KR19980061680A - Color-transparent, one-part coating composition - Google Patents
Color-transparent, one-part coating composition Download PDFInfo
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- KR19980061680A KR19980061680A KR1019960081052A KR19960081052A KR19980061680A KR 19980061680 A KR19980061680 A KR 19980061680A KR 1019960081052 A KR1019960081052 A KR 1019960081052A KR 19960081052 A KR19960081052 A KR 19960081052A KR 19980061680 A KR19980061680 A KR 19980061680A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
본 발명은 칼라-투명 1액형 도료 조성물에 관한 것으로서, 특히 자동차 상도용으로 적당한 도료 조성물에 관한 것이다.FIELD OF THE INVENTION The present invention relates to color-transparent, one-part coating compositions, and in particular to coating compositions suitable for automotive coatings.
본 발명의 칼라-투명 1액형 도료 도성물은 주제로서 분자내에 적어도 2개 이상의 수산기를 함유하는 폴리올과, 경화제로서 분자내에 적어도 1개 이상의 반응성 실란을 함유하며 이소시아네이트기가 봉쇄된 폴리올 변성 이소시아네이트를 사용하고, 여기에 도료 제조에 통상적으로 쓰이는 희석제, 안료 및 기타 성분들이 선택적으로 함유되도록 한 것이다.The color-transparent, one-part coating composition of the present invention uses a polyol containing at least two or more hydroxyl groups in a molecule as a subject, and a polyol-modified isocyanate containing at least one reactive silane in a molecule as a curing agent and containing an isocyanate group. It is intended to optionally contain diluents, pigments and other components commonly used in paint preparation.
이와 같이 구성된 1액형 도료 조성물은 폴리올변성 이소시아네이트를 기재로 사용하여 상용성 및 용해도가 매우 양호한 동시에 분자내 함유된 반응성 실란을 통해 타소지와의 우수한 밀착성 발현이 가능하여 재도장시 부착 불량이 발생하지 않으며, 또한 경화후 도막내에 형성된 실록산 결합부위의 놓은 결합에너지로 경도 및 내흠집성의 향상은 물론 내산성이 극히 우수한 도막을 형성할 수 있는 장점을 갖는다.The one-component coating composition configured as described above has excellent compatibility and solubility using polyol-modified isocyanate as a substrate, and at the same time, excellent adhesion to other materials can be expressed through reactive silanes contained in the molecule, so that poor adhesion occurs during repainting. In addition, it has the advantage of improving the hardness and scratch resistance of the siloxane bond portion formed in the coating film after curing, as well as forming a coating film excellent in acid resistance.
Description
본 발명은 칼라-투명 1액형 도료 조성물에 관한 것으로서, 보다 상세하게는 상용성 및 용해도가 우수하고 타소지와의 밀착성이 우수하여 재도장시 부착 불량이 발생하지 않으며 또한 경화 도막의 경도, 내흠집성 및 내산성이 우수한 도막을 형성할 수 있어 솔리드 칼라 및 칼라-투명 도장용, 특히 자동차 상도용으로 적합한 1액형 도료 조성물에 관한 것이다.The present invention relates to a color-transparent one-part coating composition, and more particularly, has excellent compatibility and solubility, and excellent adhesion to other materials, so that poor adhesion does not occur when repainting and hardness and scratch resistance of the cured coating film. The present invention relates to a one-part coating composition suitable for solid color and color-transparent coating, particularly for automotive top coat, because it can form a coating film having excellent resistance and acid resistance.
최근들어 자동차 상도 도장은 색감만을 내기 위한 칼라 도장 마감형태인 솔리드칼라 도장에서 투명도료를 덧도장하는 형식의 칼라-투명 도장이 널리 선호되고 있으며, 이러한 칼라도료 조성물은 USP 4220679, USP 4403003 및 USP 4147569 등에 개시된 바 있다.Recently, automotive top coats have been widely favored in the form of color-transparent coatings in the form of a solid color coating, which is a color-coated finish for producing only a sense of color, and such color coating compositions are USP 4220679, USP 4403003 and USP 4147569. And the like.
이와 같이 칼라-투명 도장이 선호되는 이유 중의 하나는 광택, 영상 선명성(Distinctness of Image) 등 외관 면에서 매우 뛰어나기 때문이다. 이러한 소비자의 외관 중시 경향은 자동차 자동세척기의 급속한 보급으로 인해 내흠집성 개량에 대한 또다른 요구 현상으로 이어지고 있다. 그러나 자동세척기에 의한 흠집 발생 현상은 손세척의 경우에 비해 매우 다른 양상으로 나타난다. 그것은 가해지는 힘의 크기, 속도, 방향 및 접촉물질의 형상, 경도, 마찰계수의 차이점 등 물리적 현상에 기인하는 것으로 그 개량에 어려움을 더하고 있다. 더욱이 날로 심해지고 있는 산성비, 대기 오염 등의 문제는 도막의 손상을 가중시킴으로서 내산성이 우수한 도막의 개발을 부추기고 있는 실정이다. 예로서 검은색 도막의 경우 여름철에 70℃ 이상까지 상승하는 경우도 종종 있으며 산성비에 젖었던 부위는 Ph가 3∼4 까지 달하므로 매우 심한 도막 손상을 초래하게 된다.One reason why color-transparent coating is preferred is that it is very good in terms of appearance such as gloss and distinctness of image. This trend toward consumer appearance is leading to another demand for improvement of scratch resistance due to the rapid spread of auto washing machines. However, the phenomenon of scratches caused by the automatic washing machine is very different from that of the hand washing machine. It is due to physical phenomena such as the magnitude of the applied force, the speed, the direction, and the difference in the shape, hardness, and friction coefficient of the contacting material. In addition, the problems of acid rain, air pollution, etc., which are increasing day by day, increase the damage of the coating film, and thus, encourage the development of the coating film having excellent acid resistance. For example, the black coating film is often raised to more than 70 ℃ in the summer, and the area wetted by acid rain reaches 3 to 4, causing very severe coating damage.
이러한 예로서 아크릴릭폴리올-멜라민을 사용하는 경화 도막은 외관이 우수하며 가격적인 면에서 매우 유리한 장점이 있어 널리 사용되어 왔다. 그러나 산성비에 해리되기 쉬운 에테르 부위를 다량 함유함으로서 도막의 내산성이 매우 취약하여 그 개량이 요구되고 있다.As such an example, a cured coating film using an acrylic polyol-melamine has been widely used because of its excellent appearance and very advantageous price. However, the acid resistance of a coating film is very weak by containing a large amount of the ether site | part which is easy to dissociate by acid rain, and the improvement is calculated | required.
또다른 도료 조성물로는 폴리에스테르폴리올, 폴리에테르폴리올, 폴리우레탄폴리올 및 아크릴릭폴리올 등의 폴리올류에 이소시아네이트를 경화제로 하는 2액형 도료 조성물이 공업적으로 널리 사용되어 왔다.As another coating composition, a two-part coating composition having an isocyanate as a curing agent in polyols such as polyester polyol, polyether polyol, polyurethane polyol, and acrylic polyol has been widely used industrially.
그러나 2액형 도료 조성물은 우수한 광택, 영상 선명성, 내산성을 제공할 수는 있으나 이소시아네이트를 경화제 성분으로 사용하기 때문에 취급이 어렵고, 수분에 민감하여 안전 예방에 신중해야 하는 등 문제점을 갖고 있다.However, the two-part coating composition may provide excellent gloss, image clarity, and acid resistance, but is difficult to handle because it uses isocyanates as a curing agent, and is sensitive to moisture.
따라서 상기 문제점을 해결하기 위한 수단으로 이소시아네이트를 봉쇄제로 봉쇄시켜 1액형의 도료 조성물을 제조하는 방법이 등장하였다.Therefore, a method of preparing a one-component coating composition by blocking isocyanate with a blocking agent has been introduced as a means for solving the above problems.
봉쇄제로는 페놀류, 알콜류, 활성메틸렌류, 메르캅탄류, 이미드류, 아민류, 피라졸류, 옥심류, 아황산염류 등이 있으며, 이러한 도료 조성물은 고온에서 봉쇄제를 다시 해리시켜 이소시아네이트기를 재생시킴으로서 경화가 달성된다. 그러나 봉쇄화된 이소시아네이트는 용해도 및 상용성을 저하시키고 도막 층간 부착성 및 도막 외관이 나빠지는 단점을 초래한다. 또한 경화 후 미해리된 이소시아네이트가 잔존함으로서 경도 및 내흠집성 등이 2액형 도료 조성물에 비해 떨어지는 단점이 있으며 특히 내산성의 부족으로 산성비에 대한 도막의 손상이 심각한 실정이다.Blocking agents include phenols, alcohols, active methylenes, mercaptans, imides, amines, pyrazoles, oximes, and sulfites. Such coating compositions dissociate the blocking agent at high temperature to regenerate the isocyanate group, thereby curing Is achieved. However, the blocked isocyanates lead to the disadvantages of lowering solubility and compatibility and deteriorating coating interlayer adhesion and coating appearance. In addition, since the undissociated isocyanate remains after curing, hardness and scratch resistance are inferior to those of the two-component coating composition. In particular, the coating film is severely damaged due to acid rain due to lack of acid resistance.
도막의 내산성을 높이기 위한 예로서 USP 4499151 에서 아크릴폴리올 제조시 γ-메타크릴로일옥시프로필트리메톡시실란, γ-메타크릴로일옥시프로필메틸디메톡시실란, 비닐트리메톡시실란과 같은 반응성 실란 함유 에틸렌성불포화 단량체를 공중합하는 방법을 제시되었다. 그러나 반응성실란 변성 아크릴릭폴리올류는 내산성이 우수한 경화 도막의 제공은 가능하나 광택, 맑기감, 영상 선명성 등 외관이 떨어지며 내균열성이 불량한 단점이 있다. 또한 당업계에서 에틸렌성불포화공중합체 제조시 통상적으로 층간 부착성 부여 및 안료, 첨가물의 분산성 향상 등의 목적으로 사용되는 아크릴릭엑시드, 메타크릴릭엑시드와 같은 에틸렌성불포화단량체를 공중합할 경우 높은 점도 상승 또는 겔화 현상을 유발시킴으로서 적용 자체가 불가능한 단점을 가지고 있으며 가격 또한 매우 높아지는 문제점이 있다.Reactive silanes such as γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and vinyltrimethoxysilane when preparing an acrylic polyol in USP 4499151 as an example to increase the acid resistance of the coating film. A method of copolymerizing containing ethylenically unsaturated monomers has been presented. However, reactive silane-modified acrylic polyols are capable of providing a cured coating film having excellent acid resistance, but are poor in appearance such as gloss, clearness, image sharpness, and poor crack resistance. In addition, high viscosity when copolymerizing ethylenically unsaturated monomers such as acrylic acid and methacrylic acid, which are commonly used for the purpose of imparting interlayer adhesion and improving the dispersibility of pigments and additives when preparing ethylenically unsaturated copolymers in the art. It causes a rise or gelation phenomenon has the disadvantage that the application itself is impossible and the price is also very high.
본 발명의 목적은 상용성 및 용해도가 매우 양호한 동시에 타소지와의 밀착성도 우수하여 재도장시 부착 불량이 발생하지 않으며, 경화 도막의 경도, 내흠집성 및 내산성이 우수한 도막을 형성할 수 있는 칼라-투명 1액형 도료 조성물을 제공하는 데에 있다.An object of the present invention is very good compatibility and solubility at the same time and excellent adhesion to other materials, so that the adhesion failure does not occur when re-coating, a color that can form a coating film excellent in hardness, scratch resistance and acid resistance of the cured coating film To provide a transparent one-part coating composition.
상기와 같은 본 발명의 목적은 폴리올을 주제로 사용하고 실란 함유 봉쇄화된 폴리올 변성 이소시아네이트를 경화제로 사용에 의해 달성된다.The above object of the present invention is achieved by using polyol as the subject and using silane containing blocked polyol modified isocyanates as curing agent.
구체적으로 본 발명에 의한 1액형 도료 조성물은 주제로 분자내에 적어도 2개 이상의 수산기를 함유하는 폴리올(이하 성분 A라 한다)과, 경화제로 분자내에 적어도 1개 이상의 반응성 실란을 함유하며 이소시아네이트기가 봉쇄된 폴리올 변성 이소시아네이트(이하 성분 B라 한다)를 사용하고, 여기에 통상의 도료 제조에 사용되는 희석제, 안료 및 기타 성분들을 사용하여 구성한 데에 그 특징이 있다.Specifically, the one-part coating composition according to the present invention mainly contains a polyol containing at least two or more hydroxyl groups in the molecule (hereinafter referred to as component A), and at least one reactive silane in the molecule as a curing agent and isocyanate group is blocked. It is characterized by using polyol-modified isocyanates (hereinafter referred to as component B) and using diluents, pigments and other components used in conventional paint production.
이와 같이 구성된 본 발명의 1액형 도료 조성물은 폴리올 변성 이소시아네이트를 기재로 사용하여 상용성 및 용해도의 증진과 동시에 분자내 함유된 실란을 통해 타소지와의 밀착성이 향상된다. 또한 경화후 도막내에 형성된 실록산 결합 부위의 높은 결합 에너지에 의해 경도 및 내흠집성이 우수함은 물론 내산성이 극히 탁월한 도막을 형성할 수 있다.The one-part coating composition of the present invention configured as described above uses polyol-modified isocyanate as a substrate to improve compatibility and solubility, and at the same time, improve adhesion to other materials through silane contained in the molecule. In addition, due to the high binding energy of the siloxane bonding sites formed in the coating film after curing, it is possible to form a coating film having excellent hardness and scratch resistance as well as extremely excellent acid resistance.
성분 A에 대해 구체적으로 설명한다.The component A is demonstrated concretely.
성분 A는 우레탄 수지를 형성하기 위해 사용하는 당분야에 공지화된 폴리올 성분으로서 분자내 적어도 2개 이상의 수산기를 함유하는 폴리올인 것이 좋다.Component A is preferably a polyol containing at least two or more hydroxyl groups in the molecule as a polyol component known in the art for use in forming urethane resins.
성분 A의 구체적인 예로는 폴리에틸렌글리콜, 폴리플로필렌글리콜과 같은 폴리에테르폴리올류; 폴리카보네이트폴리올류; 폴리에스테르폴리올류; 폴리우레탄폴리올류; 아크릴릭폴리올, 비닐폴리올과 같은 에틸렌성불포화공중합체폴리올류; 에폭시폴리올류; 셀룰로즈류; 다가알콜류 등이 있으며, 이중에 바람직하게는 도막의 물성조절이 용이한 에틸렌성불포화공중합체폴리올류가 적당하다.Specific examples of component A include polyether polyols such as polyethylene glycol and polyflolene glycol; Polycarbonate polyols; Polyester polyols; Polyurethane polyols; Ethylenically unsaturated copolymer polyols such as acrylic polyols and vinyl polyols; Epoxy polyols; Celluloses; Polyhydric alcohols and the like, and among them, ethylenically unsaturated copolymer polyols, which easily control physical properties of the coating film, are preferable.
본 발명에 있어 유용한 에틸렌성불포화공중합체폴리올류는 본 발명의 범위를 한정하는 것은 아니지만 수평균분자량이 1000∼100000이고 수산당량이 250∼3000 인 것이 적당하다. 이러한 에틸렌성불포화공중합체를 형성하기 위한 수산기 함유 에틸렌성불포화단량체류로는 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시프로필(메타)아크릴레이트, 3-하이드록시프로필(메타)아크릴레이트, 4-하이드록시부틸(메타)아클릴레이트, 4-하이드록시부틸비닐에테르, 4-하이드록시싸이클로헥실비닐에테르, 에틸렌옥사이드 또는 프로필렌옥사이드부가형 말단수산기 함유 에틸렌성불포화단량체류, 카프로락톤 부가형 말단수산기 함유 에틸렌불포화성단량체류 등을 들수 있다.The ethylenically unsaturated copolymer polyols useful in the present invention do not limit the scope of the present invention, but the number average molecular weight is 1000 to 100,000 and the acid equivalent is preferably 250 to 3000. The hydroxyl group-containing ethylenically unsaturated monomers for forming such ethylenically unsaturated copolymers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acryl. Ethyle, 4-hydroxybutyl (meth) acrylate, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, ethylene oxide or propylene oxide addition type hydroxyl group containing ethylenically unsaturated monomer, caprolactone addition type terminal And hydroxyl group-containing ethylene unsaturated monomers.
또한 본 발명에 있어 수산기 함유 에틸렌성불포화단량체는 점성, 상용성, 용해성 및 도막의 경도, 광택, 유리전이온도 등의 조절 목적으로 공지의 에틸렌성불포화단량체와 공중합하여 사용하는 것이 보다 효과적이다. 본 발명에 의한 에틸렌성불포화공중합체 폴리올은 당 분야에 있어 공지화된 중합방법에 의해 얻을 수 있으며, 이러한 예로서 희석용제를 사용하여 제조하는 용액중합방식이 가장 적당하고 수평균분자량이 100∼100000 범위가 되도록 사용개시제 및 중합온도를 조절하여 주는 것이 좋다.In addition, in the present invention, the hydroxyl group-containing ethylenically unsaturated monomer is more effectively used in copolymerization with a known ethylenically unsaturated monomer for the purpose of controlling viscosity, compatibility, solubility and hardness, gloss, glass transition temperature, etc. of the coating film. The ethylenically unsaturated copolymer polyol according to the present invention can be obtained by a polymerization method known in the art. For example, a solution polymerization method using a dilution solvent is most suitable and the number average molecular weight is 100 to 100,000. It is good to control the initiator and polymerization temperature so as to be within the range.
성분 B에 대해 구체적으로 설명한다.The component B is demonstrated concretely.
성분 B는 성분 A에 반응성실란을 함유하는 실란결합제(이하 성분 C라 한다)를 적어도 1당량 이상 1차 반응시킨 후, 봉쇄제로 이소시아네이트기가 일부 봉쇄화된 이소시아네이트(이하 성분 D라 한다)로 잔여수산기와 2차 반응시켜 제조할 수 있다.Component B is a residual hydroxyl group with isocyanate (hereinafter referred to as component D) in which isocyanate group is partially blocked by a blocking agent after at least one equivalent of the first reaction of component silane containing a reactive silane (hereinafter referred to as component C). It can be prepared by secondary reaction with.
또한 성분 B는 성분 A에 봉쇄제인 성분 D를 가하여 1차 반응시킨 후, 성분 C를 적어도 1당량 이상 사용하여 잔여 수산기와 2차 반응시켜 수득할 수도 있으며, 필요시 희석용제를 사용하여 반응시켜도 무방하다. 이때 반응온도는 특별한 제한은 없지만 상온∼150℃ 범위가 적당하며 반응의 진행상태는 수산기, 에폭시기, 이소시아네이트기 등의 반응성기 함량을 IR분광분석기 또는 습식분석에 의해 확인할 수 있다.In addition, component B may be obtained by first reacting component A with component D as a blocking agent, followed by secondary reaction with component C using at least one equivalent or more, and may be reacted with a diluent solvent if necessary. Do. At this time, the reaction temperature is not particularly limited, but the normal temperature ~ 150 ℃ range is appropriate, the progress of the reaction can be confirmed by IR spectroscopy or wet analysis of the content of the reactive group, such as hydroxyl group, epoxy group, isocyanate group.
성분 C로는 2-(3,4-에폭시싸이클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시싸이클로헥실)에틸메틸디메톡시실란, 2-(3,4-에폭싸이클로헥실)에틸트리에톡시실란, 3-글리시딜옥시프로필트리메톡시실란, 3-글리시딜옥시프로필메틸디메톡시실란, 3-글리시딜옥시프로필트리에톡시실란과 같은 같은 에폭시기 함유 반응성 실란류; 3-이소시아네이트프로필트리메톡시실란, 3-이소시아네이트프로필트리에톡시실란과 같은 이소시아네이트기 함유 반응성 실란류 등이 있다.Component C includes 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxyhexyl) ethyltri Epoxy group-containing reactive silanes such as ethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyltriethoxysilane; Isocyanate group containing reactive silanes, such as 3-isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane, etc. are mentioned.
성분 D로는 2가 이상의 이소시아네이트 화합물(이하 성분 E라 한다)를 봉쇄화제(이하 성분 F라 한다)로 분자내의 이소시아네이트기 일부를 봉쇄화시켜 사용한다. 이때 붕쇄화 당량수 비율은 특별한 제한은 없지만 해당 성분 E의 분자내 이소시아네이트기가 적어도 1개 이상 남도록 조절하는 것이 적당하며, 보다 바람직하게는 이소시아네이트 당량수의 절반 정도가 좋다. 봉쇄화 비율이 지나치게 높으면 상용성 및 용해도 조절이 어려운 단점이 발생되며 반대로 봉쇄화 당량수 비율이 너무 낮으면 조성물의 점도가 너무 높고 경화도 조절이 어려운 단점이 발생된다.As the component D, a divalent or higher isocyanate compound (hereinafter referred to as component E) is used by blocking a part of the isocyanate group in the molecule with a blocking agent (hereinafter referred to as component F). At this time, the ratio of the number of borated equivalents is not particularly limited, but it is appropriate to adjust the amount of at least one isocyanate group in the molecule of the component E, more preferably about half of the number of isocyanate equivalents. If the ratio of blockade is too high, it is difficult to control compatibility and solubility. On the contrary, if the ratio of blockage equivalent number is too low, the viscosity of the composition is too high and the degree of hardening is difficult to control.
성분 D를 제조하기 위한 반응온도는 특별한 제한은 없지만 상온∼150℃ 범위가 적당하며, 습식분석을 통해 계내의 유리이소시아네이트 함량을 정량함으로서 반응도를 조절하면 된다. 필요에 따라 희석용제 및 촉매의 사용도 가능하다.The reaction temperature for preparing the component D is not particularly limited, but is suitable in the range from room temperature to 150 ° C., and the reaction rate may be controlled by quantifying the free isocyanate content in the system through wet analysis. Diluents and catalysts may be used if necessary.
성분 E로는 2,4-톨로엔디이소시아네이트, 2,4-톨루엔디이소시아네이트의 이량체, 토일렌디이소시아네이트, 자일랜디이소시아네이트, O-나프탈렌디이소시아네이트, 디페닐메탄디이소시아네이트, 트리페닐메탄트리이소시아네이트, 트리스-(P-이소시아네이토페닐)치오포스페이트, 폴리메틸렌폴리페닐이소시아네이트와 같은 방향족계 이소시아네이트류; 헥사메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 1,4-싸이클로헥실디이소시아네이트 등과 같은 지환족 또는 지방족계 이소시아네이트류; 트리메틸올프로판과 같은 다가알콜과의 부가형 또는 뷰렛트형 등이 있으며, 이중에 내황변성이 우수한 지환족 또는 지방족 이소시아네이트류를 사용하는 것이 보다 바람직하다.Examples of the component E include 2,4-toluene diisocyanate, dimer of 2,4-toluene diisocyanate, toylene diisocyanate, xylan diisocyanate, O-naphthalene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris- Aromatic isocyanates such as (P-isocyanatophenyl) thiophosphate and polymethylenepolyphenylisocyanate; Alicyclic or aliphatic isocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexyl diisocyanate and the like; There exists an addition type or biuret type with polyhydric alcohols, such as a trimethylol propane, and it is more preferable to use alicyclic or aliphatic isocyanates which are excellent in yellowing resistance among these.
성분 F로는 페놀, 크레졸, O-이소프로필페놀, 티몰, P-tert-부틸페놀, P-니트로페놀과 같은 페놀류; 메탄올, 에탄올, 부탄올, 에틸렌글리콜, 부틸셀로솔브, 벤질알콜, 싸이클로헥산올과 같은 알콜류; 디메틸말로네이트, 디에틸말로네이트, 에틸아세토아세테이트와 같은 활성메틸렌류; 부틸메르캅탄, 티오페놀, 도데실메르캅탄과 같은 메르캅탄류; 썩신산이미드, 말레인산이미드와 같은 이미드류; 디페닐아민, 페닐나프틸아민, 아릴린과 같은 아민류; 2-에틸이미다졸과 같은 이미다졸류; 요소, 티오요소, 에틸렌요소와 같은 요소류; 에틸렌이민과 같은 이민류; 아릴메틸메타아크리로일옥시헥사믹엑시드에스테르와 같은 헥사믹엑시드에스테르류; 아세톤옥심, 2-부탄온옥심, 싸이클로헥산온옥심과 같은 옥심류; 3,5-디메틸피라졸과 같은 피라졸류; ε-카프로락탐과 같은 락탐류 등이 있다.Component F includes phenols such as phenol, cresol, O-isopropylphenol, thymol, P-tert-butylphenol and P-nitrophenol; Alcohols such as methanol, ethanol, butanol, ethylene glycol, butyl cellosolve, benzyl alcohol and cyclohexanol; Active methylenes such as dimethylmalonate, diethyl malonate and ethyl acetoacetate; Mercaptans such as butyl mercaptan, thiophenol, and dodecyl mercaptan; Imides such as succinimide and maleic acid imide; Amines such as diphenylamine, phenylnaphthylamine and arylene; Imidazoles such as 2-ethylimidazole; Urea such as urea, thiourea, ethylene urea; Imines, such as ethyleneimine; Hexamic acid esters such as arylmethylmethacryloyloxy hexamic acid ester; Oximes such as acetone oxime, 2-butanone oxime and cyclohexanone oxime; Pyrazoles such as 3,5-dimethylpyrazole; lactams such as ε-caprolactam and the like.
본 발명에 있어 성분 A의 수산기 당량수에 대한 성분 B의 이소시아네이트기 당량수 비율은 0.7∼1.3 범위가 적당하며, 0.7 범위 이하에서는 저장성이 떨어지고 가격이 높아지는 단점이 있으며 1.3 범위 이상에서는 경화도가 낮고 내산성 등이 떨어지는 단점이 발생한다.In the present invention, the ratio of the equivalent number of isocyanate groups of component B to the equivalent number of hydroxyl groups of component A is in the range of 0.7 to 1.3, and has a disadvantage in that the storage property is lower and the price is higher in the range below 0.7. The disadvantage of falling back occurs.
본 발명에 의한 1액형 도료조성물은 성분 A와 성분 B에 보조수지와 희석용제 및 도료에 사용되는 기타 성분들을 더하여 1액형으로 사용하는 것으로, 필요에 따라 안료를 더 첨가할 수 있다.The one-component coating composition according to the present invention is used in one-component form by adding auxiliary resins, diluent solvents, and other components used in paints to components A and B, and further adding a pigment as necessary.
보조수지로는 멜라민 수지, 폴리에스테르 수지, 실리콘변성폴리에스테르 수지, 실리콘 수지, 비닐 수지 등을 있으며, 희석용제로는 자일렌, 톨루엔, 부틸아세테이트, 에틸셀로솔브, 한솔, 부탄올, 메닐에틸케논, 메틸이소부틸케톤과 같은 용매가 사용된다. 또한 본 발명에 의한 도료조성물에 사용되는 기타성분으로는 트리메틸오르쏘아세테이트, 트리메틸오르쏘부틸레이트, 옷사졸린류, 모노이소시아네이트류와 같은 제습제; 유기금속염류, 3급아민류, 아민염류와 같은 반응촉매; 증점제; 유동성조절제(Rheology Modifier); 습윤제; 핀홀제거제(Popping Agent); 도막평활성부여제(Levelling Agent); 자외선흡수제; 산화방지제와 같은 공지의 첨가제들을 사용할 수 있다.Auxiliary resins include melamine resins, polyester resins, silicone modified polyester resins, silicone resins and vinyl resins, and diluent solvents include xylene, toluene, butyl acetate, ethyl cellosolve, Hansol, butanol, and methylyl ethylenone. Solvents such as methyl isobutyl ketone are used. In addition, other components used in the paint composition according to the present invention include a dehumidifying agent such as trimethyl ortho acetate, trimethyl ortho butyrate, oxazolins, and monoisocyanates; Reaction catalysts such as organometallic salts, tertiary amines and amine salts; Thickeners; Rheology modifiers; Wetting agents; Popping agent; Leveling agent; UV absorbers; Known additives such as antioxidants can be used.
또한 본 발명에 의한 도료 조성물은 솔리드 칼라용 도료 조성물로 적용 가능하며, 도막의 외관, 광택 등을 향상시키기 위해 칼라도장을 한 다음 젖은 상태에서 본 발명에 의한 도료 조성물을 덧 도장한 후 가열 경화시키는 소위 2 coat 1 bake 방식을 적용하는 것도 가능하다. 이때 가열 경화조건은 120∼180℃ 에서 15 ∼60분 정도가 적당하며, 이때 가열온도가 지나치게 낮으면 경화시간이 길어지고 미경화물이 발생되는 문제점이 있으며 가열온도가 지나치게 높으면 에너지 소비가 크고 황변 도막이 발생되는 등의 문제점이 발생하게 된다.In addition, the coating composition according to the present invention can be applied as a coating composition for a solid color, and to heat the coating after coating the coating composition according to the present invention in a wet state after the color coating to improve the appearance, gloss, etc. of the coating film It is also possible to apply the so-called 2 coat 1 bake method. At this time, the heat curing condition is suitable for about 15 to 60 minutes at 120 to 180 ° C. At this time, if the heating temperature is too low, there is a problem that the curing time is long and uncured products are generated. If the heating temperature is too high, the energy consumption is large and the yellowing film is Problems such as that occur.
이하 성분 A∼D의 제조예를 상세히 설명하면 다음과 같다.Hereinafter, the production examples of the components A to D will be described in detail.
[성분A의제조][Production of Component A]
제조예 A-1Preparation Example A-1
교반기, 냉각기와 온도계가 장착된 4구 플라스크내에 100중량부의 부틸아세테이트, 100중량부의 톨루엔, 200중량부의 자일렌을 넣고 가열 및 교반하여 용제 환류상태로 유지시킨 다음, 300중량부의 2-하이드록시에틸메타아크릴레이트, 270중량부의 스틸렌, 50중량부의 메틸메타아크릴레이트, 250중량부의 N-부틸메타아크릴레이트, 100중량부의 부틸아크릴레이트, 30중량부의 메타아크리릭엑시드 및 70중량부의 1,1'-아조비스(1-싸이클로헥산카보니트릴) 혼합액을 2시간에 걸쳐 균일하게 적가한 후 2시간 유지시켜 준다. 상온으로 냉각한 다음 자일렌을 사용하여 고형분함량 70%가 되게 조절하여 가드너 점도가 Y-Z인 에틸렌성불포화공중합체 폴리올 용액 성분 A-1을 수득하였다.In a four-necked flask equipped with a stirrer, a cooler and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene, and 200 parts by weight of xylene were added and heated and stirred to keep the solvent at reflux, followed by 300 parts by weight of 2-hydroxyethyl. Methacrylate, 270 parts by weight of styrene, 50 parts by weight of methyl methacrylate, 250 parts by weight of N-butylmethacrylate, 100 parts by weight of butyl acrylate, 30 parts by weight of metaacrylic acid and 70 parts by weight of 1,1'- Azobis (1-cyclohexanecarbonitrile) mixture is added dropwise uniformly over 2 hours and then maintained for 2 hours. After cooling to room temperature, it was adjusted to a solid content of 70% by using xylene to obtain an ethylenically unsaturated copolymer polyol solution component A-1 having a Gardner viscosity of Y-Z.
제조예 A-2Preparation Example A-2
교반기, 냉각기와 온도계가 장착된 4구 플라스크내에 100중량부의 부틸아에테이트, 100중량부의 톨루엔, 200중량부의 자일렌을 넣고 가열 및 교반하여 용제 환류상태로 유지시킨 다음, 150중량부의 4-하이드록시부틸아크릴레이트, 50중량부의 2-하이드록시프로필아크릴레이트, 200중량부의 메틸메타아크릴레이트, 250중량부의 부틸아크릴레이트, 50중량부의 에틸헥실아크릴레이트, 100중량부의 이소보닐아크릴레이트, 200중량부의 싸이클로헥실메타이크릴레이트, 50중량부의 tert-부틸퍼아세테이트의 혼합액을 3시간에 걸쳐 균일하게 적가한 다음 2시간 유지시켜 준다. 상온으로 냉각한 후 자일렌을 사용 고형분함량이 70%가 되게 조절하여 가드너 점도가 V-W인 에닐렌성불포화공중합체 폴리올 용액 성분 A-2를 수득하였다.In a four-necked flask equipped with a stirrer, a cooler and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene and 200 parts by weight of xylene were added and heated and stirred to keep the solvent at reflux. Oxybutyl acrylate, 50 parts by weight of 2-hydroxypropyl acrylate, 200 parts by weight of methyl methacrylate, 250 parts by weight of butyl acrylate, 50 parts by weight of ethylhexyl acrylate, 100 parts by weight of isobornyl acrylate, 200 parts by weight Cyclohexyl methacrylate and a mixture of 50 parts by weight of tert-butylperacetate are added dropwise uniformly over 3 hours and then maintained for 2 hours. After cooling to room temperature, xylene was used to adjust the solid content to 70% to obtain an enylene-unsaturated copolymer polyol solution component A-2 having a Gardner viscosity of V-W.
제조예 A-3Preparation Example A-3
교반기, 냉각기, 온도계가 장착된 4구 플라스크에 100중량부의 부틸아세테이트, 100중량부의 메틸이소부틸케톤, 200중량부의 자일렌, 260중량부의 1,3-비스〔3-(2,3-에폭시프로폭시)프로필〕테트라메틸디실록산, 500중량부의 2,2-비스〔4-(2,3-에폭시프로필)싸이클로헥실〕프로판 혼합액을 넣고 400중량부의 디에탄올아민을 상온에서 발열에 주의하면서 3시간에 거쳐 적가한 다음 2시간에 걸쳐 60℃로 승온시켜 준다. IR분광분석기 및 습식분석을 통해 에폭시기가 다 소멸된 시점에서 반응을 종결하여 상온으로 냉각한다. 자일렌을 사용 고형분 함량 70%가 되도록 조절하여 가드너 점도가 S인 에폴시폴리올용액 성분 A-3를 수득하였다.A four-necked flask equipped with a stirrer, a cooler, and a thermometer, includes 100 parts by weight of butyl acetate, 100 parts by weight of methyl isobutyl ketone, 200 parts by weight of xylene, and 260 parts by weight of 1,3-bis [3- (2,3-epoxypro Poxy) propyl] tetramethyldisiloxane, 500 parts by weight of 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane mixed solution, and 400 parts by weight of diethanolamine at room temperature for 3 hours while paying attention to heat generation. After dropwise addition, the mixture was heated to 60 ° C. over 2 hours. IR spectroscopy and wet analysis terminate the reaction at the time when the epoxy group disappears to cool to room temperature. Xylene was adjusted to a solids content of 70% to obtain an epoxypolyol solution component A-3 having a Gardner viscosity of S.
제조예 A-4Preparation Example A-4
교반기, 냉각기, 응축기, 온도계가 장착된 4구 플라스크내에 110중량부의 네오펜틸그리콜, 130중량부의 1,6-헥산디올, 200중량부의 트리메틸올프로판, 510중량부의 디메틸이소프탈레이트, 120중량부의 아젤라익엑시드를 넣고 질소주입하에 가열하여 내용물을 서서히 용융시킨다. 단계적으로 온도를 승온하여 축합수를 연속적으로 제거하면서 최종으로 220℃ 상태를 유지시켜 준다. 습식분석을 통해 산가가 4.5인 시점에서 반응을 종결지어 상온으로 냉각한다. 자일렌으로 희석하여 고형분 함량 70중량%가 되도록 조절하여 폴리스틸렌 상대비교 수평균분자량이 2300이고 수산가가 130인 폴리에스테르폴리올용액 성분 A-4를 수득하였다.110 parts by weight neopentylglycol, 130 parts by weight 1,6-hexanediol, 200 parts by weight trimethylolpropane, 510 parts by weight dimethyl isophthalate, 120 parts by weight azela in a four-necked flask equipped with a stirrer, a cooler, a condenser and a thermometer. The Ixexide is added and heated under nitrogen injection to slowly melt the contents. The temperature is raised step by step to remove the condensed water continuously and finally maintain the 220 ℃ state. Through wet analysis, the reaction is terminated at the acid value of 4.5 and cooled to room temperature. Dilution with xylene was performed to obtain a solid content of 70% by weight to obtain a polyester polyol solution component A-4 having a polystyrene relative comparison number average molecular weight of 2300 and a hydroxyl value of 130.
제조예 A-5Preparation Example A-5
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 100중량부의 부틸아세테이트, 100중량부의 톨루엔, 200중량부의 자일렌을 넣고 가열 및 교반하여 용제 환류 상태로 유지시킨 다음 300중량부의 2-하이드록시에틸메타아크릴레이트, 70중량부의 메틸메타아크릴레이트, 100중량부의 스틸렌, 200중량부의 N-부틸아크릴레이트, 30중량부의 아크릴릭엑시드, 300중량부의 메타아크릴로일옥시에틸프로필트리메톡시실란, 60중량부의 tert-부틸퍼아세테이트 혼합액을 1분당 5중량부의 속도로 적가하였다. 적가 시작후 약 40분 경과 시점에서 겔화하여 반응을 종결하였다.In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene, and 200 parts by weight of xylene were added and heated and stirred to keep the solvent at reflux, followed by 300 parts by weight of 2-hydroxyethyl meta. Acrylate, 70 parts by weight of methyl methacrylate, 100 parts by weight of styrene, 200 parts by weight of N-butyl acrylate, 30 parts by weight of acrylic acid, 300 parts by weight of methacryloyloxyethylpropyltrimethoxysilane, 60 parts by weight of tert The butylperacetate mixture was added dropwise at a rate of 5 parts by weight per minute. The reaction was terminated by gelation at about 40 minutes after the start of the dropping.
비교제조예 A-6Comparative Production Example A-6
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 100중량부의 부틸아세테이트, 100중량부의 톨루엔, 200중량부의 자일렌을 넣고 가열 및 교반하여 용제 환류 상태로 유지시킨 다음 300중량부의 2-하이드록시에틸메타아크릴레이트 300중량부, 100중량부의 메틸메타아크릴레이트, 100중량부의 스틸렌, 200중량부의 N-부틸아크릴레이트, 300중량부의 메타아클릴로일옥시에틸프로필트리메톡시실란, 70중량부의 1,1'-비스아조(1-싸이클로헥산카보니트릴 혼합액을 3시간에 걸쳐 균일하게 적가한 다음 2시간 유지시켜 준다. 이를 상온으로 냉각한 다음 자일렌을 사용하여 고형분 함량 70%가 되도록 조절하여 가드러점도가 Z인 성분 A-5를 수득하였다.In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of butyl acetate, 100 parts by weight of toluene, and 200 parts by weight of xylene were added and heated and stirred to keep the solvent at reflux, followed by 300 parts by weight of 2-hydroxyethyl meta. 300 parts by weight of acrylate, 100 parts by weight of methyl methacrylate, 100 parts by weight of styrene, 200 parts by weight of N-butyl acrylate, 300 parts by weight of methacryloyloxyethylpropyltrimethoxysilane, 70 parts by weight of 1,1 ' The bis-azo (1-cyclohexanecarbonitrile mixture is added dropwise evenly over 3 hours and then maintained for 2 hours. Cooling down to room temperature and adjusting it to 70% solids content using xylene, Obtained component A-5 which is Z.
[성분D의제조][Production of Component D]
제조예 D-1Preparation Example D-1
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 150중량부의 건조된 부틸아세테이트, 665중량부의 이소포론디이소시아네이트 혼합액을 넣고 200중량부의 건조된 부틸아세테이트, 295중량부의 3,5-디메틸피라졸 혼합액을 1시간에 걸쳐 적가하여 준다. 상온서 1일간 방치한 후 60℃로 승온하여 습식분석을 통해 유리이소시아네이트 함량이 9.6중량%인 시점에서 반응을 종결지어 상온으로 식혀준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 D-1을 수득하였다.150 parts by weight of dried butyl acetate and 665 parts by weight of isophorone diisocyanate mixture were placed in a four-necked flask equipped with a stirrer, a cooler and a thermometer, and 200 parts by weight of dried butyl acetate and 295 parts by weight of 3,5-dimethylpyrazole mixture were added. Add dropwise for 1 hour. After standing at room temperature for 1 day, the temperature was raised to 60 ° C., and the reaction was terminated when the free isocyanate content was 9.6% by weight through wet analysis to cool down to room temperature. It was adjusted to 70% by weight of solid content with dried butyl acetate to obtain component D-1.
제조예 D-2Preparation Example D-2
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 100중량부의 건조딘 부틸아세테이트 100중량부, 670중량부의 1,3,5-트리스(6-이소시아네이토헥실)-뷰렛 혼합액을 넣고 300중량부의 건조된 부틸아세테이트, 460중량부의 아릴메타크릴록시하이드록사믹엑시드에스테르 혼합액을 1시간에 걸쳐 적가한다. 이어서 60℃로 승온한 다음 습식분석을 통해 유리이소시아네이트 함량이 4.1중량%인 시점에서 반응을 종결지어 상온으로 식혀 준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 D-2를 수득하였다.In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of 100 parts by weight of dried butyl acetate and 670 parts by weight of 1,3,5-tris (6-isocyanatohexyl) -buret mixture were added and 300 parts by weight. Dried butyl acetate and 460 parts by weight of the arylmethacryloxyhydroxyxamic acid ester mixed solution are added dropwise over 1 hour. Subsequently, the temperature was raised to 60 ° C., and then wet analysis to terminate the reaction when the free isocyanate content was 4.1% by weight to cool to room temperature. Component D-2 was obtained by adjusting to 70% by weight of solid content with dried butyl acetate.
제조예 D-3Preparation Example D-3
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 200중량부의 건조된 부낼아세테이트, 505중량부의 트리스(6-이소시아네이토헥실)-이소시아눌레이트 혼합액을 넣고 85중량부의 2-부탄온옥심을 1시간에 걸쳐 적가한 다음 60℃로 승온시미고, 2중량부의 디부틸틴디라우레이트를 넣고 유지반응 시킨다. 습식분석을 통해 유리이소시아네이트 함량이 10.6중량%인 시점에서 반응을 종결지어 상온으로 식혀 준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 D-3을 수득하였다.Into a four-necked flask equipped with a stirrer, a cooler and a thermometer, 200 parts by weight of dried butylacetate and 505 parts by weight of tris (6-isocyanatohexyl) -isocyanurate mixture were added, and 85 parts by weight of 2-butanone oxime was added. The mixture was added dropwise over 1 hour, and the temperature was raised to 60 ° C., and 2 parts by weight of dibutyl tin dilaurate was added and the reaction was carried out. Through wet analysis, the reaction is terminated when the free isocyanate content is 10.6% by weight and cooled to room temperature. Component D-3 was obtained by adjusting to 70% by weight of solid content with dried butyl acetate.
[성분B의제조][Production of Component B]
제조예 B-1Preparation Example B-1
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 620중량부의 성분 A-1에 100중량부의 3-이소시아네이토프로필트리메톡시실란을 1시간에 걸쳐 적가한 다음 70℃로 승온시켜 준다. 2중량부의 디부틸틴디라우레이트를 넣고 유지반응시켜 IR 분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 1차 반응을 종결한다. 다음 230중량부의 성분 D-1을 넣고 2차 반응시켜 IR분광분석기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 반응을 종결지어 상온으로 식혀 준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 B-1을 수득하였다.In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 100 parts by weight of 3-isocyanatopropyltrimethoxysilane was added dropwise over 1 hour to 620 parts by weight of component A-1, followed by raising the temperature to 70 ° C. 2 parts by weight of dibutyl tin dilaurate was added and the reaction was maintained by IR spectroscopy and wet analysis to terminate the first reaction when the isocyanate group disappeared. Then, 230 parts by weight of component D-1 was added thereto, followed by secondary reaction. The reaction was terminated when the isocyanate group disappeared through IR spectroscopy and wet analysis to cool to room temperature. The component B-1 was obtained by adjusting it to 70 weight% of solid content with the dried butyl acetate.
제조예 B-2Preparation Example B-2
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 620중량부의 성분 A-1에 230중량부의 성분 D-1을 1시간에 걸쳐 적가한 다음 70℃로 승온시켜 준다. 2중량부의 디부틸디라우레이트를 넣고 유지반응시켜 IR분광분석기 및 습식분석을 통해 이소시아테이트기가 소멸된 시점에서 1차 반응을 종결한다. 다음 100중량부의 3-이소시아네이토프로필트리메톡시실란을 1시간에 걸쳐 적가하여 2차 반응시킨 후 IR 분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 반응을 종결지어 상온으로 식혀 준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 B-2를 수득하였다.In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 230 parts by weight of component D-1 is added dropwise to the 620 parts by weight of component A-1 over 1 hour, followed by raising the temperature to 70 ° C. 2 parts by weight of dibutyl dilaurate was added and the reaction was terminated by IR spectroscopy and wet analysis to terminate the first reaction when the isocyanate group disappeared. Next, 100 parts by weight of 3-isocyanatopropyltrimethoxysilane was added dropwise over 1 hour, followed by secondary reaction, and the reaction was terminated at the point where the isocyanate group disappeared through IR spectroscopy and wet analysis to cool to room temperature. Component B-2 was obtained by adjusting to 70% by weight of solid content with dried butyl acetate.
제조예 B-3Preparation Example B-3
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 100중량부의 부틸아세테이느, 135중량부의 트리메틸올프로판 혼합액에 235중량부의 3-글리시딜옥시프로필트리메톡시실란을 넣고 140℃로 승온시킨다. 반응촉매인 트리에틸아민 3중량부를 넣고 유지반응시켜 IR 분광기 및 습식분석을 통해 에폭시기가 소멸된 시점에서 1차 반응을 종결한다. 다음 1370중량부의 성분 D-1을 1시간에 걸쳐 적가하여 2차 유지반응시키고 IR 분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 반응을 종결지어 상온으로 식혀준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 B-3을 수득하였다.In a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 235 parts by weight of 3-glycidyloxypropyltrimethoxysilane was added to 100 parts by weight of butyl acetate and 135 parts by weight of trimethylolpropane mixed solution, and the temperature was raised to 140 ° C. After adding 3 parts by weight of triethylamine, a reaction catalyst, and maintaining the reaction, the first reaction was terminated when the epoxy group disappeared through IR spectroscopy and wet analysis. Next, 1370 parts by weight of component D-1 was added dropwise over 1 hour, followed by a second maintenance reaction, and the reaction was terminated and cooled to room temperature when the isocyanate group disappeared through IR spectroscopy and wet analysis. Component B-3 was obtained by adjusting to 70% by weight of solid content with dried butyl acetate.
제조예 B-4Preparation Example B-4
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 215중량부의 성분 A-3, 150중량부의 3-이소시아네이토프로필트리메톡시실란을 1시간에 걸쳐 적가한 다음 60℃로 승온 유지시킨다. 다음 반응촉매인 징크디에틸헥사노에이트 5중량부를 넣고 유지반응시켜 IR 분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 1차 반응을 종결한다. 800중량부의 성분 D-2을 넣고 유지반응시켜 IR분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 다시 2차 반응을 종결한 다음 상온으로 식혀 준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 B-4를 수득하였다.Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 215 parts by weight of component A-3 and 150 parts by weight of 3-isocyanatopropyltrimethoxysilane were added dropwise over 1 hour, followed by maintaining the temperature at 60 ° C. Next, 5 parts by weight of zinc diethylhexanoate, a reaction catalyst, was added thereto, followed by a holding reaction to terminate the first reaction when the isocyanate group disappeared through IR spectroscopy and wet analysis. After 800 parts by weight of component D-2 was added, the reaction was terminated by an IR spectrometer and a wet analysis to terminate the second reaction at the time when the isocyanate group disappeared, and then cooled to room temperature. Component B-4 was obtained by adjusting to 70% by weight of solid content with dried butyl acetate.
제조예 B-5Preparation Example B-5
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 450중량부의 평균중합도가 10인 폴리에틸렌글리콜, 215중량부의 성분 A-3 혼합액을 넣고 375중량부의 3-이소시아네이토프로필트리에톡시실란을 1시간에 걸쳐 적가한 다음 60℃로 승온 유지시키고, IR 분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 1차 반응을 종결한다. 다음 915중량부의 성분 D-1을 넣고 유지반응시켜 다시 IR 분광기 및 습식분석을 통해 이소기아네이트기가 소멸된 시점에서 2차 반응을 종결하고 상온으로 식혀준다. 건조된 부틸아세테이트로 고형분 함량 70중량%가 되도록 조절하여 성분 B-5를 수득하였다.Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 450 parts by weight of polyethylene glycol having an average degree of polymerization of 10 and 215 parts by weight of a component A-3 mixture were added, and 375 parts by weight of 3-isocyanatopropyltriethoxysilane was added for 1 hour. The mixture was added dropwise over and maintained at 60 ° C., and the first reaction was terminated when the isocyanate group disappeared through IR spectroscopy and wet analysis. Then, 915 parts by weight of the component D-1 was added thereto, followed by a maintenance reaction, and the IR reaction was terminated by the IR spectroscopy and wet analysis, and the secondary reaction was terminated and cooled to room temperature. It was adjusted to a solid content of 70% by weight with dried butyl acetate to obtain component B-5.
제조예 B-6Preparation Example B-6
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 920중량부의 성분 A-4를 넣고 230중량부의 성분 D-1, 210중량부의 성분 D-3 혼합액을 1시간에 걸쳐 적가한다음 60℃로 승온 유지시키고, IR 분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 1차 반응를 종결한다. 다음 100중량부의 3-이소시아네이토프로필트리메톡시실란을 넣고 유지반응시켜 다시 IR 분광분석기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 2차 반응를 종결한 후 상온으로 식혀 준다. 건조된 부틸아세테이트로 고형분 함량 70 중량%가 되도록 조절하여 성분 B-6를 수득하였다.Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 920 parts by weight of component A-4 was added, and 230 parts by weight of component D-1 and 210 parts by weight of component D-3 mixture were added dropwise over 1 hour, followed by maintaining the temperature at 60 ° C. The first reaction is terminated at the point where the isocyanate group disappears through IR spectroscopy and wet analysis. Next, 100 parts by weight of 3-isocyanatopropyltrimethoxysilane was added thereto, followed by maintenance reaction. After completion of the secondary reaction at the time when the isocyanate group disappeared through IR spectroscopy and wet analysis, the mixture was cooled to room temperature. It was adjusted to a solid content of 70% by weight with dried butyl acetate to obtain component B-6.
제조예 B-7Preparation Example B-7
교반기, 냉각기, 온도계가 장착된 4구 플라스크내에 67중량부의 트리메틸올프로판, 620중량부의 성분 A-1 혼합액을 넣고 300중량부의 이소시아네이토프로필트리메톡시실란을 1시간에 걸쳐 적가한 다음 60℃로 승온시켜 유지반응 시키고, IR 분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 1차 반응를 종결한다. 다음 460중량부의 성분 D-1을 1시간에 걸쳐 적가한 다음 유지반응시키고, 다시 IR분광기 및 습식분석을 통해 이소시아네이트기가 소멸된 시점에서 2차 반응을 종결하고 상온으로 식혀 준다. 건조된 부틸아세테이트로 고형분 함량 70 중량%가 되도록 조절하여 성분 B-7을 수득하였다.Into a four-necked flask equipped with a stirrer, a cooler and a thermometer, 67 parts by weight of trimethylolpropane and 620 parts by weight of the component A-1 mixture were added and 300 parts by weight of isocyanatopropyltrimethoxysilane were added dropwise over 1 hour, followed by 60 The reaction was carried out by heating to ℃, and the first reaction was terminated when the isocyanate group disappeared through IR spectroscopy and wet analysis. Next, 460 parts by weight of component D-1 was added dropwise over 1 hour, followed by a holding reaction, and after the isocyanate group disappeared through IR spectroscopy and wet analysis, the secondary reaction was terminated and cooled to room temperature. Component B-7 was obtained by adjusting to 70% by weight of solid content with dried butyl acetate.
이하 실시예를 통해 본 발명을 상세히 설명한다.The present invention will be described in detail through the following examples.
[실시예 1]Example 1
635중량부의 성분 A-1, 50중량부의 경화촉매(도데실벤젠술폰산디에탄올아민염), 5중량부의 도막평활성부여제(디스파론 LC-951, 일본 구스모토사), 20중량부의 자외선흡수제(2,4-디하이드록시벤조페논)를 하이스피드디졸버를 사용하여 2000rpm의 속도로 30분간 교반하여 잘 분산시킨 후, 20중량부의 점탄성조절제(칙사트록 289, 미국 엔엘사)를 넣고 다시 15분간 교반하여 분산하고, 320중량부의 성분 B-3, 30중량부의 멜라민수지(사이멜 303, 미국 몬산토사)를 넣고 15분간 추가 교반한다. 이를 자일렌을 사용 포드컵 NO.4로 60초가 되도록 점도를 조절하여 원하는 도료 조성물 1-1을 수득하였다.635 parts by weight of component A-1, 50 parts by weight of a curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 5 parts by weight of a film smoothing agent (disparon LC-951, Kusumoto, Japan), 20 parts by weight of an ultraviolet absorber (2,4-Dihydroxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissolver, and then 20 parts by weight of viscoelastic modifier (Chicksartlock 289, Enel Co., Ltd.) was added thereto. The mixture is stirred for 5 minutes to disperse, and 320 parts by weight of component B-3 and 30 parts by weight of melamine resin (Cymer 303, Monsanto, USA) are added and further stirred for 15 minutes. The viscosity was adjusted to 60 seconds using xylene in pod cup NO. 4 to obtain the desired coating composition 1-1.
[실시예 2]Example 2
160중량부의 성분 A-2, 15중량부의 트리메틸올프로판, 50중량부의 경화촉매(도데실벤젠술폰산디에탄올아민염), 5중량부의 도막평활성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제(2,4-하이드록시벤조페논)를 하이스피드디졸버를 사용하여 2000rpm의 속도로 30분 교반하여 잘 분산시킨 후, 20중량부의 점탄성조절제(칙사트롤 289, 미국 엔엘사)를 넣고 다시 15분간 교반하여 분산하고, 820중량부의 성분 B-1을 넣고 15분간 추가 교반한다. 이를 자일렌을 사용 포드컵 NO.4로 55초가 되도록 점도를 조절하여 원하는 도료 조성물 1-2를 수득하였다.160 parts by weight of component A-2, 15 parts by weight of trimethylolpropane, 50 parts by weight of curing catalyst (dodecylbenzenesulfonic acid diethanolamine salt), 5 parts by weight of coating film leveling agent (polybutyl acrylate), 20 parts by weight of ultraviolet absorber (2,4-hydroxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissolver, and then added 20 parts by weight of a viscoelastic modifier (Chicksarol 289, Enel Corporation, USA) for 15 minutes. The mixture is stirred and dispersed, and 820 parts by weight of component B-1 is added thereto, followed by further stirring for 15 minutes. This was adjusted to a viscosity of 55 seconds using xylene with Pod Cup NO.4 to obtain the desired coating composition 1-2.
[실시예 3Example 3
440중량부의 성분 A-2, 65중량부의 성분 A-3, 60중량부의 경화촉매(N-(4-메톡시벤질 O-N,N-디메틸아닐리튬 P-도데실벤젠슬포네이트), 10중량부의 도막평활성부여제(폴리붕틸아크릴레이트), 20중량부의 자외선흡수제(2,4-하이드록시벤조페논), 10중량부의 금속불활성화제(니켈-비스(디-n-부틸-디치오카바메이트))를 하이스피드디졸바를 사용하여 2000rpm의 속도로 30분 교반하여 잘 분산시킨 후 20중량부의 점탄성조절제(칙사트롤 289, 미국 엔엘사)를 넣고 다시 15분간 교반하여 분산한 다음 495중량부의 성분 B-4를 넣고 15분간 추가 교반하여 분산시킨다. 다음 자일렌을 사용하여 포드컵 NO.4로 60초가 되도록 점도를 조절하여 원하는 도료 조성물 1-3을 수득하였다.440 parts by weight of component A-2, 65 parts by weight of component A-3, 60 parts by weight of curing catalyst (N- (4-methoxybenzyl ON, N-dimethylanilithium P-dodecylbenzenesulfonate), 10 parts by weight of coating film Leveling agent (polybothyl acrylate), 20 parts by weight of ultraviolet absorber (2,4-hydroxybenzophenone), 10 parts by weight of metal deactivator (nickel-bis (di-n-butyl-dithiocarbamate)) After stirring for 30 minutes at a speed of 2000rpm using a high speed dissolba to disperse well, 20 parts by weight of viscoelastic modifier (Chicksarol 289, Enel Co., Ltd.) was added thereto, followed by stirring for 15 minutes to disperse, followed by 495 parts by weight of component B-4. The mixture was added and stirred for 15 minutes to further disperse The viscosity was adjusted to 60 seconds with Pod Cup NO.4 using xylene to obtain the desired coating composition 1-3.
[실시예 4]Example 4
255중량부의 성분 A-4, 50중량부의 경화촉매(도데실벤젠술폰산디에탄올아민염), 10중량부의 도막평활성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제(2,4-하이드록시벤조페논)를 하이스피드디졸바를 사용하여 2000rpm 속도로 30분간 교반하여 잘 분산시킨 후 20중량부의 점탄성조절제(칙사트롤 289, 미국 엔엘사)를 넣고 15분간 교반하여 분산시킨다. 다음 415중량부의 성분 B-6, 330중량부의 성분 B-7을 넣고 15분간 추가 교반하고 자일렌을 사용하여 포드컵 NO.4로 60초가 되도록 점도를 조절하여 원하는 도료 조성물 1-4를 수득하였다.255 parts by weight of component A-4, 50 parts by weight of curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 10 parts by weight of coating film leveling agent (polybutyl acrylate), 20 parts by weight of ultraviolet absorber (2,4-hydroxy Benzophenone) was stirred for 30 minutes at a speed of 2000 rpm using a high speed dissol bar, and then dispersed well. 20 parts by weight of viscoelastic modifier (Chicsarrol 289, Enel Co., Ltd.) was added thereto, followed by stirring for 15 minutes. Then, 415 parts by weight of component B-6 and 330 parts by weight of component B-7 were added and stirred for 15 minutes, and the viscosity was adjusted to 60 seconds with pod cup NO.4 using xylene to obtain a desired coating composition 1-4. .
[실시예 5]Example 5
370중량부의 성분 A-1, 50중량부의 경화촉매(도데실벤젠술폰산 디에탄올아민염), 10중량부의 도막평활성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제(2,4-디하이드록시벤조페논)를 하이스피드디졸바를 사용하여 2000rpm의 속도로 30분간 교반하여 잘 분산시킨 후 20중량부의 점탄성조절제(칙사트를 289, 미국 엔엘사)를 넣고 15분간 교반하여 분산시킨다. 다음 600중량부의 성분 B-6, 20중량부의 멜라민 수지(사이멜 222, 미국 사이텍사)를 넣고 15분간 추가 교반하고 자일렌을 사용하여 포드컵 NO.4로 60초가 되도록 점도를 조절하여 원하는 도료 조성물 1-5를 수득하였다.370 parts by weight of component A-1, 50 parts by weight of a curing catalyst (dodecylbenzenesulfonic acid diethanolamine salt), 10 parts by weight of a film smoothing agent (polybutyl acrylate), 20 parts by weight of an ultraviolet absorber (2,4-dihydro Roxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissol bar, and then 20 parts by weight of viscoelastic modifier (Chicksart 289, Enel Corporation, USA) was added and stirred for 15 minutes. Next, add 600 parts by weight of component B-6, 20 parts by weight of melamine resin (Cymel 222, Cytec, USA), and further stir for 15 minutes, and adjust the viscosity to 60 seconds with pod cup NO. Composition 1-5 was obtained.
[실시예 6]Example 6
520중량부의 성분 A-1, 20중량부의 경화촉매(도데실벤젠술폰산 디에탄올아민염), 20중량부의 도막평활성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제(2,4-디하이드록시벤조페논)를 하이스피드디졸바를 사용하여 2000rpm의 속도로 30분간 교반하여 잘 분산시킨 후 20중량부의 점탄성조절제(칙사트를 289, 미국 엔엘사) 20중량부를 넣고 15분간 다시 교반하여 분산시킨다. 다음 2-부탄온옥심으로 봉쇄화된 이소포론디이소시아테이트를 건조된 부틸아세테이트에 녹혀 고형분 함량70중량%가 되도록 한 용액 480중량부를 넣고 15분간 추가 교반하고 자일렌을 사용하여 포드컵 NO.4로 55초가 되도록 점도를 조절하여 비교 도료 조성물 1-6을 수득하였다.520 parts by weight of component A-1, 20 parts by weight of curing catalyst (dodecylbenzenesulfonic acid diethanolamine salt), 20 parts by weight of coating film leveling agent (polybutyl acrylate), 20 parts by weight of ultraviolet absorber (2,4-dihydro Roxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissol bar, and 20 parts by weight of 20 parts by weight of a viscoelastic modifier (Chicksart 289, Enel Co., Ltd.) were added thereto, followed by stirring again for 15 minutes. Next, 480 parts by weight of a solution of 2-butanone oxime-blocked isophorone diisocyanate dissolved in dried butyl acetate to a solid content of 70% by weight was added, followed by additional stirring for 15 minutes. The viscosity was adjusted to 55 seconds to obtain Comparative Paint Composition 1-6.
[비교실시예 7]Comparative Example 7
870중량부의 성분 A-1, 50중량부의 경화촉매(도데실벤젠술폰산디에탄올아민염), 10중량부의 도막평화성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제(2,4-디하이드록시벤조페논)를 하이스피드디졸바를 사용하여 2000rpm의 속도로 30분간 교반하여 잘 분산시킨 후 20중량부의 점탄성부여제(칙사트롤 289, 미국 엔엘사)를 넣고 15분간 교반하여 분산시킨다. 다음 90중량부의 멜라민 수지(사이멜 303, 미국 사이텍사)를 넣고 15분간 추가 교반하고 자일렌을 사용하여 포드컵 NO.4로 55초가 되도록 점도를 조절하여 비교 도료 조성물 1-7을 수득하였다.870 parts by weight of component A-1, 50 parts by weight of a curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 10 parts by weight of a coating film imparting agent (polybutyl acrylate), 20 parts by weight of an ultraviolet absorber (2,4-dihydrate Roxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissol bar, and then added by 20 parts by weight of a viscoelastic imparting agent (Chyxanthrol 289, Enel Corporation, USA) and stirred for 15 minutes. Next, 90 parts by weight of melamine resin (Cymel 303, Cytec, USA) was added thereto, and further stirred for 15 minutes, and the viscosity was adjusted to 55 seconds with Pod Cup NO.4 using xylene to obtain Comparative Coating Composition 1-7.
[비교실시예 8]Comparative Example 8
520중량부의 성분 A-6, 50중량부의 경화촉매(도데실벤젠술폰산디에탄올아민염), 10중량부의 도막평활성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제 (2,4-디하이드록시벤조페논)를 하이스피드디졸바를 사용하여 2000rpm의 속도로 30분 교반하여 잘 분산시킨 후 20중량부의 점탄성부여제(칙사트롤 289, 미국 엔엘사)를 넣고 15분간 다시 교반하여 분산시킨다. 다음 2-부탄논옥심으로 봉쇄화된 이소포론디이소시아네이트를 건조된 부틸아세테이트에 녹혀 고형분 함량 70중량%가 되도록 한 용액 480중량부를 넣고 15분간 추가 교반하고 자일렌을 사용하여 포드컵 NO.4로 55초가 되도록 점도를 조절하여 비교 도료 조성물 1-8을 수득하였다.520 parts by weight of component A-6, 50 parts by weight of curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 10 parts by weight of coating film leveling agent (polybutyl acrylate), 20 parts by weight of ultraviolet absorber (2,4-dihydro Roxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissol bar, and then added by 20 parts by weight of a viscoelastic agent (Chyxanthrol 289, Enel Co., Ltd.) and stirred again for 15 minutes. Next, 480 parts by weight of a solution of 2-butanone oxime-blocked isophorone diisocyanate dissolved in dried butyl acetate to a solid content of 70% by weight was added and stirred for 15 minutes. The viscosity was adjusted to 55 seconds to obtain Comparative Paint Composition 1-8.
[비교실시예 9]Comparative Example 9
870중량부의 성분 A-6, 50중량부의 경화촉매(도데실벤젠술폰산디에탄올아민염), 10중량부의 도막평활성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제(2,4-디하이드록시벤조페논)를 하이스피드디졸바를 사용하여 2000rpm의 속도로 30분 교반하여 잘 분산시킨 후 20중량부의 점탄성부여제(칙사트롤 289, 미국 엔엘사)를 넣고 15분간 다시 교반하여 분산시킨다. 멜라민 수지(싸이멜 303, 미국 싸이텍사)를 건조된 부틸아세테이트에 녹여 고형분 함량이 70중량%가 되도록 한 용액 90중량부를 넣고 15분간 추가 교반한 다음 자일렌을 사용하여 포드컵 NO.4로 55초가 되도록 점도를 조절하여 비교 도료 조성물 1-9를 수득하였다.870 parts by weight of component A-6, 50 parts by weight of a curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 10 parts by weight of a film smoothing agent (polybutyl acrylate), 20 parts by weight of an ultraviolet absorber (2,4-dihydro Roxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissol bar, and then added by 20 parts by weight of a viscoelastic agent (Chyxanthrol 289, Enel Co., Ltd.) and stirred again for 15 minutes. Melamine resin (Cymel 303, Cytec, USA) was dissolved in dried butyl acetate to obtain a solids content of 70% by weight, 90 parts by weight of the solution was added and stirred for 15 minutes. The viscosity was adjusted so as to be a second to obtain Comparative Coating Composition 1-9.
[비교실시예 9]Comparative Example 9
1000중량부의 성분 A-6, 50중량부의 경화촉매(도데실벤젠술폰산디에탄올아민염), 10중량부의 도막평활성부여제(폴리부틸아크릴레이트), 20중량부의 자외선흡수제(2,4-디하이드록시벤조페논)를 하이스피드디졸바를 사용하여 2000rpm의 속도로 30분간 교반하여 잘 분산시킨 후 20중량부의 점탄성부여제(칙사트롤 289, 미국 엔엘사)를 넣고 15분간 교반하여 분산시킨다. 다음 자일렌을 사용하여 포드컵 NO.4로 55초가 되도록 점도를 조절하여 비교 도료 조성물 1-10을 수득하였다.1000 parts by weight of component A-6, 50 parts by weight of curing catalyst (dodecylbenzenesulfonic acid ethanolamine salt), 10 parts by weight of coating film leveling agent (polybutyl acrylate), 20 parts by weight of ultraviolet absorber (2,4-dihydrate Roxybenzophenone) was dispersed well by stirring for 30 minutes at a speed of 2000 rpm using a high speed dissol bar, and then added by 20 parts by weight of a viscoelastic imparting agent (Chyxanthrol 289, Enel Corporation, USA) and stirred for 15 minutes. The viscosity was adjusted to 55 seconds with Pod Cup NO.4 using xylene to obtain Comparative Paint Composition 1-10.
[도료의응용물성비교결과][Comparison of Application Properties of Paints]
전착 및 중도 도장이 마감된 가로 × 세로 = 200㎜ × 200㎜ 크기의 아연강판에 벨형 자동도장기를 사용하여 20㎛의 두께로 칼라 도장한 후, 상대습도 70% × 상온에서 5분간 방치시킨다. 제조예 및 비교제조예들의 도료 조성물을 자일렌을 사용하여 포드컵 NO.4로 30초가 되도록 점도를 조절한 다음, 2회에 걸쳐 40㎛의 두께로 곧 바로 후속 도장한 후 10분간 방치한 다음 145℃로 조절된 오븐내에서 25분간 경화시켜 도막물성시험용 시편을 제작하였다. 이에 대한 물성시험결과는 표 1 및 표 2와 같다.After the electrodeposition and the intermediate coating finish, the horizontal × vertical = 200㎜ × 200㎜ size zinc coated steel sheet using a bell type automatic coating machine to color the thickness of 20㎛, and left for 5 minutes at 70% relative humidity × room temperature. The viscosity of the coating composition of Preparation Examples and Comparative Preparation Examples was adjusted to 30 seconds with Pod Cup NO.4 using xylene, followed by immediately following a two-time thickness of 40 μm and left for 10 minutes. Hardening for 25 minutes in an oven adjusted to 145 ℃ to prepare a test film for physical properties test. Physical property test results for this are shown in Table 1 and Table 2.
c: 시편균열 발생.c: specimen cracking.
외관: 육안판정. ○ = 우수, △ = 양호, × = 미흡, ×× = 불량Appearance: Visual judgment. ○ = good, △ = good, × = poor, × × = bad
재도장성: 상기 도막물성시험용 시편을 150℃에서 1시간 추가 방치후 칼라 도료 및 투명도로를 동일 방법으로 재 도장후 145℃에서 25분간 경화시킨 시편을 ASTM D3359에 기재된 DROSS CUT TAPE ADHESION 시험법으로 평가후 하기 방법에 의해 기재하였다.Repaintability: After the coating material test specimen is left at 150 ° C. for 1 hour and then repainted in the same manner with the color paint and transparency, the specimen cured for 25 minutes at 145 ° C. is evaluated by the DROSS CUT TAPE ADHESION test method described in ASTM D3359. It described afterwards by the following method.
내마모성: ASTM D 4060에 기재된 방법으로 TABER ABRASER기를 사용하는 시험법에 준해 평가 표시하였다.Abrasion resistance: Evaluation was indicated according to the test method using a TABER ABRASER group by the method described in ASTM D 4060.
연필경도: ASTM D 3363 시험법에 준해 평가하여 표시하였다.Pencil Hardness: Evaluated and marked according to ASTM D 3363 test method.
내산성: 도막위에 10% 황산용액을 스포이드로 1 방울 떨어뜨린후 70℃ 오븐 내에 5분간 방치한 다음 도막 손상 정도를 육안 판정하여 표시하였다.Acid resistance: After dropping a drop of 10% sulfuric acid solution on the coating film with a dropper, the resultant was left in an oven at 70 ° C. for 5 minutes and then visually judged and marked the degree of coating damage.
○=손상부위 없슴, △=자국만 남음, ×=파인자국 발생, ××=파인자국 심함○ = No damage area, △ = Frequency only, × = Fine marks, ×× = Fine marks
내황변성: COLORY-METER로 상기 도막물성시험용 시편의 E값을 측정한 다음 150℃에서 1시간 추가 방치시킨 후 다시 E값을 측정하여 변화값인 △E로 표시하였다.Yellowing resistance: After measuring the E value of the coating material test specimen by COLORY-METER, and further left for 1 hour at 150 ℃, the value of E was measured again and expressed as ΔE.
내후성: 미국 아리조나 EMMAQUQ 테스트와 플로리다 폭로시험을 병행하여 광택손실 정도를 ASTM D 523 시험법에 준해 비교 표시하였다.Weatherability: The degree of gloss loss was compared according to the ASTM D 523 test method in combination with the American Arizona EMMAQUQ test and the Florida exposure test.
상기 시험 결과에서 알 수 있듯이, 본 발명에 의한 1액형 도료 조성물은 폴리올변성 이소시아네이트를 기재로 사용하여 상용성 및 용해도가 매우 양호한 동시에 분자내 함유된 반응성 실란을 통해 타소지와의 우수한 밀착성 발현이 가능하여 재도장시 부착 불량이 발생하지 않는다. 또한 경화후 도막내에 형성된 실록산 결합부위의 놓은 결합에너지로 경도 및 내흠집성의 향상은 물론 내산성이 극히 우수한 도막을 형성할 수 있음을 명백히 알 수 있다.As can be seen from the above test results, the one-part coating composition according to the present invention is very good in compatibility and solubility using polyol-modified isocyanate as a substrate, and at the same time, excellent adhesion to other materials can be expressed through the reactive silane contained in the molecule. This prevents adhesion failure when repainting. In addition, it can be clearly seen that the coating energy of the siloxane bonding portion formed in the coating film after curing can improve the hardness and scratch resistance as well as form a coating film having extremely excellent acid resistance.
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| KR20190047831A (en) * | 2017-10-30 | 2019-05-09 | 주식회사 케이씨씨 | Paint composition |
| WO2019088551A1 (en) * | 2017-10-30 | 2019-05-09 | 주식회사 케이씨씨 | Coating composition |
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| JPS6084365A (en) * | 1983-10-13 | 1985-05-13 | Dainippon Toryo Co Ltd | Paint composition for stainless steel |
| US4892906A (en) * | 1988-09-28 | 1990-01-09 | Ppg Industries, Inc. | Urethane coating composition |
| KR0127783B1 (en) * | 1994-06-03 | 1997-12-26 | 김충세 | Composition for 1-component automobile paint |
| JPH07331131A (en) * | 1994-06-09 | 1995-12-19 | Shinto Paint Co Ltd | Cationic electrodeposition coating resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190047831A (en) * | 2017-10-30 | 2019-05-09 | 주식회사 케이씨씨 | Paint composition |
| WO2019088551A1 (en) * | 2017-10-30 | 2019-05-09 | 주식회사 케이씨씨 | Coating composition |
| CN111295425A (en) * | 2017-10-30 | 2020-06-16 | Ｋｃｃ公司 | Coating composition |
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