℃로 승온시켜 2∼3시간 반응시킨다.37% formaldehyde was completely added as described above, and then heated to 180 ° C. for 2 to 3 hours.

상기 수지의 점도가 실온 기준으로 20000∼40000 cps/20℃가 되면 온도를 80℃로 낮춘후에 벤질 알콜 (Benzyl Alcohol)을 10.40중량부를 투입하고, 다시 온도를 60∼70℃로 유지하면서 페놀 3.1중량부와 경화촉진제인 아민촉매 K54를 0.51중량%정도를 투입하여 1 시간정도 교반시킨후 반응을 종료시키면 폴리아미드수지인 WS-051(폴리아미드계 경화제(Wooshin Chem,korea. 에폭시 당량:220∼270g/eq))를 100중량부가 생성된다.When the viscosity of the resin is 20000 to 40000 cps / 20 ℃ based on the room temperature, after the temperature is lowered to 80 ℃ 10.40 parts by weight of benzyl alcohol, and the temperature is maintained at 60 to 70 ℃ again 3.1 weight of phenol After the reaction was terminated by adding about 0.51% by weight of the amine catalyst K54, which is a curing accelerator, and the reaction was completed, WS-051 (polyamide-based curing agent (Wooshin Chem, Korea. Epoxy equivalent: 220-270g) was used. / eq)) to 100 parts by weight.

상기 우레탄 변성에폭시수지와 기타첨가제를 혼합한 주제혼합물 75중량부와 폴리아미드계 경화성수지 25중량부로 혼합한 고경도 부식 방지 코팅 조성물을 제조한다.A high hardness anti-corrosion coating composition is prepared by mixing 75 parts by weight of the main mixture in which the urethane-modified epoxy resin and other additives are mixed with 25 parts by weight of a polyamide-based curable resin.

상기와 같이 제조된 고경도 부식 방지 코팅 조성물의 성능을 실험한 결과, 경도는 98A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 28㎏f/㎠, 압축강도는 254㎏f/㎠, 인장강도는 96 ㎏f/㎠, 흡수율 0.01% 이하로 나타났으며, 염수분무상태에서 360hr에서도 아무이상이 나타나지 않은 것으로 효과가 매우 뛰어나게 나타났다.As a result of experiments on the performance of the high hardness anti-corrosion coating composition prepared as described above, the hardness was 98A (SHORE A), the adhesive strength at the time of coating 28kgf / ㎠, compressive strength is 254㎏f / ㎠, tensile The strength was 96 kgf / ㎠, the absorption rate was 0.01% or less, and no effect was found even at 360hr in the salt spray state.

또한, 속건조시간은 2시간으로 나타났으며, 완전경화시간은 24시간으로 나타난 것으로 종래의 보수제보다 빠른 경화시간을 보여주었으며, 습윤상태에서도 부착력이 좋으며, 경화되었을때의 외관상태도 양호한 것으로 나타났다.In addition, the fast drying time was 2 hours, the complete curing time was 24 hours, showing a faster curing time than the conventional repair agent, the adhesion is good even in the wet state, the appearance was good when cured.

실시예 2Example 2

실시예 1과 같은 배합비율로 이루어진 주제혼합물중 85중량부를, WS-051을 80중량부 및 경화촉진제 K-54 를 20중량부로 혼합하여 이루어진 폴리아미드계 경화성수지 15중량부와 혼합하여 고경도 부식 방지 코팅 조성물을 제조하였다.High hardness corrosion by mixing 85 parts by weight of the main mixture of the same mixing ratio as in Example 1 with 15 parts by weight of polyamide-based curable resin formed by mixing 80 parts by weight of WS-051 and 20 parts by weight of the curing accelerator K-54 An anti-coat composition was prepared.

상기와 같이 제조된 본 실시예의 고경도 부식 방지 코팅 조성물은 폴리아미드계 경화성수지에 경화촉진제 K-54만을 첨가하여 사용한 것으로, 본 실시예 2의 고경도 부식 방지 코팅 조성물의 성능을 실험한 결과, 경도는 99A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 29㎏f/㎠, 압축강도는 259㎏f/㎠, 인장강도는 115 ㎏f/㎠, 흡수율 0.01% 이하로 나타났으며, 염수분무로 360hr에서 아무이상이 나타나지 않은 것으로 효과가 매우 뛰어나게 나타났다.The high hardness anti-corrosion coating composition of the present Example prepared as described above was used by adding only the curing accelerator K-54 to the polyamide-based curable resin, and as a result of testing the performance of the high hardness corrosion-resistant coating composition of Example 2, The hardness was 99A (SHORE A), the adhesive strength at the time of coating was 29㎏f / ㎠, the compressive strength was 259㎏f / ㎠, the tensile strength was 115 ㎏f / ㎠, the absorption rate was less than 0.01%, and the brine The spray showed no abnormality at 360hr, which was very effective.

또한, 속건조시간은 1.5시간으로 나타났으며, 완전경화시간은 18시간으로 나타난 것으로 실시예 1 에 실시된 것보다 빠른 경화시간을 보여주었으며, 모든 물성에 비하여 뛰어날 뿐만 아니라 반응성이 매우 빠르고, 습윤상태에서의 건조상태도 매우 양호한 것으로 나타났다.In addition, the fast drying time was found to be 1.5 hours, the complete curing time was 18 hours, showing a faster curing time than that performed in Example 1, not only superior to all physical properties but also very fast reactivity, wet The dry state in the state was also found to be very good.

비교예 1Comparative Example 1

실시예 1과 같은 배합비율로 이루어진 주제혼합물중 80중량부를, 폴리아미드계 경화성 수지 H-3038 (폴리아미드계 경화성수지(Kukdo Chem Korea) 아민가: 310∼380mg KOH/g) 20중량부와 혼합하여 고경도 부식 방지 코팅 조성물을 제조하였다.80 parts by weight of the main mixture having the same mixing ratio as in Example 1 was mixed with 20 parts by weight of a polyamide-based curable resin H-3038 (polyamide-based curable resin (Kukdo Chem Korea) amine number: 310-380 mg KOH / g) High hardness anti-corrosion coating compositions were prepared.

상기와 같이 제조된 비교예 1의 고경도 부식 방지 코팅 조성물은 폴리아미드계 경화성수지를 실시예 1 에서 사용한 것과는 다른 것을 사용하여 제조하였다.The high hardness anti-corrosion coating composition of Comparative Example 1 prepared as described above was prepared using a polyamide-based curable resin different from that used in Example 1.

본 비교예의 고경도 부식 방지 코팅 조성물의 성능을 실험한 결과, 경도는 86A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 14㎏f/㎠, 압축강도는 143㎏f/㎠, 인장강도는 76 ㎏f/㎠, 흡수율 0.01% 이하로 나타났으며, 염수분무상태에서는 360hr로 아무이상이 나타나지 않았다.Experimental results of the high hardness anti-corrosion coating composition of the present comparative example, the hardness was 86A (SHORE A), the adhesive strength at the time of coating 14kgf / ㎠, compressive strength is 143㎏f / ㎠, tensile strength is 76 ㎏f / ㎠, the absorption rate was less than 0.01%, and in the salt sprayed state did not appear anything at 360hr.

또한, 속건조시간은 4시간으로 나타났으며, 완전경화시간은 36시간으로 나타난 것으로 실시예 1 과 비교하여 주제혼합물의 성분은 같고 아민기가 다른 경화성수지인 H-3038을 사용한 결과 습윤상태에서의 건조상태는 양호하나 물성이 떨어지고 경화시간도 늦어지는 것으로 나타났다.In addition, the fast drying time was 4 hours, the complete curing time was 36 hours, and compared with Example 1, H-3038, a curable resin having the same composition and different amine groups, was used in the wet state. The drying condition was good, but the physical properties were lowered and the curing time was delayed.

비교예2Comparative Example 2

우레탄 변성에폭시수지 WS-815를 29.89중량부로 회전수가 40rpm인 교반기를 이용하여 액온도를 50±5℃로 10분정도 교반시킨다.The urethane modified epoxy resin WS-815 is 29.89 parts by weight, and the liquid temperature is stirred at 50 ± 5 ° C. for 10 minutes using an agitator having a rotation speed of 40 rpm.

상기와 같이 교반된 우레탄 변성 에폭시수지에 기타 첨가제로서, 내부물성 개선제로 FOAMEX-N을 0.05중량부와 Tego-910을 0.05중량부와, Tego-1484를 0.05중량부로 총 0.15중량부를 첨가하고, 항균제로는 ANBIGENT 20을 0.10중량부로 첨가한다.As other additives to the stirred urethane-modified epoxy resin, 0.05 parts by weight of FOAMEX-N, 0.05 parts by weight of Tego-910, and 0.05 parts by weight of Tego-1484 were added as an internal physical property improving agent. The furnace is added with 0.10 parts by weight of ANBIGENT 20.

안정제로는 TPP를 0.10중량부로 첨가하고, 실란계 결합제인 3-글리시독시 프로필트리메톡시실란 (S-510(Chisso Corporation,USA)) 을 0.12중량부로 첨가하고, 흐름방지제인 텍사ST를 1.10중량부를 첨가하여 액온도를 50±5℃로 20분정도 교반시킨다.As a stabilizer, 0.15 parts by weight of TPP was added, 0.12 parts by weight of 3-glycidoxy propyltrimethoxysilane (S-510 (Chisso Corporation, USA)), a silane-based binder, and 1.10 parts by weight of TEXA ST, a flow inhibitor, was added. Add a weight part and stir the liquid temperature at 50 ± 5 ° C. for about 20 minutes.

그 후에, 충진제로 실리카 20.84 중량부 및 탈크 31.0중량부와 Zinc-Dust를 16.70중량부로 첨가시켜 주제혼합물을 100중량부를 제조하고, 상기의 주제혼합물을 85중량부를, 폴리아미드 경화성수지를 WS-051을 80중량부 및 경화촉진제 K-54 를 15중량부와를 혼합하여 본 비교예의 고경도 부식 방지 코팅 조성물을 제조한다.Thereafter, 20.84 parts by weight of silica, 31.0 parts by weight of talc, and 16.70 parts by weight of Zinc-Dust were added to prepare a 100 parts by weight of the main mixture, 85 parts by weight of the main mixture, and a polyamide curable resin WS-051. 80 parts by weight and 15 parts by weight of a curing accelerator K-54 were mixed to prepare a high hardness anti-corrosion coating composition of this Comparative Example.

상기와 같이 제조된 고경도 부식 방지 코팅 조성물의 성능을 실험한 결과, 경도는 83A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 25㎏f/㎠, 압축강도는 232㎏f/㎠, 인장강도는 85 ㎏f/㎠, 흡수율 0.05% 이하로 나타났으며, 염수분무상태에서 250hr에서 코팅막이 벗겨지는 현상이 나타났다.As a result of experiments on the performance of the high hardness anti-corrosion coating composition prepared as described above, the hardness was 83A (SHORE A), the adhesion at the time of coating 25㎏f / ㎠, compressive strength is 232㎏f / ㎠, tensile The strength was 85 kgf / ㎠, the absorption rate was 0.05% or less, and the coating film was peeled off at 250hr in the salt spray state.

또한, 속건조시간은 1.5 시간으로 나타났으며, 완전경화시간은 48시간이 걸렸다.In addition, the quick drying time was 1.5 hours, and the complete curing time was 48 hours.

지르코늄 대신 첨가된 실리카 및 탈크로 인해 건조시간이 지연된 것으로 나타났을 뿐만 아니라, 습윤상태에서도 물에 용해현상이 발생되어 접착력이 현저하게 감소되는 것으로 나타났다.Silica and talc added in place of zirconium not only delayed the drying time, but also resulted in dissolution in water even when wet, resulting in a significant decrease in adhesion.

비교예 3Comparative Example 3

비스페놀 A형 에폭시수지인 KD-115CA(Kukdo Chem Korea, 에폭시 당량 : 220∼270g/eq) 29.89중량부와, 기타 첨가제로서, 내부물성 개선제로 FOAMEX-N을 0.05중량부와 Tego-910을 0.05중량부와, Tego-1484를 0.05중량부로 총 0.15중량부를 첨가하고, 항균제로는 ANBIGENT 20을 0.10중량부 첨가한다.29.89 parts by weight of KD-115CA (Kukdo Chem Korea, Epoxy equivalent: 220-270 g / eq), a bisphenol A type epoxy resin, 0.05 parts by weight of FOAMEX-N and 0.05 parts by weight of Tego-910 as an internal properties improving agent. And 0.15 parts by weight of Tego-1484 at 0.05 parts by weight, and 0.10 parts by weight of ANBIGENT 20 as an antimicrobial agent.

안정제로는 TPP를 0.10중량부로 첨가하고, 실란계 결합제인 3-글리시독시 프로필트리메톡시실란 (S-510(Chisso Corporation,USA)) 을 0.12중량부로 첨가하고, 흐름방지제인 텍사ST를 1.10중량부를 첨가하여 액온도를 50±5℃로 20분정도 교반시킨다.As a stabilizer, 0.15 parts by weight of TPP was added, 0.12 parts by weight of 3-glycidoxy propyltrimethoxysilane (S-510 (Chisso Corporation, USA)), a silane-based binder, and 1.10 parts by weight of TEXA ST, a flow inhibitor, was added. Add a weight part and stir the liquid temperature at 50 ± 5 ° C. for about 20 minutes.

그 후에, 충진제로 지르코늄 51.48중량부 및 Zinc-Dust를 16.70중량부로 첨가시켜 주제혼합물을 100중량부를 제조한후, 상기 주제혼합물 75중량부를, 폴리아미드 경화성수지를 WS-051을 80중량부 및 경화촉진제 K-54 를 20중량부를 혼합하여 이루어진 경화성수지 25중량부만을 혼합하여 본 비교예의 고경도 부식 방지 코팅 조성물을 제조한다.Thereafter, 51.48 parts by weight of zirconium and 16.70 parts by weight of Zinc-Dust were added as a filler to prepare 100 parts by weight of the main mixture, 75 parts by weight of the main mixture, and 80 parts by weight of polyamide curable resin and WS-051. Only 25 parts by weight of the curable resin made by mixing 20 parts by weight of accelerator K-54 was mixed to prepare a high hardness corrosion resistant coating composition of the present comparative example.

상기와 같이 제조된 고경도 부식 방지 코팅 조성물을 실험한 결과, 경도는 85A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 22㎏f/㎠, 압축강도는 145㎏f/㎠, 인장강도는 80 ㎏f/㎠, 흡수율 0.25% 이하로 나타났으며, 염수분무상태로 120hr에서 코팅막이 벗겨지는 현상이 나타났다.As a result of experimenting with the high hardness anti-corrosion coating composition prepared as described above, the hardness was 85A (SHORE A), the adhesive strength at the time of coating 22kgf / ㎠, compressive strength is 145kgf / ㎠, tensile strength is 80 ㎏f / ㎠, the absorption rate appeared to be 0.25% or less, the coating film was peeled off at 120hr in the salt spray state.

또한, 속건조시간은 2.2 시간으로 나타났으며, 완전경화시간은 48시간이 걸렸다.In addition, the quick drying time was 2.2 hours, and the complete curing time was 48 hours.

주제혼합수지로 우레탄 변성에폭시수지 대신에 비스페놀 A형 에폭시수지를 사용하였더니 물성이 감소하고 경화시간이 지연되며, 습윤상태에서 부착력이 떨어질 뿐만 아니라, 물에 용해되는 문제가 발생되었다.Bisphenol A epoxy resin was used as the main mixed resin instead of the urethane modified epoxy resin, resulting in a decrease in physical properties, delay in curing time, adhesion loss in wet conditions, and dissolution in water.

비교예 4Comparative Example 4

우레탄 변성에폭시수지 WS-815 15.0중량부 및 비스페놀 A형 에폭시수지 KD-115CA 14.89 중량부와 기타 첨가제로서, 내부물성 개선제로 FOAMEX-N을 0.05중량부와 Tego-910을 0.05중량부와, Tego-1484를 0.05중량부로 총 0.15중량부를 첨가하고, 항균제로는 ANBIGENT 20을 0.10중량부를 첨가한다.15.0 parts by weight of urethane modified epoxy resin WS-815 and 14.89 parts by weight of bisphenol A epoxy resin KD-115CA and other additives; 0.05 parts by weight of FOAMEX-N, 0.05 parts by weight of Tego-910, Tego- 0.148 parts by weight of 1484 is added in a total of 0.05 parts by weight, and 0.10 parts by weight of ANBIGENT 20 is added as an antimicrobial agent.

안정제로는 TPP를 0.10중량부로 첨가하고, 실란계 결합제인 3-글리시독시 프로필트리메톡시실란 (S-510(Chisso Corporation,USA)) 을 0.12중량부로 첨가하고, 흐름방지제인 텍사ST를 1.10중량부를 첨가하여 액온도를 50±5℃로 20분정도 교반시킨다.As a stabilizer, 0.15 parts by weight of TPP was added, 0.12 parts by weight of 3-glycidoxy propyltrimethoxysilane (S-510 (Chisso Corporation, USA)), a silane-based binder, and 1.10 parts by weight of TEXA ST, a flow inhibitor, was added. Add a weight part and stir the liquid temperature at 50 ± 5 ° C. for about 20 minutes.

그 후에, 충진제로 지르코늄 51.48중량부와 Zinc-Dust 16.70중량부로 첨가시켜 주제혼합물을 100중량부를 제조하여 주제혼합물중 75중량부만을 아래와 같이 혼합한다.Thereafter, 51.48 parts by weight of zirconium and 16.70 parts by weight of Zinc-Dust were added as a filler to prepare 100 parts by weight of the main mixture, and only 75 parts by weight of the main mixture were mixed as follows.

우레탄 변성 에폭시수지 및 비스페놀 A형 에폭시수지와 기타 첨가제를 혼합한 주제혼합물 75중량부를, 폴리아미드 경화성수지를 WS-051을 80중량부 및 경화촉진제 K-54 를 20중량부로 혼합한 경화성수지 25중량부와를 다시 혼합하여 본 비교예의 고경도 부식 방지 코팅 조성물을 제조한다.75 parts by weight of a main mixture of urethane-modified epoxy resin, bisphenol A type epoxy resin and other additives, 25 parts by weight of curable resin containing 80 parts by weight of polyamide curable resin and 20 parts by weight of curing accelerator K-54. The mixture was mixed again to prepare a high hardness anti-corrosion coating composition of this Comparative Example.

상기와 같이 제조된 고경도 부식 방지 코팅 조성물의 성능을 실험한 결과, 경도는 85A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 23㎏f/㎠, 압축강도는 223㎏f/㎠, 인장강도는 75 ㎏f/㎠, 흡수율 0.18% 이하로 나타났으며, 염수분무상태에서 2500hr에서 코팅막이 벗겨지는 현상이 나타났다.As a result of testing the performance of the high hardness anti-corrosion coating composition prepared as described above, the hardness was 85A (SHORE A), the adhesive strength at the time of coating 23㎏f / ㎠, compressive strength is 223㎏f / ㎠, tensile The strength was 75 kgf / ㎠, the absorption rate was 0.18% or less, and the coating film was peeled off at 2500hr in the salt spray state.

또한, 속건조시간은 2.0 시간으로 나타났으며, 완전경화시간은 48시간이 걸렸다.In addition, the quick drying time was 2.0 hours, and the complete curing time was 48 hours.

주제혼합수지를 우레탄 변성에폭시수지 및 비스페놀 A형수지를 혼용하여 사용하였더니 우레탄 변성에폭시수지 단독으로 사용한 것보다 습윤상태에서 부착력이 떨어질뿐만 아니라, 물에 용해성이 있고 물성이 떨어지는 문제점이 발생되었다.When the main mixed resin was used in combination with a urethane modified epoxy resin and bisphenol A resin, the adhesive strength in wet state was lowered than that of the urethane modified epoxy resin alone, and solubility in water and poor physical properties occurred.

비교예 5Comparative Example 5

실시예1과 같이 혼합비율로 이루어진 주제혼합물중 67중량부만을, 폴리아미드계 경화성수지 WS-051을 80중량부 및 경화촉진제 K-54를 20중량부를 혼합하여 이루어진 폴리아미드계 경화성 수지 경화성수지 33중량부만으로 혼합하여 고경도 부식 방지 코팅 조성물을 제조하였다.Polyamide-based curable resin 33 comprising only 67 parts by weight of the main mixture composed of the mixing ratio as in Example 1, 80 parts by weight of polyamide-based curable resin WS-051 and 20 parts by weight of curing accelerator K-54. By mixing only parts by weight to prepare a high hardness anti-corrosion coating composition.

상기와 같이 제조된 고경도 부식 방지 코팅 조성물은 폴리아미드계 경화성수지와 주제혼합물의 비율만을 상이하게 혼합하여 제조한 것으로, 본 비교예의 고경도 부식 방지 코팅 조성물의 성능을 실험한 결과, 경도는 99A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 27㎏f/㎠, 압축강도는 245㎏f/㎠, 인장강도는 110 ㎏f/㎠, 흡수율 0.01% 이하로 나타났으며, 염수분무상태에서 360hr에서는 아무이상이 나타나지 않았다.The high hardness anti-corrosion coating composition prepared as described above was prepared by mixing only the ratio of the polyamide-based curable resin and the main mixture differently. As a result of testing the performance of the high hardness anti-corrosion coating composition of the present comparative example, the hardness is 99A (SHORE A), and the adhesive strength at the time of coating was 27㎏f / ㎠, the compressive strength was 245㎏f / ㎠, the tensile strength was 110 ㎏f / ㎠, the absorption rate was less than 0.01%, in the salt spray Nothing appeared at 360hr.

또한, 속건조시간은 2.0시간으로 나타났으며, 완전경화시간은 20시간으로 나타난 것으로, 실시예 2 와 비교하여 보면, 본 비교예에서는 3:1 의 혼합비율로 제조된 것으로 주제혼합물과 경화제의 혼합비율 4:1 로 혼합했을때보다는 물성 및 반응성이 떨어졌다.In addition, the fast drying time was 2.0 hours, and the complete curing time was 20 hours. Compared with Example 2, the comparative example was prepared in a mixing ratio of 3: 1. The physical properties and reactivity were lower than when the mixing ratio was 4: 1.

비교예 6Comparative Example 6

실시예 1과 같은 배합비율로 이루어진 주제혼합물중 83.33중량부만을, 폴리아미드계 경화성수지 WS-051을 80중량부 및 경화촉진제 K-54 를 20중량부를 혼합하여 이루어진 폴리아미드계 경화성수지 16.66중량부만으로 혼합하여 고경도 부식 코팅 조성물을 제조하였다.16.66 parts by weight of a polyamide curable resin obtained by mixing only 83.33 parts by weight of a main mixture having the same mixing ratio as in Example 1 with 80 parts by weight of polyamide curable resin WS-051 and 20 parts by weight of curing accelerator K-54. Mixing alone to prepare a high hardness corrosion coating composition.

상기와 같이 제조된 고경도 방식코팅 보수제는 폴리아미드계 경화성수지와 주제혼합물의 비율만을 상이하게 제조한 것으로, 본 비교예의 고경도 부식 방지 코팅 조성물의 성능을 실험한 결과, 경도는 94A(SHORE A) 를 나타내었으며, 코팅시의 접착력은 28㎏f/㎠, 압축강도는 247㎏f/㎠, 인장강도는 112 ㎏f/㎠, 흡수율 0.01% 이하로 나타났으며, 염수분무상태에서 360hr에서는 아무이상이 나타나지 않았다.The high hardness anticorrosive coating repair agent prepared as described above was prepared in different ratios of the polyamide-based curable resin and the main mixture, and as a result of experimenting with the performance of the high hardness anti-corrosion coating composition of the present comparative example, the hardness was 94 A (SHORE A Adhesion at coating was 28㎏f / ㎠, compressive strength was 247㎏f / ㎠, tensile strength was 112 ㎏f / ㎠, water absorption was 0.01% or less. No abnormality appeared.

또한, 속건조시간은 2.5시간으로 나타났으며, 완전경화시간은 24시간으로 나타난 것으로, 실시예 2 와 비교하여 보면, 주제혼합물과 경화제의 혼합비가 4:1 로 혼합했을때보다는 물성 및 반응성이 떨어졌다.In addition, the fast drying time was 2.5 hours, the complete curing time was 24 hours, and compared with Example 2, the physical properties and reactivity of the main mixture and the curing agent when compared with 4: 1 fell.

상기와 같은 실시예 1,2 및 비교예 1∼6의 첨가비 및 결과치를 아래의 표1 및 표 2 와 같이 나타낸다.The addition ratios and resultant values of Examples 1 and 2 and Comparative Examples 1 to 6 described above are shown in Tables 1 and 2 below.

실시예 및 비교예의 혼합비율Mixing ratio of Examples and Comparative Examples 실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6 (A)주제혼합물(A) Topic Blend WS-815WS-815 29.8929.89 29.8929.89 29.8929.89 29.8929.89 -- 15.015.0 29.8929.89 29.8929.89 KD-115CAKD-115CA -- -- -- -- 29.8929.89 14.8914.89 -- -- FOAMEX-NFOAMEX-N 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 Tego-910Tego-910 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 TPPTPP 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 Tego-1484Tego-1484 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05 S-510S-510 0.120.12 0.120.12 0.120.12 0.120.12 0.120.12 0.120.12 0.120.12 0.120.12 THIXA STTHIXA ST 1.101.10 1.101.10 1.101.10 1.101.10 1.101.10 1.101.10 1.101.10 1.101.10 ZIRCONIUMZIRCONIUM 51.8451.84 51.8451.84 51.8451.84 -- 51.8451.84 51.8451.84 51.8451.84 51.8451.84 SILICASILICA -- -- -- 20.8420.84 -- -- -- -- TALCTALC -- -- -- 31.031.0 -- -- -- -- ZINC-DUSTZINC-DUST 16.7016.70 16.7016.70 16.7016.70 16.7016.70 16.7016.70 16.7016.70 16.7016.70 16.7016.70 ANBIZENT 20ANBIZENT 20 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 0.100.10 gun 100100 100100 100100 100100 100100 100100 100100 100100 (B)경화성 수지(B) curable resin WS-051WS-051 100100 8080 -- 8080 8080 8080 100100 100100 H-3038H-3038 -- -- 100100 -- -- -- -- -- K-54K-54 -- 2020 2020 2020 2020 -- -- gun 100100 100100 100100 100100 100100 100100 100100 100100 배합비(주제혼합물: 경화성수지)Compounding ratio (topic mixture: curable resin) 4:14: 1 4:14: 1 4:14: 1 4:14: 1 4:14: 1 4:14: 1 3:13: 1 5:15: 1

실시예 및 비교예의 효과 비교Comparison of the effects of Examples and Comparative Examples 항목Item 실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6 경도(Shore A)Shore A 9898 9999 8686 8383 8585 8585 9595 9494 접착력(Kg f/㎠)Adhesive force (Kg f / ㎠) 2828 2929 1414 2525 2222 2323 2727 2828 압축강도(Kg f/㎠)Compressive strength (Kg f / ㎠) 254254 259259 143143 232232 145145 223223 245245 247247 인장강도(hr)Tensile strength (hr) 9696 115115 7676 8585 8080 7575 110110 112112 흡수율(hr)Absorption rate (hr) 0.01%이하0.01% or less 0.01%이하0.01% or less 0.01%이하0.01% or less 0.15%0.15% 0.25%0.25% 0.18%0.18% 0.01%0.01% 0.01%0.01% 염수분무(hr)Brine spray (hr) 360이상무More than 360 360이상무More than 360 360이상무More than 360 250이하250 or less 120이하120 or less 250이하250 or less 360이상무More than 360 360이상무More than 360 속건조시간(hr)Quick Drying Time (hr) 22 1.51.5 33 1.51.5 2.22.2 22 22 2.52.5 완전경화시간(hr)Complete Curing Time (hr) 2424 1818 3636 4848 4848 4848 2020 2424 결 과result 좋음good 매우 좋음Very good 보통usually 불량Bad 불량Bad 불량Bad 보통usually 보통usually

상기와 같이 실시예 1,2에서 제조된 고경도 방식코팅 보수제중 실시예 2에 의해 제조된 고경도 부식 코팅 조성물의 실험결과 매우 좋게 나타났으며, 실시예 1 또한 실시예 2와 비슷한 결과로 나타나 있는 것으로 보아 본 발명의 배합비율내에서 혼합되는 것이 바람직하다.As described above, the high hardness corrosion coating composition prepared in Example 2 of the high hardness anticorrosive coating repair agent prepared in Examples 1 and 2 was found to be very good, and Example 1 was also shown to be similar to Example 2. As it exists, it is preferable to mix in the compounding ratio of this invention.

그 반면, 비교예 1∼6에 의해 제조된 고경도 부식 방지 코팅 조성물을 보면, 비교예 1 은 경도, 접착력, 압축강도, 인장강도 등이 현저하게 떨어지는 문제점이 발생되었으며, 비교예 2는 압축강도를 제외한 경도, 접착력 인장강도 등이 불량한 것으로 나타났다.On the other hand, when looking at the high hardness anti-corrosion coating composition prepared by Comparative Examples 1 to 6, Comparative Example 1 has a problem that the hardness, adhesive strength, compressive strength, tensile strength, etc. significantly decreased, Comparative Example 2 has a compressive strength Except for hardness, adhesive strength and tensile strength was poor.

그뿐만 아니라, 비교예 2 및 비교예3, 4 는 주제혼합물에 혼합되는 비율 및 물질을 다른 것을 사용하였을 때에 제조된 조성물은, 흡수율이 다른 것에 비해 증가되는 현상을 나타냈으며, 비교예 5 및 비교예 6 에서 제조된 것은 제품의 성질은 보통으로 나타나 있다.In addition, Comparative Example 2 and Comparative Examples 3 and 4 exhibited a phenomenon in which the composition produced when the ratio and substance mixed in the main mixture were used differently increased compared to the other, and Comparative Example 5 and Comparative Prepared in Example 6, the properties of the product are shown as normal.

상기와 같은 실시된 실시예 및 비교예에 의해 주제혼합물과 경화성수지와의 혼합비율은 4:1 이 가장 바람직한 것으로 나타났으며, 주제혼합물중에는 KD-115CA 보다는 WS-815 를 사용하는 것이 좋으며, 충진제중 실리카 및 탈크는 좋지 않는 결과를 보였기 때문에 기타 첨가제중 충진제는 지르코늄 및 ZINC-DUST를 사용하는 것이 더욱 바람직하다.According to the examples and comparative examples carried out as described above, the mixing ratio of the main mixture and the curable resin was found to be 4: 1, and the main mixture was preferably WS-815 rather than KD-115CA. Since heavy silica and talc showed poor results, it is more preferable to use zirconium and ZINC-DUST as fillers among other additives.

따라서, 상기와 같이 제조된 본 발명의 고경도 부식 방지 코팅 조성물에 의해 수분의 존재하에서도 경화가 빠르고 접착력이 우수한 화합물로 수중 구조물-교각, 수문, 댐 등의 보수, 보강 및 신구콘크리트의 접착, 습윤상태에서도 코팅이 가능할 뿐만 아니라, 작업이 용이한 효과가 있다.Therefore, the above-described high hardness anti-corrosion coating composition of the present invention prepared in the presence of moisture in the presence of moisture and excellent adhesion, repair, reinforcement and adhesion of old and new concrete structures, bridges, water gates, dams, Not only can the coating be wet, there is an easy operation.

Claims (8)

에폭시 당량이 180∼270g/eq 인 우레탄 변성에폭시 수지 77.88 ∼ 29.42 중량부 및 기타 첨가제 70.58 ∼ 22.12 중량부로 이루어진 주제혼합물 75∼85중량부와, 아민가 280∼380 KOH/g 인 폴리아미드계 경화성수지 15∼25중량부가 혼합됨을 특징으로 하는 고경도 부식 방지 코팅 조성물.75 to 85 parts by weight of a main mixture consisting of 77.88 to 29.42 parts by weight of urethane-modified epoxy resin having an epoxy equivalent of 180 to 270 g / eq and 70.58 to 22.12 parts by weight of other additives, and a polyamide-based curable resin having an amine of 280 to 380 KOH / g. A high hardness anti-corrosion coating composition, characterized in that ˜25 parts by weight is mixed. 제 1 항에 있어서, 상기 첨가제는 실란계 결합제, 충진제, 개선제, 안정제, 흐름방지제, 항균제로 이루어지는 것을 특징으로 하는 고경도 부식 방지 코팅 조성물.The method of claim 1, wherein the additive is a high hardness anti-corrosion coating composition, characterized in that consisting of a silane-based binder, filler, improver, stabilizer, anti-flow agent, antibacterial agent. 제 2 항에 있어서, 실란 결합제는 3-글리시독시 프로필 트리메톡시실란 ( 3-Glycidoxy propyl trimethoxysilane) 인 것을 특징으로 하는 고경도 부식 방지 코팅 조성물.3. The high hardness anti-corrosion coating composition of claim 2, wherein the silane binder is 3-glycidoxy propyl trimethoxysilane. 제 2 항에 있어서, 상기 항균제는 ANBIGENT 20이고, 충진제는 지르코늄 및 Zinc-Dust인 것을 특징으로 하는 고경도 부식 방지 코팅 조성물.3. The high hardness anti-corrosion coating composition of claim 2 wherein the antimicrobial agent is ANBIGENT 20 and the fillers are zirconium and Zinc-Dust. 제 2 항에 있어서, 상기 흐름방지제는, 클레이 볼락 수퍼 또는 텍사 ST인 것을 특징으로 하는 고경도 부식 방지 코팅 조성물.The high hardness anti-corrosion coating composition of claim 2, wherein the anti-flow agent is clay ballac super or Texa ST. 제 2 항에 있어서, 상기 충진제는, 지르코늄 또는 Zinc-Dust 인 것을 특징으로 하는 고경도 부식 방지 코팅 조성물.3. The high hardness anti-corrosion coating composition of claim 2, wherein the filler is zirconium or Zinc-Dust. 제 1 항에 있어서, 폴리아미드계 경화수지는 WS-051 인 것을 특징으로 하는 고경도 부식 방지 코팅 조성물.The high hardness anti-corrosion coating composition according to claim 1, wherein the polyamide cured resin is WS-051. 제 6 항에 있어서, 상기 폴리아미드계 경화성수지에는, 경화촉진제 K-54가 더 첨가됨을 특징으로 하는 고경도 부식 방지 코팅 조성물.The high hardness anti-corrosion coating composition according to claim 6, wherein a curing accelerator K-54 is further added to the polyamide curable resin.
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KR100494953B1 (en) * 2002-08-29 2005-06-14 주식회사 자산유리 Coating composition for cover used in prevention of corrosion of mirror edge, and method for covering mirror edge using the same
KR100619100B1 (en) * 2006-02-20 2006-09-05 김희영 Composition for reducing fugitive dust for spray paint

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KR102214271B1 (en) 2019-03-21 2021-02-22 주식회사 터보이온코리아 Far-infrared ray hair dryer
KR102224041B1 (en) 2019-03-21 2021-03-09 주식회사 터보이온코리아 Hair dryer with expansion nozzle to emit far infrared rays
KR102086954B1 (en) 2019-06-11 2020-03-10 주식회사 터보이온코리아 Far-infrared ray hair dryer

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JPH0726080B2 (en) * 1987-11-30 1995-03-22 サンスター技研株式会社 Structural adhesive with high corrosion resistance
KR920009737B1 (en) * 1988-01-09 1992-10-22 산스타기겐 가부시키가이샤 Epoxy resin composition

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KR100494953B1 (en) * 2002-08-29 2005-06-14 주식회사 자산유리 Coating composition for cover used in prevention of corrosion of mirror edge, and method for covering mirror edge using the same
KR100619100B1 (en) * 2006-02-20 2006-09-05 김희영 Composition for reducing fugitive dust for spray paint

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