KR100354346B1 - Process for Producing Anti-corrosive Water Soluable Acrylic Polymer Vehicle - Google Patents
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Abstract
본 발명은 방청성을 갖는 수용성 아크릴 중합체 전색제의 제조 방법에 관한 것으로, 그 목적은 수용성 아크릴계 중합체 전색제의 사용시 도막 부착성의 열등함으로 인한 내후성 및 내구성상의 문제 및 다량의 함유 수분으로 인한 표면 발청 문제를 해소키 위한 것이다.이를 위해 본 발명에 따른 방청성을 갖는 수용성 아크릴 중합체 전색제의 제조 방법에 의하면, 우수한 건조성을 나타내도록 자기 가교성을 부여하기 위한 비닐 술폰산계 또는 아크릴 아미도 술폰산계 모노머 및 발청 억제를 위해 인을 함유한 아크릴 모노머가 공중합되어 있어서, 이러한 전색제를 이용하여 제조되는 환경 친화적 방청 도료는 부착성, 내후성, 내수성, 특히 금속 표면 도장시 방청성이 우수한 작용효과가 있다.The present invention relates to a method for producing a water-soluble acrylic polymer developer having rust resistance, and its object is to solve the problem of weathering and durability due to inferior coating adhesion when using a water-soluble acrylic polymer developer and surface rusting problem due to a large amount of moisture. To this end, according to the method for preparing a water-soluble acrylic polymer developer having rust resistance according to the present invention, a vinyl sulfonic acid-based or acrylic amido sulfonic acid-based monomer for imparting self-crosslinking property to exhibit excellent dryness, and Since the acrylic monomer containing the copolymer is copolymerized, the environmentally-friendly rust-preventive paint prepared using such a colorant has an effect of excellent adhesion, weather resistance, water resistance, and particularly rust resistance when painting a metal surface.
Description
본 발명은 방청성을 갖는 수용성 아크릴 중합체 전색제의 제조 방법에 관한 것으로, 더욱 상세하게는 자기 가교성을 부여하기 위한 비닐 술폰산계 또는 아크릴 아미도 술폰산계 모노머 및 발청 억제를 위해 인이 함유된 아크릴 모노머를 이용한 방청성을 갖는 수용성 아크릴 중합체 전색제의 제조 방법에 관한 것이다.The present invention relates to a method for preparing a water-soluble acrylic polymer developer having rust resistance, and more particularly, to a vinyl sulfonic acid-based or acrylic amido sulfonic acid-based monomer for imparting self-crosslinking property, and an acrylic monomer containing phosphorus to prevent rusting. It relates to a method for producing a water-soluble acrylic polymer developer having rust resistance.
종래, 금속 플라스틱, 콘크리트, 또는 목재 등과 같은 소재 표면에 대한 제막(製膜) 분야에서 널리 사용되고 있는 수용성 도료는 전색제로서 유화제 또는 아민 중화형 폴리머를 사용하고 있다.그러나, 이러한 종래의 전색제는 비교적 다량의 수분을 포함하고 있는 관계로 소재 표면에 대한 도장시 표면 발청에 의한 도막 부착 불량, 내수성 및 내구성에 있어 열등한 문제점이 있으며, 이로 인해 콘크리트 표면에 대한 도장 이외의 기타 소재, 특히 금속에 대한 도장에는 많은 문제점을 내포하고 있다.Conventionally, water-soluble paints widely used in the field of film-forming on material surfaces such as metal, plastic, concrete, or wood use emulsifiers or amine neutralizing polymers as a colorant. However, these conventional colorants are relatively large. Due to the inclusion of water, there is an inferior problem in coating adhesion, water resistance and durability due to surface rusting when painting on the surface of the material. There are many problems.
특히, 종래의 에멀젼 중합체는 중합시 인 함유 비이온계 유화제(2-8 중량%)나 보호 콜로이드를 다량 사용하고 있어서, 이를 이용한 도료 도포시 도막의 내부 건조가 늦고 내수성이 열등하기 때문에 통상적인 콘크리트의 표면 도장 이외에는 적용하기 곤란한 문제점이 있다.In particular, conventional emulsion polymers use a large amount of phosphorus-containing nonionic emulsifiers (2-8% by weight) or protective colloids during polymerization, and since the internal drying of the coating film is slow and the water resistance is inferior when coating the paint using the same, conventional concrete There is a problem that is difficult to apply other than the surface coating.
또한, 최근에는 환경 개선을 위한 무용제 타입으로서 목재, 금속, 또는 플라스틱 등에 대해 사용 가능한 환경 친화성 도료의 개발이 더욱 요청되고 있으나, 상기한 바와 같은 종래의 방청 도료용 전색제로서는 이와 같은 요청에 부응할 수 없는 문제점이 있다.In addition, in recent years, the development of environmentally friendly paints that can be used for wood, metal, plastics, etc. as a solvent-free type for improving the environment, there is a further request, but as the above-described conventional anti-corrosive paints for colorants to meet such a request There is no problem.
본 발명은 이러한 문제점을 해결하기 위한 것으로; 본 발명의 목적은 부착성과 내후성 및 내수성이 우수하며 특히 금속 표면 도장 시 방청성이 우수한 자기 가교형의 인을 함유한 방청성을 갖는 수용성 아크릴 중합체 전색제의 제조 방법을 제공하는 것이다.The present invention is to solve this problem; An object of the present invention is to provide a method for preparing a water-soluble acrylic polymer developer having phosphorus of self-crosslinking type which is excellent in adhesion, weather resistance and water resistance and particularly excellent in rust resistance when coating metal surfaces.
이러한 목적을 달성하기 위한 본 발명은;방청성을 갖는 수용성 아크릴 중합체 전색제의 제조 방법에 있어서,전체 전색제 중량에 대해 20 - 90중량%으로 마련된 주모노머로서의 (메타)아크릴산 알킬 에스테르와,자기 가교성을 부여하여 건조성을 향상시키기 위해 전체 전색제 중량에 대해 0.1 - 5중량%로 마련되며 비닐술폰산 또는 아마이드기를 함유한 알킬 술폰산계 모노머로 이루어진 자기 가교성 모노머와,방청성을 향상시키기 위해 전체 전색제 중량에 대해 0.1 - 5중량%으로 마련된 인을 함유한 아크릴 모노머와,전체 전색제 중량에 대해 0.5 - 20중량%으로 마련되며 (메타)아크릴산, 말레인산 또는 그 무수물, 이타콘산, 크로톤산 및, 무수 메틸말레인산으로 이루어지는 군으로부터 선택되는 가교성인 -COOH기를 함유한 비닐계의 불포화 모노머와,도막면에서 접착성을 향상시키기 위해 전체 전색제 중량에 대해 0.1 - 5중량%로 마련되며 글리시딜, 비닐 알콕시 및, 아크릴 알킬 알콕시 실란으로 이루어지는 군으로부터 선택되는 에폭시기를 함유한 모노머를 공중합시키는 것을 특징으로 한다.또한, 자기 가교성 모노머는,비닐 술폰산 또는 아크릴아미도 t-부틸 술폰산(ATBS)인 것을 특징으로 한다.또한, 인을 함유한 아크릴 모노머는,(메타)아크릴옥시에틸포스페이트(CH2C(CH)3COOCH2CH2OP(OH)2O), 비스-(메타)아크릴옥시에틸포스페이트((CH2C(CH)3COOCH2CH2O)2POOH) 및 (메타)아크릴옥시에틸페닐산 포스페이트로 이루어지는 군으로부터 선택되는 적어도 어느 하나인 것을 특징으로 한다.이하, 본 발명에 관하여 더욱 상세히 설명하기로 한다.In order to achieve the above object, the present invention provides a method for producing a water-soluble acrylic polymer developer having anti-corrosion, (meth) acrylic acid alkyl ester as a main monomer prepared in 20 to 90% by weight relative to the total weight of the total developer, and self-crosslinkability It is provided in an amount of 0.1 to 5% by weight based on the total weight of the total colorant to impart an improved drying property, and a self-crosslinkable monomer composed of an alkyl sulfonic acid monomer containing vinylsulfonic acid or an amide group, and 0.1% by weight of the total colorant to improve the rust resistance. A phosphorus-containing acrylic monomer prepared at 5% by weight, and 0.5-20% by weight based on the total weight of the total colorant, consisting of (meth) acrylic acid, maleic acid or its anhydride, itaconic acid, crotonic acid, and methylmaleic anhydride; Vinyl-containing unsaturated monomer containing a cross-linkable -COOH group selected from It is characterized by copolymerizing a monomer containing 0.1 to 5% by weight relative to the total weight of the developer to improve adhesion and containing an epoxy group selected from the group consisting of glycidyl, vinyl alkoxy and acrylic alkyl alkoxy silane. In addition, the self-crosslinking monomer is vinyl sulfonic acid or acrylamido t-butyl sulfonic acid (ATBS). The acrylic monomer containing phosphorus is (meth) acryloxyethyl phosphate (CH 2 C (CH). ) 3 COOCH 2 CH 2 OP (OH) 2 O), bis- (meth) acryloxyethylphosphate ((CH 2 C (CH) 3 COOCH 2 CH 2 O) 2 POOH) and (meth) acryloxyethylphenyl acid At least one selected from the group consisting of phosphates. Hereinafter, the present invention will be described in more detail.
먼저 본 발명의 방청성을 갖는 수용성 아크릴 중합체 전색제로 사용되는 아크릴 모노머(단량체)의 조성은, 주모노머로서 알킬기의 탄소수가 1-14개인 (메타)아크릴산 알킬 에스테르 20-90 중량%과, 가교성 모노머로서 카르복실기(-COOH) 또는 하이드록실기(-OH)를 함유하는 불포화 모노머 5-20 중량%과, 자기 가교성 모노머로서 아마이드기(-NH2) 함유 모노머 0.1-10 중량%과, 자기 가교성 모노머로서 에폭시기를 함유하는 모노머 0.1-3 중량%과, 인을 함유한 모노머 0.1-5 중량%과, 기능성 및 가교성 모노머로서 비닐술폰산계 또는 아마이드기를 함유하는 알킬 술폰산계 모노머 0.1-5 중량%로 이루어져 있다.First of all, the composition of the acrylic monomer (monomer) used as the water-soluble acrylic polymer developer having the rust resistance of the present invention is 20-90 wt% of a (meth) acrylic acid alkyl ester having 1 to 14 carbon atoms of an alkyl group as a main monomer, and a crosslinkable monomer. 5-20% by weight of an unsaturated monomer containing a carboxyl group (-COOH) or a hydroxyl group (-OH) as a polymer, 0.1-10% by weight of an amide group (-NH 2 ) -containing monomer as a self-crosslinking monomer, and a self-crosslinking property. 0.1-3% by weight of monomers containing epoxy groups as monomers, 0.1-5% by weight of monomers containing phosphorus, and 0.1-5% by weight of alkyl sulfonic acid monomers containing vinylsulfonic acid or amide groups as functional and crosslinkable monomers. consist of.
상기한 주모노머로서의 탄소수 1-14개의 알킬기를 갖는 (메타)아크릴산 알킬 에스테르의 바람직한 예로서는, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, 이소아밀(메타)아크릴레이트, 2-에틸(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 스테아릴(메타)아크릴레이트 등을 들 수 있으나, 이에 한정되는 것은 아니다. 이러한 (메타)아크릴산 알킬 에스테르의 중합 첨가량은 전 중합체 중량의 20-90 중량%이며, 바람직하게는 60-80 중량%이다. 첨가량이 20중량%에 미달하는 경우에는 방청 도료에 있어서의 안료 분산성 및 도막 형성성이 열등하게 되므로 바람직하지 못하며, 반면에 90 중량%를 초과하는 경우에는 방청성, 내구성 및 부착성이 열등하게 될 우려가 있으므로 역시 바람직하지 못하다.As a preferable example of the (meth) acrylic-acid alkylester which has a C1-C14 alkyl group as said main monomer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acryl Acrylate, isoamyl (meth) acrylate, 2-ethyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like, but is not limited thereto. It doesn't happen. The polymerization addition amount of this (meth) acrylic-acid alkylester is 20-90 weight% of the weight of all the polymers, Preferably it is 60-80 weight%. If the added amount is less than 20% by weight, it is not preferable because the pigment dispersibility and coating film formation property of the rust-preventive paint is inferior, whereas if it exceeds 90% by weight, the rust resistance, durability and adhesion will be inferior. It is also undesirable because there is concern.
그리고 가교성 모노머로서 -OH기 함유 불포화 모노머의 바람직한 예로서는 하이드록시에틸(메타)아크릴레이트, 하이록시프로필(메타)아크릴레이트 등을 들 수 있으나 본 발명은 이에 한정되는 것은 아니며 이들과 동일한 가교성 및 반응성을 갖는 것이라면 특별한 제한 없이 사용될 수 있다. 이러한 가교성 모노머의 중합 첨가량은 0.5-20 중량%, 바람직하게는 2-10 중량%이다. 첨가량이 0.5 중량% 미만인 경우에는 그 첨가 효과가 기대에 미치지 못할 우려가 있으므로 바람직하지 못하며 반면에 20 중량%를 초과하는 경우에는 더 이상 가교 효과의 증대를 기대키 곤란하므로 역시 바람직하지 못하다.Preferable examples of the -OH group-containing unsaturated monomer as a crosslinkable monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like, but the present invention is not limited thereto. Any reactive material can be used without particular limitation. The polymerization addition amount of such a crosslinkable monomer is 0.5-20 weight%, Preferably it is 2-10 weight%. If the amount is less than 0.5% by weight, it is not preferable because the effect of the addition may not meet the expectation, whereas if it is more than 20% by weight, it is not preferable to increase the crosslinking effect any more.
또한, 또다른 가교성 모노머로서 -COOH기 함유 불포화 모노머의 바람직한 예로서는, (메타)아크릴산, 말레인산 또는 그 무수물, 이타콘산, 크로톤산, 또는 무수 메틸말레인산 등을 들 수 있으나, 이에 한정되는 것은 아니며, 이들은 후술하는 아마이드기 함유 자기 가교형 모노머 사용시의 아민 중화(수용화)용 관능기로 사용된다. 이러한 다른 가교성 모노머의 중합 첨가량은 0.5-20 중량%, 바람직하게는 2-15 중량%이다. 첨가량이 0.5 중량% 미만인 경우에는 아민 중화 효과가 기대에 미치지 못하게 되므로 바람직하지 못하며 반면에 20 중량%를 초과하는 경우에는 가교 및 아민 중화 효과의 증대를 기대키 곤란하므로 역시 바람직하지 못하다.In addition, preferred examples of the -COOH group-containing unsaturated monomer as another crosslinkable monomer include (meth) acrylic acid, maleic acid or its anhydride, itaconic acid, crotonic acid, or methyl maleic anhydride, but are not limited thereto. These are used as a functional group for amine neutralization (water solubilization) at the time of using the amide group containing self-crosslinking monomer mentioned later. The polymerization amount of such other crosslinkable monomers is 0.5-20% by weight, preferably 2-15% by weight. If the added amount is less than 0.5% by weight, the amine neutralization effect is not desirable because it is less than expected, while if it is more than 20% by weight it is not preferable because it is difficult to expect an increase in the crosslinking and amine neutralization effect.
또한, 상기한 -OH기 함유 불포화 모노머와 -COOH기를 함유한 불포화 모노머는, 본 발명에 있어서 어느 하나만을 단독으로 또는 양자를 조합하여 사용할 수 있으며, 조합시의 첨가량 역시 상기한 범위내이다.In addition, in the present invention, only one of the above-mentioned -OH group-containing unsaturated monomers and -COOH group-containing unsaturated monomers can be used alone or in combination thereof, and the amount of addition at the time of combination is also within the above range.
자기 가교성 모노머로서의 아마이드기 함유 모노머의 대표적인 예로서는, 아크릴(메타)아미드 또는 N-메틸롤아크릴아미드를 들 수 있으며, 그 중합 첨가량은 0.1-10 중량%, 바람직하게는 1-3 중량%이다. 첨가량이 0.1 중량% 미만인 경우에는 자기 가교 효과가 충분치 못하게 될 우려가 있어 바람직하지 못하며 반면에 10 중량%를 초과하는 경우에는 자기 가교도가 지나치게 높아질 우려가 있으므로 역시 바람직하지 못하다.Representative examples of the amide group-containing monomer as the self-crosslinkable monomer include acryl (meth) amide or N-methylol acrylamide, and the amount of polymerization added thereof is 0.1-10% by weight, preferably 1-3% by weight. If the amount is less than 0.1% by weight, the self-crosslinking effect may not be sufficient, whereas if it is more than 10% by weight, the self-crosslinking degree may be too high, which is not preferable.
자기 가교성 모노머로서의 에폭시기 함유 모노머의 대표적인 예로서는, 글리시딜계 모노머, 비닐 알콕시계 모노머, 또는 아크릴 알킬 알콕시계 실란 등을 들 수 있으며, 그 중합 첨가량은 0.1-5 중량%이며, 바람직하게는 0.1-3 중량%이다. 첨가량이 0.1 중량% 미만인 경우에는 자기 가교 효과가 충분치 못하고 반면에 5 중량%를 초과하는 경우에는 자기 가교도가 지나치게 높아져서 도막의 물리적 특성이 열화될 우려가 있으므로 역시 바람직하지 못하다.Representative examples of the epoxy group-containing monomer as the self-crosslinkable monomer include glycidyl monomers, vinyl alkoxy monomers, or acrylic alkyl alkoxy silanes, and the like, and the amount of polymerization added thereof is 0.1-5% by weight, preferably 0.1-. 3 wt%. If the added amount is less than 0.1% by weight, the self-crosslinking effect is not sufficient, whereas if it is more than 5% by weight, the self-crosslinking degree is too high, which may deteriorate the physical properties of the coating film, which is also undesirable.
기능성 및 (자기)가교성 모노머로서는 비닐술폰산계 또는 아마이드기 함유 알킬 술폰산계 또는 실란계 모노머를 들 수 있으며, 방청 도료의 안료분산성, 접착성, 내구성, 내수성, 내후성 및 도막간의 층간 부착성을 증대시킨다. 이들의 대표적인 예로서는, 이에 한정되는 것은 아니나, 비닐 술폰산 또는 아크릴아미도 t-부틸 술폰산(ATBS)을 들 수 있으며, 그 중합 첨가량은 0.1-5 중량%이다. 첨가량이 0.1 중량% 미만인 경우에는 상기한 특성의 충분한 향상 효과를 기대키 곤란하고 반면에 5 중량%를 초과하는 경우에는 도막의 물리적 특성이 오히려 열등하게 될 우려가 있으므로 역시 바람직하지 못하다.Examples of the functional and (magnetic) crosslinkable monomers include vinyl sulfonic acid-based or amide-containing alkyl sulfonic acid-based or silane-based monomers, and include pigment dispersibility, adhesion, durability, water resistance, weather resistance, and interlayer adhesion between coatings. Increase Representative examples thereof include, but are not limited to, vinyl sulfonic acid or acrylamido t-butyl sulfonic acid (ATBS), and the amount of polymerization added thereof is 0.1-5% by weight. If the added amount is less than 0.1% by weight, it is difficult to expect a sufficient improvement effect of the above properties, while if it is more than 5% by weight, the physical properties of the coating film may be rather inferior.
본 발명의 제조 방법에 있어서의 가장 주요한 특징은 인 함유 아크릴 모노머를 사용하는 것에 의하여 비유화제형 수용성 아크릴 중합체 전색제를 제공 가능하게 하는 것에 있다. 본 발명의 제조 방법에 따른 전색제에 방청성을 부여하기 위한 가교성 모노머의 대표적인 예로서는, 이에 한정되는 것은 아니나, (메타)아크릴옥시에틸포스페이트(CH2C(CH)3COOCH2CH2OP(OH)2O), 비스-(메타)아크릴옥시에틸포스페이트((CH2C(CH)3COOCH2CH2O)2POOH), 또는 (메타)아크릴옥시에틸페닐산 포스페이트 등을 들 수 있으며, 중합시 첨가량은 0.5-5 중량%이다. 첨가량이 0.5 중량% 미만인 경우에는 방청성의 향상 효과가 충분치 못하게 될 우려가 있으므로 바람직하지 못하며 반면에 5 중량%를 초과하는 경우에는 도막의 물리적 특성이 열등하게 될 우려가 있으므로 역시 바람직하지 못하다.The main characteristic in the manufacturing method of this invention is making it possible to provide a non-emulsifier type water-soluble acrylic polymer developer by using a phosphorus containing acrylic monomer. Representative examples of crosslinkable monomers for imparting rust resistance to a colorant according to the production method of the present invention include, but are not limited to, (meth) acryloxyethyl phosphate (CH 2 C (CH) 3 COOCH 2 CH 2 OP (OH)). 2 O), bis- (meth) acryloxyethyl phosphate, ((CH 2 C (CH) 3 COOCH 2 CH 2 O) 2 POOH), or (meth) and the like acryloxy ethyl phenyl acid phosphate, the polymerization The amount added is 0.5-5% by weight. If the added amount is less than 0.5% by weight, the effect of improving the rust preventive property may not be sufficient. On the other hand, if the amount is more than 5% by weight, the physical properties of the coating film may be inferior.
상기한 모노머들은 상기한 중합 첨가량 범위로 혼합되어 알코올성 용액 중합되며, 알코올성 용액 중합에 사용되는 용제로서는, 알코올의 알킬기가 4 이하인 알코올, 즉 메틸알코올, 이소프로판올(IPA), 부틸알코올 등과, 에틸렌 글리콜 또는 프로필렌 글리콜계의 알킬 에테르 즉, 에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 모노부틸에테르, 프로필렌글리콜 모노메틸에테르 또는 모노부틸에테르 등을 알코올과 에테르 용제의 혼합비가 1:1-10:1의 비율이 되도록 혼합하여 전체 휘발성 물질(물 포함)중의 함량이 10% 이하가 되도록 사용한다.The monomers are mixed in the above-described polymerization addition range to perform alcoholic solution polymerization. Examples of the solvent used for the alcoholic solution polymerization include alcohols having an alkyl group of 4 or less, ie, methyl alcohol, isopropanol (IPA), butyl alcohol, etc., ethylene glycol or Propylene glycol-based alkyl ethers, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, or monobutyl ether, are mixed so that the mixing ratio of alcohol and ether solvent is 1: 1-10: 1. Therefore, the content of the total volatiles (including water) is used to 10% or less.
본 발명의 제조 발법에 있어서, 바람직한 알코올계 용제로서는 IPA, 부탄올(노르말 또는 이소)을 들 수 있으며, 바람직한 에테르계 용제로서는 에틸렌글리콜 모노부틸에테르 또는 프로필렌글리콜 모노메틸에테르를 들 수 있다.In the production method of the present invention, preferred alcohol solvents include IPA and butanol (normal or iso), and preferred ether solvents include ethylene glycol monobutyl ether or propylene glycol monomethyl ether.
한편, 중합 개시제로서는, 초기 분해 온도가 50-90℃ 범위인 AIBN(α,α´-아조비스이소부티로니트릴), BPO(벤조일 퍼옥사이드), LPC(라우릴 퍼옥사이드), TBPO(t-부틸퍼옥테이트), PCBPO(파라-클로로벤조일퍼옥사이드), TAPA(t-아밀퍼옥시아세테이트), TAPB(t-아밀퍼옥시벤조에이트), OMPBO(오르쏘-메틸벤조일퍼옥사이드) 등을 사용할 수 있으며, 첨가량은 총 모노머량의 1-4 중량%로 사용한다. 본 발명의 제조 방법에 있어서 특히 바람직한 중합 개시제로서는, AIBN, BPO, TBPO, TBPB 등을 들 수 있다.On the other hand, as the polymerization initiator, AIBN (α, α'-azobisisobutyronitrile), BPO (benzoyl peroxide), LPC (lauryl peroxide), TBPO (t-) having an initial decomposition temperature of 50-90 ° C Butyl perocate), PCBPO (para-chlorobenzoyl peroxide), TAPA (t-amyl peroxyacetate), TAPB (t-amyl peroxybenzoate), OMPBO (ortho-methylbenzoyl peroxide) and the like can be used. The addition amount is used as 1-4 weight% of the total monomer amount. Particularly preferred polymerization initiators in the production method of the present invention include AIBN, BPO, TBPO, TBPB, and the like.
용액(알코올성) 중합시의 반응 온도는 85-110℃에서 진행되며, 반응은 한 번에 단량체, 용제 및 중합 개시제를 넣고 진행시킬 수도 있으나, 총모노머 중량의 15-25 중량%의 모노머와 용제 전량의 혼합물을 가열 환류시켜서 20-50분간 유지한 다음, 총모노머 중량의 35-45 중량%의 모노머 혼합물(개시제를 포함시킬 수도 있으며 별도의 용기에서 혼합)을 2-3 시간에 걸쳐 분할 첨가하고 100-110℃에서 1-3 시간 유지시키는 것이 반응을 원활화시킬 수 있으므로 바람직하다.When the solution (alcoholic) polymerization is carried out at 85-110 ° C., the reaction may be carried out by adding a monomer, a solvent and a polymerization initiator at a time, but the total amount of monomer and solvent of 15-25% by weight of the total monomer weight The mixture was heated to reflux for 20-50 minutes, then 35-45% by weight of the monomer mixture (which may include initiators and mixed in a separate vessel) was added in portions over 2-3 hours and 100 Maintaining 1-3 hours at -110 ° C is preferred because it can facilitate the reaction.
상기한 알코올 용액 중합 단계에 이어서, 알코올 중합후의 결과물을 중화 수용화시키기 위한 중화·수용화 단계가 수행되며, 이 단계에서는 아민류가 사용되고, 그 바람직한 예로서는, 암모니아수, 트리에틸아민, 또는 아미노 알코올계로서의 2-아미노프로판, 이소프로판올 아민 및 2-아미노프로필 알코올 등을 들 수 있으며, 이들을 결과물의 pH가 7-9가 되도록 첨가한다. 알코올 중합후의 결과물을 90℃ 이하의 온도로 냉각시킨 다음 상기한 아민류와 총 단량체 중량의 0.8-1.2배 중량의 이온 교환수의 혼합물을 20-30분간에 걸쳐 첨가한 후, 80-85℃에서 1-3 시간 동안유지한다. 이러한 중화·수용화 단계에 있어서의 아민류의 첨가 당량비는 베이스 중합체의 산당량에 대하여 0.8-1.1 이며, 중합체의 말단 아미드기를 안정화시키게 된다.Following the alcohol solution polymerization step, a neutralization and solubilization step for neutralizing and accepting the resultant after the alcohol polymerization is carried out. In this step, amines are used, and examples thereof include ammonia water, triethylamine, or amino alcohols. 2-aminopropane, isopropanol amine, 2-aminopropyl alcohol, and the like, and the like are added so that the pH of the resultant is 7-9. After alcohol polymerization, the resultant was cooled to a temperature of 90 ° C. or lower, and then a mixture of the above-described amines and 0.8-1.2 times the weight of ion-exchanged water of the total monomer weight was added over 20-30 minutes, followed by 1 at 80-85 ° C. Hold for 3 hours. The addition equivalent ratio of the amines in this neutralization and aqueous solubilization step is 0.8-1.1 with respect to the acid equivalent of a base polymer, and stabilizes the terminal amide group of a polymer.
이어서, 분자량 제어를 위한 액상 혼성 부가 중합 단계가 수행되며, 이 단계에서 첨가되는 모노머의 량은 총모노머 중량의 30-50 중량% 범위이며 별도의 용기에서 혼합한 후 85-95℃에서 2-3 시간 동안 분할 첨가한 다음 1-3 시간 유지시킨 후, 냉각시키는 것에 의하여 고형분 함량이 40-55 중량%인 목적 중합체로서의 유백색의 액상의 수용성 아크릴 중합체 전색제가 제조된다.Subsequently, a liquid hybrid addition polymerization step for molecular weight control is performed, wherein the amount of monomer added in this step is in the range of 30-50% by weight of the total monomer weight and is mixed in a separate vessel, followed by 2-3 at 85-95 ° C. After the addition in portions for hours and holding for 1-3 hours, cooling affords a milky, liquid, water-soluble acrylic polymer developer as the desired polymer having a solids content of 40-55% by weight.
상기한 액상 수용성 아크릴 중합체 전색제를 이용한 방청 도료의 제조 방법에 관하여 간단히 설명하면, 방청 도료에 흔히 사용되는 산화철 15-25 중량%, 방청제로서의 스트론튬 아연 포스포실리케이트 3-8 중량%, 이온 교환체인 알루미노 실리케이트 10-20 중량%, 암모니아수 0.01-0.5 중량% 및, 이온교환수 10-20 중량%를 고속혼합기중에서 1500 rpm 이상의 회전 속도로 혼합하여 연화도(NS) 4 이상이 될 때까지 고속 분산시키는 고속분산 혼합 단계를 수행한다. 선택적으로, 습윤제 0.1-0.5 중량% 및/또는 분산제 0.01-0.5 중량%를 첨가할 수도 있다.Briefly describing the production method of the rust-preventive paint using the above-mentioned liquid water-soluble acrylic polymer developer, 15-25% by weight of iron oxide commonly used in rust-preventive paint, 3-8% by weight of strontium zinc phosphosilicate as a rust preventive agent, alumine which is an ion exchanger 10-20% by weight of no-silicate, 0.01-0.5% by weight of ammonia water and 10-20% by weight of ion-exchanged water are mixed in a high speed mixer at a rotational speed of 1500 rpm or more to rapidly disperse until the softening degree (NS) is 4 or more. Perform a fast dispersion mixing step. Optionally, 0.1-0.5% by weight wetting agent and / or 0.01-0.5% by weight dispersant may be added.
이어서, 본 발명의 제조 방법에 따른 전색제 35-55 중량%를 첨가한 후 균질하게 될 때 까지 철저히 혼합하는 전색제 첨가 단계가 수행된다. 이 때, 텍사놀, 소포제 및/또는 방부제를 트레이스량 첨가할 수도 있다.Subsequently, after the addition of 35-55% by weight of the colorant according to the preparation method of the present invention, a colorant addition step of mixing thoroughly until homogeneous is performed. At this time, a trace amount of texanol, an antifoaming agent and / or a preservative may be added.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
실시예 1Example 1
2ℓ 용량의 4구 유리제 플라스크에 용제로서 IPA 75g 및 에틸렌글리콜 모노부틸에테르 15g, 단량체로서 MMA 24g, 아크릴산 부틸 36g, 아크릴산 에틸 18g, 아크릴산 12g, 이타콘산 6g, 아크릴아마이드 9g, 아크릴아미도부틸술폰산(이하, ATBS) 3g, 및 2-(메타)아크릴옥시에틸포스페이트 6g을 중합개시제 TBPB 1.8g과 함께 혼합하여 장입하고, 플라스크 하부에 불활성 기체(질소 또는 CO2)를 주입하여 반응물 표면의 산소를 제거한 후 서서히 가열하였다.In a 2-liter four-necked glass flask, 75 g of IPA and 15 g of ethylene glycol monobutyl ether as solvent, 24 g of MMA as monomer, 36 g of butyl acrylate, 18 g of ethyl acrylate, 12 g of acrylic acid, 6 g of itaconic acid, 9 g of acrylamide, acrylamidobutyl sulfonic acid ( Hereinafter, 3 g of ATBS and 6 g of 2- (meth) acryloxyethyl phosphate were mixed with the polymerization initiator TBPB 1.8 g, charged, and an inert gas (nitrogen or CO 2) was injected into the bottom of the flask to remove oxygen from the reactant surface. Then slowly heated.
반응물의 온도가 80℃로 상승하자 서서히 발열하기 시작하였으며 105℃에서 환류되기 시작하여 점도 상승이 일어났으며 같은 환류 온도에서 35분간 유지한 후, MMA 48g, 아크릴산 부틸 84g, 아크릴산 에틸 42g, 아크릴산 24g, 이타콘산 12g, 아크릴 아마이드 21g, ATBS 6g, 2-메타크릴옥시 에틸포스페이트 9g, 및 TBPB 3.6g을 별도의 용기에서 혼합하여 3 시간 동안 서서히 분할 첨가(적가)하고 105℃에서 2시간 유지후 90℃로 냉각시킨 다음, 이온 교환수 528g, 암모니아수 50g의 혼합액을 25분간에 걸쳐 첨가한 후, 85℃에서 1시간 유지 반응시킨 다음, MMA 144g, 아크릴산 부틸 96g 및 TBPO 4.8g을 별도의 용기에 혼합하여 90℃에서 2 시간 동안 첨가한 후 2시간 유지시킨 다음 냉각시켜 유백상의 액상 수용성 아크릴 중합체를 제조하였다.When the temperature of the reactant rose to 80 ° C., it gradually started to exotherm and began to reflux at 105 ° C., resulting in an increase in viscosity. After maintaining at the same reflux temperature for 35 minutes, MMA 48g, butyl acrylate 84g, ethyl acrylate 42g, and acrylic acid 24g , 12 g of itaconic acid, 21 g of acrylamide, 6 g of ATBS, 9 g of 2-methacryloxy ethyl phosphate, and 3.6 g of TBPB were mixed in a separate container and gradually added (dropwise) for 3 hours, and maintained at 105 ° C. for 2 hours. After cooling to 占 폚, a mixed solution of 528 g of ion-exchanged water and 50 g of ammonia water was added over 25 minutes, followed by a reaction for 1 hour at 85 占 폚, followed by mixing 144 g of MMA, 96 g of butyl acrylate, and 4.8 g of TBPO in a separate container. After adding for 2 hours at 90 ℃ and maintained for 2 hours to cool to prepare a milky liquid soluble acrylic polymer.
실시예 2Example 2
실시예 1과 같은 조건에서, MMA 30g, 아크릴산 부틸 30g, 아크릴산 에틸 24g, (메타)아크릴산 12g, 이타콘산 6g, 2-하이드록시에틸(메타)아크릴산 3g, 스티렌 술폰산 소다 3g 및 2-(메타)아크릴옥시 에틸포스페이트 6g을 TBPB 1.8g과 함께 반응시킨 후, MMA 60g, 아크릴산 부틸 60g, 아크릴산 에틸 42g, (메타)아크릴산 24g, 이타콘산 12g, 2-HEMA 1.8g, 글리시딜(메타)아크릴산 3g, 스티렌술폰산 소다 6g, 2-(메타)아크릴옥시 에틸포스페이트 9g을 별도의 용기에서 균일하게 혼합하여 분할 첨가(적가)하여 반응시킨 후, 이온 교환수 530g, 암모니아수 45g의 혼합액을 첨가하여 중화 수용화하고, 이어서 MMA 144g, 아크릴산 부틸 96g 및 TBPO 4.8g을 혼합하여 부가 중합시켰다.Under the same conditions as in Example 1, 30 g of MMA, 30 g of butyl acrylate, 24 g of ethyl acrylate, 12 g of (meth) acrylic acid, 6 g of itaconic acid, 3 g of 2-hydroxyethyl (meth) acrylic acid, 3 g of styrene sulfonic acid soda and 2- (meth) After 6 g of acryloxy ethylphosphate was reacted with 1.8 g of TBPB, 60 g of MMA, 60 g of butyl acrylate, 42 g of ethyl acrylate, 24 g of (meth) acrylic acid, 12 g of itaconic acid, 1.8 g of 2-HEMA, 3 g of glycidyl (meth) acrylic acid , 6 g of styrenesulfonic acid soda and 9 g of 2- (meth) acryloxy ethyl phosphate were uniformly mixed in a separate container and reacted by adding a portion (dropwise), followed by adding a mixed solution of 530 g of ion-exchanged water and 45 g of ammonia to neutralize and Subsequently, addition polymerization was carried out by mixing 144 g of MMA, 96 g of butyl acrylate and 4.8 g of TBPO.
실시예 3 및 4 - 실시예 1, 2의 생성물을 이용한 방청 도료 실험Examples 3 and 4 Antirust Coating Experiments Using Products of Examples 1 and 2
실시예 1 및 2에서 제조한 수용성 아크릴 중합체를 기제로 한 방청 도료를 제조하였으며 이에 대하여 시험하였다.An antirust coating based on the water-soluble acrylic polymers prepared in Examples 1 and 2 was prepared and tested.
방청 도료에는, 표 1에 나타낸 바와 같이, 도막의 2차 물리화학적 방청성을 부여하기 위하여 스트론튬 아연 포스포실리케이트(상품명:HALOX , SZP-39I)계 방청 안료를 첨가하여 제조하였다.As shown in Table 1, rustproof paints were prepared by adding strontium zinc phosphosilicate (trade name: HALOX, SZP-39I) -based rust preventive pigments in order to impart secondary physicochemical rust resistance.
제조된 방청 도료의 조성을 표 1에, 시험 결과를 표 2에 실시예 3 및 4로 각각 나타냈으며, 이들 방청 도료는 총고형분 함량 61% 이상, 안료분 함량 40% 이상, 전색제(N.V.)분 함량 20% 이상, 점도(KU) 90-95, pH 7-9, 색상은 적갈색이었다.The composition of the prepared rust-preventive paints is shown in Table 1 and the test results in Tables 2 and 4, respectively, and these rust-preventive paints had a total solid content of at least 61%, a pigment content of at least 40%, and a colorant (NV) content. 20% or more, viscosity (KU) 90-95, pH 7-9, color was reddish brown.
한편, 제막(製膜)된 도막 시험은 KSM 5400(도료시험방법)에 따라 시험하였으며, 그 결과를 표 2에 나타낸다.On the other hand, the film coating test was tested in accordance with KSM 5400 (Paint Test Method), the results are shown in Table 2.
이상에서 상세히 설명한 바와 같이, 본 발명의 제조 방법에 따른 전색제를 이용하여 제조되는 환경 친화적 방청 도료는 부착성, 내후성, 내수성, 특히 금속 표면 도장시 방청성이 우수하다.As described in detail above, the environmentally friendly anticorrosive paint prepared by using the colorant according to the manufacturing method of the present invention is excellent in adhesion, weather resistance, water resistance, in particular rust resistance when painting the metal surface.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS56104974A (en) * | 1980-01-25 | 1981-08-21 | Fujikura Kasei Kk | Photosetting paint for concrete foundation |
| JPS57126869A (en) * | 1981-01-31 | 1982-08-06 | Kikusui Kagaku Kogyo Kk | Rust-inhibiting water paint composition |
| EP0206814A2 (en) * | 1985-06-26 | 1986-12-30 | Rohm And Haas Company | Water-soluble polymers and their use in the stabilization of aqueous systems |
| JPH06287478A (en) * | 1993-03-30 | 1994-10-11 | Showa Highpolymer Co Ltd | Water-dispersing resin composition having rust proof to oil face |
| KR0178842B1 (en) * | 1995-12-02 | 1999-05-15 | 도정민 | Process for producing aqueous acrylic adhesives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS56104974A (en) * | 1980-01-25 | 1981-08-21 | Fujikura Kasei Kk | Photosetting paint for concrete foundation |
| JPS57126869A (en) * | 1981-01-31 | 1982-08-06 | Kikusui Kagaku Kogyo Kk | Rust-inhibiting water paint composition |
| EP0206814A2 (en) * | 1985-06-26 | 1986-12-30 | Rohm And Haas Company | Water-soluble polymers and their use in the stabilization of aqueous systems |
| EP0206814B2 (en) * | 1985-06-26 | 1995-12-13 | Rohm And Haas Company | Water-soluble polymers and their use in the stabilization of aqueous systems |
| JPH06287478A (en) * | 1993-03-30 | 1994-10-11 | Showa Highpolymer Co Ltd | Water-dispersing resin composition having rust proof to oil face |
| KR0178842B1 (en) * | 1995-12-02 | 1999-05-15 | 도정민 | Process for producing aqueous acrylic adhesives |
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