KR20190016303A - Cationic urethane curing agent and electro-deposition paint composition comprising the same - Google Patents
Cationic urethane curing agent and electro-deposition paint composition comprising the same Download PDFInfo
- Publication number
- KR20190016303A KR20190016303A KR1020170100363A KR20170100363A KR20190016303A KR 20190016303 A KR20190016303 A KR 20190016303A KR 1020170100363 A KR1020170100363 A KR 1020170100363A KR 20170100363 A KR20170100363 A KR 20170100363A KR 20190016303 A KR20190016303 A KR 20190016303A
- Authority
- KR
- South Korea
- Prior art keywords
- diisocyanate
- curing agent
- acid
- glycidyl
- amine compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4453—Polyepoxides characterised by the nature of the curing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
-
- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
-
- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
Description
본 발명은 양이온성을 갖는 우레탄 경화제 및 이를 포함하는 전착 도료 조성물에 관한 것이다.The present invention relates to a cationic urethane curing agent and an electrodeposition coating composition containing the same.
자동차 생산공장에서 전착 도장 시 대부분의 에너지는 도장된 전착 도료를 경화시키는 오븐에서 소비된다. 이때, 오븐 설비 공간과 경화효율은 한정되어 있는데 반해 자동차의 차체는 점차 커지고 있어 경화취약부가 발생하는 문제점이 대두되고 있다. 즉, 자동차의 차체가 커지면서 두꺼워지는 것으로 인해 차체 위에 도장된 전착 도료가 경화에 필요한 온도에 도달하기까지 걸리는 시간, 즉, PMT(Peak Metal Temperature)이 길어져 기존 경화 시스템에서의 경화 효율이 떨어진다.In electroplating at automotive plants, most of the energy is consumed in the oven to cure the painted electrodeposition coatings. At this time, oven facility space and curing efficiency are limited, but the body of the automobile is getting bigger, so that there is a problem that the hardening is weak. That is, the time required for the electrodeposition painted on the vehicle body to reach the temperature required for curing, that is, the peak metal temperature (PMT), becomes long due to the increase in the car body of the automobile, resulting in a decrease in the curing efficiency in the existing curing system.
이에 따라 경화에 소비되는 에너지 절감과 한정된 오븐 설비 공간 안에서 큰 차체의 경화성을 확보하기 위해 자동차 업계에서는 보다 낮은 온도에서 경화가 이루어질 수 있는 전착 도료의 개발이 요구되고 있다.Accordingly, in order to reduce energy consumption for curing and to secure the curability of a large body in a limited oven facility space, development of an electrodeposition coating that can be cured at a lower temperature is required in the automobile industry.
이러한 요구에 따라 전착 도료에 포함되는 경화 촉진제 또는 경화제의 함량을 증가시키는 방향으로 대응하는 움직임이 있었다. 그러나 경화 촉진제의 함량을 증가시키는 경우에는 도막의 외관(광택 및 조도)이 저하되고, 경화제의 함량을 증가시키는 경우에는 주제의 함량 저하로 인해 내부도장성, 내식성 등이 저하되는 문제점이 발생하였다.According to this demand, there was a corresponding movement in the direction of increasing the content of the curing accelerator or curing agent contained in the electrodeposition paint. However, when the content of the curing accelerator is increased, the appearance (gloss and roughness) of the coating film is lowered. When the content of the curing agent is increased, the content of the curing agent is lowered and the internal coating and corrosion resistance are deteriorated.
이외에도 해리 온도가 낮은 알코올, 페놀, 옥심, 락탐 등의 차단제가 결합된 경화제를 사용하여 전착 도료의 경화성을 확보하고자 하는 시도가 이루어진 바 있다. 특히, 차단제로 옥심이 결합된 경화제는 경화성이 향상된다는 사례가 다수 보고되고 있다. 그러나 옥심은 해리 온도가 매우 낮아 경화제로 사용되는 방향족 이소시아네이트와의 조합 시에는 전착 수지의 안정성을 매우 떨어뜨려 지방족 이소시아네이트에만 한정적으로 사용할 수 있었다.In addition, efforts have been made to secure the curability of electrodeposition paints using a curing agent having a low dissociation temperature and a blocking agent such as alcohol, phenol, oxime, and lactam. In particular, many cases have been reported in which curing agents having oxime bonds as blocking agents are improved in curability. However, since oxime has a very low dissociation temperature, the stability of the electrodeposited resin is very poor when used in combination with an aromatic isocyanate used as a curing agent, so that the oxime can be limitedly used only in an aliphatic isocyanate.
이에 따라 도막의 물성을 저하시키지 않으면서 비교적 저온에서도 경화성을 확보할 수 있는 기술의 개발이 요구되고 있는 실정이다.Accordingly, there is a need to develop a technique capable of securing curability at a relatively low temperature without lowering the physical properties of the coating film.
본 발명은 비교적 저온에서도 전착 도료 조성물의 경화성을 확보시킬 수 있는 양이온성 우레탄 경화제를 제공한다.The present invention provides a cationic urethane curing agent capable of ensuring the curability of the electrodeposition coating composition even at a relatively low temperature.
또한 본 발명은 물성이 우수한 도막을 형성할 수 있는 전착 도료 조성물을 제공한다.The present invention also provides an electrodeposition coating composition capable of forming a coating film having excellent physical properties.
본 발명은, 히드록시기를 갖는 3급 아민 화합물과 이소시아네이트 화합물의 반응물을 산 중화제로 중화시켜 얻어진 것인 양이온성 우레탄 경화제를 제공한다.The present invention provides a cationic urethane curing agent obtained by neutralizing a reaction product of a tertiary amine compound having a hydroxy group and an isocyanate compound with an acid neutralizing agent.
또한 본 발명은, 전착 수지부, 안료부, 상기 양이온성 우레탄 경화제를 포함하는 경화 첨가제부, 및 용매부를 포함하는 전착 도료 조성물을 제공한다.The present invention also provides an electrodeposition coating composition comprising an electrodeposition resin portion, a pigment portion, a curing additive portion including the cationic urethane curing agent, and a solvent portion.
본 발명의 양이온성 우레탄 경화제는 전착 도료 조성물의 경화에 참여할 수 있는 반응기(이소시아네이트기)를 원활히 제공할 수 있어 비교적 저온(예를 들어, 150 ℃ 이하)에서도 안정적으로 도막의 경화가 이루어지도록 할 수 있다. 또한 본 발명의 양이온성 우레탄 경화제는 단분자이면서 양이온성으로 인해 전착 도료 조성물에 적용 시 전착 도료 조성물의 전기전도도를 증가시켜 전착 도료 조성물의 내부도장성을 높일 수 있다.The cationic urethane curing agent of the present invention can smoothly provide a reactor (isocyanate group) capable of participating in the curing of the electrodeposition coating composition, and can harden the coating film stably at a relatively low temperature (for example, 150 ° C or lower) have. In addition, the cationic urethane curing agent of the present invention can increase the internal conductivity of the electrodeposition coating composition by increasing the electrical conductivity of the electrodeposition coating composition when applied to the electrodeposition coating composition due to its monomolecular and cationic nature.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
1. One. 양이온성Cationic 우레탄 경화제 Urethane hardener
본 발명의 양이온성 우레탄 경화제는 히드록시기를 갖는 3급 아민 화합물과 이소시아네이트 화합물을 1차적으로 반응시켜 얻어진 반응물을 2차적으로 산 중화제로 중화시켜 얻어진 것으로, 각 반응에 사용되는 성분에 대해 구체적으로 설명하면 다음과 같다.The cationic urethane curing agent of the present invention is obtained by firstly neutralizing a reaction product obtained by reacting a tertiary amine compound having a hydroxy group with an isocyanate compound with a secondary acid neutralizing agent and specifically explaining the components used in each reaction As follows.
상기 반응물을 얻기 위해 사용되는 3급 아민 화합물은 히드록시기(OH)가 결합된 것으로, 양이온성 우레탄 경화제에 수용성, 양이온성 등의 성질을 부여하며 양이온성 우레탄 경화제의 경화반응성을 차단하는 역할을 한다. 구체적으로 3급 아민 화합물에 결합된 히드록시기가 이소시아네이트 화합물에 결합된 이소시아네이트기(NCO)와 우레탄 결합을 형성하여 이소시아네이트기의 반응성을 차단함으로써 양이온성 우레탄 경화제의 경화반응성을 차단하는 것이다.The tertiary amine compound used to obtain the reactant is a compound having a hydroxy group (OH) bonded thereto. The cationic urethane curing agent imparts water-soluble or cationic properties to the curing agent and blocks the curing reaction of the cationic urethane curing agent. Specifically, the hydroxyl group bonded to the tertiary amine compound forms a urethane bond with an isocyanate group (NCO) bonded to the isocyanate compound to block the reactivity of the isocyanate group, thereby blocking the curing reaction of the cationic urethane curing agent.
이러한 3급 아민 화합물로는 2-디메틸아미노에탄올, 1-디메틸아미노-2-프로판올, 3-디메틸아미노-1-프로판올, 2-디에틸아미노에탄올, 4-디메틸아미노-1-부탄올, 2-디메틸아미노-2-메틸프로판올, 및 4-디메틸아미노-1-부탄올로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.These tertiary amine compounds include 2-dimethylaminoethanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-diethylaminoethanol, Amino-2-methylpropanol, and 4-dimethylamino-1-butanol can be used.
또한 3급 아민 화합물로는 1급 아민 화합물, 또는 2급 아민 화합물을 모노에폭사이드(monoepoxide)와 반응시켜 얻어진 화합물이 사용될 수 있다. 상기 1급 아민 화합물, 또는 2급 아민 화합물은 활성수소가 존재하여 후술되는 이소시아네이트 화합물과 원하지 않는 부반응이 유발될 수 있기 때문에, 이들을 직접적으로 사용하기 보다 모노에폭사이드와 반응시켜 얻어진 화합물을 사용할 수 있다.As the tertiary amine compound, a compound obtained by reacting a primary amine compound or a secondary amine compound with monoepoxide may be used. The primary amine compound or the secondary amine compound may be a compound obtained by reacting monoepoxide with the isocyanate compound described below, because active hydrogen is present and undesired side reactions may occur with the isocyanate compound described later have.
상기 1급 아민 화합물과 상기 모노에폭사이드의 반응 시 반응비율은 1:2.0 내지 2.5의 당량비일 수 있고, 구체적으로는 1:2.01 내지 2.1의 당량비일 수 있다. 또한 상기 2급 아민 화합물과 상기 모노에폭사이드의 반응 시 반응비율은 1:1.0 내지 1.5의 당량비일 수 있고, 구체적으로는 1:1.01 내지 1.1의 당량비일 수 있다.The reaction ratio of the primary amine compound to the monoepoxide may be an equivalent ratio of 1: 2.0 to 2.5, and may be an equivalent ratio of 1: 2.01 to 2.1. The reaction ratio of the secondary amine compound to the monoepoxide may be an equivalent ratio of 1: 1.0 to 1.5, and more specifically, an equivalent ratio of 1: 1.01 to 1.1.
상기 1급 아민 화합물로는 에탄올아민, 3-아미노-1-프로판올, 아미노-2-프로판올, 2-아미노-2-메틸-1-프로판올, 2-아미노-3-메틸-1-부탄올, 및 5-아미노-1-펜탄올로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.Examples of the primary amine compound include ethanolamine, 3-amino-1-propanol, amino-2-propanol, 2- -Amino-1-pentanol can be used.
상기 2급 아민 화합물로는 2-메틸아미노에탄올, 2-에틸아미노에탄올, 3-메틸아미노-1-프로판올, 및 2-이소프로필아미노에탄올로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.As the secondary amine compound, at least one selected from the group consisting of 2-methylamino ethanol, 2-ethylamino ethanol, 3-methylamino-1-propanol, and 2-isopropylamino ethanol can be used.
상기 모노에폭사이드로는 1가산의 글리시딜 에스테르, 또는 글리시딜 에테르가 사용될 수 있다. 구체적으로 모노에폭사이드로는 글리시딜 아크릴레이트, 글리시딜 메타크릴레이트, 글리시딜 아세테이트, 글리시딜 부티레이트, 글리시딜 팔미테이트, 글리시딜 라우레이트, 부틸 글리시딜 에테르, 2-에틸헥실 글리시딜 에테르, 페닐 글리시딜 에테르, 및 P-(3급부틸)페닐 글리시딜 에테르로 이루어진 군에서 선택된 1종 이상이 사용되거나 하기 화학식 1로 표시되는 화합물이 사용될 수 있다.As the monoepoxide, glycidyl esters of monosaccharides or glycidyl ethers may be used. Specific examples of monoepoxide include glycidyl acrylate, glycidyl methacrylate, glycidyl acetate, glycidyl butyrate, glycidyl palmitate, glycidyl laurate, butyl glycidyl ether, 2 -Ethylhexyl glycidyl ether, phenyl glycidyl ether, and P- (tertiary butyl) phenyl glycidyl ether may be used, or a compound represented by the following formula (1) may be used.
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 10의 알킬기이다.In the above formula (1), R 1 and R 2 are the same or different and each independently an alkyl group having 1 to 10 carbon atoms.
상기 반응물을 얻기 위해 사용되는 이소시아네이트 화합물은 경화반응에 참여하는 이소시아네이트기를 제공하는 역할을 한다.The isocyanate compound used to obtain the reactant serves to provide an isocyanate group that participates in the curing reaction.
이러한 이소시아네이트 화합물로는 4,4'-메틸렌비스(페닐이소시아네이트)(MDI), 4-메틸-1,3-페닐렌 디이소시아네이트, 폴리머릭 메틸렌디페닐 디이소시아네이트(폴리머릭 MDI), 헥사메틸렌디이소시아네이트(HDI), 크실릴렌디이소시아네이트(XDI), 2,4,6-트리이소프로필페닐디이소시아네이트(TIDI), 디페닐에테르디이소시아네이트, 이소포론디이소시아네이트(IPDI), 4,4'-디시클로헥실메탄디이소시아네이트(MDI), 테트라메틸크실렌디이소시아네이트(TMXDI), 2,2,4-트리메틸헥사메틸렌디이소시아네이트(TMHDI), 및 2,4,4-트리메틸헥사메틸렌디이소시아네이트(TMDI)로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.Examples of such isocyanate compounds include 4,4'-methylenebis (phenylisocyanate) (MDI), 4-methyl-1,3-phenylene diisocyanate, polymeric methylene diphenyl diisocyanate (polymeric MDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), 2,4,6-triisopropylphenyl diisocyanate (TIDI), diphenyl ether diisocyanate, isophorone diisocyanate (IPDI), 4,4'-dicyclohexyl (TMDI), methane diisocyanate (MDI), tetramethylxylylene diisocyanate (TMXDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI) and 2,4,4-trimethylhexamethylene diisocyanate At least one selected may be used.
상기 이소시아네이트 화합물과 상기 3급 아민 화합물의 반응 시 반응비율(이소시아네이트기:히드록시기)은 1:1.0 내지 1.1의 당량비일 수 있고, 구체적으로는 1:1.01 내지 1.05의 당량비일 수 있다.The reaction ratio (isocyanate group: hydroxyl group) in the reaction between the isocyanate compound and the tertiary amine compound may be an equivalent ratio of 1: 1.0 to 1.1, and more specifically, an equivalent ratio of 1: 1.01 to 1.05.
이와 같은 3급 아민 화합물과 이소시아네이트 화합물의 반응을 통해 얻어진 반응물은 산 중화제와의 중화반응(구체적으로 3급 아민 화합물에서 유래된 아민기의 중화)을 거쳐 본 발명의 양이온성 우레탄 경화제가 얻어지게 된다.The reaction product obtained through the reaction between the tertiary amine compound and the isocyanate compound is subjected to a neutralization reaction with an acid neutralizing agent (specifically, neutralization of an amine group derived from a tertiary amine compound) to obtain the cationic urethane curing agent of the present invention .
상기 산 중화제로 중화되지 않은 반응물을 전착 도료 조성물의 경화제 성분으로 사용할 경우, 전착 도료 조성물 내에서 경화제 성분의 적절한 혼합이 이루어지지 않고 침전될 수 있다. 그러나 본 발명의 양이온성 우레탄 경화제는 상기 반응물을 상기 산 중화제로 중화시켜 얻어진 것이기 때문에 전착 도료 조성물의 경화제 성분으로 사용할 경우 침전되지 않으면서 혼합이 잘 이루어질 수 있다.When a reactant that has not been neutralized with the acid neutralizing agent is used as the curing agent component of the electrodeposition coating composition, the curing agent component may be precipitated without proper mixing in the electrodeposition coating composition. However, since the cationic urethane curing agent of the present invention is obtained by neutralizing the reactant with the acid neutralizing agent, it can be mixed well without precipitation when used as a curing agent component of the electrodeposition coating composition.
상기 반응물을 중화시키기 위한 산 중화제로는 초산, 젖산, 개미산, 술폰산, 및 메탄술폰산으로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.As the acid neutralizing agent for neutralizing the reactant, at least one selected from the group consisting of acetic acid, lactic acid, formic acid, sulfonic acid, and methanesulfonic acid may be used.
상기 반응물과 상기 산 중화제의 중화율은 하기 수학식 1로 정의될 수 있다. 이때, 하기 수학식 1에 의해 얻어진 중화율은 5 내지 150 %일 수 있고, 구체적으로는 70 내지 120 %일 수 있다. 상기 중화율이 5 % 미만일 경우에는 수분산성이 저하될 수 있고, 150 %를 초과할 경우에는 산 함량이 많아져 전착 도료 조성물의 pH를 낮춤에 따라 도막 재용해 등과 같은 외관 불량이 초래될 수 있다.The neutralization ratio of the reactant and the acid neutralizer may be defined by the following equation (1). At this time, the neutralization ratio obtained by the following formula (1) may be 5 to 150%, and may be 70 to 120%. If the neutralization ratio is less than 5%, the water dispersibility may be lowered. If the neutralization ratio is more than 150%, the acid content may be increased to lower the pH of the electrodeposition coating composition, resulting in poor appearance such as re- .
[수학식 1][Equation 1]
(산 중화제의 산 당량/반응물의 아민 당량)×100(Acid equivalent of acid neutralizer / amine equivalent of reactant) x 100
이러한 중화반응을 거쳐 얻어진 본 발명의 양이온성 우레탄 경화제는 경화반응에 참여할 수 있는 이소시아네이트기가 증가되어 이를 전착 도료 조성물에 사용할 경우 보다 낮은 온도에서도 안정적인 경화성을 확보할 수 있고 도막의 가교밀도를 높여 내식성 등의 물성이 우수한 도막을 형성시키는데 기여할 수 있다. 또한 중화반응에 의해 3급 아민 화합물이 양이온성을 띠게 되고 이로 인해 수용성의 성질도 갖게 되어 본 발명의 양이온성 우레탄 경화제를 전착 도료 조성물에 사용할 경우 전착 도료 조성물의 전기전도도가 상승되어 내부도장성도 높일 수 있다.The cationic urethane curing agent of the present invention obtained through such a neutralization reaction has an increased isocyanate group capable of participating in the curing reaction and can secure a stable curing property even at a lower temperature than when used in an electrodeposition coating composition, Can contribute to formation of a coating film having excellent physical properties. In addition, the tertiary amine compound is cationic due to the neutralization reaction, and thus has a water-soluble property. Thus, when the cationic urethane curing agent of the present invention is used in the electrodeposition coating composition, the electrical conductivity of the electrodeposition coating composition is increased to increase the internal coating property .
이와 같은 본 발명의 양이온성 우레탄 경화제는 전착 도료 조성물에 사용할 경우, 반응성이 차단되어 있던 이소시아네이트기가 일정 온도 이상에서 해리되어 전착 수지부 내에 존재하던 경화제와 함께 경화반응에 참여하게 된다. 구체적으로, 본 발명의 양이온성 우레탄 경화제를 포함하는 전착 도료 조성물을 설명하면 다음과 같다.When the cationic urethane curing agent of the present invention is used in an electrodeposition coating composition, the isocyanate group in which the reactivity is blocked is dissociated at a temperature higher than a certain temperature, and is involved in the curing reaction together with the curing agent present in the electrodeposited resin. Specifically, the electrodeposition coating composition comprising the cationic urethane curing agent of the present invention will be described as follows.
2. 전착 도료 조성물2. Electrodeposition coating composition
본 발명의 전착 도료 조성물은 전착 수지부, 안료부, 경화 첨가제부, 및 용매부를 포함한다.The electrodeposition coating composition of the present invention comprises an electrodeposition resin portion, a pigment portion, a curing additive portion, and a solvent portion.
본 발명의 전착 도료 조성물에 포함되는 전착 수지부는 도막에 주요 물성(부착성, 내식성 등)을 부여하는 역할을 한다. 이러한 전착 수지부는 도막을 형성하기 위한 전착 수지, 경화를 위한 경화제, 보조 물성 조절을 위한 제1 용매, 및 기타 첨가제 등을 포함할 수 있다.The electrodeposited resin part included in the electrodeposition coating composition of the present invention plays a role of imparting main properties (adhesion, corrosion resistance, etc.) to the coating film. The electrodeposited resin part may include an electrodeposition resin for forming a coating film, a curing agent for curing, a first solvent for controlling an auxiliary property, and other additives.
상기 전착 수지로는 전착 도료 조성물 제조 시 통상적으로 사용되는 수지를 사용할 수 있다. 구체적으로 전착 수지로는 에폭시 당량이 180 내지 2,000인 에폭시 수지를 사용할 수 있다. 상기 에폭시 수지로는 폴리페놀의 폴리글리시딜 에테르 또는 비스페놀 A와 같은 아로마틱 폴리올의 폴리글리시딜 에테르 등을 들 수 있다.As the electrodeposition resin, a resin conventionally used in the production of electrodeposition coating composition can be used. Specifically, as the electrodeposition resin, an epoxy resin having an epoxy equivalent of 180 to 2,000 can be used. Examples of the epoxy resin include polyglycidyl ether of polyphenol, polyglycidyl ether of aromatic polyol such as bisphenol A, and the like.
상기 경화제로는 통상적으로 사용되는 우레탄 경화제를 사용할 수 있다.As the curing agent, a urethane curing agent which is conventionally used may be used.
상기 제1 용매로는 통상적으로 사용되는 탈이온수, 방향족계 용매, 알코올계 용매, 케톤계 용매 등을 사용할 수 있다.Examples of the first solvent include deionized water, an aromatic solvent, an alcohol solvent, a ketone solvent, and the like.
상기 기타 첨가제로는 통상적으로 사용되는 유분개선제, 소포제 등을 사용할 수 있다.As the other additives, commonly used oil improvers and defoaming agents may be used.
이러한 전착 수지부는 전착 도료 조성물 100 중량부를 기준으로 40 내지 50 중량부로 포함될 수 있다. 상기 전착 수지부의 함량이 40 중량부 미만일 경우에는 도막의 물성이 저하될 수 있고, 50 중량부를 초과할 경우에는 저점도화로 인해 도장성이 저하될 수 있다.The electrodeposited resin may be included in an amount of 40 to 50 parts by weight based on 100 parts by weight of the electrodeposition coating composition. If the content of the electrodeposition resin portion is less than 40 parts by weight, the physical properties of the coating film may be deteriorated. If the amount is more than 50 parts by weight, paintability may be lowered due to low viscosity.
본 발명의 전착 도료 조성물에 포함되는 안료부는 도막의 기계적 강도를 높이거나 도막에 색상을 부여하는 역할을 한다. 이러한 안료부는 유무기 안료, 분산 수지, 촉매, 안정화를 위한 산 성분, 및 점도조절을 위한 제2 용매를 포함할 수 있다.The pigment part included in the electrodeposition coating composition of the present invention enhances the mechanical strength of the coating film or imparts color to the coating film. Such a pigment part may comprise an organic pigment, a dispersing resin, a catalyst, an acid component for stabilization, and a second solvent for viscosity control.
상기 유무기 안료로는 통상적으로 사용되는 유무기 안료(예를 들어, 이산화티탄, 카본블랙, 실리케이트 등)를 사용할 수 있다.As the organic or inorganic pigment, a conventional organic or inorganic pigment (for example, titanium dioxide, carbon black, silicate, etc.) may be used.
상기 분산 수지로는 통상적으로 사용되는 안료 분산용 수지를 사용할 수 있다.As the dispersion resin, a pigment dispersion resin which is conventionally used can be used.
상기 촉매로는 통상적으로 사용되는 주석계 촉매를 사용할 수 있다.As the catalyst, a tin-based catalyst which is conventionally used can be used.
상기 산 성분으로는 통상적으로 사용되는 산 성분(예를 들어, 아세트산 등)을 사용할 수 있다.As the acid component, an acid component (for example, acetic acid or the like) that is commonly used may be used.
상기 제2 용매로는 통상적으로 사용되는 탈이온수, 방향족계 용매, 알코올계 용매, 케톤계 용매 등을 사용할 수 있다.Examples of the second solvent include deionized water, an aromatic solvent, an alcohol solvent, a ketone solvent and the like which are commonly used.
이러한 안료부는 전착 도료 조성물 100 중량부를 기준으로 5 내지 10 중량부로 포함될 수 있다. 상기 안료부의 함량이 5 중량부 미만일 경우에는 도막의 기계적 강도가 저하되거나 요구되는 색상을 도막에 부여하기 어려울 수 있고, 10 중량부를 초과할 경우에는 경제성 및 도장성이 저하될 수 있다.Such a pigment part may be included in an amount of 5 to 10 parts by weight based on 100 parts by weight of the electrodeposition coating composition. If the content of the pigment part is less than 5 parts by weight, the mechanical strength of the coating film may be lowered or the desired color may not be imparted to the coating film. If the content of the pigment part is more than 10 parts by weight, economical efficiency and paintability may be deteriorated.
본 발명의 전착 도료 조성물에 포함되는 경화 첨가제부는 전착 수지부의 경화반응을 유도하는 역할을 한다. 이러한 경화 첨가제부는 양이온성 우레탄 경화제, 및 분산/점도 조절을 위한 제3 용매를 포함한다.The curing additive part included in the electrodeposition coating composition of the present invention serves to induce a curing reaction of the electrodeposited resin part. This curing additive portion comprises a cationic urethane curing agent and a third solvent for dispersion / viscosity control.
상기 양이온성 우레탄 경화제에 대한 설명은 상기 '1. 양이온성 우레탄 경화제’항목에서 설명한 바와 동일하므로 생략하기로 한다.The description of the cationic urethane curing agent is as follows. Quot; cationic urethane curing agent ", respectively.
상기 제3 용매로는 통상적으로 사용되는 탈이온수, 방향족계 용매, 알코올계 용매, 케톤계 용매 등을 사용할 수 있다.Examples of the third solvent include deionized water, an aromatic solvent, an alcohol solvent, a ketone solvent and the like which are commonly used.
이러한 경화 첨가제부는 전착 도료 조성물 100 중량부를 기준으로 1 내지 5 중량부로 포함될 수 있다. 상기 경화 첨가제부의 함량이 1 중량부 미만일 경우에는 도막의 미경화가 유발될 수 있고, 5 중량부를 초과할 경우에는 과경화로 인해 도막의 물성이 저하될 수 있다.The curing additive portion may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the electrodeposition coating composition. If the content of the curing additive part is less than 1 part by weight, the coating film may be uncured. If it exceeds 5 parts by weight, the physical properties of the coating film may be reduced due to overcuring.
본 발명의 전착 도료 조성물에 포함되는 용매부는 전착 도료 조성물의 분산성 및 점도를 조절하는 역할을 한다. 이러한 용매부는 통상적으로 사용되는 제4 용매를 포함하는 것으로, 상기 제4 용매로는 탈이온수, 방향족계 용매, 알코올계 용매, 케톤계 용매 등을 사용할 수 있다.The solvent portion included in the electrodeposition coating composition of the present invention has a role of controlling the dispersibility and viscosity of the electrodeposition coating composition. Such a solvent portion includes a commonly used fourth solvent, and as the fourth solvent, deionized water, an aromatic solvent, an alcohol solvent, a ketone solvent and the like can be used.
이러한 용매부는 전착 도료 조성물 100 중량부를 기준으로 40 내지 50 중량부로 포함될 수 있다. 상기 용매부의 함량이 40 중량부 미만일 경우에는 저점도화로 인해 도장성이 저하될 수 있고, 50 중량부를 초과할 경우에는 도막의 물성이 저하되거나 경화에 장시간이 소비될 수 있다.Such a solvent portion may be contained in an amount of 40 to 50 parts by weight based on 100 parts by weight of the electrodeposition coating composition. If the content of the solvent portion is less than 40 parts by weight, the coating property may be lowered due to the lower viscosity. If the content of the solvent portion is more than 50 parts by weight, physical properties of the coating film may be deteriorated or a long time may be required for curing.
이와 같은 본 발명의 전착 도료 조성물은 고형분의 함량이 중량기준으로 15 내지 25 %일 수 있다.The electrodeposition coating composition of the present invention may have a solid content of 15 to 25% by weight.
본 발명의 전착 도료 조성물은 통상적인 전착 도장 방법을 통해 도장될 수 있다. 구체적으로 전착 도료 조성물을 음극 기재와 양극 기재에 각각 접촉시킨 후 수 V 내지 수백 V에 이르는 직류전압을 인가하여 전착 도장을 수행할 수 있다. 상기 전착 도장 후에는 수세 공정과 경화공정을 거쳐 경화된 도막을 형성할 수 있다.The electrodeposition coating composition of the present invention can be applied by a conventional electrodeposition coating method. Specifically, the electrodeposition coating composition may be brought into contact with the cathode substrate and the cathode substrate, respectively, and a DC voltage ranging from several V to several hundreds V may be applied to perform the electrodeposition coating. After the electrodeposition coating, a cured coating film can be formed through a water washing step and a curing step.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
[[ 실시예Example 1] 경화 첨가제부 1 제조 1] Preparation of curing additive part 1
에탄올아민 62.7 g을 반응기에 투입하고 60 ℃로 승온시킨 후 글리시딜 에스테르(Shell사, Cardura E-10P) 498.0 g을 1-2시간 동안 천천히 적가하였다. 적가를 완료한 후 질소 분위기 하에서 반응기의 온도를 80 ℃로 승온시키고 4-8시간 동안 반응을 유지시킨 후 적정을 통하여 잔류 에폭시기의 유무를 확인하였다.Ethanolamine (62.7 g) was added to the reactor and the temperature was raised to 60 ° C. Then, 498.0 g of glycidyl ester (Shell, Cardura E-10P) was slowly added dropwise for 1 to 2 hours. After completion of dropwise addition, the temperature of the reactor was raised to 80 DEG C under a nitrogen atmosphere, and the reaction was maintained for 4-8 hours, and the presence or absence of residual epoxy groups was confirmed through titration.
잔류 에폭시기가 없는 것으로 확인되면 메틸 이소부틸 케톤 36.8 g을 추가한 후 온도를 80 내지 90 ℃로 유지시키면서 폴리머릭 메틸렌디페닐 디이소시아네이트(다우케미컬, PAPI2940) 139.3 g을 2시간에 걸쳐 적가하였다. 적가를 완료한 후 질소 분위기 하에서 반응물을 90 ℃에서 90분 이상 방치하여 NCO-가 전혀 남아있지 않도록 하였다.When it was confirmed that there was no residual epoxy group, 36.8 g of methyl isobutyl ketone was added, and 139.3 g of polymeric methylene diphenyl diisocyanate (PAPI2940) was added dropwise over 2 hours while maintaining the temperature at 80 to 90 ° C. After the dropwise addition was completed, the reaction was allowed to stand at 90 DEG C for 90 minutes or more in a nitrogen atmosphere so that no NCO- remained.
잔류 NCO-가 없는 것으로 확인되면 반응물의 온도를 60 ℃까지 냉각한 후 초산(99.5%) 49.3 g을 추가하고 30분 동안 교반시킨 후 부틸셀로솔브 86.7 g을 추가하여 반응물을 희석하고 탈이온수 127.2 g을 추가하여 수용화하는 과정을 거쳐 경화 첨가제부 1을 제조하였다(중화율: 80 %).After confirming that there is no residual NCO-, the temperature of the reaction was cooled to 60 ° C, and then 49.3 g of acetic acid (99.5%) was added. After stirring for 30 minutes, 86.7 g of butyl cellosolve was added to dilute the reaction and deionized water 127.2 g to obtain a curing additive part 1 (neutralization ratio: 80%).
[[ 실시예Example 2] 경화 첨가제부 2 제조 2] Production of curing additive part 2
에탄올아민 대신에 2-메틸아미노에탄올을 사용한 것을 제외하고는 실시예 1과 동일한 과정을 거쳐 경화 첨가제부 2를 제조하였다(중화율: 80 %).Except that 2-methylaminoethanol was used in place of ethanolamine, to prepare a curing additive part 2 (neutralization ratio: 80%).
[[ 실시예Example 3] 경화 첨가제부 3 제조 3] Preparation of curing additive part 3
에탄올아민과 글리시딜 에스테르를 반응시킨 것 대신에 2-디메틸 아미노에탄올을 사용한 것을 제외하고는 실시예 1과 동일한 과정을 거쳐 경화 첨가제부 3을 제조하였다(중화율: 80 %).A curing additive part 3 was prepared in the same manner as in Example 1 except that 2-dimethylamino ethanol was used instead of reacting ethanolamine and glycidyl ester (neutralization ratio: 80%).
[[ 실시예Example 4] 4] 안료부Pigment part 제조 Produce
안료용 분산수지(KCC사. 양이온 안료 분산 수지) 227.3 g을 반응기에 투입하고, 초산(50%) 3.0 g, 카본블랙 3.0 g, 디부틸틴 옥사이드 49.6 g, 이산화티탄(케머러스사, R900) 226.5 g, 알루미늄 실리케이트(BASF사, Sationtone 5HB) 95.9 g을 교반하면서 순차적으로 첨가하였다. 다음, 점도를 조절하기 위해 탈이온수 150.0 g을 1차적으로 첨가하여 균일화되도록 교반한 후 탈이온수 244.7 g을 2차적으로 첨가하여 희석하였다. 다음, SL-703(BYK사) 분산기로 헤그만 번호 8+가 될 때까지 분산시켰다.(50%), 3.0 g of carbon black, 49.6 g of dibutyltin oxide, titanium dioxide (manufactured by KEMERUS Co., Ltd., R900) were added to a reactor, and 227.3 g of a dispersion resin for pigment (KCC Co., And 95.9 g of aluminum silicate (BASF, Sationtone 5HB) were added sequentially with stirring. Next, to adjust the viscosity, 150.0 g of deionized water was firstly added, stirred to homogenize, and then diluted by addition of 244.7 g of deionized water. Then, the mixture was dispersed by a SL-703 (BYK) dispersing machine until the hem number became 8+.
[[ 실시예Example 5] 전착 5] electrodeposition 수지부Resin part 제조 Produce
디글리시딜 에테르(국도화학, 에폰 828) 140.2 g, 비스페놀 A 59.7 g 및 프로필렌 글리콜 모노메틸 에테르 9.8 g을 반응기에 투입하고, 질소 분위기 하에 140 ℃로 가열한 후 벤질디메틸아민 0.7 g을 첨가하였다. 다음, 반응 혼합물을 약 185 ℃로 자연 발열시킨 후 환류시키고, 존재하는 물을 공비 제거한 후 20-40분 동안 방치하였다. 상기 반응 혼합물의 에폭시 당량이 900-950에 도달하면 충분히 교반시키면서 우레탄 경화제를 첨가하고 30분 동안 교반시키면서 온도가 100-110 ℃가 될 때까지 냉각하였다. 그 다음, 73% 메틸이소부틸케톤 용액(에어프로덕츠사, KT22) 14.9 g과 디에탄올아민 16.8 g을 첨가하면서 반응 혼합물을 발열시킨 후 온도를 120 ℃로 유지시켰다. 다음, 반응 혼합물에 진공을 걸어 고형분이 중량기준으로 96 %가 될 때까지 진공회수하여 용매를 제거(-41 g)한 후 70% 메탄 설포닉 에시드(BASF사) 12.4 g과 탈이온수 332.6 g을 첨가하여 분산시켰다. 그 다음, 분산액에 탈이온수 280 g을 서서히 첨가하여 희석시켜 고형분이 중량기준으로 36 %인 전착 수지부를 제조하였다.140.2 g of diglycidyl ether (Kido Chemical, Epon 828), 59.7 g of bisphenol A and 9.8 g of propylene glycol monomethyl ether were charged into a reactor, heated to 140 DEG C under a nitrogen atmosphere, and then 0.7 g of benzyldimethylamine was added . The reaction mixture was then spontaneously heated to about 185 째 C, refluxed, and the existing water was azeotropically removed and left for 20-40 minutes. When the epoxy equivalent of the reaction mixture reached 900-950, the urethane curing agent was added while stirring sufficiently, and the mixture was cooled to 100-110 캜 while stirring for 30 minutes. Then, while 14.9 g of a 73% methyl isobutyl ketone solution (KT22, manufactured by Air Products) and 16.8 g of diethanolamine were added, the reaction mixture was heated, and then the temperature was maintained at 120 ° C. Then, the reaction mixture was vacuum-dried to remove the solvent (-41 g) by vacuum recovery until the solid content reached 96% by weight, and then 12.4 g of 70% methanesulfonic acid (BASF) and 332.6 g of deionized water And dispersed. Then, 280 g of deionized water was slowly added to the dispersion to dilute it to prepare an electrodeposited resin portion having a solid content of 36% by weight.
이때, 우레탄 경화제는 다음과 같이 제조된 것을 사용하였다.At this time, the urethane curing agent was prepared as follows.
폴리머릭 메틸렌디페닐 디이소시아네이트(다우케미컬, PAPI2940) 382.6 g, 메틸 이소부틸 케톤 199.9 g, 및 디부틸주석 디라우레이트 0.1 g을 반응기에 투입하고, 질소 분위기 하에서 30 ℃로 가열하였다. 다음, 온도를 60-65 ℃로 유지하면서 2-(2-부톡시에톡시)에탄올 398 g을 서서히 첨가하였다. 그 다음, 반응 혼합물을 65 ℃에서 90분 동안 방치하였다. 다음, 트리메틸올 프로판 19.4 g을 첨가하고 110 ℃로 가열한 후 이 온도에서 3시간 동안 방치하고 적외선 분석에 의해 미반응 NCO-가 전혀 남아있지 않을 때까지 계속 110 ℃로 방치하는 과정을 거쳐 우레탄 경화제를 제조하였다.382.6 g of polymeric methylene diphenyl diisocyanate (Dow Chemical, PAPI2940), 199.9 g of methyl isobutyl ketone, and 0.1 g of dibutyltin dilaurate were charged into the reactor and heated to 30 DEG C under a nitrogen atmosphere. Then 398 g of 2- (2-butoxyethoxy) ethanol was slowly added while maintaining the temperature at 60-65 占 폚. The reaction mixture was then allowed to stand at 65 DEG C for 90 minutes. Then, 19.4 g of trimethylolpropane was added, and the mixture was heated to 110 ° C., left at this temperature for 3 hours, and kept at 110 ° C. until no unreacted NCO- remained by infrared analysis. Thus, a urethane curing agent .
[[ 제조예Manufacturing example 1 내지 3 및 1 to 3 and 비교제조예Comparative Manufacturing Example 1] 전착 도료 조성물 제조 1] Preparation of Electrodeposition Coating Composition
하기 표 2의 조성으로 각 성분을 혼합하여 전착 도료 조성물을 제조하였다.The components shown in Table 2 were mixed to prepare an electrodeposition coating composition.
(탈이온수)Solvent portion
(Deionized water)
경화 첨가제부
Curing additive part
[[ 실험예Experimental Example 1] One]
28 ℃ 조건에서 제조예 및 비교제조예 각각의 전착 도료 조성물에 180초 동안 일정한 전압을 인가하여 전착 도장을 실시하였다. 이때, 전착 도장 시편으로는 인산아연으로 전처리된 강판을 사용하였다. 다음, 전착 도장된 시편을 150-160 ℃의 오븐에 투입하고 25분 동안 경화시켜 도막을 형성하였다. 이후, 물성을 다음과 같은 방법으로 평가하였으며, 그 결과를 하기 표 3에 나타내었다.Electrodeposition coating was performed by applying a constant voltage for 180 seconds to each of the electrodeposition coating compositions of the Production Examples and Comparative Production Examples at 28 占 폚. At this time, a steel sheet pretreated with zinc phosphate was used as the electrodeposition coating specimen. Next, the electrodeposited coated specimen was placed in an oven at 150-160 DEG C and cured for 25 minutes to form a coating film. Then, the physical properties were evaluated by the following methods, and the results are shown in Table 3 below.
1. 내부침투성(cm): 10×30 ㎝ 시편 두 장 사이의 양끝에 PVC 막대를 대어 투명 테이프로 고정시키고, 전착 도료 조성물에 시편 25 ㎝를 담그고 상술한 과정으로 전착 도장을 실시한 후 앞 시편의 뒷면에 도장된 높이를 측정함.1. Permeability (cm): 10 × 30 cm The PVC rod was placed on both ends of two specimens and fixed with a transparent tape. After immersing 25 cm of the specimen in the electrodeposition coating composition, electrodeposition was carried out as described above. Measure the painted height on the back.
2. 조도값(Ra): 테일러-홉슨(Taylor-Hobson)사의 surtronic3+를 이용하여 도막의 표면조도를 측정함.2. Roughness (Ra): The surface roughness of the coating is measured using a Taylor-Hobson surtronic 3+.
3. 기계적 물성(mm): 도장된 시편에 반경 1.5 ㎝의 구를 이용하여 압력을 가한 후 도막이 벗겨지거나 깨지는 시점에서 시편의 패인 깊이를 측정함.3. Mechanical properties (mm): The depth of the specimen is measured at the point where the coating peels or breaks after applying pressure to the coated specimen using a 1.5 ㎝ radius sphere.
4. 경화성: 1 ㎏의 하중을 가하면서 MIBK(Methyl isobutyl ketone)를 침지시킨 천을 10회 왕복하여 도막의 표면 변화, 또는 전착 도료 조성물이 천에 묻어나는지 여부를 확인함.4. Curability: A cloth immersed with MIBK (Methyl isobutyl ketone) was applied 10 times while applying a load of 1 kg to check whether the surface of the coating was changed or whether the electrodeposition coating composition appeared on the cloth.
×: 전착 도료 조성물이 천에 많이 묻어남X: The electrodeposition coating composition was buried in a lot of cloth
△: 전착 도료 조성물이 천에 약하게 묻어남?: The electrodeposition coating composition was slightly buried in the cloth
○: 전착 도료 조성물이 천에 묻어나지 않으나 도막의 표면 변화가 있음○: Electrodeposition coating composition does not float on the cloth, but the surface of the coating film changes.
◎: 전착 도료 조성물이 천에 묻어나지 않으며, 도막의 표면 변화가 없음&Amp; cir &: The electrodeposition coating composition does not deposit on the cloth, and the surface of the coating film does not change.
5. 내식성(mm): 염수분무시험(Salt-fog) 기기를 이용하여 도장된 시편을 1,000시간 동안 시험한 후 투명테이프로 박리(peel-off) 테스트를 진행하여 도막박리 거리를 측정함.5. Corrosion resistance (mm): The coated specimen is tested for 1,000 hours using a salt-fog apparatus, and peel-off test is performed with transparent tape to measure the film peel distance.
상기 표 3을 참조하면, 본 발명의 양이온성 우레탄 경화제가 첨가된 전착 도료 조성물로 전착 도장을 실시함에 따라 비교적 저온에서도 경화성이 확보되면서 전착 도료 조성물의 내부도장성이 우수하고 내식성 및 강도 등이 우수한 도막이 형성되는 것을 확인할 수 있다.Referring to Table 3, when the electrodeposition coating composition containing the cationic urethane curing agent of the present invention is applied, the curability is secured even at a relatively low temperature, so that the electrodeposition coating composition is excellent in internal stiffness and excellent in corrosion resistance and strength It can be confirmed that a coating film is formed.
Claims (11)
상기 3급 아민 화합물은 1급 아민 화합물, 또는 2급 아민 화합물을 모노에폭사이드와 반응시켜 얻어지는 것인 양이온성 우레탄 경화제.The method according to claim 1,
Wherein the tertiary amine compound is obtained by reacting a primary amine compound or a secondary amine compound with a monoepoxide.
상기 1급 아민 화합물은 에탄올아민, 3-아미노-1-프로판올, 아미노-2-프로판올, 2-아미노-2-메틸-1-프로판올, 2-아미노-3-메틸-1-부탄올, 및 5-아미노-1-펜탄올로 이루어진 군에서 선택된 1종 이상인 것인 양이온성 우레탄 경화제.The method of claim 2,
The primary amine compound is selected from the group consisting of ethanolamine, 3-amino-1-propanol, amino-2-propanol, Amino-1-pentanol, and mixtures thereof.
상기 2급 아민 화합물은 2-메틸아미노에탄올, 2-에틸아미노에탄올, 3-메틸아미노-1-프로판올, 및 2-이소프로필아미노에탄올로 이루어진 군에서 선택된 1종 이상인 것인 양이온성 우레탄 경화제.The method of claim 2,
Wherein said secondary amine compound is at least one selected from the group consisting of 2-methylamino ethanol, 2-ethylamino ethanol, 3-methylamino-1-propanol, and 2-isopropylamino ethanol.
상기 모노에폭사이드는 글리시딜 아크릴레이트, 글리시딜 메타크릴레이트, 글리시딜 아세테이트, 글리시딜 부티레이트, 글리시딜 팔미테이트, 글리시딜 라우레이트, 부틸 글리시딜 에테르, 2-에틸헥실 글리시딜 에테르, 페닐 글리시딜 에테르, 및 P-(3급부틸)페닐 글리시딜 에테르로 이루어진 군에서 선택된 1종 이상인 것인 양이온성 우레탄 경화제.The method of claim 2,
Wherein the monoepoxide is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, glycidyl acetate, glycidyl butyrate, glycidyl palmitate, glycidyl laurate, butyl glycidyl ether, 2-ethyl Wherein the at least one cationic urethane curing agent is at least one selected from the group consisting of hexyl glycidyl ether, phenyl glycidyl ether, and P- (tertiary butyl) phenyl glycidyl ether.
상기 모노에폭사이드가 하기 화학식 1로 표시되는 화합물인 것인 양이온성 우레탄 경화제.
[화학식 1]
(상기 화학식 1에서, R1 및 R2는 서로 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 10의 알킬기이다.)The method of claim 2,
Wherein the monoepoxide is a compound represented by the following formula (1).
[Chemical Formula 1]
Wherein R 1 and R 2 are the same or different and each independently an alkyl group having 1 to 10 carbon atoms.
상기 3급 아민 화합물은 2-디메틸아미노에탄올, 1-디메틸아미노-2-프로판올, 3-디메틸아미노-1-프로판올, 2-디에틸아미노에탄올, 4-디메틸아미노-1-부탄올, 2-디메틸아미노-2-메틸프로판올, 및 4-디메틸아미노-1-부탄올로 이루어진 군에서 선택된 1종 이상인 것인 양이온성 우레탄 경화제.The method according to claim 1,
The tertiary amine compound may be selected from the group consisting of 2-dimethylaminoethanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-diethylaminoethanol, Methyl propanol, and 4-dimethylamino-1-butanol.
상기 이소시아네이트 화합물은 4,4'-메틸렌비스(페닐이소시아네이트), 4-메틸-1,3-페닐렌 디이소시아네이트, 폴리머릭 메틸렌디페닐 디이소시아네이트, 헥사메틸렌디이소시아네이트, 크실릴렌디이소시아네이트, 2,4,6-트리이소프로필페닐디이소시아네이트, 디페닐에테르디이소시아네이트, 이소포론디이소시아네이트, 4,4'-디시클로헥실메탄디이소시아네이트, 테트라메틸크실렌디이소시아네이트, 2,2,4-트리메틸헥사메틸렌디이소시아네이트, 및 2,4,4-트리메틸헥사메틸렌디이소시아네이트로 이루어진 군에서 선택된 1종 이상인 것인 양이온성 우레탄 경화제.The method according to claim 1,
Examples of the isocyanate compound include 4,4'-methylene bis (phenyl isocyanate), 4-methyl-1,3-phenylene diisocyanate, polymeric methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,4 , 6-triisopropylphenyl diisocyanate, diphenyl ether diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate , And 2,4,4-trimethylhexamethylene diisocyanate. The cationic urethane curing agent according to claim 1,
상기 산 중화제는 초산, 젖산, 개미산, 술폰산, 및 메탄술폰산으로 이루어진 군에서 선택된 1종 이상인 것인 양이온성 우레탄 경화제.The method according to claim 1,
Wherein the acid neutralizing agent is at least one selected from the group consisting of acetic acid, lactic acid, formic acid, sulfonic acid, and methanesulfonic acid.
상기 반응물과 상기 산 중화제의 중화율이 하기 수학식 1로 정의되며,
상기 중화율이 5 내지 150 %인 것인 양이온성 우레탄 경화제.
[수학식 1]
(산 중화제의 산 당량/반응물의 아민 당량)×100The method according to claim 1,
Wherein the neutralization ratio of the reactant and the acid neutralizer is defined by the following equation (1)
Wherein the neutralization ratio is 5 to 150%.
[Equation 1]
(Acid equivalent of acid neutralizer / amine equivalent of reactant) x 100
안료부,
청구항 1 내지 청구항 10 중 어느 한 항에 따른 양이온성 우레탄 경화제를 포함하는 경화 첨가제부, 및
용매부를 포함하는 전착 도료 조성물.Electrodeposited resin portion,
Pigment part,
A curing additive portion comprising a cationic urethane curing agent according to any one of claims 1 to 10, and
And a solvent portion.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170100363A KR102042239B1 (en) | 2017-08-08 | 2017-08-08 | Cationic urethane curing agent and electro-deposition paint composition comprising the same |
| PCT/KR2018/009032 WO2019031844A1 (en) | 2017-08-08 | 2018-08-08 | Cationic urethane curing agent and electrodeposition paint composition comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170100363A KR102042239B1 (en) | 2017-08-08 | 2017-08-08 | Cationic urethane curing agent and electro-deposition paint composition comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20190016303A true KR20190016303A (en) | 2019-02-18 |
| KR102042239B1 KR102042239B1 (en) | 2019-11-08 |
Family
ID=65271661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020170100363A Active KR102042239B1 (en) | 2017-08-08 | 2017-08-08 | Cationic urethane curing agent and electro-deposition paint composition comprising the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR102042239B1 (en) |
| WO (1) | WO2019031844A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117362589B (en) * | 2023-11-01 | 2024-05-10 | 湖北泊瑞高分子材料有限公司 | Antibacterial flexible aqueous epoxy resin curing agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61233068A (en) * | 1985-04-10 | 1986-10-17 | Nippon Oil & Fats Co Ltd | Production of resin for cationic electrodeposition coating |
| KR19980080601A (en) | 1997-03-25 | 1998-11-25 | 후지이히로시 | Cationic Electrodeposition Coating Composition |
| KR20070009662A (en) * | 2004-03-31 | 2007-01-18 | 아사히 가세이 케미칼즈 가부시키가이샤 | Curing agent for epoxy resin and epoxy resin composition |
| WO2009005135A1 (en) * | 2007-07-05 | 2009-01-08 | Asahi Kasei E-Materials Corporation | Curing agent for epoxy resin and curing agent composition for epoxy resin |
| KR20090027370A (en) * | 2007-09-12 | 2009-03-17 | 주식회사 케이씨씨 | Process for producing blocked polyisocyanate curing agent, and cationic resin composition and electrodeposition coating composition for electrodeposition paint comprising the curing agent |
| KR20100036708A (en) * | 2008-09-30 | 2010-04-08 | 주식회사 케이씨씨 | Resin composition for cathodic electrodeposition coating with good throw power comprising aromatic sulfonic acid and urethane-fuctional rheology control agent |
| KR20140135471A (en) * | 2013-05-16 | 2014-11-26 | 주식회사 케이씨씨 | Method for preparing urethane curing agent for electrodeposition paint, a cationic resin composition for electrodeposition paint and an electrodeposition paint composition comprising the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3809695A1 (en) * | 1988-03-23 | 1989-10-12 | Hoechst Ag | HARDENERS FOR SYNTHETIC RESINS, THESE CONTAINABLE MIXTURES AND THE USE THEREOF |
| US6398934B1 (en) * | 2000-10-19 | 2002-06-04 | E. I. Du Pont De Nemours And Company | Concentrate suitable for the preparation of cathodic electrodeposition coating compositions |
| KR100929040B1 (en) * | 2007-01-23 | 2009-11-26 | 주식회사 케이씨씨 | Electrodeposit coating composition comprising a method for producing a cationic microgel for electrodeposition paint and a microgel manufactured therefrom |
-
2017
- 2017-08-08 KR KR1020170100363A patent/KR102042239B1/en active Active
-
2018
- 2018-08-08 WO PCT/KR2018/009032 patent/WO2019031844A1/en not_active Ceased
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61233068A (en) * | 1985-04-10 | 1986-10-17 | Nippon Oil & Fats Co Ltd | Production of resin for cationic electrodeposition coating |
| KR19980080601A (en) | 1997-03-25 | 1998-11-25 | 후지이히로시 | Cationic Electrodeposition Coating Composition |
| KR20070009662A (en) * | 2004-03-31 | 2007-01-18 | 아사히 가세이 케미칼즈 가부시키가이샤 | Curing agent for epoxy resin and epoxy resin composition |
| WO2009005135A1 (en) * | 2007-07-05 | 2009-01-08 | Asahi Kasei E-Materials Corporation | Curing agent for epoxy resin and curing agent composition for epoxy resin |
| KR20090027370A (en) * | 2007-09-12 | 2009-03-17 | 주식회사 케이씨씨 | Process for producing blocked polyisocyanate curing agent, and cationic resin composition and electrodeposition coating composition for electrodeposition paint comprising the curing agent |
| KR20100036708A (en) * | 2008-09-30 | 2010-04-08 | 주식회사 케이씨씨 | Resin composition for cathodic electrodeposition coating with good throw power comprising aromatic sulfonic acid and urethane-fuctional rheology control agent |
| KR20140135471A (en) * | 2013-05-16 | 2014-11-26 | 주식회사 케이씨씨 | Method for preparing urethane curing agent for electrodeposition paint, a cationic resin composition for electrodeposition paint and an electrodeposition paint composition comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019031844A1 (en) | 2019-02-14 |
| KR102042239B1 (en) | 2019-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1030894B2 (en) | Conductive organic coatings | |
| EP0789732B1 (en) | Cationic resin and capped polyisocyanate curing agent suitable for use in electrodeposition | |
| TW201518443A (en) | Blocked isocyanate, coating composition, adhesive agent composition, and article | |
| JP6795435B2 (en) | Epoxy viscous agent and cationic electrodeposition coating composition | |
| KR20020077265A (en) | Method for preventing cratering of cationic electrodeposition coating, and anti-cratering agent used therefor | |
| KR101517191B1 (en) | Urethane curing agent for electrodeposition coating with improved appearance and corrosion resistance, and a cationic resin composition for electrodeposition paint and an electrodeposition coating composition comprising the same | |
| US6410146B2 (en) | Cationic electrodeposition coating composition | |
| US9193878B2 (en) | Anticrater agent for electrocoating composition | |
| US11034855B2 (en) | Cationic electrodeposition coating material composition | |
| EP3771720B1 (en) | Blocked polyisocyanate composition, resin composition, resin film and laminate | |
| EP3354701B1 (en) | Method for preparing cationic electrodeposition coating composition | |
| DE69532410T2 (en) | HARDENABLE COMPOSITION | |
| KR100929040B1 (en) | Electrodeposit coating composition comprising a method for producing a cationic microgel for electrodeposition paint and a microgel manufactured therefrom | |
| KR101858272B1 (en) | Method for preparing urethane curing agent for electrodeposition paint, a cationic resin composition for electrodeposition paint and an electrodeposition paint composition comprising the same | |
| KR20190016303A (en) | Cationic urethane curing agent and electro-deposition paint composition comprising the same | |
| US20090321270A1 (en) | Electroconductivity-controlling agent for cationic electrodeposition coating composition and method for adjusting electroconductivity of cationic electrodeposition coating composition therewith | |
| KR20090027370A (en) | Process for producing blocked polyisocyanate curing agent, and cationic resin composition and electrodeposition coating composition for electrodeposition paint comprising the curing agent | |
| KR20060129973A (en) | Preparation Method of Amine Modified Epoxy Resin and Cationic Electrodeposition Coating Composition | |
| US20220332960A1 (en) | Cationic electrodeposition coating composition | |
| KR102229059B1 (en) | Electrodeposition Resin Composition and Electrodeposition Paint Comprising The Same | |
| JP2002129100A (en) | Cationic electrodeposition paint composition | |
| KR20210152299A (en) | Cationic urethane curing additive | |
| KR100804416B1 (en) | High functional cationic electrodeposition resin composition excellent in rust resistance and curability | |
| JP2020164626A (en) | Cationic electrodeposition coating composition | |
| EP3354700A1 (en) | Method for preparing cationic electrodeposition coating material composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| PA0109 | Patent application |
St.27 status event code: A-0-1-A10-A12-nap-PA0109 |
|
| PA0201 | Request for examination |
St.27 status event code: A-1-2-D10-D11-exm-PA0201 |
|
| D13-X000 | Search requested |
St.27 status event code: A-1-2-D10-D13-srh-X000 |
|
| D14-X000 | Search report completed |
St.27 status event code: A-1-2-D10-D14-srh-X000 |
|
| PG1501 | Laying open of application |
St.27 status event code: A-1-1-Q10-Q12-nap-PG1501 |
|
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
St.27 status event code: A-1-2-D10-D21-exm-PE0902 |
|
| T11-X000 | Administrative time limit extension requested |
St.27 status event code: U-3-3-T10-T11-oth-X000 |
|
| T11-X000 | Administrative time limit extension requested |
St.27 status event code: U-3-3-T10-T11-oth-X000 |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
St.27 status event code: A-1-2-D10-D22-exm-PE0701 |
|
| PN2301 | Change of applicant |
St.27 status event code: A-3-3-R10-R13-asn-PN2301 St.27 status event code: A-3-3-R10-R11-asn-PN2301 |
|
| PR0701 | Registration of establishment |
St.27 status event code: A-2-4-F10-F11-exm-PR0701 |
|
| PR1002 | Payment of registration fee |
St.27 status event code: A-2-2-U10-U11-oth-PR1002 Fee payment year number: 1 |
|
| PG1601 | Publication of registration |
St.27 status event code: A-4-4-Q10-Q13-nap-PG1601 |
|
| PR1001 | Payment of annual fee |
St.27 status event code: A-4-4-U10-U11-oth-PR1001 Fee payment year number: 4 |
|
| PR1001 | Payment of annual fee |
St.27 status event code: A-4-4-U10-U11-oth-PR1001 Fee payment year number: 5 |
|
| R18-X000 | Changes to party contact information recorded |
St.27 status event code: A-5-5-R10-R18-oth-X000 |
|
| PR1001 | Payment of annual fee |
St.27 status event code: A-4-4-U10-U11-oth-PR1001 Fee payment year number: 6 |
|
| L13 | Limitation or reissue of ip right requested |
Free format text: ST27 STATUS EVENT CODE: A-2-3-L10-L13-LIM-X000 (AS PROVIDED BY THE NATIONAL OFFICE) |
|
| L13-X000 | Limitation or reissue of ip right requested |
St.27 status event code: A-2-3-L10-L13-lim-X000 |
|
| PR1001 | Payment of annual fee |
St.27 status event code: A-4-4-U10-U11-oth-PR1001 Fee payment year number: 7 |