KR100503946B1 - Non Aqueous Dispersion Copolymer Composition And Method for Preparing the Same - Google Patents
Non Aqueous Dispersion Copolymer Composition And Method for Preparing the Same Download PDFInfo
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Abstract
자동차용 금속제의 중, 상도 도장용 도료에 적용되는 비수분산성 혼성중합체 조성물 및 이의 제조방법이 개시되어 있다. 아크릴계 단관능성 모노머 100 중량부에 대하여 다관능성 모노머 5 내지 20 중량부를 중합 반응하여 수득한 결정형 비수분산성 혼성중합체 조성물을 제조한다. 그리고, 아크릴계 단관능성 모노머 100 중량부에 대하여 다관능성 모노머 5 내지 20 중량부를 중합반응에 의해 제조되는 결정형 비수분산성 혼성중합체 조성물의 제조 방법이 있다. 아크릴, 에폭시, 폴리에스테르, 알키드, 멜라민, 우레탄 등 다양한 도료용 수지에 적용할 수 있는 장점을 갖고 있으면서 광택 및 선영성, 부착성 및 경도를 저하시키지 않는 비수분산성 혼성중합체 조성물 및 이의 제조방법에 관한 것이다.Disclosed are a non-water-dispersible interpolymer composition and a method for producing the same, which are applied to a paint for a medium and top coat of an automobile metal. A crystalline non-water-dispersible interpolymer composition obtained by polymerizing 5 to 20 parts by weight of a polyfunctional monomer with respect to 100 parts by weight of an acrylic monofunctional monomer is prepared. In addition, there is a method for producing a crystalline non-water-dispersible interpolymer composition prepared by a polymerization reaction with 5 to 20 parts by weight of a polyfunctional monomer based on 100 parts by weight of an acrylic monofunctional monomer. Non-dispersible interpolymer composition having a merit that can be applied to various paint resins such as acrylic, epoxy, polyester, alkyd, melamine, urethane, etc., and does not reduce gloss and lightness, adhesion and hardness, and a method of preparing the same. It is about.
Description
본 발명은 비수분산성(Non Aqueous Dispersion ; NAD) 혼성중합체 조성물 및 이의 제조 방법에 관한 것으로 보다 상세하게는 우수한 도료 분산성과 광택 및 선영성이 동시에 요구되는 금속제의 도료용으로 이용되는 비수분산성 혼성중합체 조성물 및 이의 제조 방법에 관한 것이다.The present invention relates to a non-aqueous dispersion (NAD) interpolymer composition and a method for preparing the same, and more particularly, to a non-water dispersible hybrid used for a metal coating which requires excellent paint dispersibility and gloss and clarity. It relates to a polymer composition and a method of making the same.
일반적으로 공업 도료 또는 자동차용 도료로서 고광택 및 선영성이 우수한 금속성 도료의 안료 침강 방지 및 도장부위의 모서리 부위의 흐름성을 방지하기 위해 흐름 억제제(Rheology controller)로 마이크로겔(microgel)이나 fumed silica 가 가장 많이 사용된다.In general, microgel or fumed silica is used as a rheology controller to prevent pigment settling and to prevent flow of corners of the coating area of an industrial paint or automotive paint, which has a high gloss and stiffness. Most used.
상기 마이크로겔은 흐름 억제성(Rheology control)이 우수하나 도료용 수지와의 상용성이 극히 저조하여 균일하게 분산하는데 많은 시간과 특별한 분산 설비가 요구되어 지고 안료와의 불일치성을 유발하여 도료 입도가 높아 자동차 도료가 요구되어지는 고광택성 및 선영성을 저해하는 요인이 되곤 하였다. 상기 Fumed silica는 분산성과 흐름 억제성이 우수하나 도료용 수지와의 굴절율이 달라 도료용 수지의 투명성 및 선영성, 광택성을 저하시켜 사용량이 극히 제한되고, 도막의 경도를 떨어뜨리는 요인이 되기도 한다. The microgel has excellent rheology control, but it has a very low compatibility with the coating resin, which requires a lot of time and a special dispersing facility to uniformly disperse and causes a mismatch with the pigment, resulting in high paint particle size. Automotive paints have often been a deterrent to high glossiness and sensibility. Fumed silica is excellent in dispersibility and flow inhibitory, but because the refractive index of the coating resin is different, the transparency, contrast, glossiness of the coating resin is reduced, the amount of use is extremely limited, and the hardness of the coating film may be reduced. .
지금까지 고광택성과 선영성, 세깅성(Sag resistance)) 및 작업성이 요구되는 공업용 도료나 특히 금속성의 자동차용 도료의 흐름 억제제로서 주로 마이크로겔 혼성중합체(copolymer)가 주종을 이루고 있다. 상기 마이크로겔 혼성중합체는 주로 유화, 현탁, 침전 중합법등이 상용화되어 있으며, 유성도료에 적용하기 위해서는 상기 중합법에서 얻은 마이크로겔 혼성중합체의 용매(물)를 유기용매로 치환하여 재 분산시켜야하는 어려움이 있다. 또한 계면 활성제에 의한 마이크로겔 결정 표면의 오염으로 인한 도료용 수지와의 분산성이 극히 나쁘고 상용성도 저하되어 선영성 및 광택성의 한계가 있다. 이러한 상기 도료에서의 악 영향을 방지하기 위해서는 계면 활성제 제거 및 수분 제거 공정에 많은 어려움이 따른다. 또한 마이크로겔 혼성중합체 자체의 저장 안정성이 취약하여 보관중에 침전의 문제가 발생되고, 도료 적용시 도막에 핀홀(Pin hole)이나 분화구 형상이 생성되어 결함의 원인이 되기도 한다. 상기 이러한 문제점을 해결하기 위해, 수지 및 안료 분산성이 매우 우수하고, 선영성, 광택성 및 도막의 경도가 우수한 새로운 타입의 흐름 억제제인 비수분산성 류인 결정형태의 혼성중합체가 필요하다. Until now, microgel copolymers have been mainly used as flow inhibitors for industrial paints, especially metallic automotive paints, which require high gloss, sensibility, sagging resistance, and workability. The microgel interpolymers are mainly commercialized in emulsification, suspension, and precipitation polymerization methods, and in order to apply them to oil paints, it is difficult to disperse and disperse the solvent (water) of the microgel interpolymers obtained by the polymerization method with an organic solvent. There is this. In addition, the dispersibility with the coating resin due to the contamination of the surface of the microgel crystal by the surfactant is extremely bad and the compatibility is also lowered, there is a limit of clarity and gloss. In order to prevent such adverse effects in the paint, there are many difficulties in the surfactant removal and water removal processes. In addition, due to the poor storage stability of the microgel copolymer itself, problems of precipitation occur during storage, and pinholes or craters are formed in the coating film during coating, which may cause defects. In order to solve the above problems, there is a need for a non-aqueous dispersant, a crystalline form of interpolymer, which is a new type of flow inhibitor which is very excellent in resin and pigment dispersibility and excellent in clarity, gloss and hardness of a coating film.
따라서 본 발명의 목적은 우수한 금속제의 안료 분산성 및 작업성과 동시에 고광택 및 선영성이 요구되는 공업용 특히 자동차 도료용 중, 상도 도료에 적용되는 비수분산성 혼성중합체 조성물을 제공하는데 있다. Accordingly, an object of the present invention is to provide a non-water-dispersible interpolymer composition applied to a top coat in an industrial, especially automotive paint, which requires excellent pigment dispersibility and workability and high gloss and lightness.
본 발명의 다른 목적은 우수한 금속제의 안료 분산성 및 작업성과 동시에 고 광택 및 선영성이 요구되는 공업용 특히 자동차 도료용 중, 상도 도료에 적용되는 비수분산성 혼성중합체 조성물의 제조 방법을 제공하는데 있다.Another object of the present invention is to provide a method for producing a non-water-dispersible interpolymer composition applied to a top coat in an industrial, especially automotive coating, which requires excellent metallic pigment dispersibility and workability as well as high gloss and lightness.
상기한 본 발명의 목적을 달성하기 위하여 본 발명은 The present invention to achieve the above object of the present invention
아크릴계 단관능성 모노머 100 중량부에 대하여 다관능성 모노머 5 내지 20중량부를 중합 반응하여 수득한 결정형 비수분산성 혼성중합체 조성물을 제공한다.It provides a crystalline non-water-dispersible interpolymer composition obtained by polymerizing 5 to 20 parts by weight of a polyfunctional monomer with respect to 100 parts by weight of an acrylic monofunctional monomer.
본 발명의 다른 목적을 달성하기 위하여 본 발명은 In order to achieve the other object of the present invention
아크릴계 단관능성 모노머 100 중량부에 대하여 다관능성 모노머 5 내지 20 중량부를 중합반응에 의해 제조되는 결정형 비수분산성 공중합체 조성물의 제조 방법을 제공한다.Provided is a method for producing a crystalline non-water-dispersible copolymer composition prepared by polymerization by 5 to 20 parts by weight of a polyfunctional monomer with respect to 100 parts by weight of an acrylic monofunctional monomer.
상기 본 발명에 따른 비수분산성 혼성중합체 조성물을 사용함으로 인해 아크릴, 에폭시, 폴리에스테르, 알키드, 멜라민, 우레탄 등 다양한 도료용 수지에 적용할 수 있는 장점을 갖고 있으면서 광택 및 선영성을 저하시키지 않는 도료 조성물을 제공할 수 있다. By using the non-water-dispersible interpolymer composition according to the present invention has a merit that can be applied to a variety of paint resins, such as acrylic, epoxy, polyester, alkyd, melamine, urethane, while not reducing gloss and striation A composition can be provided.
이하, 본 발명을 더욱 상세히 설명하기로 한다. Hereinafter, the present invention will be described in more detail.
아크릴계 단관능성 모노머 100 중량부에 대하여 다관능성 모노머 5 내지 20 중량부를 중합 반응하여 비수분산성 혼성중합체 조성물이 제조된다.A non-water-dispersible interpolymer composition is prepared by polymerizing 5 to 20 parts by weight of a polyfunctional monomer with respect to 100 parts by weight of an acrylic monofunctional monomer.
상기 비수분산성 혼성중합체의 조성물은 일반 아크릴계 단관능성 모노머와 다관능성 모노머의 혼합 무게비를 조절하여 유기 용제에 적절히 분산중합 반응시켜 저장중 침전되지 않는 분자량과 입자크기를 갖는 구형 류의 결정형 혼성중합체를 합성해야 하며 중량 평균 분자량이 100,000 내지 8,000,000이고, 입자의 직경이 0.03 내지 0.2 마이크론이고, 수산기 값(Hydroxyl Value)이 30 내지 80이고, 산 값이 3 이하이고, 유리 전이 온도가 60내지 130℃가 되도록 설계되어야 최적의 물성을 얻을 수 있었다. The composition of the non-water-dispersible interpolymer is a spherical crystalline interpolymer having a molecular weight and a particle size that does not precipitate during storage by controlling the mixing weight ratio of a general acrylic monofunctional monomer and a polyfunctional monomer to appropriately disperse and polymerize in an organic solvent. It should be synthesized and has a weight average molecular weight of 100,000 to 8,000,000, a particle diameter of 0.03 to 0.2 micron, a hydroxyl value of 30 to 80, an acid value of 3 or less, and a glass transition temperature of 60 to 130 ° C. It should be designed so as to obtain optimum physical properties.
상기 단관능성 모노머에 대한 다관능성 모노머 비율에 따라 비수분산성 혼성중합체 분자의 분자량과 결정 입자 크기가 좌우되며 저장 안정성과 합성시 용제에 대한 용해력에도 큰 영향을 미친다. 상기 단관능성 모노머에 대한 다관능성 모노머의 비율이 5%이하이면, 상기 비수분산성 혼성중합체의 입자 크기가 너무 작아 상대적인 결정의 표면 저하로 일반 아크릴 수지와 혼용시 흐름성의 특성이 크게 감소하였다. 반면 단관능성 모노머에 대한 다관능성 모노머의 비율이 20% 이상 초과되면 코어-쉘(core-shell) 중합시 거대 고분자가 되어 내부 가교 결합 밀도 증가로 Solvent와 층분리 되거나 합성 중에 겔화가 일어난다. 바람직하게는 단관능성 모노머에 대한 다관능성 모노머의 비율이 5 내지 20%범위이고, 더 바람직하기는 10 내지 15%범위이다.The molecular weight and crystal grain size of the non-water dispersible interpolymer molecules depend on the ratio of the multifunctional monomer to the monofunctional monomer, and have a great influence on the storage stability and the solvent dissolution ability during the synthesis. When the ratio of the polyfunctional monomer to the monofunctional monomer is 5% or less, the particle size of the non-water-dispersible interpolymer is too small to decrease the surface of the relative crystals, thereby greatly reducing the flowability when mixed with the general acrylic resin. On the other hand, when the ratio of the polyfunctional monomer to the monofunctional monomer exceeds 20%, it becomes a macromolecular polymer during core-shell polymerization, and due to the increase in internal crosslinking density, the layer is separated from the solvent and gelation occurs during synthesis. Preferably the ratio of the polyfunctional monomer to the monofunctional monomer is in the range of 5 to 20%, more preferably in the range of 10 to 15%.
상기 비수분산성 혼합중합체 조성물에 있어서 중량 평균 분자량이 100,000 이하가 되면 용제내에서 결정이 용해되어 결정 안정성 특성이 크게 감소할 수 있다. 그리고, 상기 비수분산성 혼합중합체 조성물의 중량 평균 분자량이 8,000,000 초과되면 용제내에서 균일하게 분산되지 않고 결정이 분리 또는 침강 현상이 일어날 수 있기 때문이다. 그럼으로 상기 비수분산성 혼성중합체의 조성물은 중량 평균 분자량이 100,000 내지 8,000,00의 범위를 갖는 것이 바람직하다. 더 바람직하게는 250,000내지 5,500,000이다.When the weight average molecular weight of the non-water-dispersible mixed polymer composition is 100,000 or less, crystals may be dissolved in a solvent, thereby greatly reducing crystal stability characteristics. When the weight average molecular weight of the non-water-dispersible mixed polymer composition is more than 8,000,000, crystals may be separated or precipitated without uniformly dispersing in the solvent. Therefore, the composition of the non-water dispersible interpolymer preferably has a weight average molecular weight in the range of 100,000 to 8,000,00. More preferably 250,000 to 5,500,000.
또한, 상기 비수분산성 혼합중합체 조성물에 있어서 상기 입자 직경이 0.03 마이크론 이하이면, 결정 표면적이 작아서 바람직한 흐름 억제제(Rheology controller)효과를 발휘 할 수 없다. 그리고, 상기 입자직경이 0.2 마이크론 초과되면 결정 표면적이 크기 때문에 최종 도료 제조시 선영성 및 광택성을 저하시키기때문이다. 그럼으로 상기 비수분산성 혼성중합체의 조성물은 입자직경이 0.03 내지 0.2 마이크론의 범위를 갖는 것이 바람직하다. 더 바람직하게는 0.04 내지 0,1마이크론이다.In addition, in the non-water-dispersible mixed polymer composition, when the particle diameter is 0.03 microns or less, the crystal surface area is small, so that a preferable rheology controller effect cannot be exhibited. When the particle diameter exceeds 0.2 micron, since the crystal surface area is large, the lightness and glossiness of the final coating may be reduced. Therefore, it is preferable that the composition of the non-water dispersible interpolymer has a particle diameter in the range of 0.03 to 0.2 micron. More preferably 0.04 to 0,1 micron.
상기 비수분산성 혼합중합체 조성물에 있어서 상기 수산기 값(Hydroxyl Value)이 30 이하이면, 도료용 수지와 혼용성이 떨어지고, 아미노 수지를 사용한 소부 도료나 우레탄 수지를 이용한 반응 경화형 도료에서 직접 반응에 참가하지 못하고, 상기 비수분산성 혼합중합체가 별도로 거동하게 되어 도막의 부착이나 경화 밀도를 저하시켜 경도가 떨어지는 결과가 나타났다. 반면에 상기 수산기 값(Hydroxyl Value)이 80 이상을 초과하면, 상기 비수분산성 혼합중합체가 털복숭아 모양으로 형성되어 저장 중 비수분산성 결정간의 응집이 일어난다. 그리고, 분자량을 높이기가 어려워 고분자 결정 형성이 되지 않아 유기 용제에 쉽게 용해되어 용제 내에 결정 상태로 분산이 되지 않았다. 그럼으로, 상기 비수분산성 혼성중합체의 조성물은 수산기 값(Hydroxyl Value)이 30 내지 80의 범위를 갖는 것이 바람직하다. In the non-water-dispersible mixed polymer composition, when the hydroxyl value is 30 or less, it is incompatible with the resin for coating, and does not participate in the reaction directly in the baking paint using an amino resin or the reaction curable paint using a urethane resin. In addition, the non-water-dispersible mixed polymer behaves separately, resulting in a decrease in hardness due to a decrease in adhesion or curing density of the coating film. On the other hand, if the hydroxyl value (Hydroxyl Value) exceeds 80, the non-water-dispersible mixed polymer is formed into a hair peach shape agglomeration between the non-water-dispersible crystals during storage. In addition, it is difficult to increase the molecular weight, so that polymer crystals do not form, are easily dissolved in an organic solvent, and are not dispersed in a crystalline state in the solvent. Therefore, it is preferable that the composition of the non-water dispersible interpolymer has a hydroxyl value (Hydroxyl Value) in the range of 30 to 80.
상기 비수분산성 혼합중합체 조성물에 있어서 상기 유리 전이 온도가 60℃이하이면, 유기 용제에 쉽게 용해되어 결정형 고분자가 되지 않고, 선형성 고분자로 합성되고, 인위적으로 결정화가 형성되었더라도 장기 보관시 유기 용제에 용해되거나 서로 응집되어 결정이 파괴되고, 침전 또는 일반 아크릴 수지 형태로 변하게 된다. 반면에, 상기 유리전이 온도가 130℃이상 초과되면, 비수분산성 혼성중합체 조성물 형성은 양호하나 도막의 부착성 및 내 충격성을 저하시키고, 도료용 수지와의 상용성 및 안료와의 분산성도 저하가 된다. 본 발명에서 바람직한 유리 전이 온도 값의 범위는 60 내지 130℃가 바람직하다. In the non-water-dispersible mixed polymer composition, when the glass transition temperature is 60 ° C. or less, it is easily dissolved in an organic solvent and does not become a crystalline polymer, but is synthesized as a linear polymer and dissolved in an organic solvent when stored for a long time even if artificially crystallized. Or agglomerate with each other, causing the crystals to break and become precipitated or converted into a common acrylic resin. On the other hand, when the glass transition temperature is higher than 130 ° C., the formation of the non-water dispersible interpolymer composition is good but the adhesion and impact resistance of the coating film is lowered, and the compatibility with the coating resin and the dispersibility with the pigment are also reduced. do. As for the range of the preferable glass transition temperature value in this invention, 60-130 degreeC is preferable.
바람직하게는, 상기 아크릴계 비수분산성 혼성중합체에 사용되는 단관능성 모노머로는 스타이렌 모노머, 메틸메타 아크릴레이트 모노머, 비닐톨루엔 모노머, 부틸아크릴레이트 모노머, 아크로 나이트릴 모노머, 에틸 아크릴레이트 모노머, 부틸 아크릴레이트 모노머, 부틸메타 아크릴레이트 모노머, 에틸메타 아크릴레이트 모노머, 2-하이드록시에틸 아크릴레이트 모노머, 2-하이드록시에틸 메타 아크릴레이트 모노머, 2-하이드록시 프로필 아크릴레이트 모노머, 2-하이드록시 프로필 메타 아크릴레이트 모노머, 2-에틸 헥실 아크릴레이트 모노머, 2-에틸 헥실 메타 아크릴레이트 모노머, 아크릴릭 애시드, 메타 아크릴릭 애시드, 글리시딜 메타 아크릴레이트 모노머, 아크릴릭 아미드(acrylic amide), 프말산, 말레익산 등을 예를 들 수 있다. 이들은 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 이들 이외의 단관능성 모노머를 사용할 수도 있다. Preferably, the monofunctional monomer used in the acrylic non-water-dispersible interpolymer is a styrene monomer, a methyl methacrylate monomer, a vinyltoluene monomer, a butyl acrylate monomer, an acrylonitrile monomer, an ethyl acrylate monomer, or a butyl acryl. Acrylate monomer, butyl methacrylate monomer, ethyl methacrylate monomer, 2-hydroxyethyl acrylate monomer, 2-hydroxyethyl methacrylate monomer, 2-hydroxy propyl acrylate monomer, 2-hydroxy propyl methacrylate Examples of acrylate monomers, 2-ethyl hexyl acrylate monomers, 2-ethyl hexyl methacrylate monomers, acrylic acids, methacrylic acids, glycidyl methacrylate monomers, acrylic amides, pmaric acid, maleic acid and the like Can be mentioned. These can be used individually or in mixture of 2 or more types. Monofunctional monomers other than these can also be used.
바람직하게는, 상기 다관능성 모노머는 알릴글리시딜에테르, 1,6헥산디올디아크릴레이트, 1,6헥산디올디메타아크릴레이트, 에틸렌글리콜디메타아크릴레이트, 트리프로필렌글리콜디메타아크릴레이트, 트리메치롤프로판트리아크릴레이트, 트리메틸올프로판 디알릴 에테르(trimethylol diallyl ether), 디에틸렌글리콜디아크릴레이트, 펜타에리스리톨테트라아크릴레이트, 네오펜틸글리콜디아크릴레이트, 디알릴프탈레이트,에톡실레이티드트리메틸올프로판트리아크릴레이트(ethoxylated trim ethylolpropane triacrylate), 에틸렌글리콜디아크릴레이트, 디비닐벤젠 등을 예를 들 수 있다. 이들은 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 이들 이외의 다관능성 모노머를 사용할 수도 있다. Preferably, the multifunctional monomer is allyl glycidyl ether, 1,6 hexanediol diacrylate, 1,6 hexanediol dimethacrylate, ethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tri Methrol propane triacrylate, trimethylol propane diallyl ether, diethylene glycol diacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, diallyl phthalate, ethoxylated trimethylol propane Ethyllated trim ethylolpropane triacrylate, ethylene glycol diacrylate, divinylbenzene, etc. are mentioned. These can be used individually or in mixture of 2 or more types. Polyfunctional monomers other than these can also be used.
본 발명에서 단관능성 모노머와 다관능성 모노머에 적용되는 중합반응 개시제로는 일반 아크릴 수지 중합과 유사하나 일반적인 선형 아크릴 폴리머와는 달리 0.03 내지 0.2 마이크론의 직경을 갖는 미세한 구형의 폴리머를 얻어야하고, 유기 용매 속에서 중합된 폴리머끼리 재 응집이 되지 않도록 방지하기 위해서는 적합한 개시제 선정이 매우 중요하다.In the present invention, the polymerization initiator applied to the monofunctional monomer and the polyfunctional monomer is similar to the general acrylic resin polymerization, but unlike the general linear acrylic polymer, a fine spherical polymer having a diameter of 0.03 to 0.2 micron should be obtained, and an organic solvent. In order to prevent re-aggregation of polymers polymerized in the inside, selection of a suitable initiator is very important.
상기 비수분산성 혼성중합체 조성물 제조에 있어 적용된 개시제로는 이소부틸퍼옥사이드, 라우로일퍼옥사이드(lauroyl peroxide), 벤조일퍼옥사이드, 디터셔리부틸퍼옥사이드, 디큐밀퍼옥사이드, 사이클로헥사논퍼옥사이드, 터셔리부틸하이드로퍼옥사이드, 디이소프로필벤젠하이드로퍼옥사이드, 2,2'-아조비스(이소부티로나이트릴), 2,2'-아조비스(2,4-디메틸펜탄나이트릴), 2,2'-아조비스(메틸부티로나이트릴), 1,1'-아조비스(시아노사이클로헥산), 터셔리부틸퍼옥시2-에틸헥사노에이트(tert-butyl peroxy 2-ethylhexanoate) 등을 예를 들 수 있다. 이들은 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 여기에 언급된 상기 개시제 만이 본 발명에 대한 요구사항을 제약하지는 않는다.Initiators applied in the preparation of the non-water-dispersible interpolymer composition are isobutyl peroxide, lauroyl peroxide, benzoyl peroxide, dietary butyl peroxide, dicumyl peroxide, cyclohexanone peroxide, tertiary butyl Hydroperoxide, diisopropylbenzenehydroperoxide, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylpentanenitrile), 2,2'- Azobis (methylbutyronitrile), 1,1'- azobis (cyanocyclohexane), tert-butyl peroxy 2-ethylhexanoate, etc. are mentioned, for example. have. These can be used individually or in mixture of 2 or more types. The initiators mentioned herein alone do not limit the requirements for the present invention.
또한, 상기 개시제는 모노머와 용제 종류, 반응온도에 따라 적합한 반감기를 갖고 분해 온도에 맞는 개시제를 적절히 선택해야 한다. 일반적으로 아크릴 수지 중합 시에 사용되는 개시제를 선택하여 사용해도 무방하나, 균일한 입자 분포와 크기, 분자량, 합성 또는 저장시 비수분산성 혼성중합체 간의 부가 응집이나 반응중 극성기에 그라프트 중합을 방지하기 위해 선택에 신중을 기해야 한다. 상기에 언급한 개시제 중에서 한종류 또는 공정 단계별로 서로 다른 개시제를 혼용하여 사용할 수도 있기 때문이다. In addition, the initiator should have a suitable half-life according to the monomer, solvent type, and reaction temperature and appropriately select an initiator suitable for the decomposition temperature. In general, the initiator used in the polymerization of the acrylic resin may be selected and used, but uniform particle distribution and size, molecular weight, addition cohesion between non-dispersible copolymers during synthesis or storage, or to prevent graft polymerization during the polar group during the reaction Be careful about your choices. This is because different initiators may be used in combination in one kind or process step among the above-mentioned initiators.
바람직하게는, 본 발명에 사용된 유기 용제로서는 톨루엔, 크실렌, 메틸에틸케톤, 부틸아세테이트, 메틸이소부틸케톤, 메틸아밀케톤, 하이드로카본솔벤트, 부틸셀루솔브(butyl cellosolve, ethylene glycol monobutyl ether), 사이클로헥사논, Kocosol-100등을 예를 들 수 있다. 이들은 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.Preferably, as the organic solvent used in the present invention, toluene, xylene, methyl ethyl ketone, butyl acetate, methyl isobutyl ketone, methyl amyl ketone, hydrocarbon solvent, butyl cellosolve (ethylene glycol monobutyl ether), cyclo Hexanone, Kocosol-100, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
상기 비수분산성 혼성중합체에 대하여 용해력이 높은 강 용제를 사용하여 합성할 경우에는 외관은 투명하고 양호하지만은, 비수분산성 혼성중합체 결정이 부분적으로 용해되고, 결정 분포가 불 균일하고, 입자간의 부분적인 응집 현상이 발생될 수 있다. 반면에, 용해력이 너무 낮은 약 용제를 사용하여 합성할 경우 비수분산성 혼성중합체에 대한 상용성 불량으로 혼탁 현상 또는 침전에 따른 층 분리 현상으로 인해 적용할 수가 없다. 바람직하게는 최종 도료 적용 시에도 문제가 되지 않고 균일한 입자 분포와 일정한 분자량을 얻으면서 안정적인 분산으로 저장 안정성이 우수한 용제를 선택해야 한다. When synthesized using a strong solvent having high solubility with respect to the non-water-dispersible interpolymer, the appearance is transparent and good, but the non-water-dispersible interpolymer crystal is partially dissolved, the crystal distribution is uneven, and the part between particles Aggregation may occur. On the other hand, when synthesized using a weak solvent having a too low dissolving power is not compatible with the non-water-dispersible interpolymer due to turbidity or layer separation due to precipitation can not be applied. Preferably, even in the final coating application, it is not a problem and a solvent having excellent storage stability should be selected with stable dispersion while obtaining uniform particle distribution and constant molecular weight.
상기 비수분산성 혼성중합체 조성물을 도료용 수지에 분산 공정 또는 후첨 공정에 투입할 때 수지의 종류 및 특성에 따라 상용성 및 흐름성의 특성 등이 차이가 난다. 극성 중합체(polarity polymer) 시스템에 있어서는 소량의 카르복실기(carboxyl) 또는 수산기(hydroxyl)를 함유한 모노머를 사용함으로써 분산성 및 부착성과, 도막의 경도를 높일 수 있다. 상기 카르복실기의 함량이 너무 높으면 분자량 조절이 어렵고, 기능성 모노머와 부 반응을 초래하여 거대 고분자화 된다. 이로 인해, 반응시 용제와의 상용성 저하로 층 분리 현상이 발생되었다. 반면에, 상기 카르복실기 함량이 너무 낮으면 안료 분산성이 저하되어 최종 도막의 선영성이 저하되었다.When the non-water-dispersible interpolymer composition is added to a coating resin in a dispersing process or a post-treatment process, compatibility and flow characteristics vary depending on the type and property of the resin. In a polar polymer system, by using a monomer containing a small amount of carboxyl or hydroxyl groups, dispersibility and adhesion and hardness of the coating film can be improved. If the content of the carboxyl group is too high, it is difficult to control the molecular weight, resulting in side reactions with the functional monomers to macromolecular polymerization. As a result, a layer separation phenomenon occurred due to a decrease in compatibility with the solvent during the reaction. On the other hand, when the content of the carboxyl group is too low, pigment dispersibility is lowered, and the selectivity of the final coating film is lowered.
또한 상기 수산기가 너무 낮으면, 도료용 수지와 혼용성이 떨어지고, 아미노 수지를 사용한 소부 도료나 우레탄 수지를 이용한 반응 경화형 도료에서 직접 반응에 참가하지 못하고, 비수분산성 혼성중합체가 별도 거동하게 되어 도막의 부착이나 경화 밀도를 저하시켜 경도가 떨어지는 결과를 나타내었다. 반면에 수산기가 너무 높으면 비수분산성 혼성중합체가 털복숭아 모양으로 형성되어 저장 중 비수분산성 혼성중합체 결정간의 응집이 일어난다. 그리고, 분자량을 높이기가 어려워 고분자 결정 형성이 되지 않아 유기 용제에 쉽게 용해되어 용제 내에 결정 상태로 분산이 되지 않았다. 상기 비수분산성 혼성중합체에서 가장 바람직한 분자 구조는 입자 사이즈가 작으면서 거대 고분자량을 갖는 완벽한 구형의 결정 고분자를 유기 용제에 안정적으로 균일하게 분산하는 것이다.In addition, if the hydroxyl group is too low, it is incompatible with the resin for the paint, and it is not possible to directly participate in the reaction in the baking paint using the amino resin or the reaction curable paint using the urethane resin, and the non-water-dispersible interpolymer behaves separately. It showed the result that hardness of the adhesion was reduced by decreasing adhesion and hardening density of. On the other hand, if the hydroxyl group is too high, the non-water-dispersible interpolymer is formed into a hair peach shape, causing aggregation between the non-water-dispersible interpolymer crystals during storage. In addition, it is difficult to increase the molecular weight, so that polymer crystals do not form, are easily dissolved in an organic solvent, and do not disperse in a crystalline state in the solvent. The most preferable molecular structure in the non-water-dispersible interpolymer is to stably and uniformly disperse a perfectly spherical crystalline polymer having a high molecular weight with a small particle size in an organic solvent.
상기 비수분산성 혼성중합체 조성물은 종래의 흐름 억제제로 사용되고 있는 마이크로겔과 달리 직접 유기 용제 내에서 코어-쉘(Core-shell)형태로 중합하여 미세한 구형의 고분자를 형성하여 최대의 표면적과 입자 분자 상호간에 반발력을 부여함으로써 종전의 마이크로겔과는 달리 보관중에 분자 상호간의 재 응집현상이나 침강 현상을 방지한다.Unlike the microgel, which is used as a conventional flow inhibitor, the non-water-dispersible interpolymer composition is polymerized in a core-shell form directly in an organic solvent to form a fine spherical polymer to maximize the maximum surface area and particle molecules. Unlike the conventional microgel, the repulsive force is applied to prevent re-aggregation and sedimentation between molecules during storage.
이하, 본 발명을 구체적인 실시 예를 통하여 상세히 설명하기로 한다. 그러나, 실시예가 본 발명의 범위를 제한하지는 않는다.Hereinafter, the present invention will be described in detail through specific examples. However, the examples do not limit the scope of the invention.
실시예 1 Example 1
2ℓ용량을 갖는 4구 플라스크에 온도계, 응축기, 교반기, 드로핑펀넬 및 승온장치를 부착하였다. 여기에 크실렌 540g을 플라스크에 투입하여 교반하면서 110℃로 승온하였다. 상기 온도를 유지시킨 후 드로핑 펀넬에 메틸메타아크릴레이트모노머 250g, 스타이렌모노머 134g, 노르말부틸아크릴레이트모노머 30g, 벤조일퍼옥사이드2g을 균일하게 혼합하여 2시간 동안 적하 하였다. 이어서, 2시간 동안 유지하고 2-하이드록시에틸메타아크릴레이트 97g과 아크릴릭 애시드 1.5g, 트리메틸올프로판트리아크릴레이트 30g과 2,2'-아조비스이소부티로나이트릴 2.4g을 더 혼합하고, 균일하게 교반하여 1시간 동안 적하 하였다. 이후에 2시간 동안 유지한 후 냉각하면서 크실렌 270g으로 희석하여 수산기 값(Hydroxyl Value)이 78이고, 산 값(Acid Value)이 2.1이고, 유리 전이 온도가 76℃이고, 입자 사이즈 직경이 0.08 마이크론이고 중량평균 분자량이 1,800,000인 비수분산성 혼성중합체 조성물을 얻었다.A four-necked flask with a 2 L capacity was equipped with a thermometer, condenser, stirrer, dropping funnel, and temperature raising device. 540 g of xylene was added to the flask and heated to 110 ° C while stirring. After maintaining the above temperature, 250 g of methyl methacrylate monomer, 134 g of styrene monomer, 30 g of normal butyl acrylate monomer, and 2 g of benzoyl peroxide were dropped into the dropping funnel for 2 hours. Then hold for 2 hours and further mix 97 g of 2-hydroxyethyl methacrylate with 1.5 g of acrylic acid, 30 g of trimethylolpropanetriacrylate and 2.4 g of 2,2'-azobisisobutyronitrile and uniformly The mixture was stirred and added dropwise for 1 hour. After holding for 2 hours and diluting with 270 g of xylene while cooling, the hydroxyl value was 78, the acid value was 2.1, the glass transition temperature was 76 ° C., the particle size diameter was 0.08 micron A non-water-dispersible interpolymer composition having a weight average molecular weight of 1,800,000 was obtained.
실시예 2 Example 2
2ℓ용량을 갖는 4구 플라스크에 온도계, 응축기, 교반기, 드로핑펀넬 및 승온장치를 부착하였다. 여기에 크실렌 540g을 플라스크에 투입하여 교반하면서 110℃로 승온하였다. 상기 온도를 유지시킨 후 드로핑 펀넬에 메틸메타아크릴레이트모노머 250g, 스타이렌모노머 134g, 에틸아크릴레이트모노머 50g, 벤조일퍼옥사이드 2g을 균일하게 혼합하여 2시간 동안 적하 하였다. 이어서, 2시간 동안 유지하고 2-하이드록시에틸메타아크릴레이트 95g과 아크릴릭 애시드 1.7g, 트리메틸올프로판트리아크릴레이트 30g과 2,2'-아조비스이소부티로나이트릴 2.4g을 더 혼합하고 균일하게 교반하여 1시간 동안 적하 하였다. 이후에 2시간 동안 유지한 후 냉각하면서 크실렌 270g으로 희석하여 수산기 값(Hydroxyl Value)이 73이고, 산 값(Acid Value)이 2.4이고, 유리 전이 온도가 75℃이고, 입자 사이즈 직경이 0.09 마이크론이고 중량평균 분자량이 1,950,000인 비수분산성 혼성중합체 조성물을 얻었다.A four-necked flask with a 2 L capacity was equipped with a thermometer, condenser, stirrer, dropping funnel, and temperature raising device. 540 g of xylene was added to the flask and heated to 110 ° C while stirring. After maintaining the above temperature, 250 g of methyl methacrylate monomer, 134 g of styrene monomer, 50 g of ethyl acrylate monomer, and 2 g of benzoyl peroxide were dropped into the dropping funnel for 2 hours. Then, it was kept for 2 hours and further mixed and uniformly mixed 95 g of 2-hydroxyethyl methacrylate, 1.7 g of acrylic acid, 30 g of trimethylolpropanetriacrylate and 2.4 g of 2,2'-azobisisobutyronitrile. It stirred and dripped for 1 hour. After holding for 2 hours, the mixture was cooled and diluted with 270 g of xylene to give a hydroxyl value of 73, an acid value of 2.4, a glass transition temperature of 75 ° C, a particle size diameter of 0.09 micron, and A non-water-dispersible interpolymer composition having a weight average molecular weight of 1,950,000 was obtained.
실시예 3 Example 3
2ℓ용량을 갖는 4구 플라스크에 온도계, 응축기, 교반기, 드로핑펀넬 및 승온장치를 부착하였다. 여기에 크실렌 540g을 플라스크에 투입하여 교반하면서 110℃로 승온하였다. 상기 온도를 유지시킨 후 드로핑 펀넬에 메틸메타아크릴레이트모노머 300g, 스타이렌모노머 90g, 에틸아크릴레이트모노머 50g, 벤조일퍼옥사이드 4g을 균일하게 혼합하여 2시간 동안 적하 하였다. 이어서, 2시간 동안 유지하고 2-하이드록시에틸메타아크릴레이트 90g과 아크릴릭 애시드 1.2g, 트리메틸올프로판트리아크릴레이트 30g과 2,2'-아조비스이소부티로나이트릴 6g을 더 혼합하고, 균일하게 교반하여 1시간 동안 적하 하였다. 이후에 2시간 동안 유지한 후 냉각하면서 크실렌 270g으로 희석하여 수산기 값(Hydroxyl Value)이 69이고, 산 값(Acid Value)이 1.7이고, 유리 전이 온도가 74℃이고, 입자 사이즈 직경이 0.02 마이크론이고 중량평균 분자량이 1,560,000인 비수분산성 혼성중합체 조성물을 얻었다.A four-necked flask with a 2 L capacity was equipped with a thermometer, condenser, stirrer, dropping funnel, and temperature raising device. 540 g of xylene was added to the flask and heated to 110 ° C while stirring. After maintaining the temperature, a dropping funnel was mixed with 300 g of methyl methacrylate monomer, 90 g of styrene monomer, 50 g of ethyl acrylate monomer, and 4 g of benzoyl peroxide uniformly, and added dropwise for 2 hours. Then hold for 2 hours and further mix 90 g of 2-hydroxyethyl methacrylate with 1.2 g of acrylic acid, 30 g of trimethylolpropanetriacrylate and 6 g of 2,2'-azobisisobutyronitrile, and uniformly It stirred and dripped for 1 hour. After holding for 2 hours and diluting with 270 g of xylene while cooling, the hydroxyl value was 69, the acid value was 1.7, the glass transition temperature was 74 ° C., the particle size diameter was 0.02 micron A non-water-dispersible interpolymer composition having a weight average molecular weight of 1,560,000 was obtained.
실시예 4Example 4
2ℓ용량을 갖는 4구 플라스크에 온도계, 응축기, 교반기, 드로핑펀넬 및 승온장치를 부착하였다. 여기에 크실렌 340g과 톨루엔 200g을 플라스크에 투입하여 교반하면서 110℃로 승온 하였다. 상기 온도를 유지시킨 후 드로핑 펀넬에 메틸메타아크릴레이트모노머 100g, 스타이렌모노머 250g, 에틸아크릴레이트모노머 70g, 벤조일퍼옥사이드 2g을 균일하게 혼합하여 2시간 동안 적하 하였다. 이어서, 2시간 동안 유지하고 2-하이드록시에틸메타아크릴레이트 85g과 아크릴릭 애시드 1.5g, 에틸렌글리콜디메타아크릴레이트 54g과 벤조일퍼옥사이드 3g을 더 혼합하고, 균일하게 교반하여 1시간 동안 적하 하였다. 이후에 2시간 동안 유지한 후 냉각하면서 크실렌 270g으로 희석하여 수산기 값(Hydroxyl Value)이 65이고, 산 값(Acid Value)이 2.1이고, 유리 전이 온도가 65℃이고, 입자 사이즈 직경이 0.13 마이크론이고, 중량평균 분자량이 756,000인 비수분산성 혼성중합체 조성물을 얻었다.A four-necked flask with a 2 L capacity was equipped with a thermometer, condenser, stirrer, dropping funnel, and temperature raising device. 340 g of xylene and 200 g of toluene were added to the flask, and the temperature was raised to 110 ° C while stirring. After maintaining the above temperature, 100 g of methyl methacrylate monomer, 250 g of styrene monomer, 70 g of ethyl acrylate monomer, and 2 g of benzoyl peroxide were dropped into the dropping funnel for 2 hours. Then, the mixture was kept for 2 hours, 85 g of 2-hydroxyethyl methacrylate, 1.5 g of acrylic acid, 54 g of ethylene glycol dimethacrylate, and 3 g of benzoyl peroxide were further mixed, and stirred dropwise for 1 hour. After holding for 2 hours and diluting with 270 g of xylene while cooling, the hydroxyl value was 65, the acid value was 2.1, the glass transition temperature was 65 ° C., the particle size diameter was 0.13 micron , The non-water-dispersible interpolymer composition having a weight average molecular weight of 756,000 was obtained.
실시예 5Example 5
2ℓ용량을 갖는 4구 플라스크에 온도계, 응축기, 교반기, 드로핑펀넬 및 승온장치를 부착하였다. 여기에 톨루엔 340g과 부틸아세테이트 200g을 플라스크에 투입하여 교반하면서110℃로 승온하였다. 여기에 상기 온도를 유지시킨 후 드로핑 펀넬에 메틸메타아크릴레이트모노머 140g, 스타이렌모노머 250g, 2-하이드록시에틸아크릴레이트모노머 81g, 벤조일퍼옥사이드 3.5g을 균일하게 혼합한 후 2시간 동안 적하하였다. 이어서, 2시간 동안 유지하고, 디알릴프탈레이트 90g과 아크릴릭 애시드 1.7g, 2,2'-아조비스이소부티로나이트릴 3.5g을 더 혼합하고, 균일하게 교반하여 1시간 동안 적하 하였다. 이후에 2시간 동안 유지한 후 냉각하면서 메틸에틸케톤 270g으로 희석하여 수산기 값(Hydroxyl Value)이 70이고, 산 값(Acid Value)이 2.4이고, 유리 전이 온도가 65℃이고, 입자 사이즈 직경이 0.04 마이크론이고, 중량평균 분자량이 356,000인 비수분산성 혼성중합체 조성물을 얻었다. A four-necked flask with a capacity of 2 L was equipped with a thermometer, condenser, stirrer, dropping funnel and a temperature raising device. 340 g of toluene and 200 g of butyl acetate were added to the flask, and it heated up at 110 degreeC, stirring. After maintaining the above temperature, a dropping funnel was mixed with 140 g of methyl methacrylate monomer, 250 g of styrene monomer, 81 g of 2-hydroxyethyl acrylate monomer, and 3.5 g of benzoyl peroxide, followed by dropwise addition for 2 hours. . Then, the mixture was kept for 2 hours, 90 g of diallyl phthalate, 1.7 g of acrylic acid, and 3.5 g of 2,2'-azobisisobutyronitrile were further mixed, and stirred dropwise for 1 hour. After holding for 2 hours, the mixture was diluted with 270 g of methyl ethyl ketone while cooling to give a hydroxyl value of 70, an acid value of 2.4, a glass transition temperature of 65 ° C, and a particle size diameter of 0.04. A non-water-dispersible interpolymer composition having a micron and a weight average molecular weight of 356,000 was obtained.
실시예 6Example 6
2ℓ용량을 갖는 4구 플라스크에 온도계, 응축기, 교반기, 드로핑펀넬 및 승온장치를 부착하였다. 여기에 부틸아세테이트 540g을 플라스크에 투입하여 교반하면서 110℃로 승온하였다. 상기 온도를 유지시킨 후 드로핑 펀넬에 메틸메타아크릴레이트모노머 140g, 스타이렌모노머 200g, 에틸아크릴레이트50g, 벤조일퍼옥사이드 3.5g을 균일하게 혼합한 후 2시간 동안 적하 하였다. 이어서, 2시간 동안 유지하고 에틸렌그리콜디메타아크릴레이트 90g과 2-하이드록시에틸아크릴레이트모노머 85g 아크릴릭 애시드1.2g, 2,2'-아조비스이소부티로나이트릴 4g을 더 혼합하고, 균일하게 교반하여 1시간 적하 하였다. 이후에, 2시간 동안 유지한 후 냉각하면서 크실렌 270g으로 희석하여 수산기 값(Hydroxyl Value)이 73이고, 산 값(Acid Value)이 1.7이고, 유리 전이 온도가 51℃이고, 입자 사이즈 직경이 0.07 마이크론이고, 중량평균 분자량이 2,536,000인 비수분산성 혼성중합체 조성물을 얻었다. A four-necked flask with a capacity of 2 L was equipped with a thermometer, condenser, stirrer, dropping funnel and a temperature raising device. 540 g of butyl acetate were added to the flask, and it heated up at 110 degreeC, stirring. After maintaining the above temperature, methyl methacrylate monomer 140g, styrene monomer 200g, ethyl acrylate 50g, and 3.5g benzoyl peroxide were uniformly mixed in the dropping funnel and added dropwise for 2 hours. Then hold for 2 hours and further mix 90 g of ethylene glycol dimethacrylate with 85 g of 2-hydroxyethyl acrylate monomer and 1.2 g of 2,2'-azobisisobutyronitrile and uniformly It stirred and dripped 1 hour. Thereafter, the mixture was maintained for 2 hours, and then cooled with dilution with 270 g of xylene to give a hydroxyl value of 73, an acid value of 1.7, a glass transition temperature of 51 ° C, and a particle size diameter of 0.07 micron. To obtain a non-water-dispersible interpolymer composition having a weight average molecular weight of 2,536,000.
실시예 7Example 7
2ℓ용량을 갖는 4구 플라스크에 온도계, 응축기, 교반기, 드로핑펀넬 및 승온장치를 부착하였다. 여기에 크실렌 340g 및 부틸아세테이트 200g을 플라스크에 투입하여 교반하면서 110℃로 승온하였다. 상기 온도를 유지시킨 후 드로핑 펀넬에 메틸메타아크릴레이트모노머 250g, 스타이렌모노머 140g, 벤조일퍼옥사이드 2.0g을 균일하게 혼합한 후 2시간 동안 적하 하였다. 이어서 2시간 동안 유지하고, 트리메틸올프로판트리아크릴레이트 90g과 2-하이드록시에틸아크릴레이트모노머 85g, 아크릴릭애시드1.5g, 벤조일퍼옥사이드 4g을 더 혼합하고, 균일하게 교반하여 1시간 동안 적하하였다. 이후에, 2시간 동안 유지한 후 냉각하면서 크실렌 270g으로 희석하여 수산기 값(Hydroxyl Value)이 73이고, 산 값(Acid Value)이 2.1이고, 유리 전이 온도가 67℃이고, 입자 사이즈 직경이 0.08 마이크론이고, 중량 평균 분자량이 5,576,000인 비수분산성 혼성중합체 조성물을 얻었다. A four-necked flask with a capacity of 2 L was equipped with a thermometer, condenser, stirrer, dropping funnel and a temperature raising device. 340 g of xylene and 200 g of butyl acetate were added to the flask, and the temperature was raised to 110 ° C while stirring. After maintaining the above temperature, 250 g of methyl methacrylate monomer, 140 g of styrene monomer, and 2.0 g of benzoyl peroxide were uniformly mixed into the dropping funnel, followed by dropwise addition for 2 hours. Then, the mixture was kept for 2 hours, 90 g of trimethylolpropanetriacrylate, 85 g of 2-hydroxyethyl acrylate monomer, 1.5 g of acrylic acid, and 4 g of benzoyl peroxide were further mixed, and stirred dropwise for 1 hour. Thereafter, the mixture was kept for 2 hours and then cooled with dilution with 270 g of xylene to give a hydroxyl value of 73, an acid value of 2.1, a glass transition temperature of 67 ° C, and a particle size diameter of 0.08 micron. To obtain a non-water-dispersible interpolymer composition having a weight average molecular weight of 5,576,000.
상기 각 실시 예에서 얻어진 비수분산성 혼성중합체 조성물을 도료화한 후에 도막의 특성을 알아보기 위하여 실시예 1 내지 7에서 얻어진 조성물과 멜라민 경화제등을 포함하는 자동차용 중도 도료를 다음과 같이 얻었다. 표1에는 열경화성 아크릴 수지, 멜라민 경화제, 마이크로겔, 분산제, 산촉매, 소포제, 솔벤트, 실시예 1 내지 7에서 얻어진 조성물 등을 포함하는 도료의 조성비를 나타내었다.After coating the non-water-dispersible interpolymer composition obtained in each of the above-described examples, in order to examine the properties of the coating film, an intermediate coating material for automobiles containing the composition obtained in Examples 1 to 7 and a melamine curing agent was obtained as follows. Table 1 shows the composition ratio of the coating material including the thermosetting acrylic resin, the melamine curing agent, the microgel, the dispersant, the acid catalyst, the antifoaming agent, the solvent, the composition obtained in Examples 1 to 7, and the like.
이때 사용되는 소지로는 전착도료로 하도 처리된 강판을 사용하였고 도막의 두께는 40±2㎛로 했고 소지가 받는 표면온도는 170℃±5로하여 30분간 소부 건조를 실시하였다. 도막간의 층간 밀착을 보기 위해 중도 도장된 도막 위에 투명한 상도 도료를 별도 도장하여 동일한 조건에서 소부 건조하여 상대 비교 시험을 실시하였다.At this time, the base material used was a steel plate treated with electrodeposition paint, and the thickness of the coating film was 40 ± 2 μm, and the surface temperature received by the base material was 170 ° C. ± 5, followed by baking for 30 minutes. In order to see the interlayer adhesion between the coating films, a transparent top coat was separately coated on the half-painted coating film, followed by baking under the same conditions to perform a relative comparison test.
상기 비교를 위하여 일반적으로 공업용 및 자동차용 금속성의 도료에 사용되고 있는 크레이벨리(Crayvally)사의 마이크로겔인 COROC A-4023-M3(제품명)와 상기의 실시예1 내지 7에서 얻은 비수분산성 혼성중합체 조성물을 자동차용 소부형 중도 도료에 적용하였다. 첨가량은 도료용 열경화성 아크릴 수지의 고형분을 기준으로 하여 마이크로겔 및 비수분산성 혼성중합체 조성물 고형분을 기준에 대하여 환산하여 5 %씩 동량 첨가하여 도료화 하였다. 이후에, 이를 비교예로 하여 분산성 및 부착성, 경도, 광택성, 선영성, 저장성, 안정성과 투명성을 포함한 세깅성(sag resistance)측면에서도 비교 검토하였다 For comparison, COROC A-4023-M3 (product name), which is a microgel of Crayvally, which is generally used for industrial and automotive metallic paints, and the non-water dispersible interpolymer composition obtained in Examples 1 to 7 above. Has been applied to small-sized intermediate paints for automobiles. The amount of the coating was added to the same amount by 5% of the microgel and the non-water-dispersible interpolymer composition solids based on the solids content of the thermosetting acrylic resin for coating, and the paint was applied. Later, this was compared and examined in terms of sag resistance including dispersibility and adhesion, hardness, glossiness, lightness, storage property, stability and transparency.
상기 표1 자동차용 금속제의 도료에 사용되는 원료는 (1)열경화성 아크릴 수지 고형분 60%((주)DPI제품), (2) 알루미늄 페이스트 94-0642 (토요 아루미늄 제품), (3) 조성물 : 고형분 40%, (4) A-4023-M3 : 고형분 50%, (5) 분산제 : Disperbyk-160 (BYK-Chemie 사 제품), (6) 멜라민 경화제 : Norumine-2060((주) DPI), (7) 산촉매 : Nacure-5225(King 사 제품), (8) 소포제 : AC-303(공영사 제품), (9) 솔벤트 : Xylene, Kocosol-100, Toluene 이다.The raw materials used in the automotive metal paints of Table 1 include (1) a thermosetting acrylic resin solid content of 60% (produced by DPI), (2) aluminum paste 94-0642 (produced by Toyo Aluminium), and (3) a composition: Solid content 40%, (4) A-4023-M3: solid content 50%, (5) Dispersant: Disperbyk-160 (manufactured by BYK-Chemie), (6) Melamine curing agent: Norumine-2060 (DPI), ( 7) Acid catalyst: Nacure-5225 (manufactured by King), (8) Defoamer: AC-303 (manufactured by public corporations), (9) Solvent: Xylene, Kocosol-100, Toluene.
상기 표1에 나타난 각 도료 조성물의 특성을 알아보기 위하여 상기에서 언급된 전착 처리된 강판에 도장 후 도막의 특성을 시험하여 그 결과를 표2에 나타내었다. In order to find out the characteristics of each coating composition shown in Table 1, the characteristics of the coating film after coating on the electrodeposition-treated steel sheet mentioned above are shown in Table 2.
상기 표2에서 각 도료의 특성을 표시하는 평가 항목은 다음을 의미한다. 소지 또는 하도와의 밀착성 및 내충격성의 항목에서 ◎는 매우 양호, ○는 양호, △는 보통 그리고 X는 불량을 의미한다. In Table 2, the evaluation items indicating the characteristics of each paint means the following. ◎ is very good, ○ is good, △ is normal and X is poor in terms of adhesion or impact resistance to body or sewage.
또한 상기 표2에서 각 특성은 다음과 같은 방법으로 측정하였다. 먼저 광택은 ASTM-D-523, MEK Rubbing성은 NCCA-II-18, 가공성은 NCCA-II-19, 연필 경도는 NCCA-II-12의 방법으로 그리고 C.E.T(Cross erichsen test)의 경우에는 NCCA-II-20의 방법으로 측정 하였다. In addition, each characteristic in Table 2 was measured by the following method. First, gloss is ASTM-D-523, MEK Rubbing is NCCA-II-18, processability is NCCA-II-19, pencil hardness is NCCA-II-12, and CCA (Cross Erichsen Test) is NCCA-II. It was measured by the method of -20.
그리고 안료 분산성은 도료 제조시 일정한 입도에 도달 할 때까지 걸린 시간을 기준으로 하여 상대 비교치로 판정하였으며, 저장 안정성은 도료 제조후 상온(25℃)에서 30일 보관 후 증점 현상 유무와 더불어 안료 침강현상 및 도막의 변화 정도를 육안으로 판별하였고, 선영성의 경우에는 PDG METER을 이용하여 나타난 눈금으로 식별하였다. In addition, the pigment dispersibility was determined based on the relative comparison value based on the time taken to reach a constant particle size during the manufacture of the paint, and the storage stability was found after the storage of the paint at room temperature (25 ℃) for 30 days, with the presence of thickening phenomenon. And the degree of change of the coating film was visually determined, and in the case of sunyoungseong was identified by the scale displayed by using PDG METER.
소지 또는 하도와의 밀착성 측정 방법으로는 크로스-컷팅한 후 셀로판 페이프를 이용하여 소지 또는 하도와의 밀착이 떨어져 나가는 정도를 육안으로 판별하였고 ,더욱더 가혹한 방법으로 상대 비교 평가를 위해 10원짜리 동전을 이용하여 동일한 힘으로 눌러 긁어 줌으로써 소지 또는 상,하도와의 밀착이 떨어져 나가는 정도를 육안으로 판별하였다. As a measuring method of holding or sewage, the degree of adhesion between the holding and sewage was visually determined by using a cellophane paper after cross-cutting.In a more severe method, a 10-won coin was used for comparative evaluation. By using the same force to scrape by using to determine the degree of contact with the body or upper and lower with the naked eye was determined.
본 발명에 따른 비수분산성 혼성중합체 조성물을 사용함으로 인해 일반 아크릴 수지뿐만 아니라, 알키드 수지, 폴리에스텔 수지, 멜라민 수지, 우레탄 수지 등의 다양한 도료용 수지에 적용하는 광범위한 상용성을 갖는다. By using the non-water-dispersible interpolymer composition according to the present invention, it has a wide range of compatibility not only with general acrylic resins but also with various coating resins such as alkyd resins, polyester resins, melamine resins, urethane resins, and the like.
이로 인해, 흐름성 억제제의 특성이 우수하고, 잔류 계면 활성제나 잔류 수분이 없으므로 도료 적용시 광택성, 선영성, 부착성 및 도막의 경도가 매우 우수한 자동차 금속제 중, 상도 도장용 도료를 제공할 수 있다. 따라서 종전의 마이크로겔과 달리 직접적으로 도료나 안료에 분산이 가능하고, 후첨 공정 투입하여도 물성의 손상이 없어 특별한 분산 설비나 공정이 요구되지 않아 도료 제조 공정을 크게 단축시킬 수 있다.As a result, since the properties of the flow inhibitor are excellent, and there are no residual surfactants or residual moisture, it is possible to provide a coating for top coat among automotive metals having excellent gloss, clarity, adhesion, and hardness of the coating film when the coating is applied. have. Therefore, unlike conventional microgels, it is possible to directly disperse in paints or pigments, and there is no damage to physical properties even after the post-treatment process, so that a special dispersing facility or process is not required.
상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구의 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.
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| KR20160107883A (en) | 2015-03-06 | 2016-09-19 | (주)녹색정유 | Method of manufacturing uv curabal micro-gel resin, uv curabal micro-gel resin and paint composition comprising uv curabal micro-gel resin |
| CN115701832A (en) * | 2022-09-21 | 2023-02-14 | 张家港市德宝化工有限公司 | Preparation of metal ion dispersant by using ethylene glycol dimethacrylate wastewater |
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