KR20030092849A - Composition of hydrophobic Fluorinated Polymer Paint - Google Patents

Composition of hydrophobic Fluorinated Polymer Paint Download PDF

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Publication number
KR20030092849A
KR20030092849A KR1020020030683A KR20020030683A KR20030092849A KR 20030092849 A KR20030092849 A KR 20030092849A KR 1020020030683 A KR1020020030683 A KR 1020020030683A KR 20020030683 A KR20020030683 A KR 20020030683A KR 20030092849 A KR20030092849 A KR 20030092849A
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solvent
weight
parts
paint
resin
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KR1020020030683A
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Korean (ko)
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정은영
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현대자동차주식회사
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Publication of KR20030092849A publication Critical patent/KR20030092849A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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

Abstract

PURPOSE: A paint composition added with a fluorine resin to the usual car paint is provided to improve water repellency and prevent the pollution of wheels due to the dusts of brake pads. CONSTITUTION: The coating composition comprises: 15-35wt.% of acryl resin for paint; 15-23wt.% of solvent dissolved fluorine resin; 5-15wt.% of hardening agent; and 40-80wt.% of solvent. The solvent dissolved fluorine resin is obtained by alternately copolymerizing alkyl acrylate with trifluoroethylene and tetrafluoroethylene in a ratio of 20-50wt.% : 50-80wt.%.

Description

발수성 불소수지 도료 조성물{Composition of hydrophobic Fluorinated Polymer Paint}Composition of hydrophobic Fluorinated Polymer Paint

본 발명은 발수성 불소수지 도료 조성물에 관한 것으로서, 더욱 상세하게는 기존의 차량 휠용 도료에다 용제 가용화된 불소수지를 첨가하여 도막의 발수성을 대폭 향상 시키므로서, 특히 브레이크 패드 분진 등에 의한 차량 휠(Wheel)의 오염을 효과적으로 방지할 수 있는 도료 조성물에 관한 것이다.The present invention relates to a water-repellent fluorine resin coating composition, and more particularly, by adding a solvent-soluble solubilized fluorine resin to a conventional vehicle wheel paint to significantly improve the water repellency of the coating film, especially a vehicle wheel by brake pad dust or the like. The present invention relates to a coating composition that can effectively prevent contamination.

일반적으로 차량의 휠( 이하, 휠 커버를 포함 한다. )은 알미늄 이나 나일론과 같은 원료를 소재로 하여 사출 또는 주물 등의 방법으로 제조된다. 이러한 휠은 외관미를 향상시키고 부식을 방지하기 위하여 도료로 표면을 도장하게 되는데, 이때 도장방법은 아크릴, 폴리에스터, 폴리올 등과 같은 기본 수지에다 이소시아네이트 (-NCO基 함유)와 같은 경화제를 함유시켜서 된 도료를 휠 표면에 도포한 후, 약 80 ∼ 120℃에서 경화시키는 방식이 일반적이다.In general, a wheel of a vehicle (hereinafter, including a wheel cover) is manufactured by injection or casting, using a raw material such as aluminum or nylon. In order to improve the appearance and prevent corrosion, these wheels are coated with a paint. The coating method includes a base resin such as acrylic, polyester, and polyol, and a hardening agent such as isocyanate (containing -NCO base). The method of hardening at about 80-120 degreeC after apply | coating a paint to a wheel surface is common.

한편, 차량의 휠을 오염시키는 오염 물질은 주로 브레이크 작동 시 브레이크 디스크와 브레이크 패드의 마찰에 의하여 발생하는 브레이크 패드 분진이나 진흙,먼지 등 기타 이 물질도 오염의 원인물질이 될 수 있으나, 이 중에서 브레이크 패드 분진은 다른 오염 물질에 비해 그 오염도가 가장 높다.On the other hand, the pollutant that pollutes the wheel of the vehicle is mainly due to the friction of the brake disc and the brake pad when the brake is operated, dust, mud, dust and other foreign matter may also be a source of contamination, among these brakes Pad dust has the highest contamination compared to other pollutants.

그런데 종래의 방법으로 도장된 휠은 브레이크 패드분진이 한번 부착되면 시간이 경과함에 따라 휠 도장 표면에 오염물이 고착되어 고압세차, 고온수 세차 등에도 잘 제거되지 않으며, 시간이 더욱 경과 되면 세제를 사용하면서 거센 솔질을 하여도 제거가 불가능 해진다. 그 이유는 패드분진 내에 함유되어 있는 황(S) 성분이나 철분, 탄소, 수지, 일부 중금속 등이 다른 오염 물질과 비교하여 반응성이 높고, 특히 분진 자체의 크기가 매우 작아서 표면적이 넓어 휠 표면과의 반응성을 증가 시키기 때문이다.However, the wheels coated by the conventional method are contaminants adhered to the surface of the wheels as time passes once the brake pad dust is attached, so that the wheels are not easily removed from high-pressure car washes or hot water car washes. While brushing too hard, it becomes impossible to remove. The reason is that sulfur (S), iron, carbon, resin, and some heavy metals contained in pad dust are more reactive than other contaminants. Particularly, the size of the dust itself is very small, so that the surface area is wide. This increases the reactivity.

이러한 오염물질의 고착은 물리적인 점착이 아닌 화학적인 점착을 하기 때문에 이를 제거하기 위해서는 휠 표면을 손상시키지 않을 수 없다. 따라서 고가 재료인 알미늄 휠 등에 대한 상품력을 떨어트릴 뿐 아니라, 나일론 등 수지 휠의 경우에는 노화의 원인이 되기도 한다.Sedimentation of these contaminants results in chemical adhesion rather than physical adhesion, which is inevitable to damage the wheel surface. Therefore, it not only lowers the product power for aluminum wheels, which are expensive materials, but also causes aging of resin wheels such as nylon.

이에, 본 발명의 발명자는 기존의 차량 휠용 도료에다 용제 가용화된 불소수지를 첨가하여 도막의 발수성을 대폭 향상 시키므로서, 상기와 같은 종래 기술의 문제점을 해결할 수 있게 되었다.Thus, the inventors of the present invention can solve the problems of the prior art by significantly improving the water repellency of the coating film by adding a solvent-soluble solubilized fluorine resin to the existing vehicle wheel paint.

본 발명의 목적은 기존의 도료에 비해 도장성이나 도막의 물성에는 거의 차이가 없으면서도 브레이크 패드 분진 등에 의한 오염도가 훨씬 적어서 특히 차량휠(Wheel)의 오염을 효과적으로 방지할 수 있는 발수성 불소수지 도료 조성물을 제공하는 것이다.An object of the present invention is a water repellent fluoroplastic coating composition which can effectively prevent the contamination of the vehicle wheel (Wheel) due to much less contamination by brake pad dust, etc., while having almost no difference in the paintability or physical properties of the coating film compared to conventional paints To provide.

이하, 본 발명을 보다 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

본 발명은 도료용 아크릴 수지 15 ∼ 35 중량부, 용제 가용화된 불소수지 15 ∼ 23 중량부, 경화제 5 ∼ 15 중량부 및 용제 40 ∼ 80 중량부를 포함 하는 것을 특징으로 하는 발수성 불소수지 도료 조성물이다.The water-repellent fluororesin coating composition comprising 15 to 35 parts by weight of an acrylic resin for paint, 15 to 23 parts by weight of a solvent solubilized fluororesin, 5 to 15 parts by weight of a curing agent and 40 to 80 parts by weight of a solvent.

이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

본 발명의 발수성 불소수지 도료 조성물에서 도료용 기초수지로는 종래에 사용되어온 아크릴 수지를 사용하되 전체 조성물의 15 ∼ 35 중량부를 사용한다.In the water-repellent fluorocarbon resin coating composition of the present invention, as the base resin for coating, an acrylic resin that has been used conventionally is used, but 15 to 35 parts by weight of the total composition is used.

본 발명에서는 도료 조성물의 발수성을 증가 시키기 위하여 트리 플루오로 에틸렌( CTFE )와 테트라 플루오로 에틸렌( TFE )로 이루어진 용제 가용화된 불소 수지를 사용한다. 원래 CTFE와 TFE불소 수지는 용제에 불용인데다 불소수지의 특성상 접착성이 거의 없기 때문에 그 자체를 도료용 수지인 아크릴과 블렌딩 하여서 사용할 수는 없다. 그래서 본 발명에서는 이들 불소수지를 알킬 아크릴레이트와 교호 공중합 반응시켜서 용제 가용성 수지로 변환 시킨 다음, 도료 조성물의 구성성분으로 사용하는 것이다. 이때, 용제 가용화된 불소 수지를 제조하기 위해서는 CTFE와 TFE를 각각 따로 알킬 아크릴레이트와 합성 시키되, 각각의 Tg,굴절율, 극성度 등의 차이가 있으므로 목적하는 도료 조성물의 물성에 따라 적절히 조절, 혼합하는 것이 좋다. 특히 CTFE와 TFE의 혼합비율에 따라 불소 수지 도료의 주성능인 내오염성이 크게 차이가 나므로 유의하여야 하는데, CTFE와 TFE의 비율이 20 ∼ 50 중량% : 50 ∼ 80 중량%인 것이 가장 좋다.In the present invention, in order to increase the water repellency of the coating composition, a solvent-solubilized fluorine resin composed of trifluoroethylene (CTFE) and tetrafluoroethylene (TFE) is used. Originally, CTFE and TFE fluorine resins are insoluble in solvents, and due to the nature of the fluorine resin, they cannot be used by blending with acrylic, a resin for paints. Therefore, in the present invention, these fluororesins are converted into solvent-soluble resins by alternating copolymerization with alkyl acrylates, and then used as constituents of the coating composition. At this time, CTFE and TFE are separately synthesized with alkyl acrylates to prepare a solvent-solubilized fluororesin. However, since there are differences in Tg, refractive index, and polarity, appropriately adjusted and mixed according to the properties of the desired coating composition. It is good. In particular, it should be noted that the pollution resistance, which is the main performance of the fluororesin paint, varies greatly according to the mixing ratio of CTFE and TFE. The ratio of CTFE and TFE is 20 to 50% by weight: 50 to 80% by weight.

본 발명에서 용제 가용화된 불소수지의 함량은 전체 조성물의 15 ∼ 23 중량부 인데, 이때 15 중량부 미만이면 차량 휠과 같은 극심한 오염환경에서는 만족할 만한 효과를 얻을 수 없으며, 반대로 23 중량부 초과하면 광택 소실 및 부착성 저하가 심하여 좋지 않다.In the present invention, the content of the solvent- solubilized fluorine resin is 15 to 23 parts by weight of the total composition, in which less than 15 parts by weight does not provide a satisfactory effect in an extreme pollution environment such as a vehicle wheel. Loss and poor adhesion are not good.

용제 가용화 된 불소수지는 도막 완성을 위한 경화반응을 일으키기 위하여 관능기로서 OH기 혹은 COOH기를 가진다. 이러한 수지는 휠용 도료의 주체수지로서 이소시아네이트(-NCO)에 의해 2액형 형태로 경화( 60 ∼ 90℃) 반응시키거나, 경우에 따라 BLOCKING -NCO를 첨가하여 1액형으로 고온( 130 ∼ 160℃ ) 에서 경화시킬 수도 있는데, 이는 도장 할 휠의 재료에 따라 선택할 수 있다.Solvent solubilized fluorine resin has OH group or COOH group as a functional group to cause curing reaction to complete the coating film. These resins are cured (60-90 ° C) in a two-part form by isocyanate (-NCO) as the main resin for wheel paints, or in some cases high temperature (130-160 ° C) by adding BLOCKING-NCO. It can also be cured at, depending on the material of the wheel to be painted.

또한, 본 발명의 불소수지 도료 조성물은 경화제 5 ∼ 15 중량부 및 용제 40 ∼ 80 중량부를 포함하는데, 특히 용제로는 방향족, 케톤, 탄화수소계 용제를 사용 할 수 있다.In addition, the fluororesin coating composition of the present invention contains 5 to 15 parts by weight of a curing agent and 40 to 80 parts by weight of a solvent, and in particular, an aromatic, ketone or hydrocarbon solvent may be used.

이외에도, 종래에 사용되어온 표면 조정제, 분산제, 광안전제, 소포제 등을 포함할 수 있다.In addition, it may include a surface regulator, a dispersant, a light safety agent, an antifoaming agent and the like that have been conventionally used.

본 발명의 발수성 불소수지 도료 조성물은 발수용 도료는 도장의 표면, 즉 도막에 물을 떨어 뜨렸을 때 물과 도막 사이의 접촉각도가 매우 높다. 이와 같이 도막과 물과의 접촉각도가 높다는 것은 곧 도막에 이 물질 및 오염물을 함유한 물이 묻었을 때 쉽게 굴러 떨어지고, 기름 등 다른 이 물질이 묻었을 때도 표면에 남지 않고 쉽게 떨어진다는 것을 의미한다. 이러한 현상은 도막 표면의 낮은 표면에너지, 즉 표면장력(계면장력) 때문이다.The water-repellent fluorocarbon resin coating composition of the present invention has a very high contact angle between water and the coating film when water is dropped onto the surface of the coating, that is, the coating film. The high contact angle between the coating film and the water means that the coating film easily rolls off when the water containing the substance and the contaminant falls on it, and falls easily without remaining on the surface even when other substances such as oil are on the coating film. This phenomenon is due to the low surface energy of the surface of the coating film, that is, the surface tension (interface tension).

이하, 본 발명에 대한 실시예를 들어 보면 다음과 같다.Hereinafter, examples of the present invention will be described.

실시예Example

다음 표1과 같은 성분 및 함량으로 이루어진 도료 조성물을 제조한다. 이때, 용제 가용화된 불소수지는 CTFE와 TFE의 비율이 3 : 7이 되도록 조성 하였다.Next, to prepare a coating composition consisting of the components and contents as shown in Table 1. At this time, the solvent- solubilized fluorine resin was prepared so that the ratio of CTFE and TFE is 3: 7.

구성성분Ingredient 함량content 비고Remarks 아크릴수지Acrylic resin 30 중량부30 parts by weight 도료용 아크릴 수지Acrylic resin for paint 용제 가용화 된 불소수지Solvent Solubilized Fluororesin 20 중량부20 parts by weight 일본 아사히 글래스사 제품FLURORESIN LF-200FLURORESIN LF-200 manufactured by Asahi Glass, Japan 경화제Hardener 10 중량부10 parts by weight IPDIIPDI 표면조정제Surface conditioner 1.0 중량부1.0 parts by weight BYK사 BYK-314BYK company BYK-314 분산제Dispersant 0.7 중량부0.7 parts by weight BYK사 BYK-2000BYK company BYK-2000 광안정제Light stabilizer 1.5 중량부1.5 parts by weight SANDOZ사 제품VP-SANDUVOR TB-02Product made by SANDOZ VP-SANDUVOR TB-02 소포제Antifoam 1.0 중량부1.0 parts by weight BYK사 BYK-080BYK company BYK-080 용제solvent 60 중량부60 parts by weight 탄화수소계 용제Hydrocarbon solvents

상기 실시예에 따라 제조된 발수성 불소수지 도료 조성물을 사용하여 차량 휠에 완성 도막을 형성하고 다음 표 2와 같은 방법으로 도막의 물성을 측정한 후결과는 다음 표 2에 나타내었다.After forming a finished coating film on the vehicle wheel using the water-repellent fluorocarbon resin coating composition prepared according to the above embodiment, and measured the physical properties of the coating film in the same manner as Table 2, the results are shown in Table 2 below.

시험항목Test Items 측정결과Measurement result 시험방법Test Methods 경도Hardness BYBY 연필 경도기를 이용한 방법으로 경도를 측정하였다.Hardness was measured by the method using the pencil hardness tester. 20度 광택20˚ gloss 70∼8070-80 BYK사 GLOSS METER를 이용하여 광택을 측정하였다.Gloss was measured using a BYK GLOSS METER. 부착성Adhesion 4 급4th grade 폭 2mm CROSS CUT ( 바둑목 ) 방법으로 부착성을 측정하였다.Adhesion was measured by a 2 mm wide CROSS CUT method. 내약품성Chemical resistance 양호Good 염산 3% 혹은 황산 2% 용액을 도막에 떨어트려 도막의 침식 유무를 확인 하는 방법으로 내약품성을 측정하였다.Chemical resistance was measured by dropping a 3% hydrochloric acid or 2% sulfuric acid solution onto the coating film to confirm the erosion of the coating film. 색차Color difference 양호Good X-LIGHT사 색차 시험기로 색차를 측정하고, 기존품과 대비 하였다.The color difference was measured by X-LIGHT color difference tester and compared with existing product. 내수성Water resistance 양호Good 내수성을 관찰하였다.50℃ 이온수에 240 시간 침적한 후 외관 관찰 및 부착성( 바둑목 방법 ) 을평가하여 내수성 측정하였다.Water resistance was observed. After 240 hours of immersion in 50 ° C. ionized water, the water resistance was measured by observing the appearance and assessing the adhesiveness (checking method). 내 오염성Pollution resistance 양호Good 세차후 오염정도를 육안으로 관찰 하였다.After washing, the degree of contamination was visually observed.

상기 표 2에서 알수 있는 바와 같이, 본 발명의 발수성 불소수지 도료 조성물은 기존의 도료에 비해 도장성이나 도막의 물성에는 거의 차이가 없으면서도 브레이크 패드 분진 등에 의한 오염도가 훨씬 적으며, 오염이 발생하였다 하더라도 일반적인 물세차 및 세제에 의한 솔질 만으로서 도막으로부터 오염을 용이하게 제거해 낼 수 있는 효과가 있다.As can be seen in Table 2, the water-repellent fluorocarbon resin coating composition of the present invention is far less contaminated by brake pad dust and the like, with almost no difference in paintability or physical properties of the coating film, compared to conventional paints, and contamination occurred. Even if the brush is only brushed with a general water wash and detergent, there is an effect that can easily remove the contamination from the coating.

Claims (3)

도료용 아크릴 수지 15 ∼ 35 중량부, 용제 가용화된 불소수지 15 ∼ 23 중량부, 경화제 5 ∼ 15 중량부 및 용제 40 ∼ 80 중량부를 포함 하는 것을 특징으로 하는 발수성 불소수지 도료 조성물.15 to 35 parts by weight of an acrylic resin for paint, 15 to 23 parts by weight of a solvent solubilized fluororesin, 5 to 15 parts by weight of a curing agent, and 40 to 80 parts by weight of a solvent. 제 1 항에 있어서, 용제 가용화된 불소수지는 트리 플루오로 에틸렌 (CTFE)와 테트라 플루오로 에틸렌(TFE)를 알킬 아크릴레이트와 교호 공중합시켜서 된 것을 특징으로 하는 조성물.The composition according to claim 1, wherein the solvent-solubilized fluororesin is obtained by cross-copolymerizing trifluoroethylene (CTFE) and tetrafluoroethylene (TFE) with an alkyl acrylate. 제 2 항에 있어서, 트리 플루오로 에틸렌(CTFE)와 테트라 플루오로 에틸렌(TFE)의 비율이 20 ∼ 50 중량% : 50 ∼ 80 중량%인 것을 특징으로 하는 조성물.The composition according to claim 2, wherein the ratio of trifluoroethylene (CTFE) and tetrafluoroethylene (TFE) is 20-50 wt%: 50-80 wt%.
KR1020020030683A 2002-05-31 2002-05-31 Composition of hydrophobic Fluorinated Polymer Paint KR20030092849A (en)

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