KR100647891B1 - Multifunctional phenolic curing agent for epoxy resin type powder coating compositions - Google Patents
Multifunctional phenolic curing agent for epoxy resin type powder coating compositions Download PDFInfo
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- KR100647891B1 KR100647891B1 KR1019990065749A KR19990065749A KR100647891B1 KR 100647891 B1 KR100647891 B1 KR 100647891B1 KR 1019990065749 A KR1019990065749 A KR 1019990065749A KR 19990065749 A KR19990065749 A KR 19990065749A KR 100647891 B1 KR100647891 B1 KR 100647891B1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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Abstract
본 발명은 에폭시수지 분체도료용 다관능성 페놀 경화제의 제조방법에 관한 것으로서, 더욱 상세하게는 에폭시수지와의 경화반응에 있어 속경화가 가능하고 장기 저장시 수분흡수가 적으며 도장후 우수한 굴곡성, 소지와의 접착성, 내음극박리성 등의 뛰어난 경화 물성을 가지는 에폭시수지 분체도료용 다관능성 페놀 경화제의 제조방법에 관한 것이다.The present invention relates to a method for producing a multifunctional phenolic curing agent for epoxy resin powder coating, and more particularly, it is possible to harden quickly in the curing reaction with epoxy resin, water absorption during long-term storage, excellent flexibility, after coating The present invention relates to a method for producing a polyfunctional phenol curing agent for epoxy resin powder coating having excellent curing properties such as adhesion with a negative electrode and negative electrode peeling resistance.
에폭시수지 분체도료, 다관능성 페놀 경화제Epoxy Resin Powder Coating, Multifunctional Phenolic Curing Agent
Description
본 발명은 분체도료용 다관능성 페놀 경화제의 제조방법에 관한 것으로서, 더욱 상세하게는 에폭시수지와의 경화반응에 있어 속경화가 가능하고 장기 저장시 수분흡수가 적으며 도장후 우수한 굴곡성, 소지와의 접착성, 내음극박리성 등의 뛰어난 경화 물성을 가지는 에폭시수지 분체도료용 다관능성 페놀 경화제의 제조방법에 관한 것이다.The present invention relates to a method for producing a multifunctional phenolic curing agent for powder coating, more specifically, it is possible to harden quickly in the curing reaction with epoxy resin, water absorption during long-term storage and excellent flexibility, after coating The present invention relates to a method for producing a polyfunctional phenol curing agent for epoxy resin powder coating having excellent curing properties such as adhesion and negative electrode peeling resistance.
일반적으로 적용되는 에폭시수지 분체도료에는 에폭시수지와 경화제가 함유된다. 그 예로서, 미국특허 제4,066,625호에는 비스페놀 A형 에폭시수지를 사용하고, 경화제로 이미다졸 화합물과 페놀 노블락수지를 혼합 사용하여 폴리솔트(polysalt)화 하므로써 우수한 저장안정성을 가지는 에폭시수지 분체도료의 제조방법이 개시되어 있다. 그러나 이러한 경화제 수지는 수분에 민감하여 도료의 고온 속경화시 도막 내부에 미세 구멍(porosity)이 발생되는 단점이 있어 후막(300 ∼ 400 ㎛)의 강관 도장용(FBE) 분체도료로는 부적합하였다.Generally applied epoxy resin powder coating contains an epoxy resin and a curing agent. As an example, U.S. Patent No. 4,066,625 uses bisphenol A type epoxy resin and manufactures an epoxy resin powder coating having excellent storage stability by polysaltting a mixture of an imidazole compound and a phenol noble resin as a curing agent. A method is disclosed. However, such a curing agent resin is sensitive to moisture and has a disadvantage in that a fine pore is generated inside the coating film at high temperature of the paint, which is not suitable as a steel pipe coating (FBE) powder coating for thick films (300 to 400 μm).
또한, 미국특허 제5,798,399호에는 비스페놀 A형 에폭시수지와 경화제로 에폭시수지에 이미다졸 화합물을 어덕트하므로써 빠른 경화속도 및 보다 안정된 저장성을 가지는 도료의 제조방법이 소개되어 있다. 그러나 이러한 경화수지는 골격내에 유연기가 없어 도막화 된후 굴곡성이 저하되며 장기 저장후 반응성이 떨어지는 단점을 보였다.In addition, U.S. Patent No. 5,798,399 discloses a method for preparing a paint having a faster curing rate and a more stable shelf life by adducting an imidazole compound to an epoxy resin with a bisphenol A epoxy resin and a curing agent. However, such cured resins have no softness in the skeleton, which results in a decrease in flexibility after coating and a decrease in reactivity after long-term storage.
본 발명은 상기 종래기술의 문제점을 해결하기 위한 목적으로 에폭시수지와의 경화반응에 있어 속경화가 가능하고 장기 저장시 수분흡수가 적으며 도장후 우수한 굴곡성, 소지와의 접착성, 내음극박리성 등이 뛰어난 경화 물성을 가지는 경화수지를 제조하고자 노력하였고, 그 결과 비스페놀형 에폭시수지와 변성된 노블락 에폭시수지가 적당비율로 혼합된 에폭시수지 혼합물과 과량의 다가페놀 화합물을 촉매 존재하에 축합반응시켜 다관능성 페놀 수지를 경화제로 사용함으로써 본 발명을 완성하였다. The present invention is capable of rapid curing in the curing reaction with epoxy resin for the purpose of solving the problems of the prior art, less moisture absorption during long-term storage, excellent flexibility after coating, adhesion to the body, negative electrode peeling resistance Efforts have been made to produce cured resins with excellent curing properties, and consequently, condensation reaction of an epoxy resin mixture in which a bisphenol-type epoxy resin and a modified noblock epoxy resin are mixed at an appropriate ratio with an excess of a polyhydric phenol compound in the presence of a catalyst. This invention was completed by using a functional phenol resin as a hardening | curing agent.
따라서, 본 발명은 에폭시수지 분체도료 조성물중에 경화제로서 함유되어 저온(200℃ 이내)에서 속경화(2분 이내)가 가능하고, 수지 분자구조중에 소수성기가 포함되어 있어 내흡수성이 우수하며, 굴곡성 등의 기계적 물성도 개선하는 새로운 다관능성 페놀 경화제를 제공하는데 그 목적이 있다.
Therefore, the present invention is contained in the epoxy resin powder coating composition as a curing agent and can be hardened at a low temperature (within 200 ° C.) (within 2 minutes), and the hydrophobic group is included in the resin molecular structure, so it has excellent water absorption resistance, flexibility, and the like. It is an object of the present invention to provide a new multifunctional phenol curing agent that also improves the mechanical properties of the polymer.
본 발명은 다음 화학식 1로 표시되는 비스페놀형 에폭시수지와 다음 화학식 2로 표시되는 노블락 에폭시수지가 1 / 0.1 ∼ 3 중량비로 혼합되어 있는 에폭시수지 혼합물과, 과량의 다가페놀 화합물을 촉매 존재하에 축합반응시켜 수지 말단에 하이드록시기가 위치하는 신규 다관능성 페놀 경화제의 제조방법을 그 특징으로 한다.The present invention is a condensation reaction of an epoxy resin mixture in which a bisphenol-type epoxy resin represented by the following formula (1) and a noblock epoxy resin represented by the following formula (2) are mixed in a ratio of 1 / 0.1 to 3 by weight, and an excess polyhydric phenol compound in the presence of a catalyst. And a method for producing a novel polyfunctional phenol curing agent wherein a hydroxyl group is located at the resin terminal.
상기 화학식 1에서 : In Formula 1 above:
A는이고; X1은 수소원자 또는 탄소수 1 내지 4 의 알킬기이고; n은 0 또는 1 내지 3의 정수이고; i는 0 또는 1 내지 4의 정수이다.A is ego; X 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; n is 0 or an integer from 1 to 3; i is 0 or an integer of 1 to 4;
상기 화학식 2에서 : In Formula 2 above:
R은 를 나타내고; X1은 탄소수 1 내지 4 의 알킬기 또는 수소원자이고; X21, X22, X23 및 X24는 서로 같거나 다른 것으로서 탄소수 1 내지 3 의 알킬기 또는 수소원자이고; n은 0 또는 1 내지 4의 정수이고, m은 0 또는 1 내지 2의 정수이며, i는 0 또는 1 내지 4의 정수이다.R is Represents; X 1 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom; X 21 , X 22 , X 23 and X 24 , which are the same as or different from each other, are an alkyl group having 1 to 3 carbon atoms or a hydrogen atom; n is 0 or an integer of 1-4, m is 0 or an integer of 1-2, i is 0 or an integer of 1-4.
또한, 본 발명은 에폭시수지, 경화제, 무기질 충진제, 보조 경화제 및 기타 통상의 첨가제가 함유되어 있는 에폭시수지 분체도료 조성물에 있어서, 상기 경화제로서 상기 제조방법으로 제조된 신규 다관능성 페놀 경화제가 함유되어 있는 에폭시수지 분체도료 조성물을 또다른 특징으로 한다.The present invention also relates to an epoxy resin powder coating composition containing an epoxy resin, a curing agent, an inorganic filler, an auxiliary curing agent, and other conventional additives, wherein the novel polyfunctional phenol curing agent prepared by the manufacturing method is contained as the curing agent. Epoxy resin powder coating composition is another feature.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명에 따른 페놀 경화제는 에폭시수지와, 과량의 다가페놀 화합물을 촉매 존재하에 축합반응시켜 제조한다. 이때, 에폭시수지로는 상기 화학식 1로 표시되는 비스페놀형 에폭시수지와 상기 화학식 2로 표시되는 노블락 에폭시수지의 혼합물을 사용한다.The phenol curing agent according to the present invention is prepared by condensation reaction of an epoxy resin with an excess of a polyhydric phenol compound in the presence of a catalyst. In this case, a mixture of a bisphenol-type epoxy resin represented by Chemical Formula 1 and a noblock epoxy resin represented by Chemical Formula 2 is used as the epoxy resin.
상기 화학식 1로 표시되는 비스페놀형 에폭시수지는 다가페놀과 염소화합물인 에피클로로히디린을 과량으로 사용하여 알칼리 금속수산화물 존재하에서 반응시키고, 부가생성된 염소이온을 정제공정으로 처리하여 얻어진 생성물이다. 상기 화학식 1로 표시되는 비스페놀형 에폭시수지로서 바람직하기로는 2개의 그리시딜기 를 가지는 비스페놀 A형 에폭시수지로 에폭시당량이 180 ∼ 1,000 g/eq, 특히 에폭시당량이 180 ∼ 250 g/eq 인 수지를 사용하는 것이 좋다The bisphenol-type epoxy resin represented by the formula (1) is a product obtained by reacting in the presence of an alkali metal hydroxide by using an excessive amount of polyhydric phenol and epichlorohydrin as a chlorine compound, and treating the adducted chlorine ions by a purification process. As the bisphenol type epoxy resin represented by Formula 1, preferably, a bisphenol A type epoxy resin having two glycidyl groups is used with a resin having an epoxy equivalent of 180 to 1,000 g / eq, particularly an epoxy equivalent of 180 to 250 g / eq. Good to do
또한, 상기 화학식 2로 표시되는 노블락 에폭시수지는 1 분자중 적어도 1 개 이상의 지환기 또는 자이록 골격을 함유하는 다가 페놀수지를 에피크로로히드린과 알칼리 금속수산화물 존재하에 반응시켜 정제공정후 얻어진 생성물이다. 상기 화학식 2로 표시되는 노블락 에폭시수지로서 바람직하기로는 2개 이상의 그리시딜기를 가지는 저분자 디사이클로펜타디엔 노블락 에폭시수지로 에폭시당량이 260 ∼ 690 g/eq, 특히 에폭시당량이 260 ∼ 350 g/eq 인 수지를 사용하는 것이 좋다.In addition, the noblock epoxy resin represented by Formula 2 is a product obtained after the purification process by reacting a polyhydric phenol resin containing at least one alicyclic group or a gyrox skeleton in one molecule in the presence of epichlorohydrin and an alkali metal hydroxide. to be. The noblock epoxy resin represented by the formula (2) is preferably a low molecular dicyclopentadiene noblock epoxy resin having two or more glycidyl groups and has an epoxy equivalent of 260 to 690 g / eq, particularly an epoxy equivalent of 260 to 350 g / eq. It is good to use resin.
상기 화학식 1 및 2로 표시되는 에폭시수지는 1 / 0.1 ∼ 1 / 3 중량비, 바람직하게는 1 / 0.2 ∼ 1 / 1.5 중량비로 혼합하여 사용한다. 이때, 에폭시수지 혼합물의 중량비가 1 / 0.1 미만이면 수지 및 도료의 장기저장시 흡습에 의한 물성 저하 및 반응성, 기계적 물성의 저하를 가져오며, 반대로 1 / 3 중량비를 초과하면 반응 관능기가 많아져 겔화의 위험이 있다.The epoxy resins represented by the formulas (1) and (2) are used by mixing in a weight ratio of 1 / 0.1 to 1/3 weight, preferably in a weight ratio of 1 / 0.2 to 1 / 1.5. At this time, when the weight ratio of the epoxy resin mixture is less than 1 / 0.1, the lowering of the physical properties and the reactivity and mechanical properties due to moisture absorption during long-term storage of the resin and the paint, on the contrary, when the weight ratio exceeds 1/3 by weight, the reaction functional groups increase and gelation occurs. There is a risk.
상기한 바와 같은 에폭시수지의 혼합물과 다가페놀 화합물을 촉매 존재하에 축합반응시켜 본 발명의 페놀 경화제를 제조한다. 이때, 다가페놀 화합물로는 비스페놀 A, 비스페놀 F 및 비스페놀 S 등 중에서 선택된 단독 또는 혼합물을 사용하며, 바람직하게는 비스페놀 A를 단독 사용하는 것이다. 다가페놀 화합물의 하이드록시기와 에폭시수지의 그리시딜기의 당량비는 1 / 0.1 ∼ 1 / 0.5 범위로 유지시키는 것이 좋다. 이때 당량비가 1 / 0.1 미만이면 수지의 저점도화로 저장중 엉김현상이 발생 하며, 1 / 0.5를 초과하면 수지의 고분자화로 흐름성 저하 및 겔화의 위험이 있다.The phenol curing agent of the present invention is prepared by condensation reaction of a mixture of the epoxy resin as described above with a polyhydric phenol compound in the presence of a catalyst. In this case, as the polyhydric phenol compound, one or a mixture selected from bisphenol A, bisphenol F, bisphenol S and the like is used, and preferably bisphenol A is used alone. It is preferable to maintain the equivalent ratio of the hydroxyl group of the polyhydric phenol compound and the glycidyl group of the epoxy resin in the range of 1 / 0.1 to 1 / 0.5. At this time, if the equivalent ratio is less than 1 / 0.1, entanglement occurs during storage due to low viscosity of the resin, and if it exceeds 1 / 0.5, there is a risk of deterioration in flowability and gelation due to polymerization of the resin.
또한, 상기 축중합 반응활성화를 위한 촉매로는 포스포늄염 또는 이의 유도체 또는 아민류를 사용한다. 포스포늄염 또는 이의 유도체로서는 트리페닐포스핀, 에틸트리페닐포스포늄 브로마이드, 부틸트리페닐포스포늄 브로마이드, 부틸트리페닐포스페이트옥살산염, 부틸트리페닐포스포늄 크로라이드 등이 사용될 수 있다. 아민류로는 4급암모늄, 페닐트리메틸염화암모늄, 테트라메틸암모늄, 2-메틸이미다졸, 2-에틸-4메틸이미다졸, 2-페닐이미다졸, 2-이소프로필이미다졸, 2-운데실이미다졸 등이 사용될 수 있다. 상기 사용되는 촉매는 수지 말단에 하이드록시기가 위치할 수 있도록 충분한 반응성을 가지고 있어야 하며, 촉매는 에폭시수지 혼합물과 다가페놀 화합물 총량에 대하여 0.001 ∼ 0.1 중량% 사용한다. 또한, 원활한 분산을 위해 상기 촉매는 용제 즉, 메탄올 또는 에탄올에 10 ∼ 50 중량%로 농도로 용해하여 사용하는 것이 바람직하다.In addition, as a catalyst for activating the polycondensation reaction, a phosphonium salt or a derivative or amine thereof is used. As the phosphonium salt or derivatives thereof, triphenylphosphine, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, butyltriphenylphosphate oxalate, butyltriphenylphosphonium chloride and the like can be used. Amines are quaternary ammonium, phenyltrimethylammonium chloride, tetramethylammonium, 2-methylimidazole, 2-ethyl-4methylimidazole, 2-phenylimidazole, 2-isopropylimidazole, 2- Undecylimidazole and the like can be used. The catalyst to be used must have sufficient reactivity so that the hydroxyl group is located at the end of the resin, and the catalyst is used in an amount of 0.001 to 0.1% by weight based on the total amount of the epoxy resin mixture and the polyhydric phenol compound. In addition, for smooth dispersion, the catalyst is preferably used by dissolving at a concentration of 10 to 50% by weight in a solvent, that is, methanol or ethanol.
또한, 본 발명의 다관능 페놀수지에는 경화 촉진제로서 이미다졸 화합물, 3급 아민 화합물, 포스포늄계 화합물 등이 함유될 수 있으며, 이때 경화 촉진제의 양은 특별히 한정된 것은 아니나 에폭시수지 혼합물과 다관능성 페놀수지 총량에 대하여 0.1 ∼ 1 중량%, 바람직하게는 0.2 ∼ 0.5 중량%를 사용하는 것이 좋다.In addition, the polyfunctional phenolic resin of the present invention may contain an imidazole compound, a tertiary amine compound, a phosphonium-based compound, etc. as a curing accelerator, wherein the amount of the curing accelerator is not particularly limited, but the epoxy resin mixture and the polyfunctional phenolic resin. It is preferable to use 0.1 to 1% by weight, preferably 0.2 to 0.5% by weight based on the total amount.
또한, 첨가제는 필요에 따라 배합가능하며, 도료의 습윤성(Wetting)을 향상 시키는 폴리아크릴레이트 즉, 폴리에틸아크릴레이트, 폴리2-에틸헥실아크릴레이트, 폴리부틸아크릴 레이트 등의 흐름성 향상제를 배합하는 것이 가능하다.In addition, the additive may be blended as needed, and may be blended with a polyacrylate that improves the wettability of the paint, that is, a flow improving agent such as polyethyl acrylate, poly 2-ethylhexyl acrylate, polybutyl acrylate, or the like. It is possible.
이상의 수지제조 조건에 의해 얻어진 다관능성 페놀수지는 하이드록시당량이 150 ∼ 400 g/eq 이며, 연화점이 60 ∼ 110℃ 이고, 수평균 분자량이 250 ∼ 3,000 인 것을 특징으로 한다.The polyfunctional phenol resin obtained under the above resin production conditions is characterized by having a hydroxy equivalent weight of 150 to 400 g / eq, a softening point of 60 to 110 ° C, and a number average molecular weight of 250 to 3,000.
다음에서는 상기에서 제조된 다관능 페놀수지가 경화제로서 포함되는 본 발명의 에폭시수지 분체도료 조성물의 구체적인 조성 및 제조 공정을 상세히 설명하고자 한다.Next will be described in detail the specific composition and manufacturing process of the epoxy resin powder coating composition of the present invention that the polyfunctional phenol resin prepared above as a curing agent.
본 발명의 에폭시수지 분체도료 조성물은 에폭시수지 40 ∼ 70 중량%, 상기에서 제조된 다관능 페놀수지 5 ∼ 15 중량%, 안료 25 ∼ 45 중량% 및 통상의 첨가제 0.5 ∼ 2 중량%가 함유된다.The epoxy resin powder coating composition of the present invention contains 40 to 70% by weight of epoxy resin, 5 to 15% by weight of polyfunctional phenolic resin prepared above, 25 to 45% by weight of pigment and 0.5 to 2% by weight of conventional additives.
분체도료 조성물 제조에 사용되는 에폭시수지로는 에폭시 당량이 1750 ∼ 2200 g/eq인 비스페놀 A형 에폭시수지와 에폭시 당량이 750 ∼ 850 g/eq인 크레졸 노블락 변성 비스페놀 A형 에폭시 수지를 혼용하여 사용하고, 시판 제품으로는 OREPOXY N8070, N8039(고려화학사 제품)를 사용한다. 분체도료 조성물중의 에폭시수지의 함량은 에폭시수지의 당량과 경화제의 당량비에 따라서 조절하며, 대략적으로 전체 분체도료 조성물에 대하여 40 ∼ 70 중량% 범위로 함유된다.Epoxy resins used in powder coating composition preparation include bisphenol A epoxy resins having an epoxy equivalent of 1750-2200 g / eq and cresol noblock modified bisphenol A epoxy resins having an epoxy equivalent of 750-850 g / eq. OREPOXY N8070 and N8039 (manufactured by Korea Chemical Company) are used as commercially available products. The content of the epoxy resin in the powder coating composition is adjusted according to the equivalent ratio of the epoxy resin and the curing agent, and is contained in the range of 40 to 70% by weight based on the total powder coating composition.
안료로는 백색 안료 예를 들면 티타늄디옥사이드(TiO2) 및 기타 소량의 유기안료가 사용되며, 이때 안료의 사용량이 전체 분체도료 조성물에 대하여 25 중량% 미만이면 은폐가 불량할 수 있으며 45 중량%를 초과하면 도막의 굴곡성 저하를 가져올수 있다. 충진제로는 황산바륨(BaS04), 칼슘카보네이트(CaC03), 실리카(SiO2), 알루미늄하이드록사이드(Al(OH)3)등이 사용될 수 있다. 도료의 습윤성(Wetting)을 향상시키는 흐름성 향상제로서 폴리아크릴레이트 즉, 폴리에틸아크릴레이트, 폴리2-에틸헥실아크릴레이트, 폴리부틸아크릴레이트 등을 사용할 수 있으며, 시판 제품으로는 모다플로우Ⅰ(몬산토사 제품), 피브이-5, 피엘-201(월리사 제품), 아크로날-4에프(바스프사 제품) 등을 사용하며, 흐름성 향상제는 전체 분체도료 조성물에 대하여 0.1 ∼ 1 중량% 사용한다. 또한, 도막의 가교도 및 부착력 향상을 위해 디시안디아마이드를 전체 분체도료 조성물에 대하여 0.3 ∼ 1.3 중량% 사용하며, 그 함량이 0.3 중량% 미만이면 경화 속도가 급격히 저하되고, 1.3 중량%를 초과하면 저장중 경시 변화에 의해 도료의 유리전이 온도가 상승하며 도료 분산중 부분 겔화가 될수 있다.As the pigment, a white pigment such as titanium dioxide (TiO 2 ) and other small amounts of organic pigments are used. If the amount of the pigment is less than 25% by weight based on the total powder coating composition, concealment may be poor and 45% by weight If exceeded, the flexibility of the coating may be reduced. As the filler, barium sulfate (BaS0 4 ), calcium carbonate (CaC0 3 ), silica (SiO 2 ), aluminum hydroxide (Al (OH) 3 ), or the like may be used. Polyacrylates, that is, polyethyl acrylate, poly2-ethylhexyl acrylate, polybutyl acrylate, etc. can be used as a flow improver to improve the wetting of the paint, and as a commercial product, Modaflow I (Monsanto) Product), FV-5, PI-201 (manufactured by Wally Corporation), Acronal-4F (manufactured by BASF Corporation), etc., and a flow improving agent is used in an amount of 0.1 to 1% by weight based on the whole powder coating composition. . In addition, in order to improve the degree of crosslinking and adhesion of the coating film, dicyandiamide is used in an amount of 0.3 to 1.3% by weight based on the total powder coating composition. The glass transition temperature of the paint rises with the change over time during storage, and it may become partial gelation during paint dispersion.
다음은 분체도료 조성물의 제조 공정으로, 상기의 원료를 각각 배합한 후 콘테이너믹서를 이용하여 균일하게 혼합될수 있도록 섞어주고 혼합된 조성물을 니이더 또는 익스투루더(PLK 46, BUSS사) 등의 압출기를 통하여 90 ∼ 120℃ 에서 용융 혼합시킨 다음 분쇄기를 이용하여 평균 입도 30 ∼ 50 ㎛, 입자 분포 10 ∼ 100 ㎛인 분체도료 조성물을 제조한다.The following is a manufacturing process of the powder coating composition, each of the above raw materials are mixed and mixed so that they can be uniformly mixed using a container mixer, and the mixed composition is extruder such as kneader or extruder (PLK 46, BUSS) After melt mixing at 90 to 120 ℃ through a pulverizer to prepare a powder coating composition having an average particle size of 30 to 50 ㎛, particle distribution of 10 to 100 ㎛.
이와 같이 제조된 분체도료 조성물은 180 ∼ 250℃에서 미리 예열된 소지에 도막두께가 50 ∼ 400 ㎛ 되도록 직접 도장하며, 이때 도료는 속경화되고 내흡습성 및 굴곡성, 내음극박리성, 부착성 등이 우수한 강관 및 철근용 분체도료 조성물로 유용하게 사용된다.The powder coating composition thus prepared is directly coated with a pre-heated substrate at 180 to 250 ° C. so that the coating thickness is 50 to 400 μm. At this time, the paint is hardened quickly and hygroscopicity and flexibility, negative peel resistance and adhesion are It is usefully used as an excellent powder coating composition for steel pipes and rebars.
이하 본 발명을 좀더 구체적으로 설명하기위하여 하기 실시예 및 비교예를 예시의 목적으로 제공하였으며 하기 실시예들이 본 발명의 범주를 한정하는 것은 아니다. The following examples and comparative examples have been provided for purposes of illustration in order to illustrate the invention in more detail and the following examples do not limit the scope of the invention.
제조예 및 비교제조예 : 다관능성 페놀수지의 제조Preparation Example and Comparative Preparation Example: Preparation of Multifunctional Phenolic Resin
질소가스관 및 에어 컨덴서, 교반기, 온도계, 히터가 설치되어 있는 4구 플라스크에 상온에서 액상인 비스페놀 A형 에폭시수지로서 OREPOXY R8828(에폭시당량 189 g/eq, 고려화학사 제품) 224 g과, 디사이클로펜타디엔 노블락 에폭시수지로서 EPICLON HP-7200(에폭시당량 264 g/eq, DAINIPPON INK & CHEMICALS사 제품) 100 g을 가하고 질소가스 주입하에 서서히 교반하여 130℃까지 승온하였다. 온도가 130℃에 도달하면 비스페놀 A(하이드록시당량 114.5 g/eq, Shell사 제품) 601 g을 플라스크에 가하고 비스페놀 A가 완전히 용해되면 반응촉매인 에틸트리페닐포스포늄 브로마이드(ETPPBr) 0.15 g을 메탄올에 30 중량%로 용해하여 사입하였다. 촉매 사입후 온도를 165℃ 까지 서서히 승온하고, 165 ℃에서 약 3 시간 동안 유지반응시키면 하이드록시당량이 250 g/eq 이고 연화점이 85.7 ℃ 인 갈색의 고상수지를 얻었다. 여기에 도료 제조상 더욱 원활한 분산을 위하여 경화촉진제로 2-메틸이미다졸(2MI) 25 g과 흐름성 향상제 아크로날-4에프(A-4F, 바스프사 제품) 50 g을 첨가하였다. 그 결과, 하이드록시당량이 270 g/eq 이고, 연화점이 86.9 ℃ 이며, 수평균 분자량이 850 인 다관능성 페놀수지를 얻었다.224 g of OREPOXY R8828 (epoxy equivalent 189 g / eq, manufactured by Koryo Chemical Co., Ltd.) as a liquid bisphenol A epoxy resin at room temperature in a four-necked flask equipped with a nitrogen gas pipe, an air condenser, a stirrer, a thermometer, and a heater. 100 g of EPICLON HP-7200 (epoxy equivalent 264 g / eq, manufactured by DAINIPPON INK & CHEMICALS) was added as a diene noblock epoxy resin, and the mixture was gradually stirred under nitrogen gas injection to raise the temperature to 130 ° C. When the temperature reaches 130 ° C, 601 g of bisphenol A (hydroxy equivalent 114.5 g / eq, manufactured by Shell) is added to the flask, and when bisphenol A is completely dissolved, 0.15 g of ethyltriphenylphosphonium bromide (ETPPBr), a reaction catalyst, is added to methanol. Was dissolved in 30% by weight to buy. After the catalyst was injected, the temperature was gradually raised to 165 ° C. and maintained at 165 ° C. for about 3 hours to obtain a brown solid resin having a hydroxy equivalent weight of 250 g / eq and a softening point of 85.7 ° C. 25 g of 2-methylimidazole (2MI) and 50 g of a flow-promoting agent Acronal-4F (A-4F, manufactured by BASF Corporation) were added as a curing accelerator for smoother dispersion in paint production. As a result, a polyfunctional phenol resin having a hydroxy equivalent weight of 270 g / eq, a softening point of 86.9 ° C, and a number average molecular weight of 850 was obtained.
상기 방법으로 다음 표 1과 같은 조성성분을 사용하여 다관능성 페놀수지를 제조하였다.In the above method, a multifunctional phenolic resin was prepared using the composition components shown in Table 1 below.
실시예 및 비교예 : 분체도료 조성물의 제조Examples and Comparative Examples: Preparation of Powder Coating Composition
상기 제조예 및 비교제조예에서 제조한 다관능성 페놀수지와 비스페놀 A형 에폭시수지로서 OREPOXY N8070(에폭시당량 1,750 ∼ 2,200 g/eq, 고려화학사 제품), 크레졸 노블락 변성 비스페놀 A형 에폭시수지로서 OREPOXY N8039(에폭시당량 750 ∼ 850 g/eq, 고려화학사 제품), 흐름성 향상제로서 PV-5, 디시안디아마이드, 핀홀방지제로서 벤조인 및 체질안료로서 티타늄디옥사이드를 사용하여 다음 표 2와 같은 조성으로 분체도료 조성물을 제조하였다.OREPOXY N8070 (epoxy equivalent 1,750-2,200 g / eq, manufactured by Koryo Chemical Co., Ltd.) as a polyfunctional phenol resin and bisphenol A epoxy resin prepared in the above production examples and comparative production examples, OREPOXY N8039 (as cresol noblock modified bisphenol A type epoxy resin) Epoxy equivalent 750 ~ 850 g / eq, manufactured by Korea Chemical Co., Ltd.), PV-5, dicyanamide, as a flow improver, benzoin as a pinhole inhibitor and titanium dioxide as a extender pigment, the composition as shown in Table 2 below Was prepared.
제조된 분체도료 조성물은 230 ℃에서 60 분간 예열된 시편에 도장하고 경화시켜 도막 두께가 300 ± 50 ㎛ 인 도막시편을 제조하였다.The powder coating composition thus prepared was coated and cured on a specimen preheated at 230 ° C. for 60 minutes to prepare a coating film specimen having a thickness of 300 ± 50 μm.
상기의 결과를 통하여 알 수 있듯이, 본 발명에 따른 신규 다관능성 페놀수지를 경화제로서 함유한 에폭시수지 분체도료 조성물은 금속표면 특히 강관, 철근 등의 피복에 사용할 경우 종래의 분체도료 조성물이 가지는 내식성, 부착성 등의 일반적인 특징을 만족하며 수분에 노출된 장기 저장후에도 경화 도막내 미세구멍의 발생이 적고 경화속도의 저하가 거의 없으며 또한 음극박리성, 굴곡성 등이 우수하다.As can be seen from the above results, the epoxy resin powder coating composition containing the novel multifunctional phenolic resin according to the present invention as a curing agent is used in the coating of metal surfaces, especially steel pipes, rebars, and the like. It satisfies general characteristics such as adhesion, and after long-term storage exposed to moisture, there is little occurrence of micropores in the cured coating film, there is almost no decrease in curing rate, and it is excellent in negative electrode peelability and flexibility.
따라서 본 발명에서의 신규 다관능성 페놀수지는 종래 분체도료 조성물이 가지는 기술적 문제를 해결하였으며, 강관 및 철근용 분체도료 조성물의 신뢰성 향상에 기여하게 되었다.Therefore, the novel multifunctional phenolic resin in the present invention has solved the technical problem of the conventional powder coating composition, and contributed to improving the reliability of the steel pipe and powder coating composition for reinforcing steel.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0641278A (en) * | 1992-07-10 | 1994-02-15 | Somar Corp | Elaxible epoxy resin composition |
EP0753537A1 (en) * | 1995-07-12 | 1997-01-15 | Shell Internationale Researchmaatschappij B.V. | Epoxy resin compositions containing red phosphorus |
JPH11181049A (en) * | 1997-12-22 | 1999-07-06 | Nippon Kayaku Co Ltd | Modified epoxy resin, epoxy resin composition and its hardened product |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0641278A (en) * | 1992-07-10 | 1994-02-15 | Somar Corp | Elaxible epoxy resin composition |
JP2580444B2 (en) * | 1992-07-10 | 1997-02-12 | ソマール株式会社 | Flexible epoxy resin composition |
EP0753537A1 (en) * | 1995-07-12 | 1997-01-15 | Shell Internationale Researchmaatschappij B.V. | Epoxy resin compositions containing red phosphorus |
JPH11181049A (en) * | 1997-12-22 | 1999-07-06 | Nippon Kayaku Co Ltd | Modified epoxy resin, epoxy resin composition and its hardened product |
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06041278 |
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