KR100586272B1 - Waterborne acrylic resin composition, coating composition containing the acrylic composition and preparation method thereof - Google Patents
Waterborne acrylic resin composition, coating composition containing the acrylic composition and preparation method thereof Download PDFInfo
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- KR100586272B1 KR100586272B1 KR1020050019223A KR20050019223A KR100586272B1 KR 100586272 B1 KR100586272 B1 KR 100586272B1 KR 1020050019223 A KR1020050019223 A KR 1020050019223A KR 20050019223 A KR20050019223 A KR 20050019223A KR 100586272 B1 KR100586272 B1 KR 100586272B1
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- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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Abstract
본 발명은 3급 아민기, 산기 및 수산기를 갖는 아크릴 수지에 에폭시실란을 내부 가교시킨 3급 아민기 함유 수분산성 아크릴 수지 조성물, 상기 아크릴 수지 조성물을 주성분으로 함유하고 경화 성분으로 에폭시기 및 가수 분해성 실릴기를 갖는 에폭시실란을 함유하는 2성분계 상온 경화형 도료 조성물 및 이의 제조 방법에 관한 것이다. 본 발명에 따른 아크릴 수지 조성물 및 도료 조성물은 건조 시간, 광택, 접착성, 내용제성, 내약품성, 내후성 등이 우수하면서, 저장 안정성 및 가사 시간이 비약적으로 개선된 도막을 형성시킬 수 있다. The present invention comprises a tertiary amine group-containing water dispersible acrylic resin composition in which an epoxy silane is internally crosslinked to an acrylic resin having a tertiary amine group, an acid group and a hydroxyl group, and the acrylic resin composition as a main component and an epoxy group and a hydrolyzable silyl as a curing component. It relates to a two-component room temperature hardening coating composition containing an epoxysilane having a group and a method for producing the same. The acrylic resin composition and the coating composition according to the present invention can form a coating film having excellent drying time, gloss, adhesion, solvent resistance, chemical resistance, weather resistance, and the like, and dramatically improving storage stability and pot life.
아크릴 수지, 도료 조성물, 수분산성 Acrylic resin, paint composition, water dispersible
Description
본 발명은 3급 아민기, 산기 및 수산기를 갖는 아크릴 수지에 에폭시실란을 내부 가교시킨 3급 아민기 함유 수분산성 아크릴 수지 조성물, 상기 아크릴 수지 조성물을 주성분으로 함유하고 경화 성분으로 에폭시기 및 가수분해성 실릴기를 갖는 에폭시실란을 함유하는 2성분계 상온 경화형 도료 조성물 및 이의 제조 방법에 관한 것이다. 본 발명에 따른 아크릴 수지 조성물 및 도료 조성물은 형성되는 도막의 건조 시간, 광택, 접착성, 내용제성, 내약품성, 내후성 등이 우수하면서, 저장 안정성 및 가사 시간을 비약적으로 개선시킬 수 있다. The present invention comprises a tertiary amine group-containing water dispersible acrylic resin composition in which an epoxy silane is internally crosslinked to an acrylic resin having a tertiary amine group, an acid group and a hydroxyl group, and the epoxy resin and hydrolyzable silyl as a curing component. It relates to a two-component room temperature hardening coating composition containing an epoxysilane having a group and a method for producing the same. The acrylic resin composition and the coating composition according to the present invention are excellent in drying time, gloss, adhesiveness, solvent resistance, chemical resistance, weather resistance, etc. of the coating film formed, and can significantly improve storage stability and pot life.
최근 국내·외의 도료 개발의 목표는 환경을 고려하여 다양한 용도와 특성을 갖는 고성능ㆍ고기능성 수지 도료의 개발에 있다. 그 중에서도 수계 도료는 현재 자동차 전착 코팅, 코일 코팅, 금속 가구, 대형 기구, 여러 가지 금속 제품 및 목재 등과 같이 다양한 소재에 광범위하게 사용되고 있는 친환경적 도료로서, 국내에서도 환경 법규의 강화로 인하여 도료·도장 산업에 대한 환경적 규제가 시작됨에 따라서 그 사용이 증가하게 될 것으로 예측된다. Recently, the goal of the domestic and foreign paint development is to develop high-performance, high-functional resin paints having various uses and characteristics in consideration of the environment. Among them, water-based paints are environmentally friendly paints widely used in various materials such as automotive electrodeposition coating, coil coating, metal furniture, large appliances, various metal products and wood, etc. It is anticipated that usage will increase as environmental regulations begin.
그러나, 수계 도료에 사용되는 물은 표면 장력이 크고(73 dyne/cm), 비점이 낮은 반면, 증발 잠열이 높아서(540 cal/g) 피막형성 중 기후 조건의 영향을 크게 받는다. 또한, 유성 도료에 비해서, 선영성, 광택, 내오염성, 내곰팡이성이 낮고, 구조중에 카르복시기나 폴리에틸렌옥사이드 등과 같은 친수성 물질을 내포하고 있어서 이들을 중화시키는 것이 필요하고, 중화된 형태의 염은 피막에 남게 되어, 상용성 부족으로 투명성, 내수성, 내알카리성 및 내후성이 저하되는 문제점이 발생하게 된다.However, water used in waterborne coatings has a high surface tension (73 dyne / cm) and a low boiling point, while high latent heat of evaporation (540 cal / g) is greatly influenced by climatic conditions during film formation. In addition, compared with oil-based paints, lightness, gloss, fouling resistance, and mildew resistance are low, and a hydrophilic material such as carboxyl group or polyethylene oxide is contained in the structure, and it is necessary to neutralize them. As a result, the problem of deterioration in transparency, water resistance, alkali resistance and weather resistance is reduced.
이러한 상황에서, 이러한 문제점에 대한 대응 방안의 일환으로 내후성이 우수한 수계 도료 조성물의 개발이 요구되고 있다. 이러한 요구에 부응하여 개발된 수계 도료 조성물로서, 우선, 1성분계 수용성 아크릴/실리콘계를 들 수 있으나, 이는 수지 합성 후 알콕시실릴기 또는 실라놀기의 불안정성으로 인하여 부적절한 경화 현상을 나타낼 수 있다는 단점이 있다. 그 다음으로, 2성분계 수용성 아크릴/우레탄계를 들 수 있는데, 이는 내부에 친수성기와 미반응 수산기가 존재하게 되어 내수성이 저하된 도막을 형성할 수 있다는 단점이 있다. 또한, 2성분계 수용성 에폭시계를 들 수 있는데, 이는 에폭시 경화제 또는 미반응 관능기로 남아 있는 친수성기에 의하여 내수성이 저하된다는 단점이 있다.In this situation, development of a water-based coating composition excellent in weatherability is required as part of a countermeasure against such a problem. As a water-based coating composition developed in response to this demand, first, there may be mentioned a one-component water-soluble acrylic / silicone system, but this has the disadvantage that it may exhibit an inappropriate curing phenomenon due to the instability of the alkoxysilyl group or silanol group after the resin synthesis. Next, there may be mentioned a two-component water-soluble acrylic / urethane-based, which has a disadvantage in that a hydrophilic group and an unreacted hydroxyl group are present therein to form a coating film having reduced water resistance. In addition, there may be mentioned a two-component water-soluble epoxy, which has a disadvantage that the water resistance is lowered by the hydrophilic group remaining in the epoxy curing agent or an unreacted functional group.
수계 도료는 분산성을 위해 물과 조용제의 혼합계로 되어 있는 경우가 많기 때문에 도막 외관과 물성을 유지하면서 조용제량을 감소시켜 저VOC화 하는 연구가 지속적으로 요구된다.Since water-based paints are often made of a mixture of water and a solvent for dispersibility, research to reduce the volume of the solvent and reduce the VOC while maintaining the appearance and physical properties of the coating is continuously required.
한편, 미국 특허 USP 6,482,890는 비유기용제계 도료용 수성 상온 경화성 수지 조성물에 관하여 개시하고 있다. 상기 특허는 3급 아미노기의 염 및 산기의 염 중에서 선택되는 작용성을 갖는 겔상 수지 분산 입자와 수성 매체를 필수 성분으로 하는 수성 분산체를 주제로 하고, 에폭시기 및 가수분해성 실릴기를 함께 갖는 화합물을 경화제로서 사용하여 도막화한 후 건조 시간, 광택, 광택 유지율, 내오염성, 내용제성, 내알카라성 및 내수성 시험을 통하여 신속 경화성, 도막의 내수성, 내후성이라는 성능에 부가하여 유기용제의 대기 중으로의 배출량이 적어질 뿐 아니라 내용제성, 내약품성도 매우 우수한 도막을 얻을 수 있음을 밝히고 있다.On the other hand, US Pat. No. 6,482,890 discloses an aqueous room temperature curable resin composition for an inorganic solvent paint. The patent is based on a gel-type resin dispersed particle having a functional property selected from salts of tertiary amino groups and salts of acid groups and an aqueous dispersion containing an aqueous medium as an essential component, and a compound having an epoxy group and a hydrolyzable silyl group together as a curing agent. After the film is used as a coating film, the drying time, gloss, gloss retention rate, fouling resistance, solvent resistance, alkali resistance and water resistance test can be used in addition to the performance of rapid curing, water resistance and weather resistance of the organic solvent. In addition to being less, it is revealed that a very excellent coating film can be obtained in solvent resistance and chemical resistance.
그러나, 상기한 기술로 제조된 수성 도료의 경우 도막 물성은 양호하나 수성 분산체의 제조시 고점도의 수지를 분산시키는 반응 공정을 조절하기 곤란할 뿐만 아니라 저장 안정성이 나빠 저장중 쉽게 겔화를 초래하는 문제점과 또한 경화제와의 혼합시 가사 시간(pot-life)이 짧아 작업성이 불량한 단점이 있다.However, in the case of the aqueous coating material prepared by the above technique, the coating film properties are good, but it is difficult to control the reaction process of dispersing high-viscosity resin during the preparation of the aqueous dispersion, and the storage stability is poor, resulting in easy gelation during storage. In addition, the pot-life is short when mixing with a curing agent has a disadvantage of poor workability.
이에 따라, 수성 도료로서의 건조 시간, 광택, 내수성, 내용제성, 내약품성, 내후성 등이 우수하면서 저장 안정성 및 가사 시간이 양호한 도료에 대한 연구가 활발히 진행되고 있다.Accordingly, studies have been actively conducted on paints having excellent storage stability and pot life while being excellent in drying time, gloss, water resistance, solvent resistance, chemical resistance, weather resistance, and the like as an aqueous paint.
상기한 바와 같은 문제점을 해결하기 위하여, 본 발명은, 상기한 기술들에서 진일보하여, 수성 도료로서의 광택, 내용제성, 내후성 등의 우수한 물성은 그대로 유지하면서 저장 안정성 및 가사 시간이 양호한 도료를 제공하는 것을 목적으로 한다. In order to solve the problems as described above, the present invention, in addition to the above-described techniques, to provide a coating with good storage stability and pot life while maintaining excellent physical properties such as gloss, solvent resistance, weather resistance, etc. as an aqueous coating For the purpose of
본 발명은 3급 아민기, 산기 및 수산기를 갖는 아크릴 수지에 에폭시실란을 내부 가교시킨 3급 아민기 함유 수분산성 아크릴 수지 조성물, 상기 아크릴 수지 조성물을 주성분으로 함유하고 경화 성분으로 에폭시기 및 가수분해성 실릴기를 갖는 에폭시실란을 함유하는 2성분계 상온 경화형 도료 조성물 및 이의 제조 방법에 관한 것이다. 본 발명에 따른 아크릴 수지 조성물 및 도료 조성물은 형성되는 도막의 건조 시간, 광택, 접착성, 내용제성, 내약품성, 내후성 등이 우수하면서, 저장 안정성 및 가사 시간을 비약적으로 개선시킬 수 있다.The present invention comprises a tertiary amine group-containing water dispersible acrylic resin composition in which an epoxy silane is internally crosslinked to an acrylic resin having a tertiary amine group, an acid group and a hydroxyl group, and the epoxy resin and hydrolyzable silyl as a curing component. It relates to a two-component room temperature hardening coating composition containing an epoxysilane having a group and a method for producing the same. The acrylic resin composition and the coating composition according to the present invention are excellent in drying time, gloss, adhesiveness, solvent resistance, chemical resistance, weather resistance, etc. of the coating film formed, and can significantly improve storage stability and pot life.
본 발명자들은, 상기한 기존의 수성 도료의 문제점을 해결하기 위하여, 수성 도료 내의 친수성 관능기를 가교 반응시키게 되면 일반적인 수계의 결점인 내수성, 내알카리성 및 내후성 문제를 해결할 수 있게 됨을 발견하여 본 발명을 완성하였다. The present inventors have completed the present invention by discovering that in order to solve the problems of the conventional water-based paints, cross-reacting hydrophilic functional groups in the water-based paints can solve the problems of water resistance, alkali resistance and weather resistance, which are defects of general water-based materials. It was.
우선, 본 발명은 3급 아민 함유 단량체, 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체 및 스티렌 단량체, 산기를 갖는 아크릴계 또는 메타크릴계 단량체, 및 수산기를 갖는 아크릴계 또는 메타크릴계 단량체의 혼합물을 중합 개시제를 사용하여 중합시켜 얻어진 아크릴 수지에 에폭시실란 1 내지 10 중량%를 첨가하여 3급 아민기와 에폭시실란 간의 내부 가교를 형성시킨 수분산성 아크릴 수지 조성물을 제공한다.First, the present invention provides a polymerization initiator using a mixture of a tertiary amine-containing monomer, an acrylic or methacrylic monomer having an aliphatic group and a styrene monomer, an acrylic or methacrylic monomer having an acid group, and an acrylic or methacrylic monomer having a hydroxyl group. The water dispersible acrylic resin composition which adds 1-10 weight% of epoxy silanes to the acrylic resin obtained by superposing | polymerizing using and formed the internal bridge | crosslinking between a tertiary amine group and an epoxy silane is provided.
또한, 본 발명은 3급 아민 함유 단량체, 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체 및 스티렌 단량체, 산기를 갖는 아크릴계 또는 메타크릴계 단량 체, 및 수산기를 갖는 아크릴계 또는 메타크릴계 단량체의 혼합물을 중합 개시제와 함께 중비점 용매에서 중합시켜 아크릴 수지를 얻고; 상기 얻어진 아크릴 수지에 에폭시실란 1 내지 10 중량%를 첨가하여 3급 아민과 에폭시실란 간에 내부 가교를 형성시키는 단계를 포함하는, 수분산성 아크릴 수지 조성물의 제조 방법을 제공한다.In addition, the present invention is a polymerization initiator using a mixture of a tertiary amine-containing monomer, an acrylic or methacrylic monomer having an aliphatic group and a styrene monomer, an acrylic or methacrylic monomer having an acid group, and an acrylic or methacrylic monomer having a hydroxyl group. Polymerization in a middle boiling solvent with an acrylic resin; It provides a method for producing a water-dispersible acrylic resin composition comprising adding 1 to 10% by weight of epoxy silane to the obtained acrylic resin to form internal crosslinks between the tertiary amine and the epoxy silane.
또한, 본 발명은, 상기와 같은, 3급 아민 함유 단량체, 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체 및 스티렌 단량체, 산기를 갖는 아크릴계 또는 메타크릴계 단량체, 및 수산기를 갖는 아크릴계 또는 메타크릴계 단량체의 혼합물을 중합 개시제를 사용하여 중합시켜 얻어진 아크릴 수지에 1 내지 10 중량%의 에폭시실란을 첨가하여 내부 가교가 형성된 아크릴 수지 조성물 85 내지 95 중량부; 및 경화제로서 에폭시기와 가수 분해성 실릴기를 갖는 에폭시실란 5 내지 15 중량부를 함유하는 2성분계 상온 경화형 수분산성 아크릴/실리콘 도료 조성물을 제공한다. In addition, the present invention, the tertiary amine-containing monomer, the acrylic or methacrylic monomer having an aliphatic group and the styrene monomer, the acrylic or methacrylic monomer having an acid group, and the acrylic or methacrylic monomer having a hydroxyl group as described above 85 to 95 parts by weight of an acrylic resin composition in which internal crosslinking is formed by adding 1 to 10% by weight of epoxy silane to the acrylic resin obtained by polymerizing the mixture using a polymerization initiator; And 5 to 15 parts by weight of an epoxy silane having an epoxy group and a hydrolyzable silyl group as a curing agent, and a two-component room temperature curing type water dispersible acrylic / silicone coating composition.
또한, 본 발명은 3급 아민 함유 단량체, 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체 및 스티렌 단량체, 산기를 갖는 아크릴계 또는 메타크릴계 단량체, 및 수산기를 갖는 아크릴계 또는 메타크릴계 단량체의 혼합물을 반응 개시제와 함께 중비점 용매에서 중합시켜 아크릴 수지를 얻고; 상기 얻어진 아크릴 수지에 에폭시실란 1 내지 10 중량%를 첨가하여 내부 가교된 아크릴 수지 조성물을 얻고; 상기 내부 가교된 아크릴 수지 85 내지 95 중량부에 경화제로서 에폭시기와 가수 분해성 실릴기를 갖는 에폭시실란 5 내지 15 중량부를 첨가하여 내부 가교 밀도를 증가시키는 단계를 포함하는, 2성분계 상온 경화형 수분산성 아크릴/실리콘 도료 조성물의 제조 방법을 제공한다. The present invention also relates to a mixture of a tertiary amine-containing monomer, an acrylic or methacrylic monomer having an aliphatic group and a styrene monomer, an acrylic or methacrylic monomer having an acid group, and an acrylic or methacrylic monomer having a hydroxyl group, with a reaction initiator. Polymerization together in a middle boiling solvent to obtain an acrylic resin; Adding 1 to 10% by weight of epoxysilane to the obtained acrylic resin to obtain an internally crosslinked acrylic resin composition; To increase the internal crosslinking density by adding 5 to 15 parts by weight of an epoxy silane having an epoxy group and a hydrolyzable silyl group as a curing agent to 85 to 95 parts by weight of the internally crosslinked acrylic resin, a two-component room temperature curing type water dispersible acrylic / silicone It provides a method for producing a coating composition.
본 발명의 아크릴 수지 조성물 및 도료 조성물에 함유된 아크릴 수지에 있어서, 3급 아민기는 에폭시실란과의 가교시 고내구성 및 우수한 내스크래치성이 발현하도록 하고, 지방족기를 갖는 단량체는 유리 전이 온도를 조절하고, 산기 및 수산기를 갖는 단량체는 수분산성 및 접착성을 증가시키는 역할을 한다. 또한, 본 발명의 조성물은, 아크릴과 에폭시실란이 내부 가교됨으로써, 건조 속도, 광택, 접착성, 내용제성, 표면경도 및 내후성이 우수하고 특히, 저장안정성 및 가사시간이 양호하다. In the acrylic resin contained in the acrylic resin composition and the coating composition of the present invention, the tertiary amine group causes high durability and excellent scratch resistance upon crosslinking with the epoxy silane, and the monomer having an aliphatic group controls the glass transition temperature. Monomers having an acid group and a hydroxyl group serve to increase water dispersibility and adhesion. In addition, the composition of the present invention is excellent in drying rate, gloss, adhesiveness, solvent resistance, surface hardness and weather resistance by acrylic crosslinking of acrylic and epoxy silane, and particularly good storage stability and pot life.
본 발명의 바람직한 구체예에 있어서, 3급 아민 함유 단량체 1 내지 4 중량부, 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체 50 내지 80 중량부, 스티렌 단량체 10 중량부, 산기를 갖는 아크릴계 또는 메타크릴계 단량체 3 내지 6 중량부 및 수산기를 갖는 아크릴계 또는 메타크릴계 단량체 5 내지 20 중량부의 혼합물을 상기 단량체 혼합물 중량에 대하여 2 내지 4 중량%의 중합 개시제와 함께 중비점 용매에 5시간 내지 7시간 동안 적하하면서, 80˚С 내지 90˚С의 온도에서 8시간 내지 12시간 동안 중합시켜, 수평균 분자량이 12,000 내지 15,000이고, 유리 전이 온도가 +20˚С 내지 +40˚С, 바람직하게는, ＋25˚С 내지 ＋30˚С이고, 점도가 175 내지 180 Poises이고, 고형분 농도가 60 중량%인 아크릴 수지를 제조한다. 이와 같은 아크릴 수지에 에폭시실란 1 내지 10 중량%를 첨가하여 내부 가교 되고 점도가 5 Poise(68 KU) 내지 10.7 Poise(85 KU)이고 고형분 농도가 35 중량%인 3급 아민 함유 수분산성 아크릴 수지 조성물을 제조한다. 이와 같은 아크릴 수지 조성 물 85 내지 95 중량부에 경화제로서 에폭시실란 5 내지 15 중량부를 첨가하여 내부 가교 밀도가 증가된 2성분계 상온경화형 수분산성 아크릴/실리콘 도료 조성물을 제조한다.In a preferred embodiment of the present invention, 1 to 4 parts by weight of a tertiary amine-containing monomer, 50 to 80 parts by weight of an acrylic or methacrylic monomer having an aliphatic group, 10 parts by weight of a styrene monomer, an acrylic or methacrylic monomer having an acid group A mixture of 3 to 6 parts by weight and 5 to 20 parts by weight of an acrylic or methacrylic monomer having a hydroxyl group is added dropwise to the middle boiling point solvent with 2 to 4% by weight of the polymerization initiator with respect to the weight of the monomer mixture for 5 to 7 hours. , 8 to 12 hours at a temperature of 80˚С to 90˚С, the number average molecular weight is 12,000 to 15,000, the glass transition temperature is + 20˚С to + 40˚С, preferably, + 25˚С To acrylic resin having a viscosity of 175 to 180 Poises and a solid content concentration of 60 wt%. To this acrylic resin, tertiary amine-containing water dispersible acrylic resin composition having 1 to 10% by weight of epoxy silane and internal crosslinking having a viscosity of 5 Poise (68 KU) to 10.7 Poise (85 KU) and a solid concentration of 35% by weight. To prepare. By adding 5 to 15 parts by weight of epoxysilane as a curing agent to 85 to 95 parts by weight of such an acrylic resin composition to prepare a two-component room temperature curing type water dispersible acrylic / silicone coating composition having increased internal crosslinking density.
본 발명에 있어서 상기 3급 아민 함유 아크릴 수지는 상기한 바와 같이 3급 아민 함유 단량체, 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체, 스티렌 단량체, 산기를 갖는 아크릴계 또는 메타크릴계 단량체 및 수산기를 갖는 아크릴계 또는 메타크릴계 단량체와 같은 비닐형 이중 결합을 갖는 여러 가지 종류의 단량체들을 열분해 개시제를 사용하여 라디칼 중합시켜 제조한다. 상기 라디칼 중합은 용액 중합법에 따른다. 상기 아크릴 수지 중의 산기 및 수산기의 염을 수성 매체 중에서 분산시키고, 얻어지는 분산 입자 내에서 에폭시기로부터 선택되는 반응성기와 가수 분해성 실릴기를 함께 갖는 분자량이 300 이하인 에폭시실란 화합물을 내부 가교시킴으로써 수분산성 아크릴 수지 조성물를 제조할 수 있다.In the present invention, the tertiary amine-containing acrylic resin is a tertiary amine-containing monomer, an acrylic or methacrylic monomer having an aliphatic group, a styrene monomer, an acrylic or methacrylic monomer having an acid group as described above, or an acrylic having a hydroxyl group. Various kinds of monomers having vinyl double bonds such as methacrylic monomers are prepared by radical polymerization using a pyrolysis initiator. The radical polymerization is according to the solution polymerization method. A water-dispersible acrylic resin composition is prepared by dispersing an acid group and a salt of a hydroxyl group in the acrylic resin in an aqueous medium, and internally crosslinking an epoxysilane compound having a molecular weight of 300 or less having a reactive group selected from an epoxy group and a hydrolyzable silyl group in the dispersed particles obtained. can do.
상기 3급 아민 함유 아크릴 수지 조성물에 산기의 염을 도입하는 방법으로는, 3급 아민기와 산기를 함유하는 비닐계 단량체 및 필요에 따라 이들과 공중합 가능한 다른 비닐계 단량체를 공중합시키고, 이어서 상기 3급 아민기 또는 산기 중의 일부 내지 전부를 중화하여 염을 형성하는 방법을 들 수 있다.As a method of introducing a salt of an acid group into the tertiary amine-containing acrylic resin composition, a vinyl monomer containing a tertiary amine group and an acid group, and other vinyl monomers copolymerizable with these as necessary, are copolymerized, and then the tertiary The method of neutralizing some or all of an amine group or an acid group, and forming a salt is mentioned.
상기 3급 아민 함유 아크릴 수지 조성물에 사용되는 원료로는 아크릴산 에스테르, 메타크릴산 에스테르 등이 모두 사용될 수 있다. As the raw material used in the tertiary amine-containing acrylic resin composition, all of acrylic acid ester, methacrylic acid ester, and the like may be used.
이하, 본 발명의 조성물에 함유되는 성분들을 보다 상세히 설명하면 다음과 같다:Hereinafter, the components contained in the composition of the present invention in more detail as follows:
본 발명에서 사용되는 3급 아민 함유 단량체의 예로서 디메틸아미노에틸아크릴레이트, 디메틸아미노에틸메타크릴레이트 등을 들 수 있으며, 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체의 예로서 노말부틸아크릴레이트, 2-에틸헥실아크릴레이트, 에틸아크릴레이트, 노말부틸메타크릴레이트, 노말프로필메타크릴레이트, 메틸메타크릴레이트, 에틸메타크릴레이트, 2-에틸헥실메타크릴레이트, 옥틸메타크릴레이트, 글리시딜메타크릴레이트, 라우릴메타크릴레이트, 이소보닐메타크릴레이트 등을 들 수 있으며, 산기를 갖는 아크릴계 또 메타크릴계 단량체의 예로는 아크릴산, 메타크릴산 등을 들 수 있으며, 수산기를 갖는 아크릴계 또는 메타크릴계 단량체의 예로는 2-히드록시에틸아크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시프로필아크릴레이트, 2-히드록시프로필메타크릴레이트, 4-히드록시부틸아크릴레이트, 4-히드록시부틸메타크릴레이트 등을 들 수 있으며, 이들 중 하나 또는 두 가지 이상을 선택하여 사용한다. 내부 가교에 사용되는 에폭시실란 화합물의 예로는 γ-글리시독시프로필트리메톡시실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시프로필메틸디메톡시실란, γ-글리시독시프로필메틸디에톡시실란, β-(3,4-에폭시사이클로헥실)에틸트리메톡시실란, β-(3,4-에폭시사이클로헥실)에틸트리에톡시실란, β-(3,4-에폭시사이클로헥실)에틸메틸디에톡시실란, γ-글리시독시프로필트리이소프로페닐옥시실란 또는 γ-글리시독시프로필트리이미노옥시실란 등을 들 수 있다.Examples of tertiary amine-containing monomers used in the present invention include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like. Examples of acrylic or methacrylic monomers having aliphatic groups include normal butyl acrylate and 2- Ethylhexyl acrylate, ethyl acrylate, normal butyl methacrylate, normal propyl methacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, glycidyl methacrylate And lauryl methacrylate, isobornyl methacrylate, and the like. Examples of the acrylic or methacrylic monomer having an acid group include acrylic acid and methacrylic acid, and acrylic or methacrylic monomers having a hydroxyl group. Examples of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like, and one or two or more of these may be selected and used. Examples of the epoxysilane compound used for internal crosslinking include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropyl Methyl diethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Ethyl methyl diethoxysilane, (gamma)-glycidoxy propyl triisopropenyl silane, (gamma)-glycidoxy propyl triimino oxysilane, etc. are mentioned.
본 발명에서 사용되는 3급아민 함유 단량체의 함량은 경화제로 사용되는 에폭시실란과의 가교 결합을 고려하여 아크릴 수지의 고형분 기준으로 1 중량부 내지 4 중량부가 되도록 사용하는 것이 바람직하다. 3급 아민기 함량이 이보다 낮을 경우에는 경화제인 에폭시실란과의 가교 밀도가 낮아 도막 물성의 저하를 가져오며 이보다 높을 경우에는 가교 밀도의 과도한 증가로 도막의 경질화, 저장안정성 불량 및 황변 현상을 발생시키기 때문에 바람직하지 못하다.The content of the tertiary amine-containing monomer used in the present invention is preferably used to 1 to 4 parts by weight based on the solid content of the acrylic resin in consideration of crosslinking with the epoxy silane used as a curing agent. If the content of tertiary amine groups is lower than this, the crosslinking density with the epoxy silane, which is a curing agent, is low, resulting in deterioration of coating properties. If the content of the tertiary amine group is lower than this, the coating film becomes hard due to excessive increase in the crosslinking density, resulting in poor storage stability and yellowing. It is not preferable because it is made.
본 발명에서 사용되는 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체는 유연한 단량체와 딱딱한 단량체를 적절히 조정하여 유리 전이 온도를 조절하는 역할을 하며, 적절한 유리 전이 온도는 ＋20˚С 내지 ＋40˚С의 범위이며, ＋25˚С 내지 ＋30˚С 범위가 보다 바람직하다. 이들 지방족기를 갖는 아크릴계 또는 메타크릴계 단량체의 함량은 아크릴 수지의 고형분 기준으로 50 내지 80 중량부가 되도록 사용하는 것이 바람직하다. 이들은 도막의 경도를 조정하고 광택 및 평활성을 부여하며 내스크래치성 향상에 기여한다. The acrylic or methacrylic monomer having an aliphatic group used in the present invention serves to adjust the glass transition temperature by appropriately adjusting the flexible monomer and the hard monomer, the suitable glass transition temperature is in the range of + 20˚С to + 40˚С, The range of +25 DEG to +30 DEG is more preferred. The content of the acrylic or methacrylic monomer having an aliphatic group is preferably used to 50 to 80 parts by weight based on the solid content of the acrylic resin. They adjust the hardness of the coating film, impart gloss and smoothness and contribute to improving scratch resistance.
본 발명에서 사용되는 스티렌 단량체는 딱딱한 단량체로서 도막 경도를 향상시키고, 광택을 부여하며 가격을 낮추는 역할을 한다. 이들의 함량이 아크릴 수지의 고형분 기준으로 20 중량부 이상이 되면 도막의 내후성이 저하되어 황변 현상이 발생할 수 있다. 따라서, 본 발명에서는 10 중량부를 사용하였다. The styrene monomer used in the present invention serves as a hard monomer to improve the coating hardness, give gloss and lower the price. When the content thereof is 20 parts by weight or more based on the solid content of the acrylic resin, the weather resistance of the coating film may be lowered, and yellowing may occur. Therefore, 10 parts by weight was used in the present invention.
본 발명에서 사용되는 산기를 갖는 아크릴계 또는 메타크릴계 단량체는 단독 또는 2 가지 이상을 혼합하여 사용될 수 있으며, 아크릴 수지의 고형분 기준으로 3 내지 6 중량부의 양으로 사용하는 것이 바람직하다. 이들의 함량이 6 중량부보다 많으면 물에 대한 분산성은 양호하나 점성도 상승이 심하고 내수성이 불량해지며, 3 중량부보다 적으면 물에 대한 분산성이 불량하고 저장 안정성을 확보하기가 곤란 해진다. 이들은 경화제인 에폭시실란과의 가교 반응에 의한 도막의 경도 및 피도물과의 접착성의 증진에도 기여한다.Acrylic or methacrylic monomer having an acid group used in the present invention may be used alone or in combination of two or more, it is preferable to use in an amount of 3 to 6 parts by weight based on the solid content of the acrylic resin. If the content is more than 6 parts by weight, the dispersibility in water is good but the viscosity is increased and the water resistance is poor. If the content is less than 3 parts by weight, it is difficult to secure the storage stability. These also contribute to the improvement of the hardness of the coating film and the adhesiveness with the to-be-coated object by the crosslinking reaction with the epoxy silane which is a hardening | curing agent.
본 발명에서 사용되는 수산기를 갖는 아크릴계 또는 메타크릴계 단량체는 아크릴 수지의 고형분 기준으로 5 내지 20 중량부가 되도록 사용하는 것이 바람직하다. 이들을 함량이 20 중량부보다 많으면 경화제와의 혼합시 가사 시간은 길어지지만 내수성 및 내알카리성이 불량해지게 되고, 5 중량부보다 적으면 경화제와의 혼합시 가사 시간이 짧아지고 물에 대한 분산성이 불량하며 저장 안정성의 확보가 곤란해진다. 이들은 경화제인 에폭시실란과의 가교 반응에 의한 도막의 경도, 피도물과의 접착성 및 내용제성의 증진에도 기여한다.The acrylic or methacrylic monomer having a hydroxyl group used in the present invention is preferably used so as to be 5 to 20 parts by weight based on the solid content of the acrylic resin. If the content is more than 20 parts by weight, the pot life will be longer when mixed with the curing agent, but the water resistance and alkali resistance will be poor. If the content is less than 5 parts by weight, the pot life will be shortened and the dispersibility to water will be short. It is poor and it is difficult to secure storage stability. These contribute to the improvement of the hardness of the coating film, the adhesiveness with the to-be-coated object, and the solvent resistance by the crosslinking reaction with the epoxy silane which is a hardening agent.
본 발명에서 아크릴 수지의 내부 가교에 사용되는 에폭시실란은 아크릴 수지의 고형분 기준으로 1 중량부 내지 10 중량부가 되도록 사용하는 것이 바람직하다. 이들을 함량이 10 중량부보다 많으면 가교성 작용기와 반응하지 않고 유리되는 에폭시실란에 의해 건조속도가 느려지게 되고, 1 중량부보다 적으면 내부 가교 밀도가 낮아져서 내수성, 내후성 및 저장 안정성이 불량해진다.In the present invention, the epoxy silane used for the internal crosslinking of the acrylic resin is preferably used so as to be 1 part by weight to 10 parts by weight based on the solid content of the acrylic resin. If the content is more than 10 parts by weight, the drying rate is slowed by the epoxy silane which does not react with the crosslinkable functional group, and if it is less than 1 part by weight, the internal crosslinking density is lowered, resulting in poor water resistance, weather resistance and storage stability.
본 발명에서 라디칼 중합을 위한 중합 개시제는 과산화벤조일, 3차부틸퍼옥시벤조에이트, 3차부틸퍼옥시-2-에틸헥사노에이트, 3차아밀퍼옥시-2-에틸헥사노에이트 및 아조비스이소부티로니트릴로 이루어진 군 중에서 선택하여 단독으로 또는 2 종 이상을 혼합하여 사용할 수 있다. 중합 개시제의 사용량은 단량체 총중량에 대하여 2 내지 4 중량%가 되도록 사용하는 것이 바람직하다. 중합 개시제의 사용량이 이보다 적을 경우에는 점도와 분자량이 커져서 실끌림 현상이 발생하여 스프레 이 작업성이 불량해지고 수분산시 점성도가 높아지게 되며, 이보다 많을 경우에는 지나친 분자량 저하에 의한 도막 물성의 저하를 가져올 수 있기 때문에 바람직하지 않다.The polymerization initiator for radical polymerization in the present invention is benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy-2-ethyl hexanoate, tertiary amyl peroxy-2-ethyl hexanoate and azobisiso It can select from the group which consists of butyronitrile, and can use individually or in mixture of 2 or more types. It is preferable to use the usage-amount of a polymerization initiator so that it may become 2 to 4 weight% with respect to a monomer total weight. If the amount of the polymerization initiator is less than this, the viscosity and molecular weight will increase, leading to slippage, resulting in poor spray workability and high viscosity upon water dispersion. It is not desirable because it can.
발명에서 사용되는 용매는 톨루엔, 키실렌 등의 방향족계 탄화수소; 노말부틸아세테이트, 에틸렌글리콜에틸에테르아세테이트 등의 에스테르류; 메틸이소부틸케톤, 메틸노말아밀케톤 등의 케톤류; 이소프로판올, 노말부탄올, 이소부탄올, 3-메톡시-1-부탄올, 3-메틸-3-메톡시-부탄올 등의 알콜류; 및 에틸렌글리콜모노메틸에테르, 에틸렌글리콜프로필에테르, 에틸렌글리콜이소프로필에테르, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜디메틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디프로필렌글리콜모노메틸에테르 등의 글리콜 에테르류로 이루어진 군 중에서 선택하여 사용할 수 있다. 반응 온도가 합성 수지의 분자량과 최종 점도에 미치는 영향을 감안하여 이들 용매를 단독 또는 혼합 사용할 수 있으며, 합성 수지의 합성 온도, 용해도 파라미터, 증발 속도 등을 감안하여 용매의 비점은 100˚С 내지 200˚С인 것이 적합하며, 비점이 110˚С 내지 180˚С 범위인 것이 보다 바람직하다. 상기 용매는 물에 대한 용해성, 냄새 등을 고려하여야 하며, 사용량은 수분산성 아크릴 수지 총중량에 대하여 20 중량% 내지 30 중량%가 되도록 사용하는 것이 바람직하다. 용매의 사용량이 이보다 적을 경우에는 물에 대한 분산성과 저장 안정성이 불량해지고, 이보다 많을 경우에는 건조 속도의 지연 현상이 발생할 수 있다.The solvent used in the invention includes aromatic hydrocarbons such as toluene and xylene; Esters such as normal butyl acetate and ethylene glycol ethyl ether acetate; Ketones such as methyl isobutyl ketone and methyl normal amyl ketone; Alcohols such as isopropanol, normal butanol, isobutanol, 3-methoxy-1-butanol and 3-methyl-3-methoxy-butanol; Ethylene glycol monomethyl ether, ethylene glycol propyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, and the like. It can be used by selecting from the group consisting of glycol ethers. These solvents may be used alone or in combination in consideration of the influence of the reaction temperature on the molecular weight and the final viscosity of the synthetic resin, and the boiling point of the solvent is 100˚С to 200 in view of the synthetic temperature, solubility parameter, evaporation rate, etc. of the synthetic resin. ˚С is suitable, and the boiling point is more preferably in the range of 110˚С to 180˚С. The solvent should be considered solubility, smell, etc. in water, the amount used is preferably 20 to 30% by weight based on the total weight of the water-dispersible acrylic resin. When the amount of the solvent is less than this, the dispersibility and storage stability to water are poor, and when the amount of the solvent is greater than this, the drying rate may be delayed.
본 발명의 아크릴 수지 조성물의 합성은 상기한 단량체들과 중합 개시제와의 혼합 용액을 5시간 내지 7시간 동안 균일한 속도로 반응기 내의 용매에 적하하면서, 80˚С 내지 90˚С의 온도에서 8시간 내지 12시간 동안 중합시켜서 수행한다. 상기와 같이, 반응 조건을 안정적으로 유도함으로써 수지의 광택이 우수하고, 평활성이 양호하며, 내스크래치성이 양호한 3급 아민 함유 아크릴 수지 조성물을 수득할 수 있다. 60˚С에서 이와 같이 제조한 아크릴 수지에 중화제로서 염기성 화합물을 산기를 갖는 아크릴계 또는 메타크릴계 단량체의 이론 중화량값의 70% 내지 80%의 양으로 첨가하여 중화시키고, 30분동안 교반하여, pH를 8.5 내지 9.5가 되도록 한다. Synthesis of the acrylic resin composition of the present invention is 8 hours at a temperature of 80˚С to 90˚С while dropping the mixed solution of the monomers and the polymerization initiator in a solvent in the reactor at a uniform rate for 5 hours to 7 hours. By polymerization for from 12 hours. As described above, the tertiary amine-containing acrylic resin composition can be obtained by stably inducing the reaction conditions with excellent gloss of resin, good smoothness and good scratch resistance. At 60 ° С, the basic compound was added to the acrylic resin thus prepared at a temperature of 70% to 80% of the theoretical neutralization value of the acrylic or methacrylic monomer having an acid group as a neutralizing agent, neutralized by stirring for 30 minutes, pH To 8.5 to 9.5.
상기 중화제로서 사용 가능한 염기성 화합물로는 디메틸아민, 트리메틸아민, 디에틸아민, 트리에틸아민, n-부틸아민, 트리-n-부틸아민, 2-아미노-2-메틸-1-프로판올, 2-아미노에탄올 또는 2-디메틸아미노에탄올등의 유기아민 화합물 암모니아, 수산화리튬, 수산화나트륨 또는 수산화칼륨 등의 무기 염기성 화합물 또는 테트라메틸암모늄 하이드록사이드, 테트라부틸암모늄 하이드록사이드 또는 트리메틸벤질암모늄 하이드록사이드 등의 제4급 암모늄 하이드록사이드류 등을 들 수 있다. Basic compounds usable as the neutralizing agent include dimethylamine, trimethylamine, diethylamine, triethylamine, n-butylamine, tri-n-butylamine, 2-amino-2-methyl-1-propanol, 2-amino Organic amine compounds such as ethanol or 2-dimethylaminoethanol inorganic basic compounds such as ammonia, lithium hydroxide, sodium hydroxide or potassium hydroxide or tetramethylammonium hydroxide, tetrabutylammonium hydroxide or trimethylbenzylammonium hydroxide Quaternary ammonium hydroxides; and the like.
그리고 나서, 고형분 함량이 35 중량%가 되도록 하는 양의 이온 교환수를 1시간에 걸쳐 균일하게 첨가하고, 첨가 종료 후에도 60˚С의 온도를 1시간 30분간 유지하여 내용물을 균일하게 분산시킨다. 이어서 내부 가교에 사용되는 에폭시실란 화합물을 30분간 균일하게 첨가하고, 첨가 종료 후에도 60˚С의 온도를 1시간 30분간 유지하여 내용물을 균일하게 분산시켜, 고형분 농도가 35 중량%, 유리 전이 온도가 +20 내지 +40˚С, 바람직하게는 ＋25˚С 내지 ＋30˚С, 점도가 5 Poise(68 KU) 내지 10.7 Poise(85 KU), 수평균 분자량이 12,000 내지 15,000인 수분산성 아크릴 수지를 얻는다.Then, ion-exchanged water in an amount such that the solid content is 35% by weight is added uniformly over 1 hour, and the content is uniformly dispersed by maintaining a temperature of 60 DEG C for 1 hour and 30 minutes after the addition is completed. Subsequently, the epoxysilane compound used for internal crosslinking was added uniformly for 30 minutes, and after the addition was completed, the temperature was maintained at 60 DEG C for 1 hour and 30 minutes to uniformly disperse the contents, so that the solid content concentration was 35% by weight and the glass transition temperature was A water-dispersible acrylic resin having +20 to + 40 ° С, preferably + 25 ° С to + 30 ° С, a viscosity of 5 Poise (68 KU) to 10.7 Poise (85 KU) and a number average molecular weight of 12,000 to 15,000 is obtained.
본 발명에서 경화제로 사용되는 에폭시실란은 γ-글리시독시프로필트리메톡시실란, γ-글리시독시프로필트리에톡시실란 등을 직접 사용하거나, 이들을 중합시켜 얻어진 중합체를 사용할 수 있으며, 경화제의 사용량은 3급 아민 함유 아크릴 수지에서의 내부 가교 반응을 하고 남은 작용기의 당량수에 대하여 경화제인 에폭시실란의 당량비가 0.8 내지 1.5 (아크릴 수지에서의 내부 가교 반응 후 남은 작용기의 당량수/경화제인 에폭시실란의 당량수)인 범위인 것이 적절하고, 0.8 내지 1.2인 범위가 보다 바람직하다. 당량비가 상기 범위를 벗어날 경우에는 가교 반응에 참여하지 못한 작용기로 인하여 치밀한 가교 결합을 이루지 못하기 때문에 도막 물성의 저하를 가져온다. As the epoxy silane used as the curing agent in the present invention, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, or the like can be used directly, or a polymer obtained by polymerizing them can be used. The equivalent ratio of the epoxysilane as a curing agent is 0.8 to 1.5 (the equivalent number of functional groups remaining after the internal crosslinking reaction in the acrylic resin / the curing agent) with respect to the equivalent number of functional groups remaining after the internal crosslinking reaction in the silver tertiary amine-containing acrylic resin. Is an equivalent number), more preferably 0.8 to 1.2. If the equivalence ratio is out of the above range, because the functional groups that do not participate in the crosslinking reaction does not achieve a dense crosslinking, the coating film properties are lowered.
이하, 실시예 및 비교예를 통하여 본 발명을 보다 구체적으로 설명하겠으나, 이들 실시예에 의하여 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited by these Examples.
(실시예)(Example)
아크릴 수지 조성물의 제조: 실시예 1 내지 12 및 비교예 1 내지 11Preparation of Acrylic Resin Compositions: Examples 1-12 and Comparative Examples 1-11
온도계, 콘덴서, 적하깔대기, 교반기가 장착된 3L 4구 플라스크에 3-메틸-3-메톡시-부탄올 318.4g와 프로필렌글리콜모노메틸에테르 318.4g을 넣은 후, 질소 가스로 치환시키고 교반하면서 온도를 80˚С로 올렸다. 그리고 나서, 상기 용매의 온도를 일정하게 유지시키면서, 하기의 표 1와 같은 조성의 단량체들과 개시제로서 아조비스이소부티로니트릴(AIBN) 18g과 3차부틸퍼옥시-2-에틸헥사노에이트(TBEH) 12g의 혼합 용액을 5시간 내지 7시간에 걸쳐 균일한 속도로 적하하였다. 적하 완료 후, 3시간 내지 5시간 동안 더 숙성시켜 반응을 종료하고, 60˚С에서 중화제로 중화하여 pH가 8.5 내지 9.5로 한다. 318.4 g of 3-methyl-3-methoxy-butanol and 318.4 g of propylene glycol monomethyl ether were added to a 3-liter four-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer. Raised to ˚С. Then, while maintaining the temperature of the solvent, 18 g of azobisisobutyronitrile (AIBN) and tertiary butylperoxy-2-ethylhexanoate ( TBEH) 12 g of the mixed solution was added dropwise at a uniform rate over 5 to 7 hours. After completion of the dropping, the mixture was further aged for 3 to 5 hours to complete the reaction, and neutralized with a neutralizing agent at 60 ° C. to pH 8.5 to 9.5.
이어서, 고형분 함량이 35 중량%가 되도록 하는 양의 이온 교환수를 1시간에 걸쳐 균일하게 첨가하고, 첨가 종료 후에도 온도를 60˚С로 1시간 30분간 유지하여 내용물을 균일하게 분산시켰다. 이어서, 내부 가교에 사용되는 에폭시실란 화합물을 30분간 균일하게 첨가하고, 첨가 종료 후에도, 온도를 60˚С로 1시간 30분간 유지하여 내용물을 균일하게 분산시켰다. Subsequently, ion-exchanged water in an amount such that the solid content was 35% by weight was added uniformly over 1 hour, and the contents were uniformly dispersed by maintaining the temperature at 60 DEG C for 1 hour after the addition was completed. Subsequently, the epoxysilane compound used for internal crosslinking was added uniformly for 30 minutes, and after completion | finish of addition, the temperature was maintained at 60 degreeC for 1 hour and 30 minutes, and the content was disperse | distributed uniformly.
이와 같이 하여, 고형분 농도가 35 중량%, 유리 전이 온도가 ＋25˚С 내지 ＋30˚С, 점도가 5 Poise(68 KU) 내지 10.7 Poise(85 KU), 수평균 분자량이 12000 내지 15000인 수분산성 아크릴 수지 조성물을 얻었다. 사용된 단량체, 개시제, 에폭시실란의 양과 얻어진 아크릴 수지 조성물의 점도, 수평균 분자량 및 저장 안정성을 하기의 표 1에 나타내었다. Thus, the water-dispersible acrylic having a solid content concentration of 35% by weight, a glass transition temperature of + 25 ° С to + 30 ° С, a viscosity of 5 Poise (68 KU) to 10.7 Poise (85 KU), and a number average molecular weight of 12000 to 15000. The resin composition was obtained. The amount of monomer, initiator, epoxysilane used and the viscosity, number average molecular weight and storage stability of the obtained acrylic resin composition are shown in Table 1 below.
*1: ○(양호, ±5 KU 이내), △(보통, ±5 내지10 KU), ×(불량, ±10 KU 이상)* 1: ○ (good, within ± 5 KU), △ (normal, ± 5 to 10 KU), × (bad, ± 10 KU or more)
*2: 제조공정 변경 - 숙성 반응을 종료하고 60˚С에서 중화제로 중화하기 전에 내부 가교에 사용되는 에폭시실란 화합물을 30분간 균일하게 첨가하고, 첨가 종료 후에도 60˚С의 온도를 1시간 30분 유지하여 내용물을 균일하게 분산시킨 후에, 2-아미노-2-메틸-1-프로판올로 중화하여 pH가 8.5 내지 9.5로 한다. 이어서, 고형분 함량을 35 중량%로 하는 양의 이온 교환수를 1시간에 걸쳐 균일하게 첨가하고, 첨가 종료 후에도 60˚С의 온도를 1시간 30분 유지하여 내용물을 균일하게 분산시켰다. * 2: Change in manufacturing process-Epoxysilane compound used for internal crosslinking is added uniformly for 30 minutes before completion of the aging reaction and neutralized with neutralizing agent at 60˚С. After holding to uniformly disperse the contents, the mixture is neutralized with 2-amino-2-methyl-1-propanol to obtain a pH of 8.5 to 9.5. Subsequently, ion-exchanged water having an amount of solid content of 35% by weight was added uniformly over 1 hour, and the contents were uniformly dispersed by maintaining a temperature of 60 DEG C for 1 hour and 30 minutes after the addition was completed.
도막의 물성 평가Physical property evaluation of coating film
상기, 실시예 1 내지 12 및 비교예 1 내지 11의 수분산성 아크릴 수지 조성물로부터 형성된 도막의 특성을 알아보기 위하여, 하기의 표 2와 같이, 수분산성 아크릴 수지 조성물과 경화제인 에폭시실란의 당량비를 1:1로 하여 백색도료를 제조한 후, 도료의 가사 시간, 도막의 일반 물성인 건조 시간, 광택, 접착성, 경도, 내용제성, 내후성 시험 및 저장안정성을 비교, 검토하였다. In order to examine the properties of the coating film formed from the water dispersible acrylic resin compositions of Examples 1 to 12 and Comparative Examples 1 to 11, the equivalent ratio of the water dispersible acrylic resin composition and the epoxy silane as a curing agent is 1 as shown in Table 2 below. After the white paint was prepared as 1: 1, the pot life of the paint, the drying time, the gloss, adhesion, hardness, solvent resistance, weather resistance test, and storage stability, which are general physical properties of the coating film, were compared and examined.
도막 성능시험 시편은 상기 배합에 의하여 제조된 도료를 건조 도막 두께(DFT) 50 ㎛가 되도록 분무 도장 후, 7 일간 자연 건조시켜 시험 도막을 얻어서 도막 성능을 조사하였다.Coating performance test specimens were spray-coated the coating prepared by the above formulation to have a dry coating thickness (DFT) of 50 μm, and then naturally dried for 7 days to obtain a test coating film to investigate the coating performance.
도막 성능 시험은 다음과 같은 일반적인 도막 물성 평가 방법에 따라 수행하였다.Coating performance test was carried out according to the following general coating properties evaluation method.
1. 건조시간 측정1. Drying time measurement
KS M 5000-2512의 도료의 건조 시간 시험 방법에 따라 도료를 젖은 도막 두께가 0.05 ㎜가 되도록 Doctor film applicator(0.004 inch)로 유리판에 코팅을 한 다음 수평으로 놓고 자연 건조시키켰다. 건조 시간의 평가 방법은 고화 건조법(dry-hard method)을 사용하였다.According to the test method for drying time of paints of KS M 5000-2512, the paints were coated on a glass plate with a doctor film applicator (0.004 inch) so that the wet film thickness was 0.05 mm, and then horizontally dried and naturally dried. As a method for evaluating the drying time, a dry-hard method was used.
2. 가사시간 측정2. Pot life measurement
가사 시간은 JIS K 5400(4.9)에 따라 주제부와 경화제를 혼합하여 사용 가능한 시간을 측정하여 평가하였다.Pot life was evaluated by measuring the time available by mixing the main part and a hardener according to JIS K 5400 (4.9).
3. 광택 측정3. Gloss measurement
광택 측정은 KS M 5000-3312의 도료의 60o 경면 광택도 시험 방법을 채택하여 수행하였으며, 광택계를 사용하여 입사각과 수평각이 각각 60o 일때의 반사율을 측정하여, 표준판인 유리 표면의 경면 광택도를 100으로 하였을 때의 백분율로 표시하여 5회 측정한 평균값을 취하여 평가하였다.The gloss measurement was carried out by adopting the 60 o mirror gloss test method of the paint of KS M 5000-3312, and using the gloss meter to measure the reflectance when the angle of incidence and the horizontal angle were 60 o , respectively, the mirror surface gloss of the standard surface of the glass The average value measured 5 times was expressed by the percentage when the figure was set to 100, and evaluated.
4. 접착성 시험4. Adhesive test
접착성 시험은 ISO 2409의 도료의 접착력 시험법에 따라 수행하였으며, 시편의 위를 간격이 1mm가 되도록 가로, 세로로 11줄 긋고, 그 위에 셀로판 접착 테이프를 붙인 다음 떼어 보아서 도막 위에 100 조각의 분리된 코팅면 중 남아있는 조각의 숫자로 접착성을 평가하였다.The adhesion test was carried out according to the ISO 2409 paint test method, and the top of the specimen was 11 lines horizontally and vertically with a distance of 1 mm, and then the cellophane adhesive tape was attached thereon, and then peeled off. Adhesiveness was evaluated by the number of pieces remaining of the coated surface.
5. 도막 경도5. Coating Hardness
도막 경도는 JIS K-5400의 연필 경도법에 따라 연필 경도 시험기를 사용하여 건조된 도막을 연필의 종류별(B, HB, F, H, 2H, 3H 등)로 45o 각도로 하여 그어 보았을 때의 긁힘이 나는 정도를 육안으로 관찰하여 판정하였다.The coating film hardness is obtained by drawing the coating film dried using a pencil hardness tester according to the pencil hardness method of JIS K-5400 at a 45 ° angle according to the type of pencil (B, HB, F, H, 2H, 3H, etc.). The degree of scratching was visually observed and determined.
6. 내용제성6. Solvent resistance
내용제성은 ASTM D 4752의 MEK double rubs 시험방법을 채택하였으며, 메틸에틸케톤(MEK)을 헝겊에 충분히 묻힌 다음, 도막에 눌러 문지르는 회수에 따라 도막이 벗겨지는 것을 외관으로 관찰하여 평가하였다.Solvent resistance was measured using the MEK double rubs test method of ASTM D 4752, and methyl ethyl ketone (MEK) was sufficiently immersed in the cloth, and then evaluated by visually observing that the coating film was peeled off with the number of times it was pressed on the coating film.
7. 촉진내후성7. Promote weather resistance
촉진내후성 시험은 SWO 및 QUV의 2가지 시험을 실시하였으며, SWO 시험은 KS M 5000-3231의 도료의 촉진내후성 시험방법에 따라 sunshine weather-Ometer(Atlas Electric Devices Co., Ci65A형)를 사용하고, QUV 시험은 ASTM G-53에 따라 QUV accelerated weathering tester(The Q-Panel Co.)를 사용하였으며, 자외선 형광등은 UV-B313 램프(280∼315 ㎚)를 사용하였으며, 각각 냉간압연 강판을 사용하여 1,000 시간 경과 후의 광택 보존값 및 색상차를 평가하였다.The accelerated weather resistance test was conducted by two tests, SWO and QUV. SWO test was conducted using sunshine weather-Ometer (Atlas Electric Devices Co., Ci65A type) according to the accelerated weather resistance test method of paint of KS M 5000-3231. QUV test was carried out using the QUV accelerated weathering tester (The Q-Panel Co.) according to ASTM G-53, UV fluorescent lamp was used UV-B313 lamp (280 ~ 315 nm), each using a cold rolled steel sheet 1,000 The gloss preservation value and color difference after time passed were evaluated.
(1) 광택 보존값 측정(1) gloss retention value measurement
광택 보존값은 광택계(Pacific Scientific Co., Glossgard Ⅱ형)를 사용하여 아래의 식에 의하여 계산하였다.Gloss retention value was calculated by the following formula using a glossmeter (Pacific Scientific Co., Glossgard II).
(2) 색상차 측정(2) color difference measurement
색상차(color difference)는 2색의 차이를 시각적 개념에서 수치적 개념으로 표현한 것이다. 즉, 색공간 좌표에서 2색의 기하학적인 거리를 수치로 표시하게 된다. 확산 반사율 측정 장치인 Spectro Color Meter(Nippon Denshoku Kogyo Co., SZ-∑80형)를 사용하여 측정하였으며, 색상차는 아래의 식에 의하여 계산하였다.Color difference expresses the difference between two colors from visual to numerical concept. That is, the geometric distance of the two colors in the color space coordinates is displayed numerically. Spectro Color Meter (Dippon Denshoku Kogyo Co., SZ-∑ 80 type), which is a diffuse reflectance measuring apparatus, was used for measurement, and the color difference was calculated by the following equation.
색상차(△E) = [ (△L)2 + (△a)2 + (△b)2 ]1/2 Color difference (△ E) = [(△ L) 2 + (△ a) 2 + (△ b) 2 ] 1/2
상기 식 중, L = Hunter 색표시계의 명도지수 In the above formula, L = brightness index of Hunter color indicator
a , b = Hunter 색표시계의 크로마틱네스 계수 a, b = chromaticity coefficients of the Hunter colorimeter
8. 저장 안정성 시험8. Storage stability test
도료의 저장 안정성은 KS M 5000-2031의 도료의 저장성 시험 방법에 따라서, 용기에 도료를 3/4 정도 채우고 밀폐한 다음, 60˚С 항온 건조기에 10일 방치한 후, 수지 및 도료의 점도 변화를 측정하여 평가하였다. The storage stability of the paint was changed according to KS M 5000-2031 paint storage test method, after filling the container with about 3/4 of the paint and sealing it, leaving it in a 60˚C constant temperature dryer for 10 days, and then changing the viscosity of the resin and the paint. Was measured and evaluated.
상기와 같은 도막 물성 평가 결과를 하기의 표 3a 내지 3d에 나타내었다.The coating film property evaluation results as described above are shown in Tables 3A to 3D.
[표 3a]TABLE 3a
[표 3b]TABLE 3b
*3: ○(양호, ±5 KU 이내), △(보통, ±5 내지 10 KU), × (불량, ±10 KU 이상)* 3: ○ (good, within ± 5 KU), △ (normal, ± 5 to 10 KU), × (bad, ± 10 KU or more)
[표 3c]TABLE 3c
[표 3d]Table 3d
*3: ○(양호, ±5 KU 이내), △(보통, ±5 내지 10 KU), ×(불량, ±10 KU 이상)* 3: ○ (good, within ± 5 KU), △ (normal, ± 5 to 10 KU), × (bad, ± 10 KU or more)
상기 표 3a 내지 3d로부터 알 수 있는 바와 같이, 실시예 상기 실시예 1 내지 12에서 제조된 본 발명의 3급 아민 함유 수분산성 아크릴 수지 조성물을 사용하고 경화제로서 에폭시실란을 사용하여 제조된 2성분계 도료 조성물이 우수한 물성의 도막을 형성할 수 있음을 알 수 있다. As can be seen from Tables 3a to 3d above, Examples A two-component paint prepared using the tertiary amine-containing water dispersible acrylic resin composition of the present invention prepared in Examples 1 to 12 and using epoxysilane as a curing agent. It can be seen that the composition can form a coating film of excellent physical properties.
본 발명의 3급아민 함유 수분산성 아크릴 수지와 에폭시실란으로 제조된 도료의 경화 도막은, 종래의 경화 도막에 비해 내용제성과 내후성이 우수할 뿐만 아니라 다양한 소재에 대한 접착성이 우수하다. 특히 가사 시간이 길고, 주제부의 저장 안정성이 우수하여 작업성이 양호한 특성을 지니고 있다. 따라서, 본 발명의 도 료 조성물은 내후성이 요구되는 소재에 적용이 가능하며, 환경 보호에 이바지할 수 있는 유용한 발명이다.The cured coating film of the coating material produced from the tertiary amine-containing water dispersible acrylic resin and the epoxy silane of the present invention is excellent in solvent resistance and weather resistance as well as excellent adhesion to various materials as compared with the conventional cured coating film. In particular, the pot life is long, and the storage stability of the main part is excellent, the workability is good. Therefore, the coating composition of the present invention is a useful invention that can be applied to materials requiring weather resistance, and can contribute to environmental protection.
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| US10934449B2 (en) | 2016-07-29 | 2021-03-02 | Behr Process Corporation | Water based sealer with superior durability |
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| KR101726583B1 (en) * | 2016-08-01 | 2017-04-13 | 최용제 | Coating agent for restoring car headlights |
| CN114014989A (en) * | 2021-09-30 | 2022-02-08 | 绵阳麦思威尔科技有限公司 | Hydroxyl acrylic acid aqueous dispersion, preparation method and application thereof |
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