KR20200011738A - Fluoride coating composition - Google Patents

Fluoride coating composition Download PDF

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KR20200011738A
KR20200011738A KR1020180086554A KR20180086554A KR20200011738A KR 20200011738 A KR20200011738 A KR 20200011738A KR 1020180086554 A KR1020180086554 A KR 1020180086554A KR 20180086554 A KR20180086554 A KR 20180086554A KR 20200011738 A KR20200011738 A KR 20200011738A
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fluorine
coating composition
acrylic resin
weight
thermosetting acrylic
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KR1020180086554A
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Korean (ko)
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KR102172508B1 (en
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정용욱
김용수
김민준
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주식회사 케이씨씨
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Priority to KR1020180086554A priority Critical patent/KR102172508B1/en
Priority to CN201910614418.4A priority patent/CN110776793A/en
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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
    • 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
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C09D127/14—Homopolymers or copolymers of vinyl fluoride
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid 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
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09D5/08—Anti-corrosive paints

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to a fluorine coating composition comprising a fluorine-containing copolymer and a thermosetting acrylic resin, wherein the thermosetting acrylic resin is produced from a monomer comprising at least one of alkyl methacrylate, alkyl acrylate and acrylamide.

Description

불소도료 조성물{FLUORIDE COATING COMPOSITION}Fluorine coating composition {FLUORIDE COATING COMPOSITION}

본 발명은 내식성 및 도장작업성이 우수한 불소도료 조성물에 관한 것이다.The present invention relates to a fluorine coating composition excellent in corrosion resistance and paintability.

불소 수지를 포함하는 불소도료는 내약품성이 우수하고 수분 침투성이 작아 내식성 또한 탁월하여, 건축물의 외관이나 가로등, 가드레일, 광고판 등의 구조물에 적용되어 표면 산화를 방지하고 변색을 막아주는 역할을 한다. 또한, 폴리비닐리덴플루오라이드(PVDF) 등의 불소 수지를 포함하는 불소도료는 도막 강도가 높고, 내식성, 내후성 등 내구성이 우수하여, 자동차 부품(예를 들어, 내연기관용 파이프)에도 적용 가능하다.Fluorine paints containing fluororesin have excellent chemical resistance and low moisture permeability, so they are also excellent in corrosion resistance. They are applied to structures such as buildings, street lights, guardrails, billboards, etc. to prevent surface oxidation and to prevent discoloration. . In addition, fluorine paints containing fluorine resins such as polyvinylidene fluoride (PVDF) have high coating film strength and excellent durability such as corrosion resistance and weather resistance, and are applicable to automobile parts (for example, pipes for internal combustion engines).

불소 수지와 열가소성 아크릴 수지가 주제로 포함된 기존의 불소도료는 알루미늄 판넬과 같은 기재에 스프레이 방식으로 도장하기에 적합하다. 그러나, 이러한 불소도료를 자동차 내연기관용 파이프 등에 적용하기 위해서는 스프레이 도장 방식이 아닌 플로우 코팅(flow coating) 방식이 적용 가능해야 하는데, 기존의 불소도료는 플로우 코팅(flow coating) 방식에 요구되는 도장작업성(요변성(thixotropy) 등)이 만족되지 않아 상기 용도로 활용되기에 어려운 문제가 있다.Conventional fluorine paints containing fluorine resins and thermoplastic acrylic resins are suitable for spray coating on substrates such as aluminum panels. However, in order to apply such a fluorine paint to a pipe for an automobile internal combustion engine, a flow coating method should be applied instead of a spray coating method, and the existing fluorine paint has a painting workability required for a flow coating method. (Thixotropy, etc.) is not satisfied, there is a problem that is difficult to be used for the purpose.

본 발명은 도막 강도, 내식성, 내후성 등의 내구성 및 도장작업성이 우수한 불소도료 조성물을 제공한다.The present invention provides a fluorine coating composition excellent in durability and coating workability such as coating strength, corrosion resistance, weather resistance, and the like.

본 발명은 불소 함유 공중합체 및 열경화성 아크릴 수지를 포함하고, 상기 열경화성 아크릴 수지가 알킬메타크릴레이트, 알킬아크릴레이트 및 아크릴아마이드 중 하나 이상을 포함하는 단량체로부터 제조된 것인 불소도료 조성물을 제공한다.The present invention provides a fluorine coating composition comprising a fluorine-containing copolymer and a thermosetting acrylic resin, wherein the thermosetting acrylic resin is prepared from monomers comprising at least one of alkyl methacrylate, alkyl acrylate and acrylamide.

본 발명은 도막 강도, 내식성, 내후성 등의 내구성 및 도장작업성이 우수한 불소도료 조성물을 제공한다. 본 발명에 따른 불소도료 조성물은 자동차 부품(예를 들어, 자동차 내연기관 파이프)에 적용 가능하다.The present invention provides a fluorine coating composition excellent in durability and coating workability such as coating strength, corrosion resistance, weather resistance, and the like. The fluorine coating composition according to the present invention is applicable to automobile parts (for example, automotive internal combustion engine pipes).

이하, 본 발명에 대하여 설명한다. 그러나, 하기 내용에 의해서만 한정되는 것은 아니며, 필요에 따라 각 구성요소가 다양하게 변형되거나 선택적으로 혼용될 수 있다. 따라서, 본 발명의 사상 및 기술범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated. However, the present invention is not limited only to the following contents, and each component may be variously modified or optionally mixed as necessary. Therefore, it is to be understood that all changes, equivalents, and substitutes included in the spirit and scope of the present invention are included.

본 발명에 따른 불소도료 조성물은 불소 함유 공중합체 및 열경화성 아크릴 수지를 포함한다. 상기 열경화성 아크릴 수지는 알킬메타크릴레이트, 알킬아크릴레이트 및 아크릴아마이드 중 하나 이상을 포함하는 단량체로부터 제조된 것일 수 있다. 본 발명의 불소도료 조성물은 필요에 따라 안료, 용제 및 도료 분야에서 통상적으로 사용되는 첨가제를 더 포함할 수 있다. 이하, 본 발명의 불소도료 조성물의 조성을 살펴보면 다음과 같다.The fluorine coating composition according to the present invention includes a fluorine-containing copolymer and a thermosetting acrylic resin. The thermosetting acrylic resin may be prepared from a monomer including at least one of alkyl methacrylate, alkyl acrylate and acrylamide. The fluorine coating composition of the present invention may further include additives commonly used in the pigment, solvent and paint fields as necessary. Hereinafter, the composition of the fluorine coating composition of the present invention will be described.

불소 함유 공중합체Fluorine-containing copolymer

본 발명에서 불소 함유 공중합체는 도료 조성물의 내식성을 향상시키는 역할을 한다. 상기 불소 함유 공중합체로는 예를 들어 비닐리덴플루오라이드(VDF: vinylidenefluoride), 비닐플루오라이드(VF: vinylfluoride), 헥사플루오로프로필렌(HFP: hexafluoropropylene), 테트라플루오로에틸렌(TFE: tetrafluoroethylene), 클로로테트라플루오로에틸렌(CTFE: chlorotetrafluoroethylene) 및 퍼플루오로메틸비닐에테르(PMVE: perfluoromethylvinylether)로 이루어진 군으로부터 선택된 1종 이상의 단량체로부터 제조된 (공)중합체를 사용할 수 있다. 상기 불소 함유 공중합체는 예컨대 폴리비닐리덴플루오라이드(PVDF: polyvinylidenefluoride), 폴리비닐플루오라이드(PVF: polyvinylfluoride) 또는 이들의 혼합물일 수 있다. 폴리비닐리덴플루오라이드(PVDF) 및 폴리비닐플루오라이드(PVF)는 뛰어난 내약품성과 양호한 기계적, 열적, 전기적 특성을 겸비하고 있다.In the present invention, the fluorine-containing copolymer serves to improve the corrosion resistance of the coating composition. Examples of the fluorine-containing copolymer include vinylidene fluoride (VDF), vinylfluoride (VF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE) and chlorotetra. (Co) polymers prepared from at least one monomer selected from the group consisting of fluorotetrafluoroethylene (CTFE) and perfluoromethylvinylether (PMVE) may be used. The fluorine-containing copolymer may be, for example, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF) or a mixture thereof. Polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF) combine excellent chemical resistance with good mechanical, thermal and electrical properties.

상기 불소 함유 공중합체의 용융흐름지수(Melt Flow Index)는 2.0 내지 6.0 g/10min일 수 있고, 점도는 25 내지 35 kPs일 수 있다. Melt flow index of the fluorine-containing copolymer (Melt Flow Index) may be 2.0 to 6.0 g / 10min, the viscosity may be 25 to 35 kPs.

상기 불소 함유 공중합체는 불소도료 조성물의 총량을 기준으로 약 10 내지 30 중량%, 예를 들어 15 내지 20 중량%의 양으로 사용될 수 있다. 불소도료 성분 내의 불소 함유 공중합체 성분이 30 중량%를 초과하는 경우 불소도료를 충분히 분산시키기 어려워 균일한 도막을 형성하기 어렵고, 도장 도막의 외관이 나쁘게 되며, 수지 간의 결합력이 저하되어 피도체와의 밀착성 저하와 도막의 기계적 물성이 떨어지는 문제점이 발생할 수 있다. 반면에, 불소 함유 공중합체 성분이 10 중량% 미만일 경우 내화학성, 내식성, 내후성이 저하될 수 있다.The fluorine-containing copolymer may be used in an amount of about 10 to 30% by weight, for example 15 to 20% by weight, based on the total amount of the fluorine coating composition. When the fluorine-containing copolymer component in the fluorine paint component is more than 30% by weight, it is difficult to sufficiently disperse the fluorine paint, making it difficult to form a uniform coating film, resulting in a poor appearance of the coating film, and a decrease in bonding strength between resins. Degradation of adhesion and deterioration of mechanical properties of the coating film may occur. On the other hand, when the fluorine-containing copolymer component is less than 10% by weight, chemical resistance, corrosion resistance, and weather resistance may be lowered.

열경화성 아크릴 수지Thermosetting acrylic resin

본 발명에 따른 도료 조성물의 수지로서, 상기 불소 함유 공중합체와 함께 열경화성 아크릴 수지가 사용된다. 상기 열경화성 아크릴 수지는 도막의 외관과 경도를 향상시키는 역할을 한다.As the resin of the coating composition according to the present invention, a thermosetting acrylic resin is used together with the fluorine-containing copolymer. The thermosetting acrylic resin serves to improve the appearance and hardness of the coating film.

상기 열경화성 아크릴 수지로는 알킬메타크릴레이트, 알킬아크릴레이트 및 아크릴아마이드 중 하나 이상을 포함하는 단량체로부터 제조된 것을 사용할 수 있다.The thermosetting acrylic resin may be prepared from monomers containing at least one of alkyl methacrylate, alkyl acrylate and acrylamide.

상기 알킬메타크릴레이트로는 예를 들어 메틸메타크릴레이트, 에틸메타크릴레이트, 이소프로필메타크릴레이트, n-부틸메타크릴레이트, 이소부틸메타크릴레이트, n-헥실메타크릴레이트, 라우릴메타크릴레이트를 사용할 수 있고, 이들은 단독으로 사용되거나 2종 이상이 혼합되어 사용될 수 있다. 상기 알킬아크릴레이트로는 예를 들어 메틸아크릴레이트, 에틸아크릴레이트, 이소프로필아크릴레이트, n-부틸아크릴레이트, 2-에틸헥실아크릴레이트를 사용할 수 있고, 이들은 단독으로 사용되거나 2종 이상이 혼합되어 사용될 수 있다. 상기 아크릴아마이드로는 N-(부톡시메틸)-2-프로펜아마이드를 사용할 수 있다.Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, and lauryl methacrylate. The rates may be used, and these may be used alone or in combination of two or more thereof. As the alkyl acrylate, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate may be used, and these may be used alone or two or more kinds may be mixed. Can be used. N- (butoxymethyl) -2-propeneamide may be used as the acrylamide.

상기 열경화성 아크릴 수지는 메틸메타크릴레이트, 에틸아크릴레이트 및 아크릴아마이드 중 하나 이상을 포함하는 단량체로부터 제조될 수 있다.The thermosetting acrylic resin may be prepared from monomers including at least one of methyl methacrylate, ethyl acrylate and acrylamide.

또한, 상기 열경화성 아크릴 수지는 메틸메타크릴레이트, 에틸아크릴레이트 및 아크릴아마이드를 포함하는 단량체로부터 제조될 수 있다. In addition, the thermosetting acrylic resin may be prepared from monomers including methyl methacrylate, ethyl acrylate and acrylamide.

상기 열경화성 아크릴 수지는 알킬메타크릴레이트 5 내지 50 중량%, 예를 들어 10 내지 30 중량%, 알킬아크릴레이트 5 내지 25 중량%, 예를 들어 8 내지 18 중량% 및 아크릴아마이드 2 내지 20 중량%, 예를 들어 3 내지 10 중량%를 포함할 수 있다.The thermosetting acrylic resin is 5 to 50% by weight of alkyl methacrylate, for example 10 to 30% by weight, 5 to 25% by weight of alkyl acrylate, for example 8 to 18% by weight and 2 to 20% by weight of acrylamide, For example, it may include 3 to 10% by weight.

상기 열경화성 아크릴 수지 내의 알킬메타크릴레이트 함량이 5 중량% 미만인 경우 도막의 유연성이 저하되고, 50 중량%를 초과하는 경우 부착성이 저하될 수 있다. 알킬아크릴레이트 함량이 5 중량% 미만인 경우 불소수지와의 상용성이 저하되고, 25 중량% 초과인 경우 내후성이 저하될 수 있다. 또한 아크릴아마이드 함량이 2 중량% 미만인 경우 반응성이 저하되어 경도가 약해질 수 있고, 20 중량%를 초과하는 경우 온도에 따라 과경화 될 수 있다.When the alkyl methacrylate content in the thermosetting acrylic resin is less than 5% by weight, the flexibility of the coating film is lowered, and when it exceeds 50% by weight, adhesion may be lowered. When the alkyl acrylate content is less than 5% by weight, the compatibility with the fluororesin is lowered, and when the alkylacrylate content is greater than 25% by weight, weather resistance may be reduced. In addition, when the acrylamide content is less than 2% by weight, the reactivity may be lowered and the hardness may be weakened. When the acrylamide content is higher than 20% by weight, it may be hardened depending on the temperature.

상기 열경화성 아크릴 수지 내의 알킬메타크릴레이트, 알킬아크릴레이트 및 아크릴아마이드의 혼합비(중량비)는 예를 들어, 1 : 0.1 내지 10 : 0.1 내지 10, 다른 예로 1 : 0.1 내지 5 : 0.1 내지 3일 수 있다. 상기 열경화성 아크릴 수지의 혼합비가 상기 범위를 벗어나는 경우, 도료 조성물의 내식성 및 도장작업성이 저하될 수 있다.The mixing ratio (weight ratio) of the alkyl methacrylate, alkyl acrylate and acrylamide in the thermosetting acrylic resin may be, for example, 1: 0.1 to 10: 0.1 to 10, and other examples of 1: 0.1 to 5: 0.1 to 3 . When the mixing ratio of the thermosetting acrylic resin is out of the above range, the corrosion resistance and coating workability of the coating composition may be lowered.

상기 열경화성 아크릴 수지의 중량평균분자량은 약 30,000 내지 85,000, 예를 들어 약 35,000 내지 85,000, 다른 예로 약 35,000 내지 75,000일 수 있다. 상기 열경화성 아크릴 수지의 유리전이온도(Tg)는 30 내지 60℃, 예를 들어 약 40 내지 50℃일 수 있다.The weight average molecular weight of the thermosetting acrylic resin may be about 30,000 to 85,000, for example, about 35,000 to 85,000, other examples may be about 35,000 to 75,000. The glass transition temperature (Tg) of the thermosetting acrylic resin may be 30 to 60 ℃, for example about 40 to 50 ℃.

상기 열경화성 아크릴 수지는 불소도료 조성물의 총량을 기준으로 약 2 내지 8 중량%, 예를 들어 약 3 내지 6 중량%의 양으로 사용될 수 있다. 열경화성 아크릴 수지를 전술한 범위의 함량으로 사용할 때, 불소도료의 크랙 발생을 방지하고, 도장작업성 및 경도를 효과적으로 향상시킬 수 있다.The thermosetting acrylic resin may be used in an amount of about 2 to 8 wt%, for example about 3 to 6 wt%, based on the total amount of the fluorine coating composition. When using the thermosetting acrylic resin in the content of the above-mentioned range, it is possible to prevent the occurrence of cracks in the fluorine paint, and effectively improve the paintability and hardness.

안료Pigment

본 발명에 따른 불소도료 조성물은 필요에 따라 안료를 더 포함할 수 있다. 상기 안료는 도료에 원하는 색상(유색)을 발현하거나 도막의 강도나 광택을 증가시키기 위해 포함된다. The fluorine coating composition according to the present invention may further include a pigment as necessary. The pigment is included to express the desired color (colour) in the paint or to increase the strength or gloss of the coating.

상기 안료로는 도료 분야에서 통상적으로 사용되는 유기안료, 무기안료, 메탈릭안료, 알루미늄-페이스트(Al-paste), 펄(pearl), 체질안료 등을 제한 없이 사용할 수 있으며, 이들을 단독으로 또는 2종 이상 혼용할 수 있다. 상기 안료의 비제한적인 예로는 레드 계열, 황색/오렌지 계열, 블루 계열, 블랙 계열, 백색 계열, 펄 및 메탈릭 계열의 안료 등을 사용할 수 있다.As the pigment, organic pigments, inorganic pigments, metallic pigments, aluminum pastes (Al-paste), pearls, extender pigments, and the like, which are commonly used in the paint field, may be used without limitation, and these may be used alone or in combination. The above can be mixed. Non-limiting examples of the pigment may be a pigment of the red, yellow / orange, blue, black, white, pearl and metallic series.

본 발명에서, 안료의 함량은 특별히 한정되지 않으며, 불소도료 조성물의 총량을 기준으로 약 5 내지 15 중량%일 수 있다. 상기 안료의 함량이 전술한 범위일 경우, 분산성 및 저장 안정성의 저하 없이, 도막의 외관 특성 및 기계적 물성이 향상될 수 있다.In the present invention, the content of the pigment is not particularly limited, and may be about 5 to 15% by weight based on the total amount of the fluorine coating composition. When the content of the pigment is in the above-described range, the appearance properties and mechanical properties of the coating film can be improved without deteriorating dispersibility and storage stability.

첨가제additive

본 발명에 따른 불소도료 조성물은 필요에 따라 전술한 성분들 이외에 당 분야에 알려진 통상적인 첨가제를 선택적으로 더 포함할 수 있다. 본 발명에서 사용 가능한 첨가제의 비제한적인 예를 들면, 칙소제, 소포제, 레벨링제, 표면조정제, 자외선 흡수제, 자외선 안정제, 건조제, 흡습제, 왁스 등이 있다. The fluorine coating composition according to the present invention may optionally further include conventional additives known in the art, in addition to the aforementioned components as necessary. Non-limiting examples of the additives usable in the present invention include thixotropic agents, antifoaming agents, leveling agents, surface conditioners, ultraviolet absorbers, ultraviolet stabilizers, desiccants, hygroscopic agents, waxes and the like.

상기 첨가제의 함량은 특별히 한정되지 않으며, 불소도료 조성물의 총량을 기준으로 0.1 내지 5 중량%일 수 있다.The amount of the additive is not particularly limited and may be 0.1 to 5 wt% based on the total amount of the fluorine coating composition.

용제solvent

본 발명에 따른 불소도료 조성물은 필요에 따라 용제를 더 포함할 수 있다. 상기 용제는 도료 조성물의 점도를 조절하여 도장 작업을 용이하게 하며, 용제의 휘발 속도 조절을 통해 도막(코팅층)의 평활성 및 도장 작업성을 향상시키는 역할을 한다. The fluorine coating composition according to the present invention may further include a solvent as necessary. The solvent facilitates the painting operation by adjusting the viscosity of the coating composition, and serves to improve the smoothness and coating workability of the coating (coating layer) by adjusting the volatilization rate of the solvent.

본 발명에서 사용 가능한 용제는 당 분야에 알려진 통상적인 용제라면 특별히 한정되지 않는다. 예를 들어, 케톤(ketone)계 용제, 에스테르(ester)계 용제, 에테르(ether)계 용제, 탄화수소계 용제, 알코올(alcohol)계 용제 또는 이들의 혼합물 등이 있다. 상기 용제의 비제한적인 예로는 부틸아세테이트, 프로필렌글리콜 메틸에테르, 톨루엔, 자일렌, 메틸에틸케톤, 메틸프로필케톤, 메틸부틸케톤, 에틸프로필케톤, 메틸이소부틸케톤, 메틸아세테이트, 에틸아세테이트, 노말프로필아세테이트, 이소프로필아세테이트, 메틸셀로솔브아세테이트, 셀로솔브아세테이트, 부틸셀로솔브아세테이트, 카비톨아세테이트, 노말프로판올, 이소프로판올, 노말부탄올, 이소부탄올, 터셔리부탄올, 벤젠, 아세톤, 테트라하이드로퓨란, 디메틸포름알데히드, 디메틸프탈레이트, 시클로헥사논, 메탄올, 에탄올 등이 있다. 이들은 단독으로 사용되거나 2종 이상이 혼합되어 사용될 수 있다.The solvent usable in the present invention is not particularly limited as long as it is a conventional solvent known in the art. For example, a ketone solvent, an ester solvent, an ether solvent, a hydrocarbon solvent, an alcohol solvent, or a mixture thereof. Non-limiting examples of the solvent include butyl acetate, propylene glycol methyl ether, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, normal propyl Acetate, isopropyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, normal propanol, isopropanol, normal butanol, isobutanol, tert-butanol, benzene, acetone, tetrahydrofuran, dimethyl Formaldehyde, dimethylphthalate, cyclohexanone, methanol, ethanol and the like. These may be used alone or in combination of two or more thereof.

본 발명에서, 상기 용제의 함량은 특별히 제한되지 않으며, 불소도료 조성물의 총량이 100 중량%가 되도록 조절하는 잔량일 수 있으며, 예를 들어 50 내지 70 중량%일 수 있다. 상기 용제의 함량이 전술한 범위일 경우, 작업성 및 도막의 외관 특성이 향상될 수 있다.In the present invention, the content of the solvent is not particularly limited, and may be a residual amount adjusted so that the total amount of the fluorine coating composition is 100% by weight, for example, may be 50 to 70% by weight. When the content of the solvent is in the above-described range, workability and appearance characteristics of the coating film may be improved.

이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나, 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for the purpose of understanding the present invention, and the scope of the present invention is not limited to the examples in any sense.

[실시예 1-5 및 비교예 1-4]Example 1-5 and Comparative Example 1-4

하기 표 1에 기재된 조성에 따라 각 성분을 배합하여, 실시예 1-5 및 비교예 1-4의 불소도료 조성물을 각각 제조하였다. Each component was mix | blended according to the composition of following Table 1, and the fluorine coating composition of Example 1-5 and Comparative Example 1-4 was produced, respectively.

Figure pat00001
Figure pat00001

1) 불소 함유 공중합체 1: 폴리비닐리덴플루오라이드 수지(HYLAR5000, ARKEMA INC社, 점도 31 kPs)1) Fluorine-containing copolymer 1: polyvinylidene fluoride resin (HYLAR5000, ARKEMA INC, viscosity 31 kPs)

2) 불소 함유 공중합체 2: 폴리비닐플루오라이드 수지(ZFT-9, LANITAN社, 점도 30 kPs)2) Fluorine-containing copolymer 2: polyvinyl fluoride resin (ZFT-9, LANITAN, viscosity 30 kPs)

3) 열경화성 아크릴수지 1: Methyl Methacrylate 25%, Ethyl Acrylate 11%, N-(Butoxymethyl)-2-propenamide 5% (CRT00431, KCC社, 중량평균분자량: 68,000, Tg: 51℃)3) Thermosetting Acrylic Resin 1: Methyl Methacrylate 25%, Ethyl Acrylate 11%, N- (Butoxymethyl) -2-propenamide 5% (CRT00431, KCC, Weight Average Molecular Weight: 68,000, Tg: 51 ℃)

4) 열경화성 아크릴수지 2: Methyl Methacrylate 10%, Ethyl Acrylate 15%, N-(Butoxymethyl)-2-propenamide 10% (CRT00329, KCC社, 중량평균분자량: 37,000, Tg: 45℃)4) Thermosetting acrylic resin 2: Methyl Methacrylate 10%, Ethyl Acrylate 15%, N- (Butoxymethyl) -2-propenamide 10% (CRT00329, KCC, Weight average molecular weight: 37,000, Tg: 45 ℃)

5) 열경화성 아크릴수지 3 : Methyl Methacrylate 20%, Ethyl Acrylate 11%, N-(Butoxymethyl)-2-propenamide 25% (중량평균분자량: 43,000, Tg: 45℃)5) Thermosetting acrylic resin 3: Methyl Methacrylate 20%, Ethyl Acrylate 11%, N- (Butoxymethyl) -2-propenamide 25% (weight average molecular weight: 43,000, Tg: 45 ℃)

6) 열경화성 아크릴수지 4: Methyl Methacrylate 30%, Ethyl Acrylate 2%, N-(Butoxymethyl)-2-propenamide 9% (중량평균분자량: 54,000, Tg: 51℃)6) Thermosetting Acrylic Resin 4: Methyl Methacrylate 30%, Ethyl Acrylate 2%, N- (Butoxymethyl) -2-propenamide 9% (weight average molecular weight: 54,000, Tg: 51 ℃)

7) 열가소성 아크릴수지: SS-4007, DONGIN CHEMICAL社 (점도 Z, 고형분 40)7) Thermoplastic acrylic resin: SS-4007, DONGIN CHEMICAL (viscosity Z, solid content 40)

8) 안료 1: Chrome Antimony Titanium Buff Rutile(BBY24828)8) Pigment 1: Chrome Antimony Titanium Buff Rutile (BBY24828)

9) 안료 2: CAMOUFLAGE GREN NO179(BBG23063)9) Pigment 2: CAMOUFLAGE GREN NO179 (BBG23063)

10) 안료 3: Zinc Phosphate(BBZ53642)10) Pigment 3: Zinc Phosphate (BBZ53642)

11) 첨가제 1: Thixotropy Agent 1(BYK 410)11) Additive 1: Thixotropy Agent 1 (BYK 410)

12) 첨가제 2: Thixotropy Agent 2(BYK 430)12) Additive 2: Thixotropy Agent 2 (BYK 430)

13) 첨가제 3: Slip Agent(AEK56889)13) Additive 3: Slip Agent (AEK56889)

14) 용제: 디메틸프탈레이트14) Solvent: Dimethylphthalate

[실험예 - 물성 평가] Experimental Example-Evaluation of Properties

실시예 1-5 및 비교예 1-4에서 각각 제조된 불소도료 조성물의 물성을 하기와 같이 측정하였으며, 이의 결과를 하기 표 2에 나타내었다. Physical properties of the fluorine coating compositions prepared in Examples 1-5 and Comparative Examples 1-4, respectively, were measured as follows, and the results are shown in Table 2 below.

부착성Adhesion

ASTM D3359(크로스 컷 테이프 테스트법, cross cut tape test)에 따라 100개의 눈금(1㎜×1㎜)에 테이프를 접착한 후, 테이프를 박리한 후의 잔존하는 눈금의 개수(N)를 측정하였고, N/100으로 표시하였다.After adhering the tape to 100 scales (1 mm x 1 mm) according to ASTM D3359 (cross cut tape test), the number of remaining scales (N) after peeling off the tape was measured. It is expressed as N / 100.

뉴튼경도Newton Hardness

뉴튼경도계로 측정 시 도막이 파괴되지 않는 뉴튼값을 측정하였다.Newton's value was measured when the coating was not destroyed when measured by Newton's hardness meter.

굴곡성Flexibility

ASTM D4145 규격에 따라, 시편을 벤딩(bending)하여 굴곡 부위에서 도막의 크랙(Crack) 수준과 테이핑(Taping) 후 도막의 벗겨짐(Peel-off)을 평가하였다. According to ASTM D4145 standard, the specimen was bent to evaluate the crack level of the coating film at the bend and the peel-off of the coating film after taping.

MEK RUBBING(경화도)MEK RUBBING

거즈에 MEK(Methylethylketone) 용액을 충분히 적신 후, 약 1 내지 1.5 kg의 하중을 주어 분당 왕복 100회의 속도로 시편 내 10 cm 길이로 규정횟수를 문지르고(rubbing), 시험이 끝난 후 시편을 관찰하여 판정하였다.After sufficiently wetting the MEK (Methylethylketone) solution to the gauze, rubbing the specified number of times to 10 cm in the specimen at a rate of 100 round trips per minute with a load of about 1 to 1.5 kg, and then observing the specimen after the test. It was.

점도Viscosity

25℃에서 FORD CUP NO.4로 측정하였다.It measured by FORD CUP NO.4 at 25 degreeC.

TI(요변도)Thixotropy

LVT 점도계(Brookfield)로 측정하여 TI(요변도)를 구하였다.It was measured with an LVT viscometer (Brookfield) to obtain a TI (tesotropy).

요변도 = 5회전때의 점도/50회전때의 점도Thixotropy = viscosity at 5 rotations / viscosity at 50 rotations

절곡성Bendability

벤딩시험기를 사용하여 시험 시편(길이 35 mm 이상, 두께 4 mm 이하)에 대하여 120˚ 밴딩을 1회 실시한 후, TAPE TEST를 3회 실시하였다. 시험 전 후의 시료를 비교하여 가공면의 박리가 없을 경우 합격, 박리된 면이 있을 경우 불량으로 평하였다.Using a bending tester, the test specimen (length 35 mm or more, thickness 4 mm or less) was subjected to 120 ° bending once, and then TAPE TEST was performed three times. Samples before and after the test were compared and evaluated as defective when there was no peeling of the processed surface and when there was a peeled surface.

내식성Corrosion resistance

ASTM B117 규격에 따라, 칼로 시편의 중앙에 X자 흠집을 낸 후 1,000 시간 내식성을 시험한 후, Blister 발생 유무를 평가하였다.According to the ASTM B117 standard, after the X-shaped scratches in the center of the specimen with a knife and tested for corrosion resistance for 1,000 hours, the presence of Blister was evaluated.

저장안정성Storage stability

60℃ 오븐에 7일동안 열저장한 후 침전 유무를 관찰하였다. 침전이 없는 경우, 양호로 판정하였다.After 7 days of heat storage in an oven at 60 ℃ was observed for precipitation. If there was no precipitation, it was judged good.

Figure pat00002
Figure pat00002

본 발명에 따른 실시예 1-5의 불소도료 조성물은 측정한 물성 모두에서 우수한 물성을 나타내었다. 반면, 열경화성 아크릴수지 대신 열가소성 아크릴수지를 사용한 비교예 1의 불소도료 조성물은 경화도 및 요변도가 열악한 것으로 측정되었다. 또한 불소 함유 공중합체를 포함하지 않은 비교예 2의 불소도료 조성물은 경도, 굴곡성, 경화도, 요변도 및 내식성 등 전반적인 물성이 열악한 것으로 측정되었고, 열경화성 아크릴수지의 단량체의 조성(함량 범위)이 본원발명의 범위를 벗어나는 비교예 3 및 4의 불소도료 조성물은 부착성 및 경도 등, 전반적인 물성이 열악한 것으로 측정되었다.The fluorine coating composition of Example 1-5 according to the present invention showed excellent physical properties in all measured physical properties. On the other hand, the fluorine coating composition of Comparative Example 1 using a thermoplastic acrylic resin instead of a thermosetting acrylic resin was determined to be poor in the degree of curing and thixotropy. In addition, the fluorine coating composition of Comparative Example 2, which does not contain a fluorine-containing copolymer, was determined to have poor overall physical properties such as hardness, flexibility, curing degree, thixotropy, and corrosion resistance, and the composition (content range) of the monomer of thermosetting acrylic resin Fluorine coating compositions of Comparative Examples 3 and 4 outside the scope of the invention was determined to be poor overall physical properties such as adhesion and hardness.

Claims (8)

불소 함유 공중합체 및 열경화성 아크릴 수지를 포함하고, 상기 열경화성 아크릴 수지가 알킬메타크릴레이트 5 내지 50 중량%, 알킬아크릴레이트 5 내지 25 중량% 및 아크릴아마이드 2 내지 20 중량%를 포함하는 단량체로부터 제조된 것인 불소도료 조성물.A fluorine-containing copolymer and a thermosetting acrylic resin, wherein the thermosetting acrylic resin is prepared from monomers comprising 5 to 50% by weight of alkyl methacrylate, 5 to 25% by weight of alkyl acrylate and 2 to 20% by weight of acrylamide. Fluorine coating composition. 제1항에 있어서, 불소 함유 공중합체 10 내지 30 중량% 및 열경화성 아크릴 수지 2 내지 8 중량%를 포함하는 불소도료 조성물.The fluorine coating composition according to claim 1, comprising 10 to 30% by weight of the fluorine-containing copolymer and 2 to 8% by weight of the thermosetting acrylic resin. 제1항에 있어서, 상기 불소 함유 공중합체가 폴리비닐리덴플루오라이드(PVDF: polyvinylidenefluoride) 및 폴리비닐플루오라이드(PVF: polyvinylfluoride) 중 1종 이상인 불소도료 조성물.The fluorine coating composition according to claim 1, wherein the fluorine-containing copolymer is at least one of polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF). 제1항에 있어서, 상기 불소 함유 공중합체의 점도가 25 내지 35 kPs인 불소도료 조성물.The fluorine coating composition according to claim 1, wherein the fluorine-containing copolymer has a viscosity of 25 to 35 kPs. 제1항에 있어서, 상기 열경화성 아크릴 수지는 메틸메타크릴레이트, 에틸아크릴레이트 및 아크릴아마이드 중 하나 이상을 포함하는 단량체로부터 제조된 것인 불소도료 조성물.The fluorine coating composition of claim 1, wherein the thermosetting acrylic resin is prepared from monomers including at least one of methyl methacrylate, ethyl acrylate, and acrylamide. 제1항에 있어서, 상기 열경화성 아크릴 수지는 메틸메타크릴레이트, 에틸아크릴레이트 및 아크릴아마이드를 포함하는 단량체로부터 제조된 것인 불소도료 조성물.The fluorine coating composition according to claim 1, wherein the thermosetting acrylic resin is prepared from monomers including methyl methacrylate, ethyl acrylate and acrylamide. 제1항에 있어서, 상기 알킬메타크릴레이트, 알킬아크릴레이트 및 아크릴아마이드의 혼합비(중량비)는 1 : 0.1 내지 10 : 0.1 내지 10인 불소도료 조성물.The fluorine coating composition of claim 1, wherein a mixing ratio (weight ratio) of the alkyl methacrylate, alkyl acrylate and acrylamide is 1: 0.1 to 10: 0.1 to 10. 제1항에 있어서, 상기 열경화성 아크릴 수지의 중량평균분자량은 30,000 내지 85,000이고, 유리전이온도(Tg)는 30 내지 60℃인 불소도료 조성물.The fluorine coating composition of claim 1, wherein the thermosetting acrylic resin has a weight average molecular weight of 30,000 to 85,000, and a glass transition temperature (Tg) of 30 to 60 ° C.
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