KR20010065805A - Catalyst for powder coating composition having rapid curing - Google Patents
Catalyst for powder coating composition having rapid curing Download PDFInfo
- Publication number
- KR20010065805A KR20010065805A KR1019990065750A KR19990065750A KR20010065805A KR 20010065805 A KR20010065805 A KR 20010065805A KR 1019990065750 A KR1019990065750 A KR 1019990065750A KR 19990065750 A KR19990065750 A KR 19990065750A KR 20010065805 A KR20010065805 A KR 20010065805A
- Authority
- KR
- South Korea
- Prior art keywords
- epoxy resin
- epoxy
- powder coating
- weight
- parts
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
Abstract
Description
본 발명은 속경화형 에폭시계 분체도료용 경화촉매에 관한 것으로서, 더욱 상세하게는 에폭시계 바인더 수지와 경화제의 반응을 촉진하고, 금속 표면의 도막을 단시간에 경화 가능하게 하는 속경화형 에폭시계 분체도료용 경화촉매에 관한 것이다.The present invention relates to a curing catalyst for fast curing type epoxy powder coating, and more particularly, for a fast curing type epoxy powder coating for promoting the reaction between an epoxy binder resin and a curing agent and allowing the coating on the metal surface to be cured in a short time. It relates to a curing catalyst.
속경화형 분체도료는 바(bar) 도장, 파이프(pipe) 도장 및 그 외의 금속 표면 도장에 적용되어 짧은 시간안에 도장 부위의 경화가 종료되어야한다. 이와 같은 단시간 속경화를 가능하게 하는 방법으로는 경화촉매로서 이미다졸류나 아민류를 소량 사용하거나, 비스페놀 A형 에폭시수지와 이미다졸 또는 아민을 결합반응시켜 사용하거나[미국특허 제 5,717,011호], 페닐글리시딜에테르와 이미다졸을 어덕트시켜 이미다졸 촉매를 제조하고 이를 염화제이구리와 착체화하여 사용하는 방법[polimer bulletin 33, 347∼353(1994)]이 공지되어 있다. 그러나, 상기한 종래 방법은 도료의 분산중 조기 겔(gel)화에 의하여 작업이 불가능해지고, 조기겔을 일으킨 분체도료는 내식성이 저하되고 저장중 경시 변화가 심하며, 도장된 피도물의 유연성을 저하시키는 경향이 있다. 페닐글리시딜에테르와 이미다졸을 결합반응시키고 이를 금속과 착체화하여 사용하는 상기 종래방법은 도료 분산 중(120 ℃) 가역적인 반응에 의해 이미다졸 어덕트를 해리시키고, 이미다졸 어덕트 화합물과 에폭시수지와의 반응을 촉진하므로 속경화형 분체도료에 사용되어 조기 겔화를 부분적으로는 방지할 수 있으나 도료 제조과정중 분산기의 온도가 상승하게 되면 겔화하는 경향이 있어 바인더 수지와의 상용성이 미흡하다. 이를 방지하기 위해서는 140 ℃에서는 겔 타임이 3분 이상이고, 200 ℃에서는 겔 타임이 10초 이내가 되어야만 조기 겔화를 방지하면서 속경화가 가능하다.Fast curing powder coatings are applied to bar coating, pipe coating and other metal surface coatings and the hardening of the coating site should be completed in a short time. As a method for enabling such a short time curing, a small amount of imidazole or amines can be used as a curing catalyst, or a bisphenol A epoxy resin is used in combination with an imidazole or an amine (US Pat. No. 5,717,011), or phenylglycol. A method of preparing an imidazole catalyst by adducting cyl ether and imidazole and complexing it with copper chloride is used (polimer bulletin 33, 347-353 (1994)). However, the above-mentioned conventional method is unable to work by premature gel (gel) during the dispersion of the paint, powder coating that caused the early gel is deteriorated in corrosion resistance, severe changes over time during storage, reducing the flexibility of the coated coating There is a tendency. The conventional method of combining and reacting phenylglycidyl ether with imidazole and complexing it with a metal dissociates the imidazole adduct by a reversible reaction during paint dispersion (120 ° C.), and with the imidazole adduct compound. As it promotes reaction with epoxy resin, it can be used for fast curing powder coating to prevent premature gelation in part, but it tends to gel when the temperature of disperser increases during paint manufacturing process, so it is incompatible with binder resin. . In order to prevent this, at 140 ° C., the gel time should be 3 minutes or more, and at 200 ° C., the gel time should be less than 10 seconds to prevent rapid gelation and prevent rapid curing.
또한, 일본특허공개 평11-100546호에서는 이미다졸 어덕트 타입(EPICURE P101, Shell사)에 금속 착제를 반응시켜 이를 경화촉매로 사용하고 있으나, 이는 조기 겔화는 방지할 수 있으나 도장 후의 유연성을 결여시키는 문제가 있어 개선의 여지가 여전히 남아 있다.In addition, Japanese Patent Application Laid-Open No. 11-100546 uses a metal complex to react with an imidazole adduct type (EPICURE P101, Shell) and uses it as a curing catalyst. However, this prevents premature gelation but lacks flexibility after coating. There is still room for improvement and there is still room for improvement.
상기 종래의 속경화형 에폭시계 분체도료가 가지고 있는 문제점을 완전히 해결하기 위해서는 일단, 저장 안정성 및 유연성이 우수하면서 경화시 주제 및 경화제와의 속경화가 가능해야 한다. 이를 위해서는, 에폭시계 바인더 수지와 경화제의 반응을 촉진하고, 금속 표면의 도막을 단시간에 경화 가능케 하며, 또한 조기 겔화 방지, 저장 안정성, 유연성을 충분히 만족시킬 수 있는 경화촉매의 선정이 매우 주요하다.In order to completely solve the problems of the conventional fast-curing epoxy powder coating, it has to be excellent in storage stability and flexibility while being able to harden with the main agent and the curing agent during curing. For this purpose, it is very important to select a curing catalyst that promotes the reaction between the epoxy-based binder resin and the curing agent, enables the coating film on the metal surface to be cured in a short time, and satisfies premature gelation prevention, storage stability, and flexibility.
본 발명에서는 상기한 바와 같은 요건을 만족시킬 수 있는 속경화형 에폭시계 분체도료용 경화촉매를 제조하기 위하여 노력하였다. 그 결과 비스페놀형 에폭시수지와 함께 속경화 및 이로 인한 유연성의 결여를 방지하기 위하여 지방족 에폭시수지를 적정 함량비로 혼합 사용하였고, 이러한 에폭시수지 혼합물과 이미다졸 화합물의 어덕트화에 의한 화합물을 제조 후 저장 안정성의 확보 및 조기 겔화 방지와 고온에서의 속경화를 위하여 금속화합물과 착체화하므로써 속경화 후에도 도장후 굴곡성이 우수하며, 저장중 경시 변화 및 분산중 조기 겔화의 경향이 없고, 고온에서 속경화가 가능한 경화촉매를 제조하게 되었다.In the present invention, efforts have been made to prepare a curing catalyst for fast curing type epoxy powder coating that can satisfy the requirements as described above. As a result, aliphatic epoxy resins were mixed with bisphenol-type epoxy resins in an appropriate content ratio to prevent rapid curing and the lack of flexibility thereof, and the compound was prepared after storage by adducting the epoxy resin mixture and the imidazole compound. In order to secure stability, prevent premature gelation and fast curing at high temperature, it is complexed with a metal compound so that it is excellent in flexibility after coating even after fast curing, and there is no tendency to change over time during storage and premature gelation during dispersion, and fast curing at high temperature. Possible curing catalysts have been prepared.
따라서, 본 발명은 200 ℃ 이내에서 속경화(겔타임 10초이내)가 가능하며, 저장 안정성이 우수하고, 소지와의 접착성 및 내식성이 우수하며, 특히 유연성이 우수하여 충격성, 벤딩 등의 기계적 강도가 우수한 강관 및 철근 피막형성을 위한 에폭시계 분체도료용 경화촉매를 제공하는데 그 목적이 있다.Therefore, the present invention is capable of fast curing (within 10 seconds of gel time) within 200 ℃, excellent storage stability, excellent adhesion and corrosion resistance with the base material, in particular excellent flexibility and mechanical properties such as impact, bending It is an object of the present invention to provide a curing catalyst for epoxy-based powder coating for forming steel pipe and reinforcing film having excellent strength.
본 발명은 속경화형 에폭시계 분체도료용 경화촉매에 있어서,The present invention is a curing catalyst for rapid curing epoxy powder coating,
비스페놀형 에폭시수지와 지방족 에폭시수지로 구성되는 에폭시수지 혼합물과 이미다졸 화합물을 반응시켜 얻은 이미다졸 어덕트 화합물과 금속화합물을 반응시켜 얻은 것으로 연화점이 90 ∼ 120 ℃ 이고, 점도가 30 ∼ 50 poise(150℃)인 분체도료용 에폭시수지의 경화촉매를 그 특징으로 한다.An imidazole adduct compound obtained by reacting an imidazole compound with an epoxy resin mixture composed of a bisphenol type epoxy resin and an aliphatic epoxy resin and a metal compound. The softening point is 90 to 120 ° C., and the viscosity is 30 to 50 poise. It is characterized by the curing catalyst of epoxy resin for powder coating.
또한, 본 발명은 비스페놀형 에폭시수지, 에폭시 경화제, 경화촉매, 티타늄 디옥사이드 및 통상의 첨가제로 이루어진 분체도료 조성물에 있어서,In addition, the present invention is a powder coating composition consisting of a bisphenol-type epoxy resin, an epoxy curing agent, a curing catalyst, titanium dioxide and a conventional additive,
에폭시당량 800 ∼ 2000 g/eq의 비스페놀형 에폭시수지 60 ∼ 80 중량%, 에폭시당량 150 ∼ 400 g/eq의 에폭시 경화제 10 ∼20 중량% 및 상기한 경화촉매 3 ∼ 15 중량%, 그리고 티타늄 디옥사이드 및 통상의 첨가제가 함유되어 있는 것임을 분체도료 조성물을 포함한다.60 to 80% by weight of epoxy equivalent 800-2000 g / eq bisphenol-type epoxy resin, 10 to 20% by weight epoxy curing agent with epoxy equivalent of 150 to 400 g / eq and 3 to 15% by weight of the above curing catalyst, and titanium dioxide and The powder coating composition includes a conventional additive.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명에 따른 경화촉매의 제조과정은 에폭시수지 혼합물과 이미다졸 화합물을 반응시켜 이미다졸 어덕트 화합물을 제조하는 제 1 과정과, 상기 이미다졸 어덕트 화합물과 금속화합물을 반응시켜 금속착체 촉매를 제조하는 제 2 과정으로 구성된다. 이를 보다 상세히 설명하면 다음과 같다.The process for preparing a curing catalyst according to the present invention includes the first process of preparing an imidazole adduct compound by reacting an epoxy resin mixture with an imidazole compound, and preparing a metal complex catalyst by reacting the imidazole adduct compound with a metal compound. It consists of a second process. This will be described in more detail as follows.
제 1 과정은 이미다졸 어덕트 화합물 제조 단계로서, 지방족 에폭시수지와, 비스페놀형 에폭시수지를 이용하여 이미다졸 어덕트화하는 과정이다.The first step is a step of preparing an imidazole adduct compound, which is an imidazole adduct using an aliphatic epoxy resin and a bisphenol type epoxy resin.
상기 이미다졸 어덕트화에 적용되는 지방족 에폭시수지는 2개 이상의 에폭시기를 가지며 상온에서 액상인 평균 분자량 300 ∼ 1000인 것으로, 구체화하면 트리메틸올프로판 트리글리시딜 에테르, 트리메틸올에탄 트리글리시딜 에테르, 폴리프로필렌 글리콜 디글리시딜 에테르, 폴리에틸렌 글리콜 디글리시딜 에테르, 폴리테트라메틸렌 글리콜 디글리시딜 에테르, 네오펜틸 글리콜 디글리시딜 에테르, 1,6-헥산디올 디글리시딜 에테르, 스테아릴 글리시딜 에테르, 세틸 디글리시딜 에테르등과 이들의 유도체 등이 선택되어질 수 있다. 지방족 에폭시수지로서 탄소사슬 주쇄의 길이가 너무 길면(에폭시 당량: 1000 이상) 유연성은 우수할 수 있으나 도료의 저장중 뭉침 현상(blocking)이 나타나는 경향이 있고, 너무 짧으면(에폭시 당량: 300 이하) 저장성은 양호해지나 도료화시 유연성이 떨어져 굴곡성이 저하될 우려가 있다.The aliphatic epoxy resin applied to the imidazole adduct is a compound having an average molecular weight of 300 to 1000 which is two or more epoxy groups and is liquid at room temperature. Specifically, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, and poly Propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, stearyl glyc Cidyl ether, cetyl diglycidyl ether and the like and derivatives thereof may be selected. As an aliphatic epoxy resin, if the length of the carbon chain backbone is too long (epoxy equivalent: 1000 or more), flexibility may be excellent, but tends to block during storage of the paint, and if it is too short (epoxy equivalent: 300 or less), storage property The silver becomes good, but there is a possibility that the flexibility is lowered at the time of coating and the flexibility is reduced.
상기 이미다졸 어덕트화에 적용되는 또다른 에폭시수지로서 비스페놀형 에폭시수지는 비스페놀 A형 에폭시수지(예를 들면, 고려화학제품의 R8828, R8827), 비스페놀 에프형 에폭시수지(예를 들면, 고려화학제품의 R8130), 노블락변성 에폭시수지 등이 사용될 수 있다.As another epoxy resin to be applied to the imidazole adduct, bisphenol type epoxy resin is bisphenol A type epoxy resin (for example, R8828 and R8827 of Korea Chemicals), bisphenol F type epoxy resin (for example, Korea Chemical) Product R8130), a noblock modified epoxy resin and the like can be used.
또한, 이미다졸 화합물로는 2-메칠이미다졸, 4-메칠이미다졸, 5-메칠이미다졸, 2-페닐이미다졸, 2,4-디메칠이미다졸, 2-메칠-4-메칠이미다졸 등이 적당하다.In addition, as an imidazole compound, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, 2-phenylimidazole, 2,4- dimethylimidazole, 2-methyl-4 -Methylimidazole is suitable.
상기 이미다졸 어덕트화 과정에서 사용되는 지방족 에폭시수지는 비스페놀형 에폭시수지 100 중량부에 대해 10 ∼ 30 중량부 범위로 사용하는 바, 그 사용량이 10 중량부 미만이면 유연성이 저하되고, 30 중량부를 초과하면 촉매의 저장중 겔화가 발생할 수 있다. 또한, 이미다졸 화합물은 에폭시수지 혼합물에 대해 20 ∼ 40 중량부 범위로 사용하는 바, 그 사용량이 20 중량부 미만이면 도료의 속경화가 어려워지고, 40 중량부를 초과하면 분산중 부분적인 겔화가 일어날 수 있다.The aliphatic epoxy resin used in the imidazole adducting process is used in the range of 10 to 30 parts by weight based on 100 parts by weight of the bisphenol-type epoxy resin, and when the amount thereof is less than 10 parts by weight, the flexibility is lowered, and 30 parts by weight. If exceeded, gelation may occur during storage of the catalyst. In addition, the imidazole compound is used in the range of 20 to 40 parts by weight with respect to the epoxy resin mixture. When the amount of the imidazole compound is less than 20 parts by weight, the curing of the paint becomes difficult, and when it exceeds 40 parts by weight, partial gelation occurs during dispersion. Can be.
이상의 제조방법으로 제조된 이미다졸 어덕트 화합물은 비스페놀 디글리시딜형 에폭시수지와 폴리올 변성 지방족 에폭시수지를 혼합 사용하고 이 에폭시수지의 양 말단에 이미다졸 화합물이 개환 부가 구조를 갖는다.The imidazole adduct compound prepared by the above manufacturing method uses a bisphenol diglycidyl type epoxy resin and a polyol-modified aliphatic epoxy resin, and the imidazole compound has a ring-opening addition structure at both ends of the epoxy resin.
다음은 제 2 과정으로서, 상기 제 1 과정에서 제조된 이미다졸 어덕트 화합물과 금속화합물을 반응시켜 금속착체 촉매를 제조하는 과정이다. 이때, 금속화합물로는 Fe, Co, Ni, Cu, Zn, Al 등의 금속을 함유한 금속할로겐화물이 사용되며, 상기 이미다졸 어덕트 화합물 100 중량부에 대하여 금속화합물은 40 ∼ 60 중량부 사용한다. 이러한 금속 화합물은 전이원소가 함유된 할로겐 화합물로서 상온에서는 양호한 안정성을 가져 도료의 저장 중 겔 타임이 빨라지는 것을 방지하고, 분산 중 겔화를 방지하며 고온에서는 가역해리에 의해 이미다졸 어덕트 화합물과 바인더 수지와의 결합을 가능하게 한다.Next, as a second process, a metal complex catalyst is prepared by reacting the imidazole adduct compound prepared in the first process with a metal compound. In this case, a metal halide containing a metal such as Fe, Co, Ni, Cu, Zn, Al is used as the metal compound, and 40 to 60 parts by weight of the metal compound is used based on 100 parts by weight of the imidazole adduct compound. do. These metal compounds are halogenated compounds containing transition elements, which have good stability at room temperature, which prevents the gel time from increasing during storage of the paint, prevents gelation during dispersion, and reversible dissociation at high temperatures. Allows bonding with the resin.
이상에서 설명한 바와 같은 2 단계 제조과정에 의해 최종적으로 제조된 경화촉매는 연화점 90 ∼ 120 ℃이고, 점도 30 ∼ 50 poise(150 ℃) 이다. 또한, 본 발명의 경화촉매가 반응성이 빨라 속경화가 가능하며 유연성 및 저장 안정성이 우수한 철근 피복용 도료물성을 충분히 만족시키는 촉매임은 이하에서 설명하기로 한다.The curing catalyst finally prepared by the two-step manufacturing process as described above has a softening point of 90 to 120 ° C. and a viscosity of 30 to 50 poise (150 ° C.). In addition, the curing catalyst of the present invention is a catalyst that satisfies the properties of the reinforcing bar coating material having excellent reactivity and rapid curing and excellent flexibility and storage stability will be described below.
다음으로는 이상의 제조방법으로 제조된 경화촉매를 함유하는 에폭시계 분체도료의 제조과정을 설명하고자 한다.Next will be described the manufacturing process of the epoxy powder coating containing a curing catalyst prepared by the above manufacturing method.
본 발명에 따른 분체도료 조성물은 비스페놀형 에폭시수지 100 중량부, 경화제 10 ∼ 20 중량부, 상기에서 제조한 경화촉매 3 ∼ 15 중량부, 그리고 안료, 흐름성 향상제 및 소량의 첨가제 1 ∼ 10 중량부를 함유한다.The powder coating composition according to the present invention comprises 100 parts by weight of a bisphenol-type epoxy resin, 10 to 20 parts by weight of a curing agent, 3 to 15 parts by weight of a curing catalyst prepared above, and 1 to 10 parts by weight of a pigment, a flow improver and a small amount of additives. It contains.
상기 분체도료 조성물중에 경화촉매로서 함유되는 금속착체의 함량이 3 중량부 미만이면 속경화가 불가능하고, 15 중량부를 초과하면 속경화는 가능하나 도막이 딱딱해져 유연성 및 가요성이 저하될 수 있다.If the content of the metal complex contained as a curing catalyst in the powder coating composition is less than 3 parts by weight, it is impossible to fast cure. If the content of the metal complex exceeds 15 parts by weight, fast curing may be possible, but the coating film may be hardened, thereby decreasing flexibility and flexibility.
그리고, 경화제로는 페놀 경화제(CNE00150 : KCC사 제품) 및 아민류를 사용하고, 그 사용량은 에폭시수지의 당량과 경화제의 당량비에 따라서 조절 가능하며, 대략적으로 10 ∼ 20 중량부 범위로 사용한다. 흐름성 향상제로는 아크릴계(모다플로우 Ⅰ, 몬산토사 제품 ; 피브이-5, 피엘-201, 월리사 제품 ; 아크로날-4에프 ; 바스프사 제품)와 실리콘계 등을 0.5 ∼ 1.5 중량부 사용한다. 기타 소량의 유기 안료가 사용되고, 충진제로서 황산바륨(BAS04), 칼슘카보네이트(CaC03), 실리카(SiO2), 알루미늄 하이드록사이드(Al(OH)3) 등이 사용될 수 있다.As the curing agent, a phenol curing agent (CNE00150: manufactured by KCC Co., Ltd.) and amines are used. The amount of the curing agent can be adjusted depending on the equivalent ratio of the epoxy resin and the curing agent, and is used in the range of about 10 to 20 parts by weight. As a flow improving agent, 0.5-1.5 weight part of acryl-type (Modaflow I, Monsanto company; FV-5, PI-201, Wally Corporation; Acronal-4F; BASF company), silicone type, etc. are used. Other small amounts of organic pigments may be used, and barium sulfate (BAS0 4 ), calcium carbonate (CaC0 3 ), silica (SiO 2 ), aluminum hydroxide (Al (OH) 3 ), and the like may be used as fillers.
이상에서 설명한 원료를 각각 배합 후 콘테이너 믹서를 이용하여 균일하게 혼합될 수 있도록 섞는다. 균일하게 혼합된 조성물을 니이더 또는 익스투루더(PLK 46, BUSS사)의 압출기를 통하여 90 ∼ 120 ℃에서 용융혼합시킨 다음, 분쇄기를 이용하여 평균 입도 30 ∼ 50 ㎛, 입자 분포 10 ∼ 100 ㎛인 분체도료를 제조한다.Each of the raw materials described above are mixed so that they can be uniformly mixed using a container mixer. The homogeneously mixed composition was melt mixed at 90 to 120 ° C. through an extruder of a kneader or extruder (PLK 46, BUSS), and then an average particle size of 30 to 50 μm and a particle distribution of 10 to 100 μm using a grinder. Phosphorus powder coating is prepared.
상기한 본 발명의 분체도료는 200 ℃에서 예열된 철근을 사용하여 통상의 도장방법으로 도포하고 경화시키면 도막이 형성된다.When the powder coating of the present invention described above is applied and cured using a conventional coating method using reinforcing steel at 200 ° C., a coating film is formed.
이와 같은 본 발명은 다음의 실시예 및 비교예를 통하여 보다 상세히 설명하겠는 바, 본 발명이 다음의 실시예에 의해 한정되는 것은 아니다.Such the present invention will be described in more detail through the following examples and comparative examples, but the present invention is not limited by the following examples.
실시예 1Example 1
상온에서 고상인 2-메칠이미다졸 45 g을 톨루엔에 희석하여 플라스크에 가하고, 불활성 개스의 주입하에 60 ℃에서 약 30분동안 교반하였다. 지방족 에폭시수지(HELOXY84, 에폭시 당량 620 ∼ 680 g/eq, 미국 SHELL Co.) 20 g, 비스페놀형 에폭시수지(R8828, 에폭시 당량 184 ∼ 194 g/eq, 고려화학 제품) 90 g을 약 1 ∼ 2시간에 걸쳐 적하하였다. 3시간 환류후 진공 감압하에서 점도가 44 poise(150 ℃), 연화점이 106 ℃인 이미다졸 어덕트 화합물을 얻었다.45 g of 2-methylimidazole, which is a solid at room temperature, was diluted in toluene, added to the flask, and stirred for about 30 minutes at 60 ° C under injection of an inert gas. About 1-2 g of aliphatic epoxy resin (HELOXY84, epoxy equivalent 620-680 g / eq, USA SHELL Co.) 20 g, bisphenol type epoxy resin (R8828, epoxy equivalent 184-194 g / eq, Koryo Chemicals) 90 g It was dripped over time. After refluxing for 3 hours, an imidazole adduct compound having a viscosity of 44 poise (150 ° C.) and a softening point of 106 ° C. under vacuum reduced pressure was obtained.
상기에서 제조한 이미다졸 어덕트 화합물에, 금속화합물인 염화구리 75 g을 가열된 에틸알콜 120 g에 희석하여 투입하고, 100 ℃에서 3시간 환류후 냉각하고 여과 건조하여 금속착체를 얻었다. 그 결과로, 연화점이 105.6 ℃ 이고, 점도가 42 poise(150 ℃)인 금속착체를 얻었으며, 이를 경화촉매로 사용하였다.To the imidazole adduct compound prepared above, 75 g of copper chloride as a metal compound was diluted and added to 120 g of heated ethyl alcohol, refluxed at 100 ° C. for 3 hours, cooled, and filtered to obtain a metal complex. As a result, a metal complex having a softening point of 105.6 ° C. and a viscosity of 42 poise (150 ° C.) was obtained, which was used as a curing catalyst.
실시예 2Example 2
2-페닐이미다졸 55 g을 톨루엔에 희석하여 플라스크에 가하고 불활성 개스의 주입하에 60 ℃에서 약 30분 교반후하였다. 지방족 에폭시수지(HELOXY84, 에폭시 당량 620 ∼ 680 g/eq, 미국 SHELL Co.) 30 g과, 비스페놀형 에폭시수지(R8828, 에폭시 당량 184 ∼ 194 g/eq, 고려화학 제품) 100 g을 사용하여 상기 실시예 1과 동일한 방법으로 수행하여 점도가 40 poise(150 ℃), 연화점이 105 ℃인 이미다졸 어덕트 화합물을 제조하였다.55 g of 2-phenylimidazole was diluted in toluene, added to the flask, and stirred for about 30 minutes at 60 ° C under injection of an inert gas. Using 30 g of an aliphatic epoxy resin (HELOXY84, epoxy equivalent 620-680 g / eq, US SHELL Co.) and 100 g of bisphenol-type epoxy resin (R8828, epoxy equivalent 184-194 g / eq, Koryo Chemical) In the same manner as in Example 1, an imidazole adduct compound having a viscosity of 40 poise (150 ° C.) and a softening point of 105 ° C. was prepared.
이렇게 제조된 이미다졸 어덕트 화합물에 금속화합물인 염화아연 90 g을 100 ℃에서 가한 후 3시간 환류후 냉각하고 여과 건조하여 금속착체를 얻었다. 그결과로, 연화점이 104.8 ℃ 이고, 점도가 38 poise(150 ℃)인 금속착체를 얻었으며, 이를 경화촉매로 사용하였다.90 g of zinc chloride, a metal compound, was added to the imidazole adduct compound thus prepared at 100 ° C., refluxed for 3 hours, cooled, and filtered to obtain a metal complex. As a result, a metal complex having a softening point of 104.8 ° C. and a viscosity of 38 poise (150 ° C.) was obtained, which was used as a curing catalyst.
실시예 3Example 3
2-페닐이미다졸 52 g을 메틸에틸케톤에 희석하여 플라스크에 가하고 불활성 개스의 주입하에 100 ℃에서 약 30분 교반하였다. 지방족 에폭시수지(HELOXY84, 에폭시 당량 620 ∼ 680 g/eq, 미국 SHELL Co.) 20 g과, 비스페놀형 에폭시수지(R8828, 에폭시 당량 184 ∼ 194 g/eq, 고려화학 제품) 80 g을 사용하여 상기 실시예 1과 동일한 방법으로 수행하여 같은 방법으로 제조하여 점도가 40 poise(150 ℃), 연화점이 105 ℃인 이미다졸 어덕트 화합물을 제조하였다.52 g of 2-phenylimidazole was diluted in methyl ethyl ketone and added to the flask and stirred for about 30 minutes at 100 ° C under injection of inert gas. 20 g of aliphatic epoxy resin (HELOXY84, epoxy equivalent 620-680 g / eq, USA SHELL Co.) and 80 g of bisphenol-type epoxy resin (R8828, epoxy equivalent 184-194 g / eq, Koryo Chemical) It was prepared in the same manner as in Example 1 to prepare an imidazole adduct compound having a viscosity of 40 poise (150 ° C.) and a softening point of 105 ° C.
이렇게 제조된 이미다졸 어덕트 화합물에 금속화합물인 염화구리 80 g을 100 ℃에서 가한 후 3시간 환류후 냉각하고 여과 건조하여 금속착체를 얻었다. 그 결과로, 연화점이 104.8 ℃ 이고, 점도가 38 poise(150 ℃)인 금속착체를 얻었으며, 이를 경화촉매로 사용하였다.80 g of a copper compound, which is a metal compound, was added to the imidazole adduct compound thus prepared at 100 ° C., refluxed for 3 hours, cooled, and filtered to obtain a metal complex. As a result, a metal complex having a softening point of 104.8 ° C. and a viscosity of 38 poise (150 ° C.) was obtained, which was used as a curing catalyst.
실시예 4Example 4
2-메틸이미다졸 33 g을 톨루엔에 희석하여 플라스크에 가하고 불활성 개스의 주입하에 100 ℃에서 약 30분 교반하였다. 지방족 에폭시수지(HELOXY84, 에폭시 당량 620 ∼ 680 g/eq, 미국 SHELL Co.) 25 g과, 비스페놀형 에폭시수지(R8828, 에폭시 당량 184 ∼ 194 g/eq, 고려화학 제품) 75 g을 사용하여 상기 실시예 1과동일한 방법으로 수행하여 점도가 40 poise(150 ℃), 연화점이 105 ℃인 이미다졸 어덕트 화합물을 제조하였다.33 g of 2-methylimidazole was diluted in toluene and added to the flask and stirred at 100 ° C. for about 30 minutes under injection of an inert gas. Using 25 g of an aliphatic epoxy resin (HELOXY84, epoxy equivalent 620-680 g / eq, US SHELL Co.) and 75 g of bisphenol-type epoxy resin (R8828, epoxy equivalent 184-194 g / eq, Koryo Chemical) In the same manner as in Example 1, an imidazole adduct compound having a viscosity of 40 poise (150 ° C.) and a softening point of 105 ° C. was prepared.
이렇게 제조된 이미다졸 어덕트 화합물에 금속화합물인 염화알루미늄 60 g을 100 ℃에서 가한 후 3시간 환류 후 냉각하고 여과 건조하여 금속착체를 얻었다. 그 결과로, 연화점이 104.8 ℃ 이고, 점도가 38 poise(150 ℃)인 금속착체를 얻었으며, 이를 경화촉매로 사용하였다.To the imidazole adduct compound thus prepared was added 60 g of aluminum chloride as a metal compound at 100 ° C., refluxed for 3 hours, cooled, and filtered to obtain a metal complex. As a result, a metal complex having a softening point of 104.8 ° C. and a viscosity of 38 poise (150 ° C.) was obtained, which was used as a curing catalyst.
비교예 1Comparative Example 1
2-메틸이미다졸 42 g을 톨루엔에 희석하여 플라스크에 가하고 불활성 개스의 주입하에 100 ℃에서 약 30분 교반하였다. 지방족 에폭시수지(HELOXY84, 에폭시 당량 620 ∼ 680 g/eq, 미국 SHELL Co.) 25 g과, 비스페놀형 에폭시수지(R8828, 에폭시 당량 184 ∼ 194 g/eq, 고려화학 제품) 75 g을 사용하여 상기 실시예 1과 동일한 방법으로 수행하여 점도가 40 poise(150 ℃), 연화점이 105 ℃인 이미다졸 어덕트 화합물을 제조하였으며, 이를 경화촉매로 사용하였다.42 g of 2-methylimidazole were diluted in toluene and added to the flask and stirred for about 30 minutes at 100 ° C under injection of inert gas. Using 25 g of an aliphatic epoxy resin (HELOXY84, epoxy equivalent 620-680 g / eq, US SHELL Co.) and 75 g of bisphenol-type epoxy resin (R8828, epoxy equivalent 184-194 g / eq, Koryo Chemical) The imidazole adduct compound having a viscosity of 40 poise (150 ° C.) and a softening point of 105 ° C. was prepared in the same manner as in Example 1, which was used as a curing catalyst.
비교예 2Comparative Example 2
2-페닐이미다졸 42 g을 톨루엔에 희석하여 플라스크에 가하고 불활성 개스의 주입하에 60 ℃에서 약 30분 교반하였다. 비스페놀형 에폭시수지(R8828, 에폭시 당량 184 ∼ 194 g/eq, 고려화학 제품) 100 g을 약 1 ∼ 2시간에 걸쳐 적하하여 점도가 40 poise(150 ℃), 연화점이 105 ℃인 이미다졸 어덕트 화합물을 제조하였다.42 g of 2-phenylimidazole were diluted in toluene and added to the flask and stirred for about 30 minutes at 60 ° C under injection of inert gas. 100 g of bisphenol-type epoxy resin (R8828, epoxy equivalent of 184 to 194 g / eq, Koryo Chemicals) was added dropwise over about 1 to 2 hours to imidazole adduct having a viscosity of 40 poise (150 ° C) and a softening point of 105 ° C. The compound was prepared.
이렇게 제조된 이미다졸 어덕트 화합물에 금속화합물인 염화아연 60 g을 100 ℃에서 가한 후 3시간 환류 후 냉각하고 여과 건조하여 금속착체를 얻었다. 그 결과로, 연화점이 104.8 ℃ 이고, 점도가 38 poise(150 ℃)인 금속착체를 얻었으며, 이를 경화촉매로 사용하였다.60 g of zinc chloride, which is a metal compound, was added to the imidazole adduct compound thus prepared at 100 ° C., refluxed for 3 hours, cooled, and filtered to obtain a metal complex. As a result, a metal complex having a softening point of 104.8 ° C. and a viscosity of 38 poise (150 ° C.) was obtained, which was used as a curing catalyst.
실험예 1 : 반응 안정성 시험Experimental Example 1 Reaction Stability Test
상기 실시예 1 및 3, 비교예 1에서 제조한 금속착체 각각에 대한 에폭시수지와의 반응을 통한 점도의 변화를 알아보기 위하여 다음과 같은 실험을 수행하였다.In order to determine the change in viscosity through the reaction with the epoxy resin for each of the metal complexes prepared in Examples 1 and 3, Comparative Example 1 was carried out the following experiment.
비스페놀형 에폭시수지(R8828, 에폭시 당량 184 ∼ 194 g/eq, 고려화학 제품) 98 중량%와 상기 실시예 및 비교예에서 제조한 경화촉매 2 중량%를 반응시켜 점도를 측정하였다. 이때, 점도는 브룩필드 점도계(40 ℃)를 사용하여 측정하였으며, 그 결과는 다음 표 1에 나타내었다.The viscosity was measured by reacting 98% by weight of the bisphenol-type epoxy resin (R8828, epoxy equivalent of 184 to 194 g / eq, Koryo Chemical Co., Ltd.) with 2% by weight of the curing catalyst prepared in Examples and Comparative Examples. At this time, the viscosity was measured using a Brookfield viscometer (40 ℃), the results are shown in Table 1 below.
실험예 2 : 도료 조성물의 제조Experimental Example 2 Preparation of the Paint Composition
다음 표 2와 같은 조성으로 배합하고, 상기에서 설명한 도료 제조방법을 이용하여 분체도료를 제조하였다. 다음 표 2에 나타낸 조성성분으로서는 비스페놀형 에폭시수지로서 CNE00105(에폭시 당량 1100 ∼ 1200 g/eq, 고려화학 제품), 에폭시 경화제로서 CNN00150(에폭시 당량 240 ∼ 260 g/eq, 고려화학 제품), 아마이드 경화촉매로서 C783(SWAN사 제품), 흐름향상제로서 PV-5(월리사 제품)을 각각 사용하였다.Next, the composition was formulated as shown in Table 2, and powder coating was prepared using the coating method described above. As the composition components shown in Table 2, CNE00105 (epoxy equivalent 1100-1200 g / eq, Koryo Chemicals) as a bisphenol-type epoxy resin, CNN00150 (epoxy equivalent 240-260 g / eq, Koryo Chemicals), amide curing as an epoxy curing agent C783 (manufactured by SWAN) and PV-5 (manufactured by Wally) were used as catalysts.
상기에서 제조한 분체도료를 예열된 철근에(200℃×60분 예열) 도장 후 경화시켜 도막 두께가 300 ±50 ㎛인 도막시편을 제조하였다.The powder coating prepared above was coated on a preheated rebar (200 ° C. × 60 minutes) and cured to prepare a coating film specimen having a thickness of 300 ± 50 μm.
상기의 결과를 통하여 알 수 있듯이, 본 발명에서의 금속착체 촉매는 에폭시수지와의 저장 안정성에서도 우수한 특성을 보이며 이를 이용해 제조된 분체도료는 금속 표면 특히, 철근 피복, 파이프 등에 사용할 경우 고온 속경화에서 종래의 에폭시수지가 가지는 내식성, 내약품성 등의 일반적 특징을 만족하면서 분산 안정성, 저장 안정성, 유연성 및 내식성등이 우수한 특성을 나타내는 것을 알 수 있다.As can be seen from the above results, the metal complex catalyst in the present invention shows excellent properties in storage stability with epoxy resin, and the powder coating prepared by using the metal surface catalyst, especially when used in rebar coating, pipe, etc. It can be seen that excellent properties such as dispersion stability, storage stability, flexibility and corrosion resistance are satisfied while satisfying general characteristics such as corrosion resistance and chemical resistance of the conventional epoxy resin.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990065750A KR20010065805A (en) | 1999-12-30 | 1999-12-30 | Catalyst for powder coating composition having rapid curing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990065750A KR20010065805A (en) | 1999-12-30 | 1999-12-30 | Catalyst for powder coating composition having rapid curing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20010065805A true KR20010065805A (en) | 2001-07-11 |
Family
ID=19632928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019990065750A KR20010065805A (en) | 1999-12-30 | 1999-12-30 | Catalyst for powder coating composition having rapid curing |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20010065805A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539961A (en) * | 2022-02-17 | 2022-05-27 | 湖北回天新材料股份有限公司 | Single-component motor adhesive capable of being stored stably at normal temperature and rapidly cured at medium temperature and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR890013083A (en) * | 1988-02-12 | 1989-09-21 | 리차드 지. 워터맨 | Catalyst and Epoxy Resin Composition Containing the Same |
| JPH1030015A (en) * | 1996-07-15 | 1998-02-03 | Kansai Paint Co Ltd | Catalyst for curing epoxy resin and thermosetting coating composition using the same |
| JPH11100546A (en) * | 1997-09-29 | 1999-04-13 | Nippon Paint Co Ltd | Imidazole adduct complex catalyst for rapid-curing epoxy powder coating material and powder coating material |
-
1999
- 1999-12-30 KR KR1019990065750A patent/KR20010065805A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR890013083A (en) * | 1988-02-12 | 1989-09-21 | 리차드 지. 워터맨 | Catalyst and Epoxy Resin Composition Containing the Same |
| JPH1030015A (en) * | 1996-07-15 | 1998-02-03 | Kansai Paint Co Ltd | Catalyst for curing epoxy resin and thermosetting coating composition using the same |
| KR980009304A (en) * | 1996-07-15 | 1998-04-30 | 사사키 요시오 | Curing catalyst for epoxy resin and thermosetting coating composition containing same |
| US5789498A (en) * | 1996-07-15 | 1998-08-04 | Kansai Paint Co., Ltd. | Curing catalyst for use in epoxy resin and heat curing coating composition containing the same |
| JPH11100546A (en) * | 1997-09-29 | 1999-04-13 | Nippon Paint Co Ltd | Imidazole adduct complex catalyst for rapid-curing epoxy powder coating material and powder coating material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539961A (en) * | 2022-02-17 | 2022-05-27 | 湖北回天新材料股份有限公司 | Single-component motor adhesive capable of being stored stably at normal temperature and rapidly cured at medium temperature and preparation method thereof |
| CN114539961B (en) * | 2022-02-17 | 2023-11-17 | 湖北回天新材料股份有限公司 | Single-component motor adhesive capable of being stored stably at normal temperature and being cured rapidly at medium temperature and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0365479B1 (en) | Curable epoxide resin compositions | |
| US6329473B1 (en) | Amine-modified epoxy resin composition | |
| EP0942028B1 (en) | Epoxy resin composition | |
| US4348505A (en) | Adducts from amines and di- and polyepoxides | |
| US4540750A (en) | Diethyl toluene diamine hardener systems | |
| EP0044816B1 (en) | Adducts from amines and di- and polyepoxides | |
| US4136086A (en) | Curable epoxide resin mixtures | |
| KR101138470B1 (en) | A method of epoxy resins for a pulverulent body paints and a pulverulent body paints composition | |
| JPH08283540A (en) | Curable epoxy resin mixture containing wollastonite | |
| AU732395B2 (en) | Hardenable mixtures made of glycidyl compounds, aminic hardeners and heterocyclic accelerators | |
| JPH0414701B2 (en) | ||
| US4845172A (en) | Co-advanced resins from copolymers of polyethers of polyhydric phenols and diglycidyl ethers of di-secondary alcohols | |
| US3363026A (en) | Epoxy resin containing a curing catalyst mixture of a polymercaptan and a fused ringamine | |
| KR20010065805A (en) | Catalyst for powder coating composition having rapid curing | |
| KR20190097602A (en) | Powder coating composition | |
| KR100554352B1 (en) | Method for producing a noblock modified epoxy resin and powder coating composition using the same | |
| KR102244453B1 (en) | Powder coating composition | |
| EP0305325B1 (en) | Co-advanced epoxy resins from polyglycidyl ethers of polyhydric phenols and diglycidyl ethers of di-secondary alcohols | |
| KR100744820B1 (en) | Process for producing epoxy powder coating composition having increased flexibility and adhesive power and coating composition | |
| JPH0749553B2 (en) | Anticorrosion paint composition | |
| JPH10101773A (en) | One-pack epoxy resin composition | |
| KR20040061910A (en) | Isocyanate, core shell rubber modified epoxy resin having high glass transition temperature and advanced rust-resisting properties and its preparing method and powdered paint composition contained thereof | |
| KR100647891B1 (en) | Multifunctional phenolic curing agent for epoxy resin type powder coating compositions | |
| JPH09100425A (en) | Powder paint for casting | |
| JPS62197412A (en) | Curing agent for epoxy or urethane resin and curable mixture consisting of said resin and said curing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| N231 | Notification of change of applicant | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |