KR101086847B1 - Coating composition for sliding member - Google Patents

Coating composition for sliding member Download PDF

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Publication number
KR101086847B1
KR101086847B1 KR1020110005958A KR20110005958A KR101086847B1 KR 101086847 B1 KR101086847 B1 KR 101086847B1 KR 1020110005958 A KR1020110005958 A KR 1020110005958A KR 20110005958 A KR20110005958 A KR 20110005958A KR 101086847 B1 KR101086847 B1 KR 101086847B1
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resin
phosphate
delete delete
sliding member
adhesive
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KR1020110005958A
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Korean (ko)
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이계영
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이계영
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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: A coating composition for a sliding member is provided to obtain the sliding member with excellent abrasion resistance, non-adhesive property, and lubrication since a composition prepared by mixing a lubricant, filler and adhesive in a constant ratio is applied to the surface of a substrate. CONSTITUTION: A coating composition for a sliding member comprises: 25~60% of a solid lubricant formed by blending one or more of PTFE, MoS_2, WS_2, BN, and graphite; 5~10% of filler consisting of one of flake Muscovitum, Al_2O_3, ZrO_2, ZrSiO_3, ZnO, TiO_2 and SiO_2; 30~70% of an adhesive obtained by blending an epoxy-based resin, an alkoxysilane-based resin and metal phosphate. The solid lubricant is micropowder. The average particle diameter of polytetrafluoroethylene resin is 0.2~1.0μm.

Description

접동부재용 코팅 조성물{Coating Composition for Sliding member}Coating composition for sliding member {Coating Composition for Sliding member}

본 발명은 접동부재용 코팅 조성물에 관한 것이다. 더욱 상세하게는 기재에 내마모성, 비점착성, 내열성 및 윤활성을 부여하기 위하여 기재의 표면에 코팅하는 접동부재용 코팅 조성물에 관한 것이다.
The present invention relates to a coating composition for the sliding member. More specifically, the present invention relates to a coating composition for a sliding member coated on the surface of the substrate in order to impart wear resistance, non-tackiness, heat resistance and lubricity to the substrate.

일반적으로, 금속 혹은 세라믹 기재(기기 또는 도구) 등에 내마모성과 비점착성 및 윤활성을 부여하기 위하여 내마모 재료나 윤활제 물질을 코팅하여 사용한다.
예를 들어, 가정용 조리기의 일종인 프라이팬의 표면 코팅에 있어서, 프라이팬의 표면 즉, 알루미늄 또는 철에 유기질 또는 무기질 접착제를 이용하여 PTFE(폴리테트라플루오르에틸렌, Polytetrafluoroethylene)과 여러 가지 충전제를 배합한 조성물을 코팅한다. 코팅 작업으로 프라이팬의 표면을 내마모성이나 비점착성으로 변환시켜 음식재료의 부착을 방지하는 것이다.
종래기술에는 코팅 조성물로 윤활제는 PTFE계 수지, 인편상 이황화 몰리브덴(MoS2), 텅스텐 디설파이드(WS2), 질화붕소(BN) 및 흑연을 사용하였으며, 접착제로는 폴리아미드(Polyamide), 폴리아미드이미드(Polyamide imide) 수지, 실리콘 커플링제, 산화철 분말 및 브론즈 분말 등을 사용하였다.
그러나, 전술한 코팅 조성물 중 산화철이나 브론즈 분말의 경우 내마모성은 증대시키나, 비점착성과 윤활성이 저하되는 단점이 있었다.
또한, 폴리아미드, 폴리아미드이미드 수지 등은 가격이 높아 범용으로 대량 사용하기에는 제한적이며, MoS2, WS2, BN, 및 흑연 등과 같은 고체윤활제를 배합하여 금속 기재에 대한 접착제로 사용할 경우 기재와의 접착성 및 내마모성이 상대적으로 결여되는 단점이 있었다.
그리고, 고체윤활제, 접착제 수지 및 저융점 금속을 함유한 윤활제 필름에 관한 종래기술은 고체윤활제로 MoS2, 흑연, PTFE계를 사용하고, 접착제 수지로는 열경화성 수지인 폴리아미드이미드, 실리콘 커플링제를 사용하며, 저융점 금속으로는 Sn(주석), Pb(납), In(인듐) 및 Bi(비스무트) 등을 함유하는 합금 또는 화합물을 사용하여 저융점 금속의 잠열을 이용한 내열성이 향상되도록 하였다.
그러나, 잠열성을 이용한 내열성 향상재료인 Sn, Pb, In 및 Bi 등 중금속은 환경공해를 유발할 수 있는 우려가 있어 사용량이 제한되는 단점이 있었으며, 고체윤활제와 접착제를 배합할 경우 기재와의 접착력, 내마모성 및 윤활성 등을 동시에 향상시키지 못하는 문제점이 있었다.
또한, 고체 윤활제와 기재와의 결합에 사용되는 접착용 수지만으로 구성되는 코팅제는 내마모성이 떨어지는 단점이 있으며, 가혹한 운전조건에서 코팅이 마모되어 기재의 바닥이 단시간 내에 노출되는 문제점이 있었다.
특히, 내마모성 재료로 침상이나 인편상의 각종 충전제를 첨가하는 경우, 코팅 표면의 미끄럼 정도가 저하되어 비점착성 또는 윤활성이 저하되는 문제점이 있었다.
In general, in order to impart wear resistance, non-tackiness and lubricity to a metal or ceramic substrate (apparatus or tool), a wear resistant material or a lubricant material is coated and used.
For example, in the surface coating of a frying pan, which is a type of household cooker, a composition in which PTFE (polytetrafluoroethylene) and various fillers are mixed with an organic or inorganic adhesive on the surface of the frying pan, that is, aluminum or iron. Coating. The coating process converts the surface of the frying pan into abrasion resistant or non-tacky to prevent the attachment of food ingredients.
In the prior art, as a coating composition, lubricants include PTFE-based resins, flaky molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), boron nitride (BN) and graphite, and polyamides and polyamides are used as adhesives. A polyamide imide resin, a silicone coupling agent, iron oxide powder, bronze powder, and the like were used.
However, in the case of the iron oxide or bronze powder in the above-described coating composition, the wear resistance is increased, but non-tackiness and lubricity had a disadvantage.
In addition, polyamide, polyamideimide resin, etc., are expensive and limited for general use in large quantities, and when used as an adhesive for metal substrates by combining solid lubricants such as MoS 2 , WS 2 , BN, and graphite, etc. There was a disadvantage of relatively lack of adhesion and wear resistance.
In addition, the prior art of a lubricant film containing a solid lubricant, an adhesive resin and a low melting point metal uses MoS 2 , graphite, and PTFE as a solid lubricant, and a polyamideimide, a silicone coupling agent, which is a thermosetting resin, is used as the adhesive resin. As the low melting point metal, an alloy or a compound containing Sn (tin), Pb (lead), In (indium), Bi (bismuth), or the like was used to improve heat resistance using latent heat of the low melting point metal.
However, heavy metals such as Sn, Pb, In, and Bi, which are heat-resistant improving materials using latent heat, may cause environmental pollution, and thus the amount of use thereof is limited. When a solid lubricant and an adhesive are combined, adhesion to the substrate, There was a problem that does not improve the wear resistance and lubricity at the same time.
In addition, the coating agent consisting of only the adhesive resin used for bonding the solid lubricant and the substrate has a disadvantage of poor wear resistance, there is a problem that the bottom of the substrate is exposed in a short time due to the wear of the coating under severe operating conditions.
In particular, when various needle-like or flaky fillers are added as the wear-resistant material, there is a problem that the slippage of the coating surface is lowered and the non-tackiness or lubricity is lowered.

이와 같은 문제점을 해결하기 위하여 본 발명은 윤활제, 충전제 및 접착제를 일정배율로 혼합하여 내마모성, 비점착성, 내열성 및 윤활성을 동시에 향상시킬 수 있는 접동부재용 코팅 조성물을 제공하는데 그 목적이 있다.
또한, 본 발명은 접동부재용 코팅 조성물을 기재의 표면에 코팅하여 열처리를 시행하고, 강력하게 부착시켜 높은 면압과 고속회전 혹은 왕복운동 등의 가혹한 운전 조건하에서도 박리가 일어나지 않도록 하는 접동부재용 코팅 조성물을 제공하는데 그 목적이 있다.
In order to solve the above problems, the present invention is to provide a coating composition for the sliding member that can improve the wear resistance, non-adhesiveness, heat resistance and lubricity at the same time by mixing a lubricant, filler and adhesive in a certain ratio.
In addition, the present invention is coated with a coating composition for the sliding member on the surface of the substrate to perform a heat treatment, and strongly adhered to the coating for the sliding member to prevent peeling under severe operating conditions such as high surface pressure and high speed rotation or reciprocating motion The purpose is to provide a composition.

이와 같은 목적을 달성하기 위해 본 발명은 폴리테트라플루오르에틸렌(Polytetrafluoroethylene, PTFE)과 인편상 이황화 몰리브덴(MoS2), 텅스텐 디설파이드(WS2), 육방정질화붕소(h-BN), 및 흑연 중 어느 하나 이상을 배합한 고체윤활제 25~60%와, 인편상 운모, 산화알루미늄(Al2O3), 지르코니아(ZrO2), 규산지르코니아(ZrSiO3), 산화아연(ZnO), 산화티탄(TiO2) 및 이산화규소(SiO2) 중 어느 하나로 이루어진 충전제 5~10%와, 에폭시계 수지, 폴리실록산계 수지 및 금속인산염을 배합한 접착제 30~70%로 이루어지는 것을 특징으로 하는 접동부재용 코팅 조성물에 관한 것이다.
또한, 상기 고체윤활제는 미분말이며, 폴리테트라플루오르에틸렌(PTFE) 수지의 평균 입경은 0.2~1.0㎛이며, 인편상 이황화 몰리브덴(MoS2), 텅스텐 디설파이드(WS2) 및 육방정질화붕소(h-BN)의 평균 입경은 1㎛이하이고, 흑연의 평균 입경은 5㎛이하 혹은 100㎚이하인 것을 특징으로 하는 접동부재용 코팅 조성물에 관한 것이다.
또한, 상기 충전제는 인편상 운모, 산화알루미늄(Al2O3), 지르코니아(ZrO2), 규산지르코니아(ZrSiO3), 산화아연(ZnO), 산화티탄(TiO2) 및 이산화규소(SiO2)의 평균 입경은 졸-겔(sol-gel)방법으로 합성하여 1㎛이하인 것을 특징으로 하는 접동부재용 코팅 조성물에 관한 것이다.
또한, 상기 접착제의 에폭시(epoxy) 수지와 금속인산염 접착제를 병용하는 것을 특징으로 하는 접동부재용 코팅 조성물에 관한 것이다.
In order to achieve the above object, the present invention provides polytetrafluoroethylene (PTFE) and flaky molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), hexagonal boron nitride (h-BN), and graphite. 25 to 60% of a solid lubricant blended with at least one, flaky mica, aluminum oxide (Al 2 O 3 ), zirconia (ZrO 2 ), zirconia (ZrSiO 3 ), zinc oxide (ZnO), titanium oxide (TiO 2) ) And 5 to 10% of a filler composed of any one of silicon dioxide (SiO 2 ) and 30 to 70% of an adhesive containing an epoxy resin, a polysiloxane resin, and a metal phosphate. will be.
In addition, the solid lubricant is a fine powder, the average particle diameter of the polytetrafluoroethylene (PTFE) resin is 0.2 ~ 1.0㎛, flaky molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ) and hexagonal boron nitride (h- The average particle diameter of BN) is 1 micrometer or less, and the average particle diameter of graphite relates to the coating composition for sliding members which is 5 micrometers or less or 100 nm or less.
In addition, the filler is flaky mica, aluminum oxide (Al 2 O 3 ), zirconia (ZrO 2 ), zirconia silicate (ZrSiO 3 ), zinc oxide (ZnO), titanium oxide (TiO 2 ) and silicon dioxide (SiO 2 ) The average particle diameter of the present invention relates to a coating composition for a sliding member, characterized in that less than 1㎛ synthesized by the sol-gel (sol-gel) method.
In addition, the present invention relates to a coating composition for a sliding member, characterized by using an epoxy (epoxy) resin and a metal phosphate adhesive of the adhesive.

이와 같은 본 발명에 의하면, 윤활제, 충전제 및 접착제를 일정배율로 혼합하여 제조한 조성물을 기재의 표면에 코팅하여 제조된 접동부재가 내마모성, 비점착성, 내열성 및 윤활성을 동시에 지니도록 하는 효과가 있다.
또한, 본 발명에 의하면, 조성물을 기재의 표면에 열처리를 시행하고, 강력하게 부착하여 높은 면압과 고속회전 혹은 왕복운동 등의 가혹한 운전 조건하에서도 박리가 일어나지 않도록 하여 장시간 사용할 수 있는 효과가 있다.
According to the present invention, the sliding member prepared by coating the surface of the substrate with a composition prepared by mixing the lubricant, filler and adhesive at a constant magnification has the effect of having abrasion resistance, non-tackiness, heat resistance and lubricity at the same time.
In addition, according to the present invention, the composition is subjected to a heat treatment on the surface of the substrate, and is strongly attached to the composition so that peeling does not occur even under severe operating conditions such as high surface pressure and high speed rotation or reciprocating motion, so that the composition can be used for a long time.

이하, 본 발명의 바람직한 실시예를 첨부된 도면들을 참조하여 상세히 설명한다. 우선 도면의 구성요소들에 참조 부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략한다.
본 발명의 접동부재용 코팅 조성물은 고체윤활제, 접착제 및 충전제로 구성된다.
고체윤활제는 PTFE(폴리테트라플루오르에틸렌, Polytetrafluoroethylene), 인편상 MoS2(이황화 몰리브덴), WS2(텅스텐 디설파이드), h-BN(육방정질화붕소) 및 흑연을 혼합하여 구성되며, 이 물질들을 혼합할 경우에는 PTFE와 MoS2, WS2, h-BN 및 흑연 중 하나 혹은 그 이상을 혼합하도록 한다.
고체윤활제 중 흑연은 인편상의 자연산 인상흑연, 이를 열팽창시킨 열팽창흑연, 카본블랙, 탄소섬유분말, 및 탄소나노튜브 등을 사용하는 것을 특징으로 한다.
또한, 고체윤활제는 PTFE 수지의 평균 입경이 0.2~1.0㎛의 미분말을 사용하고, 인편상 MoS2, WS2 및 h-BN 미분말의 평균 입경이 1㎛이하인 미분말을 사용하며, 흑연의 경우 탄소나노튜브는 평균 입경이 100㎚이하, 그 외의 탄소재료는 5㎛이하인 미분말을 사용하여 내열성, 내산화성 및 윤활성을 증대시킨다.
특히, 코팅되는 기재 표면 즉, 윤활면의 부하 하중이 큰 경우에는 WS2 고체윤활제가 효과적이다.
접착제는 유기물 접착제와 무기물 접착제로 구분되어 구성된다.
유기물 접착제는 열경화성 수지 및 실리콘(silicone)계 수지로 구분되며, 열경화성수지는 에폭시(epoxy)계 수지, 실리콘계 수지는 폴리알콕시실란(polyalkoxysilane)계 수지를 사용한다.
열경화성 수지의 에폭시계 수지는 비스페놀A 디글리시딜에델(bisphenol A diglycidyl ether), 비스페놀F 글리시딜에텔(bisphenol F glycidyl ether)형 등의 다 관능 에폭시 수지로 25℃에서 100~2000cps의 액상 에폭시 수지가 바람직하다. 이때, 경화제로는 아민(amine)계 경화제를 사용하고 용매로는 알코올(alcohol)계를 사용한다.
또한, 실리콘계 수지 접착제는 고체윤활제의 기재에 대한 접착 역할을 할 뿐만 아니라 내마모성과 비점착성을 향상시키는 것으로, 폴리알콕시실란계 수지가 고체윤활제와 같이 사용할 경우 내마모성과 비점착성은 향상시킨다.
특히, 알콕시실란(alkoxysilane)계 접착제 조성은 알콕시실란과 메타아크릴산(methacrylic acid) 또는 아세틱산(acetic acid) 증류수와 혼합하여 제조한 것으로, 알콕시실란 화합물은 화학식 1과 같다.

Figure 112011069663297-pat00003

여기서, R1은 2가 지방족 탄화수소(탄소수 1~10)이고, R2, R3, R4는 각각 다른 1가 지방족 탄화수소(탄소수 1~10)이다. X는 아미노, 알킬아미노(alkylamino), 하이드로옥실(hydroxyl), 에폭시 또는 머캅토(mercapto) 그룹이다.
폴리알콕시실란계 화합물로는 아미노프로필 트리에톡시실란(aminoprophyl triethoxysilane), 아미노프로필 트리메톡시실란(aminoprophyl trimethoxysilane), 아미노에틸아미노프로필 트리에톡시실란(aminoethlyaminoprophyl triethoxysilane)과 같이 수용액에서 사용가능한 분자량이 적은 화합물이 바람직하다. 용매로는 수용액 또는 알코올에 적당한 농도로 희석시켜 사용한다.
무기물 접착제는 금속인산염을 사용한다. 특히, 금속인산염의 인산알루미늄{Al(H2PO4)3}, 인산아연{Zn(H2PO4)2}, 인산마그네슘{Mg(H2PO4)2}, 인산망간 {Mn(H2PO4)2}, 인산지르코늄{Zr(H2PO4)4} 인산칼슘{Ca(H2PO4)2} 등은 에폭시 수지에 미량으로 잔존하는 알칼리금속이온을 제거할 수 있으며, 고체윤활제의 기체에 대한 부착력을 증대시킨다. 또한, 금속인산염은 후술할 충전제인 금속산화물을 금속기재에 더욱 견고하게 부착한다.
충전제로는 인편상 운모, 산화알루미늄(Al2O3), 지르코니아(ZrO2), 규산지르코니아(ZrSiO3), 이산화티탄(TiO2), 산화아연(ZnO), 산화티탄(TiO2) 및 이산화규소(SiO2)의 미분말을 사용하여 내열성 및 내마모성을 더욱 증대시킨다. 이때, 충전제는 졸-겔(sol-gel)방법으로 합성하여 평균 입경이 1㎛이하인 것을 사용한다.
이와 같이 구성된 접동부재용 코팅 조성물의 배합 비율은 고체윤활제 25~60중량%, 접착제 30~70중량% 및 충전제 5~10중량%와 같다.
여기서, 고체윤활제의 배합비율이 25중량%미만에서는 윤활성이 저하되어 접동부재로의 역할이 감소되고, 60중량%를 초과하면 기재와의 부착력이 감소되어 기재로부터 박리 현상이 발생할 우려가 있어 고체윤활제의 배합비율은 25~60중량%가 바람직하다.
또한, 접착제의 배합비율이 30중량%이하로 감소하면 윤활제의 기재와의 접착력이 감소하고, 70중량%를 초과하면 윤활성이 저하되는 현상이 발생되므로 접착제의 배합비율은 30~70중량%가 바람직하다.
또한, 충전제의 배합비율이 5중량%이하이면 접동부재의 내마모성이 결여되고, 10중량%를 초과하면 윤활성이 저하되므로 충전제의 배합비율은 5~10중량%가 바람직하다.
한편, 고체윤활제의 구성비율은 PTFE와 MoS2, WS2 h-BN 및 흑연 중 하나 또는 2가지 이상을 배합하여 구성된다.
또한, 접착제는 에폭시수지, 인산알루미늄 및 알콕시실란을 일정비율로 혼합되어 구성된다. 이때, 에폭시수지는 폴리아미드이이드계 수지 등으로 대체 또는 병용되어 혼합될 수 있다.
다음으로 본 발명의 조성물로 코팅된 접동부재의 실시예와 비교예를 통하여 보다 구체적으로 설명하기로 한다.
표 1은 코팅 조성물인 고체윤활제, 접착제, 충전제의 종류 및 그 배합량과 코팅 조성물을 기재에 코팅하여 그 윤활특성을 조사하여 나타낸 결과이다.
고체윤활제는 PTFE, 인편상 MoS2, WS2, h-BN 및 팽창흑연을 사용하였고, 접착제는 에폭시수지, 알콕시실란 수지, 인산알루미늄을 사용하였으며, 충전제는 인편상 운모, Al2O3, ZrO2, SiO2, 등을 사용하였다.

Figure 112011069663297-pat00004
표 1과 같이 실시예 1~7에서 접착제로 에폭시수지, 알콕시실란 수지 및 금속인산염을 사용하였으며, 비교예 8~10에서는 에폭시수지만 사용하였다. 실시예와 비교예를 비교하면 실시예의 마모율은 비교예의 마모율보다 현저히 낮아진 것을 알 수 있듯이, 접착제인 알콕시실란 및 인산알루미늄을 더 첨부함으로써 내마모율은 증가함을 알 수 있다.
또한, 고체윤활제로 PTFE이외에 MoS2, WS2, h-BN 및 팽창흑연 중 하나 이상을 병용하여 사용할 경우, 비교예 8~10보다 실시예 1~7의 마찰계수가 낮음을 알 수 있다. 특히, 윤활제가 PTFE, MoS2, WS2 및 팽창흑연을 혼합되었을 때(실시예 5) 마찰계수가 가장 낮은 것을 알 수 있다.
따라서, 고체윤활제의 PTFE, MoS2, WS2, h-BN 및 팽창흑연을 병용하고, 충전재의 인편상 운모, 산화알루미늄(Al2O3), 지르코니아(ZrO2), 규산지르코니아(ZrSiO3), 산화아연(ZnO), 산화티탄(TiO2) 및 이산화규소(SiO2) 중 하나를 선택하여 혼합하며, 접착제인 에폭시계 수지, 알콕시실란계 수지 및 금속인산염을 일정비율로 배합한 조성물을 기재에 코팅하여 접동부재를 제조함으로써, 제조되는 접동부재는 내마모성, 비점착성, 내열성 및 윤활성을 동시에 가짐을 알 수 있다.
이상의 설명은 본 발명의 기술 사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동일한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. First of all, in adding reference numerals to the components of the drawings, it should be noted that the same reference numerals have the same reference numerals as much as possible even if displayed on different drawings. In describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
The coating composition for the sliding member of the present invention is composed of a solid lubricant, an adhesive and a filler.
Solid lubricants consist of a mixture of PTFE (polytetrafluoroethylene), flaky MoS 2 (molybdenum disulfide), WS 2 (tungsten disulfide), h-BN (hexagonal boron nitride) and graphite, If so, mix one or more of PTFE with MoS 2 , WS 2 , h-BN and graphite.
Graphite in the solid lubricant is characterized in that the use of natural flake graphite, scale-expanded graphite, carbon black, carbon fiber powder, carbon nanotubes and the like in the form of scale.
In addition, the solid lubricant uses fine powder having an average particle diameter of 0.2 to 1.0 μm of PTFE resin, and fine powder having an average particle diameter of flaky MoS 2 , WS 2 and h-BN fine powder of 1 μm or less, and in the case of graphite, carbon nano The tube uses fine powder having an average particle diameter of 100 nm or less and other carbon materials of 5 μm or less to increase heat resistance, oxidation resistance and lubricity.
In particular, the WS 2 solid lubricant is effective when the load load on the substrate surface to be coated, ie the lubricating surface, is large.
The adhesive is composed of organic adhesive and inorganic adhesive.
The organic adhesive is classified into a thermosetting resin and a silicone resin, and the thermosetting resin is an epoxy resin and the silicone resin is a polyalkoxysilane resin.
Epoxy resins of thermosetting resins are multifunctional epoxy resins such as bisphenol A diglycidyl ether and bisphenol F glycidyl ether. Resin is preferable. In this case, an amine curing agent is used as a curing agent and an alcohol based alcohol is used as a solvent.
In addition, the silicone-based resin adhesive not only acts as an adhesive to the substrate of the solid lubricant, but also improves abrasion resistance and non-adhesiveness, and when the polyalkoxysilane-based resin is used together with the solid lubricant, the wear resistance and non-adhesiveness are improved.
In particular, the alkoxysilane-based adhesive composition is prepared by mixing with alkoxysilane and methacrylic acid (methacrylic acid) or acetic acid (acetic acid) distilled water, the alkoxysilane compound is represented by the formula (1).
Figure 112011069663297-pat00003
Here, R <1> is a divalent aliphatic hydrocarbon (C1-C10), and R <2> , R <3> , R <4> is a different monovalent aliphatic hydrocarbon (C1-C10), respectively. X is an amino, alkylamino, hydroloxy, epoxy or mercapto group.
Examples of polyalkoxysilane compounds include low molecular weights that can be used in aqueous solutions such as aminoprophyl triethoxysilane, aminoprophyl trimethoxysilane and aminoethlyaminoprophyl triethoxysilane. Compound is preferred. As a solvent, it is diluted with aqueous solution or alcohol, and used at a suitable density | concentration.
Inorganic adhesives use metal phosphates. In particular, aluminum phosphate {Al (H 2 PO 4 ) 3 } of metal phosphate, zinc phosphate {Zn (H 2 PO 4 ) 2 }, magnesium phosphate {Mg (H 2 PO 4 ) 2 }, manganese phosphate {Mn (H 2 PO 4 ) 2 }, zirconium phosphate {Zr (H 2 PO 4 ) 4 } calcium phosphate {Ca (H 2 PO 4 ) 2 }, etc. can remove alkali metal ions remaining in a small amount in the epoxy resin, solid Increase the adhesion of the lubricant to the gas. In addition, the metal phosphate more firmly attaches a metal oxide, which is a filler to be described later, to the metal substrate.
Fillers include flaky mica, aluminum oxide (Al 2 O 3 ), zirconia (ZrO 2 ), zirconia silicate (ZrSiO 3 ), titanium dioxide (TiO 2 ), zinc oxide (ZnO), titanium oxide (TiO 2 ) and dioxide The fine powder of silicon (SiO 2 ) is used to further increase the heat resistance and wear resistance. In this case, the filler is synthesized by the sol-gel (sol-gel) method using an average particle diameter of 1㎛ or less.
The mixing ratio of the coating composition for the sliding member configured as described above is equal to 25 to 60% by weight of the solid lubricant, 30 to 70% by weight of the adhesive and 5 to 10% by weight of the filler.
Here, when the blending ratio of the solid lubricant is less than 25% by weight, the lubricity decreases and the role of the sliding member is reduced. When the blending ratio of the solid lubricant is greater than 60% by weight, the adhesion to the substrate is reduced, which may cause peeling from the substrate. As for the compounding ratio of, 25-60 weight% is preferable.
In addition, when the blending ratio of the adhesive is reduced to 30% by weight or less, the adhesive strength of the lubricant with the substrate decreases, and when the blending ratio exceeds 70% by weight, the lubricity decreases, so the blending ratio of the adhesive is preferably 30 to 70% by weight. Do.
In addition, when the blending ratio of the filler is 5% by weight or less, the wear resistance of the sliding member is insufficient, and when the blending ratio exceeds 10% by weight, the lubricity decreases, so the blending ratio of the filler is preferably 5 to 10% by weight.
On the other hand, the composition ratio of the solid lubricant is composed of one or two or more of PTFE and MoS 2 , WS 2 h-BN and graphite.
Moreover, an adhesive agent is comprised by mixing epoxy resin, aluminum phosphate, and alkoxysilane in a fixed ratio. At this time, the epoxy resin may be replaced or used in combination with polyamide-based resin or the like.
Next will be described in more detail through Examples and Comparative Examples of the sliding member coated with a composition of the present invention.
Table 1 shows the results of the coating composition coated with a solid lubricant, an adhesive, a filler, and a blending amount of the coating composition on a substrate and examining the lubricating properties thereof.
PTFE, flaky MoS 2 , WS 2 , h-BN and expanded graphite were used as solid lubricant, epoxy resin, alkoxysilane resin, aluminum phosphate, adhesive was flaky mica, Al 2 O 3 , ZrO 2 , SiO 2, and the like were used.

Figure 112011069663297-pat00004
As in Table 1, epoxy resins, alkoxysilane resins, and metal phosphates were used as adhesives in Examples 1 to 7, and only epoxy resins were used in Comparative Examples 8 to 10. Comparing the example with the comparative example, it can be seen that the wear rate of the example was significantly lower than the wear rate of the comparative example, and the abrasion resistance was increased by further attaching the alkoxysilane and aluminum phosphate as the adhesive.
In addition, when using a combination of at least one of MoS 2 , WS 2 , h-BN and expanded graphite in addition to PTFE as a solid lubricant, it can be seen that the friction coefficient of Examples 1 to 7 is lower than that of Comparative Examples 8 to 10. In particular, it can be seen that the friction coefficient is the lowest when the lubricant is mixed with PTFE, MoS 2 , WS 2 and expanded graphite (Example 5).
Therefore, PTFE, MoS 2 , WS 2 , h-BN and expanded graphite of a solid lubricant are used in combination, and flaky mica of the filler, aluminum oxide (Al 2 O 3 ), zirconia (ZrO 2 ), and zirconia silicate (ZrSiO 3 ). , A mixture of zinc oxide (ZnO), titanium oxide (TiO 2 ) and silicon dioxide (SiO 2 ) is selected and mixed, and a composition in which an epoxy resin, an alkoxysilane-based resin, and a metal phosphate, which are adhesives, are mixed at a predetermined ratio By manufacturing the sliding member by coating on, it can be seen that the prepared sliding member has abrasion resistance, non-tackiness, heat resistance and lubricity at the same time.
The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and variations without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technical ideas within the same scope should be construed as being included in the scope of the present invention.

Claims (12)

미분말이고, 평균 입경 0.2~1.0㎛인 폴리테트라플루오르에틸렌(Polytetrafluoroethylene, PTFE)와, 평균 입경 1㎛이하인 인편상 이황화 몰리브덴(MoS2), 텅스텐 디설파이드(WS2), 육방정질화붕소(h-BN), 및 평균 입경이 탄소나노튜브는 100㎚이하, 그 외의 탄소재료는 5㎛인 흑연 중 어느 하나 이상을 배합한 고체윤활제 25~60중량%와,
평균 입경이 1㎛이하인 인편상 운모, 산화알루미늄(Al2O3), 지르코니아(ZrO2), 규산지르코니아(ZrSiO3), 산화아연(ZnO), 산화티탄(TiO2) 및 이산화규소(SiO2) 중 어느 하나로 이루어지며, 졸-겔(sol-gel)방법으로 합성하여 이루어진 충전제 5~10중량%와,
에폭시계수지와, 알콕시실란계 수지 및 금속인산염을 배합한 접착제 30~70중량%로 이루어지며,
상기 에폭시계수지는 비스페놀A 디글리시딜에델(bisphenol A diglycidyl ether), 비스페놀F 글리시딜에텔(bisphenol F glycidyl ether)형의 다 관능 에폭시 수지로 25℃에서 100~2000cps의 액상 에폭시 수지를 포함하고,
상기 알콕시실란계 수지는 알콕시실란, 메타아크릴산(methacrylic acid) 또는 아세틱산(acetic acid) 증류수와 혼합하여 제조한 아미노프로필 트리에톡시실란(aminoprophyl triethoxysilane), 아미노프로필 트리메톡시실란(aminoprophyl trimethoxysilane), 아미노에틸아미노프로필 트리에톡시실란(aminoethlyaminoprophyl triethoxysilane)를 포함하고,
상기 금속인산염은 인산알루미늄{Al(H2PO4)3}, 인산아연{Zn(H2PO4)2}, 인산마그네슘{Mg(H2PO4)2}, 인산망간 {Mn(H2PO4)2}, 인산지르코늄{Zr(H2PO4)4} 인산칼슘{Ca(H2PO4)2}을 포함하는 것을 특징으로 하는 접동부재용 코팅 조성물.Fine powder, polytetrafluoroethylene (PTFE) having an average particle diameter of 0.2 to 1.0 μm, flaky molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), hexagonal boron nitride (h-BN) having an average particle diameter of 1 μm or less And 25 to 60% by weight of a solid lubricant containing at least one of graphite having an average particle diameter of 100 nm or less for carbon nanotubes and 5 m for other carbon materials,
Flaky mica, aluminum oxide (Al 2 O 3 ), zirconia (ZrO 2 ), zirconia (ZrSiO 3 ), zinc oxide (ZnO), titanium oxide (TiO 2 ) and silicon dioxide (SiO 2 ) with an average particle diameter of 1 μm or less ) Made of any one of 5 to 10% by weight of a filler synthesized by a sol-gel (sol-gel) method,
It consists of 30 to 70% by weight of an adhesive containing an epoxy resin, an alkoxysilane resin and a metal phosphate,
The epoxy resin is a bifunctional epoxy resin of bisphenol A diglycidyl ether, bisphenol F glycidyl ether type, and contains a liquid epoxy resin of 100 to 2000 cps at 25 ° C. ,
The alkoxysilane-based resin may be prepared by mixing with alkoxysilane, methacrylic acid or acetic acid distilled water, aminoprophyl triethoxysilane, aminopropyl trimethoxysilane, Aminoethylaminopropyl triethoxysilane (aminoethlyaminoprophyl triethoxysilane),
The metal phosphate is aluminum phosphate {Al (H 2 PO 4 ) 3 }, zinc phosphate {Zn (H 2 PO 4 ) 2 }, magnesium phosphate {Mg (H 2 PO 4 ) 2 }, manganese phosphate {Mn (H 2 PO 4 ) 2 }, zirconium phosphate {Zr (H 2 PO 4 ) 4 } Calcium Phosphate {Ca (H 2 PO 4 ) 2 } The coating composition for a sliding member. 삭제delete 삭제delete 삭제delete 제 1항에 있어서,
상기 접착제의 에폭시(epoxy) 수지는 폴리아미드이미드(polyamide imide) 수지로 대체 또는 병용하는 것을 특징으로 하는 접동부재용 코팅 조성물.The method of claim 1,
Epoxy (epoxy) resin of the adhesive is a coating composition for the sliding member, characterized in that the polyamide imide (polyamide imide) resin or replaced. 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete
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KR101771660B1 (en) 2015-07-28 2017-08-28 주식회사 영산테크노 sliding member sliding damper coating method using the coating composition and this
KR20170122685A (en) * 2016-04-27 2017-11-06 주식회사 한국화이어텍 Components Of Non-adhesion Typed Ceramic Paint
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CN111117425A (en) * 2019-12-30 2020-05-08 余果润 Radiation heat dissipation coating and preparation method thereof
CN112194813A (en) * 2020-10-08 2021-01-08 苏州大学 Precursor for super-hydrophobic composite material coating and preparation method thereof
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KR102216109B1 (en) * 2020-08-13 2021-02-16 이계영 Surface treatment method for the scroll of scroll compressor
CN115386410A (en) * 2022-08-11 2022-11-25 西安建筑科技大学 High-temperature solid lubricant for titanium alloy extrusion and preparation method thereof

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KR101472373B1 (en) * 2012-06-28 2014-12-12 한라비스테온공조 주식회사 Composition of surface coating for compressor sliding part and compressor sliding part using thereof
KR101729028B1 (en) * 2014-05-08 2017-04-21 이계영 Coating compositions of sliding members for the swash plate of the swash plate type compressor
US10370514B2 (en) 2014-06-23 2019-08-06 Southwire Company, Llc UV-resistant superhydrophobic coating compositions
US11001696B2 (en) 2014-06-23 2021-05-11 Southwire Company, Llc UV-resistant superhydrophobic coating compositions
EP2990432A1 (en) 2014-08-29 2016-03-02 Halla Visteon Climate Control Corporation Lubricating coating composition and compressor including the same
US9944884B2 (en) 2014-08-29 2018-04-17 Hanon Systems Lubricating coating composition and compressor including the same
US10472586B2 (en) 2014-08-29 2019-11-12 Hanon Systems Lubricating coating composition and compressor including the same
WO2016052993A1 (en) * 2014-10-01 2016-04-07 이래오토모티브시스템 주식회사 Method for forming film on swash plate of swash plate type compressor
KR101565603B1 (en) 2014-10-01 2015-11-03 한국델파이주식회사 Lubricant compound, method for forming cover film on swash plate of swash plate type compressor, and swash plate type compressor
KR101771660B1 (en) 2015-07-28 2017-08-28 주식회사 영산테크노 sliding member sliding damper coating method using the coating composition and this
KR102227283B1 (en) * 2016-04-27 2021-03-12 주식회사 한국화이어텍 Components Of Non-adhesion Typed Ceramic Paint
KR20170122685A (en) * 2016-04-27 2017-11-06 주식회사 한국화이어텍 Components Of Non-adhesion Typed Ceramic Paint
US10889727B1 (en) 2018-06-14 2021-01-12 Southwire Company, Llc Electrical cable with improved installation and durability performance
CN111117425A (en) * 2019-12-30 2020-05-08 余果润 Radiation heat dissipation coating and preparation method thereof
KR102216109B1 (en) * 2020-08-13 2021-02-16 이계영 Surface treatment method for the scroll of scroll compressor
CN112194813A (en) * 2020-10-08 2021-01-08 苏州大学 Precursor for super-hydrophobic composite material coating and preparation method thereof
CN112210272A (en) * 2020-10-08 2021-01-12 苏州大学 Wear-resistant super-hydrophobic composite material and preparation method thereof
CN115386410A (en) * 2022-08-11 2022-11-25 西安建筑科技大学 High-temperature solid lubricant for titanium alloy extrusion and preparation method thereof
CN115386410B (en) * 2022-08-11 2023-09-12 西安建筑科技大学 High-temperature solid lubricant for titanium alloy extrusion and preparation method thereof

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